Ning Zhao

Solid-state electrolytes with high ionic conductivity, large electrochemical window, good mechanical properties, and easy processability are needed for high-energy solid-state lithium batteries. In this work, composite membranes consisting of lithium garnet (i.e. Li6.4La3Zr1.4Ta0.6O12, LLZTO) particles and Li-salt-free polyethylene oxides (PEOs) are produced as solid-state electrolytes. Li-ion-conducting particles in nano-scale are crucial for the enhancement of conductivity and the membranes containing ~40 nm LLZTO particles exhibit conductivities nearly two orders of magnitude larger than those with the micro-scale ones, which is attributed to the difference in specific surface area related to the percolation effect. Compared to the conventional PEO doped with lithium salt, the insulating PEO in PEO:LLZTO membrane electrolyte is conducive to the suppression of lithium dendrite growth owing to prohibition of current flow. With PEO:LLZTO membrane electrolytes in conductivity of 2.1×10−4 S cm−1 at 30 °C and 5.6×10−4 S cm−1 at 60 °C, the solid-state LiFePO4/PEO:LLZTO/Li and LiFe0.15Mn0.85PO4/PEO:LLZTO/Li cells deliver energy densities of 345 Wh kg−1 (662 Wh L−1) and 405 Wh kg−1 (700 Wh L−1) (without the package weight or volume) with good rate capability and cycling performance. This study suggests that the conjunction of nano-scale Li-ion-conducting particles and an insulating polymer provides a promising solution to produce powerful solid-state electrolytes for high-performance solid-state lithium batteries.

To be the abundant natural feedstock, CO2 chemical utilization has attracted the great interest in recent years. The key point to CO2 conversion is the activation of either CO2 or co-reactant at different conditions. To bear this in mind, our strategy is to activate CO2 either with the presence of electron-rich chemicals or by hydrogen, and to convert CO2 with a coupling reaction in some case. In this way, catalytic conversion of CO2 has been carried out by different methodology at our lab, including CO2 reforming of methane to syngas production over bifunctional catalysis, CO2 hydrogenation for methanol synthesis by nano-structured catalyst, and synthesis of carbonates from sub- or super-critical CO2 with a coupling of in situ water removal reaction or bifunctional catalyst system. Herein, this brief review presents the recent progress of catalytic CO2 conversion and aims to shed a light into the chemical fixation of CO2.

With the development of microelectronic technology, the demand of insulating electronic encapsulation materials with high thermal conductivity is ever growing and much attractive. Surface modification of chemical inert h-BN is yet a distressing issue which hinders its applications in thermal conductive composites. Here, dopamine chemistry has been used to achieve the facile surface modification of h-BN microplatelets by forming a polydopamine (PDA) shell on its surface. The successful and effective preparation of h-BN@PDA microplatelets has been confirmed by SEM, EDS, TEM, Raman spectroscopy, and TGA investigations. The PDA coating increases the dispersibility of the filler and enhances its interaction with PVA matrix as well. Based on the combination of surface modification and doctor blading, composite films with aligned h-BN@PDA are fabricated. The oriented fillers result in much higher in-plane thermal conductivities than the films with disordered structures produced by casting or using the pristine h-BN. The thermal conductivity is as high as 5.4 W m(-1) K(-1) at 10 vol % h-BN@PDA loading. The procedure is eco-friendly, easy handling, and suitable for the practical application in large scale.

This article reviews the progress made in CO2 capture, storage, and utilization in Chinese Academy of Sciences (CAS). New concepts such as adsorption using dry regenerable solid sorbents as well as functional ionic liquids (ILs) for CO2 capture are thoroughly discussed. Carbon sequestration, such as geological sequestration, mineral carbonation and ocean storage are also covered. The utilization of CO2 as a raw material in the synthesis of chemicals and liquid energy carriers which offers a way to mitigate the increasing CO2 buildup is introduced.

We combine two amazing abilities found in nature: the superhydrophobic property of lotus leaf and the adhesive ability of mussel adhesive protein. The molecular structure mimic of the single units of adhesive proteins, dopamine, was polymerized in an alkaline aqueous solution to encapsulate microparticles. The as-formed thin polydopamine walls worked as reactive templates to generate silver nanoparticles on the capsuled particles. As a result, core/shell/satellite composite particles were generated with a hierarchical structure similar to the micromorphology of lotus leaf. The composite particles exhibited extremely water repellence after fluorination. Because dopamine can deposit and adhere to all kinds of materials, this method can be applied to diverse microparticles, from organic to inorganic. In addition, particles of different sizes and matters can be modified to superhydrophobic particles in one pot. Magnetic particles have also been prepared which could be used as oil-absorbent and magnetic controlled carriers. “Oil marbles” formed underwater were achieved for the first time.

Unusual sheets-like primary activated carbon particles interconnected into three-dimensional micrometer-level large pores were prepared from a novel biomass named willow catkins (WCs) by KOH chemical activation process and used as electrode materials for supercapacitors. The pore structures, surface area and chemical properties could be facilely adjusted by changing the activation temperature. When the activation temperature increased from 600 to 800 °C, the specific surface area of the porous carbon product increased remarkably while the contents of nitrogen and oxygen co-doped decreased, which significantly affected the electrochemical properties of the porous carbon-based supercapacitors. The activated carbons from 600 °C activation possesses despite moderate specific surface area (645 m2 g−1), concentrated pore size distribution of 0.77 nm, but high nitrogen (2.51 wt.%) and oxygen (13.28 wt.%) contents, high graphitization degree as well as good electrical conductivity. The supercapacitors with the carbon electrode reached maximal specific capacitances of 340 F g−1 and high specific surface capacitance of 52.7 μF cm−2 at the current density of 0.1 A g−1, good rate capability (231 F g−1 at 10 A g−1) and good cycling stability (92% capacitance retention over 3000 cycles). The favorable capacitive performances make the waste biomass WCs act as a new resource of carbonaceous materials for high performance supercapacitors.

<h2>Summary</h2> Solid-state batteries (SSBs) can essentially improve battery safety. Garnet-type Li₇La₃Zr₂O₁₂ (LLZO) is considered one of the most promising solid electrolytes for SSBs. However, the performance of LLZO-based SSBs is limited by the large cathode/electrolyte interfacial resistance. High-rate and long-cycling SSBs were achieved only after adding flammable polymer or liquid electrolyte in the cathode at the sacrifice of safety. Here, we show that an all-ceramic cathode/electrolyte with an extremely low interfacial resistance can be realized by thermally soldering LiCoO₂ (LCO) and LLZO together with the Li_2.3−xC_0.7+xB_0.3−xO₃ solid electrolyte interphase through the reaction between the Li_2.3C_0.7B_0.3O₃ solder and the Li₂CO₃ layers that can be conformally coated on both LLZO and LCO. The all-solid-state Li/LLZO/LCO battery with such an all-ceramic cathode/electrolyte exhibits high cycling stability and high rate performance, constituting a significant step toward the practical applications of SSBs.

The ever-increasing energy density of the Li-ion battery calls for utilization of high-capacity cathodes and anodes, which tend to be more reactive and thus bring serious safety concern. Under such context, the solid-state Li battery becomes a hotspot because of its potential in the breakthrough of energy density as well as the avoidance of uncontrollable chemical reactions. Recently, many review and perspective papers appear, addressing the urgency of improving solid-electrolytes’ ionic conductivity and constructing stable conductive interfaces between electrolyte and electrode with respect to available electrolytes, including polymers, nitrides, sulfides, and oxides. Nevertheless, each type of electrolyte has its own distinctive problems, which is worthwhile specifically elaborating in order to find effective solutions. Therefore, here, we present our viewpoints on the key issues related to the garnet electrolytes and relevant batteries, which have not ever been dedicatedly addressed previously. On the basis of our recent progress, together with others reported in the literature, we expect that the solid garnet batteries are promising for application if the best use is made of garnet advantages and disadvantages are bypassed.

A series of Cu/Zn/Al/Zr hydrotalcite-like precursors with Zr4+:(Al3++Zr4+) from 0 to 0.7 were synthesized by a co-precipitation method. X-ray diffraction and thermogravimetric measurements demonstrated that the yield of the hydrotalcite-like phase decreases with increased Zr content. The Cu/Zn/Al/Zr mixed oxides were then obtained by calcination of the hydrotalcite-like precursors and tested for methanol synthesis from CO2 hydrogenation. With increased Zr4+:(Al3++Zr4+) atomic ratio, the exposed Cu surface area and dispersion of Cu first increase until Zr4+:(Al3++Zr4+) = 0.3 and then decrease. However, the total number of basic sites on catalysts increases continuously. It is also found that the CO2 conversion is related to the exposed Cu surface area and the dispersion of Cu, while the CH3OH selectivity is related to the distribution of basic sites on the catalyst surface. The incorporation of a suitable amount of Zr is beneficial for the production of methanol, and the best catalytic performance is obtained when the Zr4+:(Al3++Zr4+) atomic ratio is 0.3.

Garnet-type solid-state electrolytes (SSEs) are very promising due to their high ionic conductivities at room temperature and high stability against Li metal. However, the poor garnet/Li interfacial contact caused by Li2CO3 surface contaminant can lead to lithium dendrite growth and the performance decay of solid-state batteries (SSBs), which still hinders their practical application. Herein, a universal and simple method of rapid acid treatment is proposed to perfectly remove the surface Li2CO3 and retrieve a lithiophilic SSE surface. The SSE/Li interfacial resistance dramatically decreases from 940 Ω cm2 to 26 Ω cm2 at 30 °C. The acid treated garnet-SSE pellets exhibit an interfacial resistance comparable to the pellets with various surface coatings. In addition, the intrinsic garnet/Li interface remains stable during cycling, which enables the Li symmetric cells continuously cycle over 700 h under 0.2 mA cm−2 at 30 °C. And the LiFePO4/Li and LiCoO2/Li cells with acid treated garnet-SSE show excellent cycle and rate performances after eliminating the surface contaminant. These results indicate that rapid acid treatment not only guides a new understanding for an intrinsic garnet/Li interface but also is a simple and high-efficiency strategy to well address the interfacial issue for SSBs.

Polyurethanes (PUs) have many applications resulting from their preeminent properties, but being commonly used toxic catalysts, and the lack of processability for PU thermosets cause limitations. Herein, we report a new class of the PU-like dynamic covalent polymers, poly(oxime-urethanes) (POUs), which are prepared from the uncatalyzed polyaddition of multifunctional oximes and hexamethylene diisocyanate (HDI) at ambient temperature. Kinetics studies reveal that almost complete polymerization (∼99% conversion) can be achieved in 3 h at 30 °C in dichloromethane (DCM), the most effective among the solvents evaluated, producing linear POUs with comparable molecular weights to the catalyzed PUs. We find that the oxime-carbamate structures are reversible at about 100 °C through oxime-enabled transcarbamoylation via a thermally dissociative mechanism. The cross-linked POUs based on oxime–carbamate bonds show efficient catalyst-free healable/recyclable properties. Density functional theory (DFT) calculations suggest that the fast oxime-urethanation and the mild thermoreversible nature are mediated by the characteristic nitrone tautomer of the oxime. Given widespread urethane-containing materials, POUs are of promising potential in applications because of the excellent mechanical performances, facile preparation, and dynamic property without using catalysts.

Garnet electrolyte-based lithium (Li) metal batteries, which employ garnet-type Li7La3Zr2O12 (LLZO) as electrolyte and Li metal as anode, are regarded as a promising candidate for high-energy batteries. However, Li dendrites formation as well as poor solid-solid contact between the electrolyte and electrodes result in high interfacial resistance, large polarizations, and low Coulombic efficiency. Herein, we demonstrated that solid polymer electrolyte (SPE) soft interface layer deposited on garnet electrolyte (Ta-doped LLZO (LLZTO)) surface along with 3D Li metal anode can address these obstacles. In this architecture, SPE layer was deposited on garnet electrolyte surface to endow connected interface between the electrolyte and electrodes and thus settled the interface contact issue. 3D Li metal anode can accomplish dendrite-suppression by increasing Li ions deposition sites to lower the effective current density and render a uniform Li nucleation with 3D frameworks. With this ingenious arrangement, the solid-state 3D Li︱SPE-LLZTO-SPE︱3D Li symmetrical cell exhibits a stable voltage profile over 700 h and solid-state LiFePO4︱SPE-LLZTO-SPE︱3D Li full cell also shows an extremely superior cyclability and high Coulombic efficiency even at 90 °C. This work provides an alternative option for manufacturing safe and stable solid-state Li metal batteries.

A mixed conductive garnet/Li interface consisting of electronic conductive nanoparticles embedded in an ionic conductive network is constructed for dendrite-free solid garnet batteries.

A series of Cu/ZnO/ZrO2 catalysts were prepared by precipitation-reduction method and tested for the synthesis of methanol by CO2 hydrogenation. The advantages of precipitation-reduction method over conventional co-precipitation method, the effect of NaBH4 content were investigated by XRD, N2 physisorption, SEM, TEM, N2O chemisorption, XPS, TPR, CO2-TPD techniques. The influence of precipitation-reduction process on the average Cu particle size, aggregation state and interaction among different elements were discussed in detail. The content of NaBH4 had an effect on the exposed Cu surface area as well as the ratio of Cu0/Cu+ and thus influenced the catalytic performance. The catalysts prepared by precipitation-reduction method increased the number of basic sites and had a significant advantage in methanol selectivity in contrast with conventional precipitation method. A suitable NaBH4 content was beneficial to the catalytic performance in Cu/ZnO/ZrO2 catalysts and a maximum space time yield of CH3OH was obtained with B/Cu = 5 at 543 K.

3D hierarchical hollow nanocubes constructed by 1D FeSe2@C core-shell nanorods were successfully prepared by a thermally-induced selenization process of their Prussian blue microcubes precursor. Such novel nanorods-based FeSe2@C hollow structures exhibit high conductivity and special structural property which provide good charge transport kinetics by facilitating the charge transfer into the inner of FeSe2 nanorods. When used as anode materials for sodium ion batteries, the hierarchically hollow nanocubes showed excellent rate performance and ultra-stable long-term cycling stability at a high current density of 10 A g−1, suggesting a good sodium-ion storage material. This simple solid-phase process demonstrated in this work can be further used for the preparation of other metal selenide with unique and fascinating structure for the potential applications in the energy storage field.

A series of promoted Cu/Zn/Al catalysts derived from hydrotalcite-like precursors were synthesized by co-precipitation method and tested for the CO2 hydrogenation to methanol. The influence of modifier (Mn, La, Ce, Zr and Y) on the physicochemical properties of Cu/Zn/Al catalysts was studied in detail. The results show that the BET specific surface area, Cu surface area and Cu dispersion increase in the order of Cu/Zn/Al < Cu/Zn/Al/Mn < Cu/Zn/Al/La < Cu/Zn/Al/Ce < Cu/Zn/Al/Zr < Cu/Zn/Al/Y. The similar trend can be observed for the total number of basic sites, while the Zr-modified Cu/Zn/Al catalyst exhibits the highest density and proportion of strongly basic sites. It is also found that the CO2 conversion depends on the exposed Cu surface area and the CH3OH selectivity increases linearly with the increase of proportion of strongly basic sites to the total basic sites. The introduction of Mn, La, Ce, Zr and Y favors the production of methanol and the Y- and Zr-modified Cu/Zn/Al catalysts exhibit the highest CO2 conversion and CH3OH selectivity, respectively.

All solid-state lithium batteries are constructed by using highly conducting Ta-doped Li7La3Zr2O12 (LLZTO) as the solid electrolytes as well as the supports, coated with composite cathodes consisting of poly(vinylidene fluoride) (PVdF):LiTFSI, Ketjen Black, and carbon-coated LiFePO4 on one side and attached with Li anode on the other side. At 60 °C, the batteries show the first discharge capacity of 150 mAh g−1 at 0.05 C and 93% capacity retention after 100 cycles. As the current density increases from 0.05 C to 1 C, the specific capacity decreases from 150 mAh g−1 to 100 mAh g−1. Further elevated temperature up to 100 °C leads to further improved performance, i.e. 126 mAh g−1 at 1 C and 99% capacity retention after 100 cycles. This good performance can be attributed to the highly conducting ceramic electrolytes, the optimum electronic and ionic conducting networks in the composite cathodes, and closely contacted cathode/LLZTO interface. These results indicate that the present strategy is promising for development of high-performance solid-state Li-ion batteries operated at medium temperature.

The surprising properties of biomaterials are the results of billions of years of evolution. Generally, biomaterials are assembled under mild conditions with very limited supply of constituents available for living organism, and their amazing properties largely result from the sophisticated hierarchical structures. Following the biomimetic principles to prepare manmade materials has drawn great research interests in materials science and engineering. In this review, we summarize the recent progress in fabricating bioinspired materials with the emphasis on mimicking the structure from one to three dimensions. Selected examples are described with a focus on the relationship between the structural characters and the corresponding functions. For one‐dimensional materials, spider fibers, polar bear hair, multichannel plant roots and so on have been involved. Natural structure color and color shifting surfaces, and the antifouling, antireflective coatings of biomaterials are chosen as the typical examples of the two‐dimensional biomimicking. The outstanding protection performance, and the stimuli responsive and self‐healing functions of biomaterials based on the sophisticated hierarchical bulk structures are the emphases of the three‐dimensional mimicking. Finally, a summary and outlook are given.

Introduction of inorganic solid electrolytes is believed to be an ultimate strategy to dismiss dendritic Li in high-energy Li-metal batteries (LMBs), and garnet-type Li7La3Zr2O12 (LLZO) electrolytes are impressive candidates. However, the current density for stable Li plating/stripping in LLZO is still quite limited. Here, we create in situ formed Li-deficient shields by the high-temperature calcination at 900 °C. By this novel process, the formation of Li2CO3 on LLZO is restrained, and then we successfully obtain Li2CO3-free LLZO after removing the Li-deficient compounds. Without any surface modification, Li2CO3-free LLZO shows an intrinsic “lithiophilicity” characteristic. The contact angles of metallic Li on LLZO garnets are assessed by the first-principle calculation to confirm the lithiophilicity characteristic of LLZO electrolytes. The wetting of metallic Li on the Li2CO3-free LLZO surface leads to a continuous and tight Li/LLZO interface, resulting in an ultralow interfacial resistance of 49 Ω cm2 and a homogeneous current distribution in the charge/discharge processes of LMBs. Consequently, the current density for the stable Li plating/stripping in LLZO increases to 900 μA cm–2 at 60 °C, one of the highest current density for LMBs based on garnet-type LLZO electrolytes. Our findings not only offer insight into the lithiophilicity characteristics of LLZO electrolytes to suppress dendritic Li at high current densities but also expand the avenue toward high-performance, safe, and long-life energy-storage systems.

Although Li metal has been regarded as one of the most promising anode materials, an unstable Li/electrolyte interface during the cycling process seriously limits its practical application in rechargeable batteries. Herein, we report a transplantable LiF-rich layer (TLL) that can suppress the side reactions between electrolyte and lithium metal. This peelable layer cross-linked by nanoscale LiF domains is obtained by electrochemically reducing NiF2 electrodes and could be used to protect Li metal anodes. Cu-Li cells using the TLL protection can operate for more than 300 cycles with a Coulombic efficiency as high as ~ 98% in carbonate-based electrolytes. In Li-LiFePO4 cells, lithium metal with a TLL still looks shiny after 1000 cycles (~ 6 months) in contrast to the black surface of bare lithium foil after ~ 500 cycles (~ 3 months). These results clearly demonstrate that the TLL could greatly limit the side reactions between lithium metal and the carbonate-based electrolytes, and may enable long-term stable operation of Li metal batteries.

Abstract Solid-state batteries (SSBs) are considered to be the next-generation lithium-ion battery technology due to their enhanced energy density and safety. However, the high electronic conductivity of solid-state electrolytes (SSEs) leads to Li dendrite nucleation and proliferation. Uneven electric-field distribution resulting from poor interfacial contact can further promote dendritic deposition and lead to rapid short circuiting of SSBs. Herein, we propose a flexible electron-blocking interfacial shield (EBS) to protect garnet electrolytes from the electronic degradation. The EBS formed by an in-situ substitution reaction can not only increase lithiophilicity but also stabilize the Li volume change, maintaining the integrity of the interface during repeated cycling. Density functional theory calculations show a high electron-tunneling energy barrier from Li metal to the EBS, indicating an excellent capacity for electron-blocking. EBS protected cells exhibit an improved critical current density of 1.2 mA cm −2 and stable cycling for over 400 h at 1 mA cm −2 (1 mAh cm −2 ) at room temperature. These results demonstrate an effective strategy for the suppression of Li dendrites and present fresh insight into the rational design of the SSE and Li metal interface.

In this work, hierarchically porous carbon/manganese monoxide nanosheets (HPC-MnO) composite materials are synthesized by a facile one-step approach, in which chemical activation of biomass precursor (wasted litchi shell) and loading of MnO nanosheets are conducted synchronously. The phase structure, chemical composition, morphology and specific surface area as well as the pores distribution are investigated for the resultant HPC-MnO composite materials. Interestingly, the as obtained HPC-MnO composite materials can serve both as the positive and negative electrodes simultaneously in a hybrid symmetric supercapacitor. High specific capacitances of 162.7F/g at a current density of 0.5 A/g and energy density of 57.7 W h/kg at a power density of 400 W/kg are obtained for the assembled symmetric HPC-MnO//HPC-MnO device, owing to the synergistic effects between electrochemical double-layer capacitance from the hierarchical porous carbons and pseudocapacitance from the redox reaction of manganese oxides. This work provides a facile and scalable strategy to synthesize carbon/metal oxides composites with promising electrochemical performances application for energy storage devices and opens a new gateway to design novel symmetric hybrid supercapacitors.

Abstract Dendrite growth and parasitic side reactions are thorny issues that seriously damage the anode–electrolyte interface during Zn plating/stripping process, leading to uncontrollable Zn deposition and restraining application of aqueous Zn‐ion batteries (AZIBs). Here, a unique facile strategy to in situ build indium (In) metal interphase on the Zn anode is first proposed. The combination of experimental and theoretical investigations demonstrate that such metallic interphase prevents the hydrogen evolution reaction (HER) and Zn corrosion, and guides preferential growth along the Zn(002) plane to achieve smooth Zn deposition. As a result, the modified Zn anodes achieve the ultrahigh cumulative capacities of 5600 and 5000 mAh cm −2 at the high current densities of 2 and 5 mA cm −2 , respectively, demonstrating an ultrastable plating/stripping behavior. More encouragingly, the rate performance and cyclic stability of the Zn–V 2 O 5 battery with the electrolyte additive can still deliver a specific capacity of 383.6 mAh g −1 after 5000 cycles at the high current density of 5 A g −1 . The strategy presented here as well as the in‐depth understanding of modified mechanism can not only provide an effective solution to address the Zn anode concerns, but also deepen the understanding of AZIBs.

Superionic conductors with ionic conductivity on the order of mS cm-1 are expected to revolutionize the development of solid-state batteries (SSBs). However, currently available superionic conductors are limited to only a few structural families such as garnet oxides and sulfide-based glass/ceramic. Interfaces in composite systems such as alumina in lithium iodide have long been identified as a viable ionic conduction channel, but practical superionic conductors employing the interfacial conduction mechanism are yet to be realized. Here we report a novel method that creates continuous interfaces in the bulk of composite thin films. Ions can conduct through the interface, and consequently, the inorganic phase can be ionically insulating in this type of bulk interface superionic conductors (BISCs). Ionic conductivities of lithium, sodium, and magnesium ion BISCs have reached 1.16 mS cm-1, 0.40 mS cm-1, and 0.23 mS cm-1 at 25 °C in 25 μm thick films, corresponding to areal conductance as high as 464 mS cm-2, 160 mS cm-2, and 92 mS cm-2, respectively. Ultralow overpotential and stable long-term cycling for up to 5000 h were obtained for solid-state Li metal symmetric batteries employing Li ion BISCs. This work opens new structural space for superionic conductors and urges for future investigations on detailed conduction mechanisms and material design principles.

Abstract Traditional hydrogels always lose their flexibility and functions in dry environments because the internal water inevitably undergoes evaporation. In this study, a skin‐inspired, facile, and versatile strategy for developing encapsulated hydrogels with excellent water retention capacity through a double‐hydrophobic coating is proposed. The robust double‐layer coating, which integrates a hydrophobic polymer coating with a hydrophobic oil layer simultaneously, can provide a barrier to prevent the evaporation of water. To overcome the weak interfacial strength between the hydrophilic hydrogel surface and the double‐hydrophobic coating, (3‐aminopropyl) triethoxysilane (APTES) is utilized as a chemical binding agent. Furthermore, the overall mechanical properties of the bulk hydrogel are not significantly affected, because the coating is only anchored to the surface and its thickness is much lower than that of the native hydrogel. Moreover, it is demonstrated that this proposed strategy particularly holds the capability of encapsulating various types and different shapes of hydrogels, leading to enhanced stability and a prolonged lifetime in air. Therefore, the proposed technology provides new insights for multifarious surface functionalization of hydrogel and broadens the range of hydrogel applications.

Bioinspired architectures are effective in enhancing the mechanical properties of materials, yet are difficult to construct in metallic systems. The structure-property relationships of bioinspired metallic composites also remain unclear. Here, Mg-Ti composites were fabricated by pressureless infiltrating pure Mg melt into three-dimensional (3-D) printed Ti-6Al-4V scaffolds. The result was composite materials where the constituents are continuous, mutually interpenetrated in 3-D space and exhibit specific spatial arrangements with bioinspired brick-and-mortar, Bouligand, and crossed-lamellar architectures. These architectures promote effective stress transfer, delocalize damage and arrest cracking, thereby bestowing improved strength and ductility than composites with discrete reinforcements. Additionally, they activate a series of extrinsic toughening mechanisms, including crack deflection/twist and uncracked-ligament bridging, which enable crack-tip shielding from the applied stress and lead to "Γ"-shaped rising fracture resistance R-curves. Quantitative relationships were established for the stiffness and strengths of the composites by adapting classical laminate theory to incorporate their architectural characteristics.

The development of solid lithium battery accords with the pursuit of advanced battery with high energy density and reliable safety. The requirement of high energy density calls for the light as well as thin solid electrolytes with good contacts with cathodes, while the safety demands the electrochemically stable interfaces between electrolytes and Li-metal anodes. Herein, the light and stable composite electrolytes with hierarchical structures are directly integrated with the interfacially friendly cathodes via layer-by-layer tape casting. Through incorporation of Li6.4La3Zr1.4Ta0.6O12 (LLZTO) superconductors with poly(ethylene oxide) (PEO) matrix layer by layer, the total thickness of composite electrolyte is minimized below 40 μm. In terms of the electrolyte-layer constitution, the conductively oriented side (PEO with 10 wt% LLZTO) is integrated with the composite cathode that is infused with the same 10 wt% LLZTO in PEO enabling the compatible cathode/electrolyte interface. The mechanically oriented side (PEO with 40 wt% LLZTO) faces the Li-metal enabling suppression of dendrite growth. Consequently, the cathode supported LiFePO4/Li cells consisting of the designed electrolytes show the discharge capacity of 129 mAh g−1 at 0.1 C and 30°C, and the stable cycle over 150 times with the capacity retention above 80.6%. Moreover, a high discharge capacity of 118 mAh g−1 is achieved with a high cathode loading of 15.2 mg cm−2 at 0.1 C and 50°C. This work demonstrates a novel strategy to construct cathode supported solid batteries based on the light, stable and interfacially friendly solid-electrolyte layers for high energy density and stable cyclability.

Abstract Sluggish transport kinetics and rapid dendrite growth are considered the main obstacles that impair the performance of Zn metal batteries. This work has developed a unique strategy of dual‐interface engineering (DIE) to design the separator as efficient ions transport modulator. The dual function of spontaneous polarization effect and high zincophilicity of BaTiO 3 (BTO) is revealed by combining the theoretical and experimental studies. Benefiting from the decoration of BTO on glass fiber and well filling of the surface interspace, the DIE‐modified separator can not only effectively capture and accelerate Zn 2+ transport between the fiber–electrolyte interface, but also redistribute the ions transport into homogenization in the separator–anode interface. Therefore, the modified Zn anodes perform highly reversible Zn plating/stripping with ultrahigh cumulative capacity even up to 9500 mAh cm −2 at the high current density of 10 mA cm −2 . Meanwhile, the modified Zn‐MnO 2 battery can retain a specific capacity of 108 mAh g −1 after 1800 cycles at 1 A g −1 . Furthermore, the capacity retention of the battery also can be improved from 37.5% up to 115% at 0.2 A g −1 after 100 cycles. Such a novel concept for separator engineering provides a new perspective to enable ultra‐stable Zn metal anodes and high‐performance Zn metal batteries.

The garnet-type Li7La3Zr2O12 (LLZO) is deemed as the promising solid electrolyte for solid lithium batteries due to its high stability and ionic conductivity. However, the rigid and brittle natures of LLZO lead to severe interfacial issues from both the cathode and the Li-metal anode sides, as well as limited applications in flexible electronics. In this work, the in-situ solidified gel polymer electrolytes (GPEs) are constructed as not only the interlayer to buffer electrode/garnet interfaces, but also the adhesive to join garnet blocks together, realizing the scale expansion and good flexibility of solid garnet batteries. For interface engineering, such GPE is conformally solidified at electrode/garnet interfaces, along with the cathode particles fully surrounded by solidified electrolytes. On anode sides, the Li/garnet interfacial resistance notably drops to 88 Ω cm2, accompanied by the symmetric cell stably cycling over 400 h with robust solid electrolyte interphases. On cathode sides, the cross-linked ion-conducting network is formed inside the cathode, and the intimate contact is built at cathode/garnet interface, arousing remarkable cycling and rate performance for LiFe0.2Mn0.8PO4/Li and LiFePO4/Li cells at 30 °C. Furthermore, the soft GPE can be used as adhesive to connect garnet blocks together without gaps, enabling the construction of flexible and large-scale solid batteries, in which the GPE functions as deformable medium to induce the bending and coiling of solid batteries. This work demonstrates a promising strategy to address both the rigidity and brittleness issues of garnets by utilizing the in-situ solidified multifunctional GPEs.

Abstract Garnet‐type electrolytes show great potential in application of solid‐state lithium batteries due to their high ionic conductivity and wide electrochemical window. However, the formation of surface Li 2 CO 3 derived from air exposure triggers uneven contact with Li‐metal, leading to undesirable dendrite growth and performance deterioration. Herein, the Li 3 PO 4 layer replacing Li 2 CO 3 contaminant is built on garnet surface by taking molten NH 4 H 2 PO 4 salt driven conversion reaction. The high‐flowability molten salt contributes to conformal formation of Li 3 PO 4 , realizing the air‐stable garnet by preventing the re‐attack of H 2 O/CO 2 in air. Besides, the high work of adhesion for Li 3 PO 4 on Li‐metal along with the transformation from Li 3 PO 4 to Li 3 P/Li 2 O when contacting with molten Li‐metal enables a lithiophilic interlayer, leading to a seamless Li/garnet contact with ultralow interfacial resistance of 13 Ω cm 2 . Such ion‐conducting but electron‐insulating layer regulates the uniform distribution of Li‐flux, enabling a large critical current density of 1.2 mA cm −2 . Furthermore, the solid LiCoO 2 /Li cell with the modified garnet delivers a discharge capacity of 130 mAh g −1 at 30 °C, accompanied by a capacity retention of 81% after 150 cycles. This study proposes a promising solution for improvement of air stability and interfacial compatibility of garnet using facile molten salt treatment.

Abstract Three-dimensional (3D) grid porous electrodes introduce vertically aligned pores as a convenient path for the transport of lithium-ions (Li-ions), thereby reducing the total transport distance of Li-ions and improving the reaction kinetics. Although there have been other studies focusing on 3D electrodes fabricated by 3D printing, there still exists a gap between electrode design and their electrochemical performance. In this study, we try to bridge this gap through a comprehensive investigation on the effects of various electrode parameters including the electrode porosity, active material particle diameter, electrode electronic conductivity, electrode thickness, line width, and pore size on the electrochemical performance. Both numerical simulations and experimental investigations are conducted to systematically examine these effects. 3D grid porous Li 4 Ti 5 O 12 (LTO) thick electrodes are fabricated by low temperature direct writing technology and the electrodes with the thickness of 1085 µm and areal mass loading of 39.44 mg·cm −2 are obtained. The electrodes display impressive electrochemical performance with the areal capacity of 5.88 mAh·cm −2 @1.0 C, areal energy density of 28.95 J·cm −2 @1.0 C, and areal power density of 8.04 mW·cm −2 @1.0 C. This study can provide design guidelines for obtaining 3D grid porous electrodes with superior electrochemical performance.

For next-generation all-solid-state metal batteries, the computation can lead to the discovery of new solid electrolytes with increased ionic conductivity and excellent safety. Based on computational predictions, a new proposed solid electrolyte with a flat energy landscape and fast ion migration is synthesized using traditional synthesis methods. Despite the promise of the predicted solid electrolyte candidates, conventional synthetic methods are frequently hampered by extensive optimization procedures and overpriced raw materials. It is impossible to rationally develop novel superionic conductors without a comprehensive understanding of ion migration mechanisms. In this review, we cover ion migration mechanisms and all emerging computational approaches that can be applied to explore ion conduction in inorganic materials. The general illustrations of sulfide and oxide electrolyte structures as well as their fundamental features, including ion migration paths, dimensionalities, defects, and ion occupancies, are systematically discussed. The major challenges to designing the solid electrolyte and their solving strategies are highlighted, such as lattice softness, polarizability, and structural disorder. In addition to an overview of recent findings, we propose a computational and experimental approach for designing high-performance solid electrolytes. This review article will contribute to a practical understanding of ion conduction, designing, rapid optimization, and screening of advanced solid electrolytes in order to eliminate liquid electrolytes.

Recently, an efficient integrated forging process has been proposed in which solutionized aluminum alloy extruded bars are directly hot forged and quenched. In this study, the hot deformation behaviors and microstructure evolution of 6082 aluminum alloy extruded bar was investigated via isothermal compression tests under the temperature range of 400–535 ℃ and strain rates range of 0.1–10 s−1 with different strains. The deformation behaviors were described by the established strain-compensated constitutive model and processing maps. The microstructure evolution of the deformed specimens was revealed by electron back scattered diffraction (EBSD) and transmission electron microscopy (TEM). It was found that the Zener-Hollomon (Z) parameter, which involved temperature and strain rate, exerted a considerable influence on the deformation behaviors and microstructure evolution. Deformation-induced extensive dislocations were pinned by the dispersoids and generated cellular substructures under high ln Z (i.e. low temperature or high strain rate), potentially triggering dynamic instability. The tangled dislocations pinned by the insoluble dispersoids continued to overcome the pinning points as ln Z decreased, while the dislocations were consumed by the rotation of subgrain boundaries. As a result, the geometrically necessary dislocation (GND) was decreased with the significant increase of the fraction of high angle grain boundaries (HAGBs). In addition, the stable-end orientations, namely, Brass {011}< 211 > and Goss {011}< 001 > texture components with high Schmid Factors (SFs) are generated during compression, facilitating the dislocation movement and thus promoting the fraction of recrystallization. The above findings demonstrate the foundation for improving forming performance and optimizing the processing parameters for the integrated forging process.

NiFeSe 4 /NiSe 2 -8 h had good overall water splitting performance. The heterostructure of the prepared NiFeSe 4 /NiSe 2 -8 h promoted the redistribution of electrons and improved the conductivity of the material.

Multi-membrane hydrogels are newly promising carriers in biomedical fields. We fabricate alginate-based onion-like multi-membrane hydrogels starting from a template gel-core to shells through a dynamic self-assembly method, and investigate the influence of various factors on the formation of the complex system in detail. By precisely controlling the process of preparation, multi-layered hydrogels of different shapes either with or without defined internal space between separated layers can be prepared. And a pulse-like delivery of macromolecule has been achieved by this architecture.

Abstract Summary: A superhydrophobic coating was facilely fabricated in one step by casting bisphenol A polycarbonate (PC) solution under moisture. Vapor‐induced phase separation occurred during the solidifying process and a rough surface with a micro‐nano‐binary structure (MNBS) similar to the microstructure shown on lotus leaf was formed. SEM image of a single micro‐flower. magnified image SEM image of a single micro‐flower.

In this article, we report a bioinspired approach to preparing stable, functional multilayer films by the integration of mussel-inspired catechol oxidative chemistry into a layer-by-layer (LbL) assembly. A polyanion of poly(acrylic acid-g-dopamine) (PAA-dopamine) bearing catechol groups, a mussel adhesive protein-mimetic polymer, was synthesized as the building block for LbL assembly with poly(allylamine hydrochloride) (PAH). The oxidization of the incorporated catechol group under mild oxidative condition yields o-quinone, which exhibits high reactivity with amine and catechol, thus endowing the chemical covalence and retaining the assembled morphology of multilayer films. The cross-linked films showed excellent stability even in extremely acidic, basic, and highly concentrated aqueous salt solutions. The efficient chemical cross-linking allows for the production of intact free-standing films without using a sacrificial layer. Moreover, thiol-modified multilayer films with good stability were exploited by a combination of thiols-catechol addition and then oxidative cross-linking. The outstanding stability under harsh conditions and the facile functionalization of the PAA-dopamine/PAH multilayer films make them attractive for barriers, separation, and biomedical devices.

Advanced MaterialsVolume 16, Issue 20 p. 1830-1833 Communication Facile Creation of a Bionic Super-Hydrophobic Block Copolymer Surface† Q. Xie, Q. Xie State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P.R.ChinaSearch for more papers by this authorG. Fan, G. Fan CAS Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P.R.ChinaSearch for more papers by this authorN. Zhao, N. Zhao State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P.R.ChinaSearch for more papers by this authorX. Guo, X. Guo State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P.R.ChinaSearch for more papers by this authorJ. Xu, J. Xu [email protected] Search for more papers by this authorJ. Dong, J. Dong [email protected] Search for more papers by this authorL. Zhang, L. Zhang CAS Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P.R.ChinaSearch for more papers by this authorY. Zhang, Y. Zhang State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P.R.ChinaSearch for more papers by this author Q. Xie, Q. Xie State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P.R.ChinaSearch for more papers by this authorG. Fan, G. Fan CAS Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P.R.ChinaSearch for more papers by this authorN. Zhao, N. Zhao State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P.R.ChinaSearch for more papers by this authorX. Guo, X. Guo State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P.R.ChinaSearch for more papers by this authorJ. Xu, J. Xu [email protected] Search for more papers by this authorJ. Dong, J. Dong [email protected] Search for more papers by this authorL. Zhang, L. Zhang CAS Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P.R.ChinaSearch for more papers by this authorY. Zhang, Y. Zhang State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P.R.ChinaSearch for more papers by this author First published: 08 November 2004 https://doi.org/10.1002/adma.200400074Citations: 175 † The authors acknowledge financial support from the Nature Science Foundation of China (No. 50373049 and the 2004 Outstanding Youth Foundation for J. Xu), the National 863 Project (No. 2001AA334060), the Key Project of CAS (KJCX2-SW-1107 and the CAS One Hundred Talent Program for J. Dong), and the Innovation Foundation if the ICCAS. The authors also thank Prof. Lianghe Shi and Prof. C. C. Han for their valuable comments. AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Graphical Abstract A super-hydrophobic surface (see Figure), possessing a microscale and nanoscale hierarchical structure similar to the surface structure of the lotus leaf, was prepared in one step from a micellar solution of polypropylene-block-poly(methyl methacrylate). REFERENCES 1 A. Nakajima, K. Hashimoto, T. Watanabe, Monatsh. Chem. 2001, 132, 31. 2 S. R. Coulson, I. Woodward, J. P. S. Badyal, S. A. Brewer, C. Willis, J. Phys. Chem. B 2000, 104, 8836. 3 A. Nakajima, A. Fujishima, K. Hashimoto, T. Watanabe, Adv. Mater. 1999, 11, 1365. 4 T. Onda, S. Shibuichi, N. Satoh, K. Tsujii, Langmuir 1996, 12, 2125. 5 H. Li, X. Wang, Y. Song, Y. Liu, Q. Li, L. Jiang, D. Zhu, Angew. Chem. Int. Ed. 2001, 40, 1743. 6 J. P. Youngblood, T. J. McCarthy, Macromolecules 1999, 32, 6800. 7 M. Morra, E. Occhiello, F. Garbassi, Langmuir 1989, 5, 872. 8 J. Genzer, K. Efimenko, Science 2000, 290, 2130. 9 Y. Wu, H. Sugimura, Y. Inoue, O. Takai, Chem. Vap. Deposition 2002, 8, 47. 10 K. Tsujii, T. Yamamoto, T. Onda, S. Shibuchi, Angew. Chem. Int. Ed. 1997, 36, 1011. 11 K. Tadanaga, N. Katata, T. Minami, J. Am. Ceram. Soc. 1997, 80, 3213. 12 J. Bico, C. Marzolin, D. Quéré, Europhys. Lett. 1999, 47, 220. 13 H. Y. Erbil, A. L. Demirel, Y. Avc, O. Mert, Science 2003, 299, 1377. 14 L. Feng, S. Li, J. Zhai, Y. Song, L. Jiang, D. Zhu, Angew. Chem. Int. Ed. 2002, 41, 1221. 15 L. Feng, Y. Song, J. Zhai, B. Liu, J. Xu, L. Jiang, D. Zhu, Angew. Chem. Int. Ed. 2003, 42, 800. 16 K. K. S. Lau, J. Bico, K. B. K. Teo, M. Chhowalla, G. A. J. Amaratunga, W. I. Milne, G. H. McKinley, K. K. Gleason, Nano Lett. 2003, 3, 1701. 17 Q. Xie, J. Xu, L. Feng, L. Jiang, W. Tang, X. Luo, X. Zhang, C. C. Han, Adv. Mater. 2004, 16, 302. 18 S. K. Wisniewska, J. Nalaskowski, E. Witka-Jezewska, J. Hupaka, J. D. Miller, Colloids Surf. 2003, 29, 131. 19a P. Behadur, G. Riess, Tenside, Surfactants, Deterg. 1991, 28, 173. 19b P. Ji, J. Xu, J. Wu, M. Ye, L. Shi, China Synth. Rubber Ind. 1998, 21, 53. 20 A. F. M. Barton, CRC Handbook of Solubility Parameters and Other Cohesion Parameters, 2nd ed., CRC Press, Boca Raton, FL 1991. 21 This is an interesting phenomenon.The water contact angle on a smooth PMMA surface is below 90°, which demonstrates that PMMA is a hydrophilic material. However, the rough, micelle-deposited surface turns out to be super-hydrophobic, which is contrary to the prediction of the Wenzel equation, that, by increasing the roughness, the wettability of materials can be enhanced (R. Wenzel, Ind. Eng. Chem. 1936, 28, 988). An X-ray photoelectron spectroscopy measurement of the micelle-deposited surface shows no preferential orientation of PP blocks. Our previous study also demonstrated that increasing the roughness of PMMA increased the contact angle rather than decreasing it [17]. Hence, the super-hydrophobicity was caused by the increase of the roughness of PMMA. We will address this problem in a more-detailed study. 22 A. Guo, G. Liu, J. Tao, Macromolecules 1996, 29, 2487. 23 T. C. Chung, J. Y. Dong, J. Am. Chem. Soc. 2001, 123, 4871. 24 S. Liu, A. Sen, Macromolecules 2001, 34, 1529. 25 K. Jankova, X. Chen, J. Kops, W. Batsberg, Macromolecules 1998, 31, 538. Citing Literature Volume16, Issue20October, 2004Pages 1830-1833 ReferencesRelatedInformation

A simple, two-phase approach using an autoclave is taken to synthesize high-quality anatase TiO2 nanocrystals with a narrow size distribution (see Figure). The size-tunable luminescence of the TiO2 nanocrystals is dominated by band-edge luminescence at room temperature. The nanocrystals could be readily dispersed in toluene after capping with stearic or oleic acid.

ADVERTISEMENT RETURN TO ISSUEPREVCommunication to the...Communication to the EditorNEXTSuperhydrophobic Surface from Vapor-Induced Phase Separation of Copolymer Micellar SolutionNing Zhao, Qiongdan Xie, Lihui Weng, Shengqing Wang, Xiaoyan Zhang, and Jian XuView Author Information State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P.R. China Cite this: Macromolecules 2005, 38, 22, 8996–8999Publication Date (Web):September 30, 2005Publication History Received18 July 2005Revised17 September 2005Published online30 September 2005Published inissue 1 November 2005https://doi.org/10.1021/ma051560rCopyright © 2005 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views2462Altmetric-Citations157LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit Read OnlinePDF (489 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information SUBJECTS:Atmospheric chemistry,Coating materials,Copolymers,Humidity,Solvents Get e-Alerts

A facile method was successfully developed for the preparation of a hierarchical nanocomposite of vertical polyaniline (PANI) nanorods aligned on the surface of functional multiwalled carbon nanotubes (FMWNTs) by in situ polymerization of PANI on the surface of FMWNTs. The formation mechanism was illustrated according to the morphological evolution of PANI-FMWNTs nanocomposite at different polymerization times. The hierarchical nanocomposite possessed higher special capacitance and better stability than each individual component as supercapacitor electrode materials due to the synergistic effect of both components, as well as to the special hierarchical structure, which not only increases the specific surface area of the nanocomposite but also facilitates the penetration of electrolyte ions. This research gives a better insight into the preparation of functional hybrid nanocomposites by combining different dimensional nanomaterials.

The MgO/Al2O3 sorbent for CO2 capture under low temperatures was investigated in a fixed bed. It was found that, with MgO loading of 10 wt %, MgO/Al2O3 sorbent showed a maximum CO2 capture capacity, which originated from the balance of physical adsorption and chemical absorption of the sorbent. The CO2 capture capacity increased with the water vapor at first and then decreased. Typically, the total CO2 capture capacities were as high as 0.97 and 1.36 mmol/g, with water vapor concentration of 0 and 13 vol %, respectively, at 60 °C with 13 vol % CO2. The high CO2 concentration could be approached by the multi-stage absorption/desorption cycles, during which the sorbent could be regenerated at 350 °C and maintained stable even after 5 cycles. In addition, a deactivation model was proposed that gave good predictions of the CO2 breakthrough curves. Results showed that sorption rate parameters obtained in the presence of water vapor were found to be larger than the corresponding values in the absence of water vapor. It was possibly caused by increasing the reactivity of the sorbent prior to the sorption of CO2 in the presence of water vapor.

Inspired by the remarkable adhesion of mussel, dopamine, a mimicking adhesive molecule, has been widely used for surface modification of various materials ranging from organic to inorganic. However, dopamine and its derivatives are expensive which impede their application in large scale. Herein, we replaced dopamine with low-cost catechol and polyamine (only 8% of the cost of dopamine), which could be polymerized in an alkaline solution and deposited on the surfaces of various materials. By using this cheap and simple modification method, polypropylene (PP) separator could be transformed from hydrophobic to hydrophilic, while the pore structure and mechanical property of the separator remained intact. The uptake of electrolyte increased from 80% to 270% after the hydrophilic modification. Electrochemical studies demonstrated that battery with the modified PP separator had a better Coulombic efficiency (80.9% to 85.3%) during the first cycle at a current density of 0.1 C, while the discharging current density increased to 15 C and the discharge capacity increased by 1.4 times compared to the battery using the bare PP separator. Additionally, the modification allowed excellent stability during manifold cycles. This study provides new insights into utilizing low-cost chemicals to mimic the mussel adhesion and has potential practical application in many fields.

Robust aerogels derived from a thiol-ene clicked bridged silsesquioxane precursor are obtained by a facile vacuum-drying method. With rather low densities, the flexible aerogels are still robust enough to bear at least 20 repeating compressions and further functionalization by wet doping. The durability and facile preparation procedure promise the aerogels' wider practical applications.

Here, we present a novel mechanical stretchable supramolecular hydrogel with a triple shape memory effect at the macro/micro scale.

Thermoreversible rubbers are prepared by the thiol-ene functionalized polybutadiene oligomers <italic>via</italic> dynamic ionic hydrogen bonds and covalent cross-links, exhibiting tailored properties for self-healing and shape memory functions.

Paramount attention has been paid on solid polymer electrolytes due to their potential in enhancement of energy density as well as improvement of safety. Herein, the composite electrolytes consisting of Li-salt-free polyethylene oxides and 200 nm-sized Li6.4La3Zr1.4Ta0.6O12 particles interfacially wetted by [BMIM]TF2N of 1.8 μL cm−2 have been prepared. Such wetted ionic liquid remains the solid state of membrane electrolytes and decreases the interface impedance between the electrodes and the electrolytes. There is no release of the liquid phase from the PEO matrix when the pressure of 5.0 × 104 Pa being applied for 24 h. The interfacially wetted membrane electrolytes show the conductivity of 2.2 × 10−4 S cm−1 at 20 °C, which is one order of magnitude greater than that of the membranes without the wetted ionic liquids. The conduction mechanism is related to a large number of lithium ions releasing from Li6.4La3Zr1.4Ta0.6O12 particles and the improved conductive paths along the ion-liquid-wetted interfaces between the polymer matrix and ceramic grains. When the membranes being used in the solid-state LiFePO4/Li and LiFe0.15Mn0.85PO4/Li cells at 25 °C, the excellent rate capability and superior cycle stability has been shown. The results provide a new prospect for solid polymer electrolytes used for room-temperature solid-state lithium batteries.

Low thermal conductivity and leakage after melting are the two main issues limited the application of phase change materials (PCMs). Here, to improve the thermal conductivity and hamper the leakage after melting, PCMs were fabricated by infiltrating paraffin into h-BN porous scaffolds with continuous thermal conductive paths. The latent heat of fusion of the resultant PCMs containing 18 wt% h-BN was 165.4 ± 1.7 J/g, and the thermal conductivity was as high as 0.85 W/mK. The thermal conductivity increased approximately 600% compared to the pure paraffin, and was over twice of the composites fabricated by conventional blending of paraffin and h-BN. The enhanced thermal conductivity obviously shortened the phase change process, indicating more efficient in energy storage and release. In addition, the h-BN scaffolds endowed the PCMs shape stability under molten state and prevented the leakage of molten paraffin. This approach to fabricate form-stable PCMs with high thermal conductivity may extend to other thermal management applications.

Superelasticity, recoverable ultimate strain of 99%, has been obtained for fibrous polyimide aerogels.

A series of La–M–Cu–Zn–O (M = Y, Ce, Mg, Zr) based perovskite-type catalysts are prepared by sol–gel method and characterized by XRD, BET, TPR, N2O-adsorption, XPS and TPD techniques. The results indicate that all the catalysts exhibit La2CuO4 perovskite structure. The addition of Ce, Mg and Zr lead to smaller particles, lower reduction temperature, higher Cu dispersion, larger amount of hydrogen desorption at low temperature and more amount of basic sites. However, Y has less affects on the physicochemical properties. The catalysts derived from perovskite-type precursors show high selectivity for methanol, which is correlated with the Cuα+ species that exists in the reduced catalysts. More exposed Cu surface area is favorable for high CO2 conversion.

Ag nanoparticles are <italic>in situ</italic> decorated on a BNNS modified with a TA–Fe complex, and the nanohybrids show excellent catalytic activity.

Three dimensional scaffolds of hBN microplatelets prepared by ice templating method are used to fabricate hBN/PDMS composites with vertically aligned hBN for thermal interface materials.

Extreme wetting behaviors have been the subject of numerous studies in recent decades. Superhydrophilic surfaces with water contact angle lower than 5° is one of the most exciting research areas which has attract much attention. The ultrafast drying of such surfaces can provide outstanding properties such as antifogging, evaporative cooling, self-cleaning, and others. We review here the basic strategies and recent progress in fabricating superhydrophilic surfaces. And smart surfaces combining superhydrophilic and superhydrophobic abilities are highlighted, including surfaces with stimuli reversible wettability, patterning wettability, and gradient wetting. We also provide insights into the applications of the highly wettable surfaces, especially in devising new potentials.

The Cu/ZnO/Al₂O₃/Y₂O₃catalyst with Y³⁺ : (Al³⁺+ Y³⁺) = 0.1 derived from hydrotalcite-like compounds exhibited the best catalytic performance with high stability.

Electrically conductive yet mechanically strong composite hydrogels are highly desired in many applications, and graphene would be the most promising candidate for these hydrogels. While previous research utilized either as-prepared or reduced graphene oxide, we herein prepared high structural integrity yet solution-processable graphene sheets for the development of graphene/polymer composite hydrogels. A percolation threshold of electrical conductivity was found at 0.4 vol% graphene for these hydrogels. At 1.0 vol%, Young's modulus and compressive strength were respectively enhanced from 1.64 to 19.03 MPa and from 0.37 to 6.90 MPa, corresponding to 1060% and 1765% improvements. These improvements were explained from the perspectives of the graphene sheets' dispersion and their interaction with the polymer and water molecules. It is worth noting that the addition of graphene improved the hydrogel pH sensitivity.

Abstract Hemostatic fabrics are most commonly used in baseline emergency treatment; however, the unnecessary blood loss due to the excessive blood absorption by traditional superhydrophilic fabrics is overlooked. Herein, for the first time, superhydrophobic/superhydrophilic Janus fabrics (superhydrophobic on one side and superhydrophilic on the other) are proposed: the superhydrophilic part absorbs water in the blood to expedite the clotting while the superhydrophobic part prevents blood from further permeating. Compared with the common counterparts, effective bleeding control with reducing blood loss more than 50% can be achieved while the breathability largely remain by using Janus fabrics. The proposed prototypes can even prolong the survival time in the rat model with serious bleeding. This strategy for reducing blood loss via simply tuning wettability is promising for the practical applications.

ABSTRACT Catalyst‐free recyclable polybutadiene (PB) elastomer cross‐linked by dynamic imine bonds is prepared by the reaction between amine functionalized PB and aldehyde cross‐linkers. The dynamic nature of imine bond is investigated by rheometry and creep‐recovery experiments. The cross‐linking degrees are regulated by incorporating different amount of aldehyde, and their influence on the cross‐linked elastomers is investigated in detail. The temperature‐induced imine exchange reactions enable recycling of the cross‐linked PB elastomers and their mechanical properties are almost unchanged after several cycles. It is important to note that the elastomers also show excellent solvent resistance even at high temperature. The good mechanical properties, solvent resistance and recycling ability of the resultant PB elastomer demonstrate the superiority of the imine bonds in the design of recyclable polymers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 2011–2018

The separation and removal of oil or organic pollutants from water is highly imperative. The oil phases in surfactant-free oil-in-water emulsions or in free oil/water mixtures can be smartly enriched and transported by using superhydrophobic/superoleophilic iron particles (SHIPs) under a magnetic field. For water-in-oil emulsion, SHIPs-based composite membranes selectively allow the oil to pass through. Their convenient and scalable preparation, excellent separation performance, and good reusability are of great advantages for practical applications in wastewater treatment, the cleanup of oil spills, emulsion concentration, and fuel purification.

A versatile strategy is developed to prepare 2D/3D superhydrophobic porous materials by simply coating substrates with dispersion of PTFPMS aggregations.

A previously developed mesoporous Ni–CaO–ZrO2 catalyst (NCZ) was submitted to dry reforming of methane (DRM), and the influence of feeding compositions on the properties of accumulated carbon was comprehensively studied. To this end, the used catalysts (NCZ-x) were characterized with a particular focus on the carbon residuals, using X-ray diffraction, N2 adsorption, transmission electron microscope, scanning electron microscopy, thermogravimetric analysis and X-ray photoelectron spectroscopy, etc. The results indicate that by varying the composition of the feeding gas, the morphology and chemical inertness of the accumulated carbon changed considerably, and the deactivation of the NCZ catalyst under CH4-rich conditions can be associated with the formation of coating carbon species that leads to the coverage of highly active Ni nano particles (NPs).

A series of Cu/Zn/Al/Zr catalysts were synthesized by calcination of hydrotalcite-containing precursors with different Cu2+/Zn2+ atomic ratios (n). Two other catalysts (n = 2) were also prepared via phase-pure hydrotalcite-like and conventional rosasite precursors for comparison. XRD and UV-Vis-NIR DRS characterizations demonstrate that most Cu2+ of hydrotalcite-containing materials did not enter the layer structure. The Cu dispersion of the catalysts decreases with the increase of Cu content, while both the exposed Cu surface area and the Cu+ and Cu0 content on the reduced surface reach a maximum when n is 2. The catalytic performance for the methanol synthesis from CO2 hydrogenation was also tested. The catalytic activity and selectivity of the catalysts (n = 0.5–4) via hydrotalcite-containing precursors rise first and then decrease with increasing Cu2+/Zn2+ ratios, and the optimum performance is obtained over the catalyst with Cu2+/Zn2+ = 2. Moreover, the Cu/Zn/Al/Zr catalyst (n = 2) via hydrotalcite-containing precursor exhibits the best catalytic performance, which is mainly due to the maximum content of active species compared with another two catalysts derived from different precursors.

The transformation of CO2 and glycerol into glycerol carbonate was carried out by using acetonitrile as coupling agent over La2O2CO3–ZnO in the present work. A series of La–Zn mixed oxide catalysts with different molar ratios were prepared and calcined at different temperatures. The catalysts were characterized by N2 physisorption, XRD, XPS, FT-infrared spectroscopy and temperature-programmed desorption of CO2. The results revealed that the formation of La2O2CO3 improved the surface basicity which then favors the CO2 activation and the carbonate yield was shown to be correlated with the amount of moderately basic sites. The XPS measurement demonstrated that La2O2CO3 favored the electron transfer from zinc atoms to lanthanum atoms or oxygen atoms which then favors the activation of glycerol. The synergism between ZnO and La2O2CO3 is responsible for the high catalytic activities of the La–Zn catalysts. The best result was obtained on the catalyst with molar ratio of La : Zn = 1 : 4 and calcination at 500 °C.

Abstract Constructing responsive and adaptive materials by dynamic covalent bonds is an attractive strategy in material design. Here, we present a kind of dynamic covalent polyureas which can be prepared from the highly efficient polyaddition reaction of pyrazoles and diisocyanates at ambient temperature in the absence of a catalyst. Owing to multiphase structural design, poly(pyrazole-ureas) (PPzUs) show excellent mechanical properties and unique crystallization behavior. Besides, the crosslinked PPzUs can be successfully recycled upon heating (~130 °C) and the molecular-level blending of polyurea and polyurethane is realized. Theoretical studies prove that the reversibility of pyrazole-urea bonds (PzUBs) arises from the unique aromatic nature of pyrazole and the N-assisting intramolecular hydrogen transfer process. The PzUBs could further broaden the scope of dynamic covalent bonds and are very promising in the fields of dynamic materials.

A facile method was successfully established to construct 3D conductive network-based free-standing polyaniline/reduced graphene oxide/carbon nanotube ternary hybrid film, in which a 3D conductive network was synergistically assembled by MWNTs and GO.

Energy-saving cooling materials with strong operability are desirable for sustainable thermal management. Inspired by the cooperative thermo-optical effect in the fur of a polar bear, we develop a flexible, superhydrophobic, and reusable cooling "skin" by laminating a poly(dimethylsiloxane) film with a highly scattering polyethylene aerogel. Owing to its high porosity (97.9%) and tailored pore size of 3.8 ± 1.4 μm, it can achieve superior solar reflectance (R̅sun ∼ 0.96) and high transparency to irradiated thermal energy (τ̅PE,MIR ∼ 0.8) at a thickness of 2.7 mm. Combined with the low thermal conductivity (0.032 W m-1 K-1) of the aerogel, the cooling skin exerts midday sub-ambient temperature drops of 5-6 °C in a metropolitan environment, with an estimated limit of 14 °C under ideal service conditions. Our generalized bilayer approach can be easily applied to different types of emitters, bridging the gap between night-time and daytime radiative cooling and paving the way for more cost-effective and scalable cooling materials.

Zn/Al/La and Zn/Al/La/M (M = Li, Mg, Zr) mixed oxides were obtained by calcination of hydrotalcites and tested for glycerol carbonate synthesis from CO₂ carbonylation.

Fabricating a single polymer network with a combination of a multi-shape memory effect (multiple-SME), solid-state plasticity, recyclability and self-healing behavior remains a challenge. We designed imine bond and ionic hydrogen bond dual cross-linked polybutadiene (PB) networks. The resulting PB networks showed a triple-shape memory effect, where imine bonds could be used to fix the permanent shape and ionic hydrogen bonds and glass transition acted as the transition segments for fixing/releasing the temporary shapes. Additionally, the dual dynamic bonds offered PB networks outstanding solid-state plasticity, recyclability and self-healing behavior. This strategy provides some insights for preparing shape memory polymers integrating multiple-SME and multi-functionality.

A novel multifunctional supramolecular hydrogel with self-healing, shape memory and adhesive properties is successfully developed on the basis of dynamic phenylboronic acid (PBA)–catechol interactions.

Abstract This article reports preparation of a crosslinked polydimethylsiloxane (PDMS) network via dynamic transesterification reaction between PDMS-diglycidyl ether and pripol 1017 with Zn(OAc) 2 as the catalyst. The thermal dynamic nature of the network was investigated by the creep-recovery and stress-relaxation tests. The synthesized PDMS elastomer showed excellent solvent resistance even under high temperature, and could be reprocessed by hot pressing at 180 °C with the mechanical properties maintained after 10 cycles. Application of the PDMS elastomer in constructing micro-patterned stamps repeatedly has been demonstrated. The high plastic temperature and good solvent resistance distinguish the research from other reported thermoplastic PDMS elastomers and broaden the practical application areas.

Abstract Superstretchable materials have many applications in advanced technological fields but are difficult to stretch to more than 1000× their original length. A superstretchable dynamic polymer network that can be stretched to 13 000× its original length is designed. It is revealed that superstretchability of the polymer network is derived from the synergistic effect of two different types of dynamic bonds, including a small number of strong dynamic imine bonds to maintain the network integrity during stretching and a large number of weak ionic hydrogen bonds to dissipate energy. This approach provides new insights into the design of superstretchable polymers.

Aerogels are a family of highly porous materials whose applications are commonly restricted by poor mechanical properties. Herein, thiol-ene chemistry is employed to synthesize a series of novel bridged silsesquioxane (BSQ) precursors with various alkoxy groups. On the basis of the different hydrolyzing rates of the methoxy and ethoxy groups, robust superhydrophobic BSQ aerogels with tailorable morphology and mechanical performances have been prepared. The flexible thioether bridge contributes to the robustness of the as-formed aerogels, and the property can be tuned on the basis of the distinct combinations of alkoxy groups with the density of the aerogels almost unchanged. To the best of our knowledge, the lowest density among the ambient pressure dried aerogels is obtained. Further, potential application of the aerogels for oil/water separation and acoustic materials has also been presented.

Flexible interfaces between Si anodes and composite electrolytes consisting of poly(propylene carbonates) (PPCs) and garnets have been fabricated. The solid polymer electrolytes (SPEs) of PPC/garnet/LiTFSI show the conductivity of 4.2 × 10−4 S cm−1 at room temperature. Their combination with the Si layer anodes allows great alleviation of internal stress resulting from the large volume variation during lithiation and delithiation process of Si anodes. As a result, the Si/SPE/Li cells exhibit 2520 mAh g−1, 2260 mAh g−1, 1902 mAh g−1, 1342 mAh g−1 at 0.1 C, 0.2 C, 0.5 C, and 1 C, respectively. Furthermore, with such compatible and stable interfaces of Si/SPE and the LiFePO4 cathodes in solid-state batteries, the specific capacity of 2296 mAh g−1 in terms of Si is obtained, which remains 82.6% after 100 cycles at room temperature and 0.1 C. The results here indicate that constructing of flexible interfaces between Si anodes and SPEs is a promising strategy to develop high performance solid-state batteries.

Solid-state interfaces play a significant role in the overall electrochemical performance of solid-state batteries (SSBs). However, the understanding of interface dynamics between solid-state electrolytes (SSEs) and Li metal remains limited, especially their effects on Li dendrite growth. Herein, three different interfaces are fabricated based on garnet-type SSEs and the Li penetration behaviors across the interfaces are investigated. The lithiophilic garnet/Li interface, with an initially low resistance, can be gradually broken and the growing voltage hysteresis drives the Li nucleation and proliferation through the grain boundary of the garnet ceramic bulk. The results indicate that a three-dimensional garnet/Li interface can remain stable due to the decreased local current density and minimized Li volume change, thus suppressing the dendrite formation. This work not only provides further understanding of the relationship between the SSE/Li interface and Li dendrite growth but also provides guidelines for the future design of dendrite-free SSBs.

In this paper, we prepared three different kinds of hollow activated carbon fibers (HACFs) from willow catkins (WCs), phenolic- and pitch-based hollow fibers, respectively. The morphology, pore structure, surface chemical composition and electrochemical properties of these hollow fibers were studied in parallel. Due to its high-hollow, cost-effective as well as eco-friendly nature, HACFs derived from WCs can be served as excellent electrode materials for electrochemical energy storage devices. Electrochemical measurements illustrate that the WCs derived HACFs exhibit not only high specific capacitance of 333 F g−1 at 0.1 A g−1 but also considerable rate capability with a retention of 62.7% (209 F g−1 at 10 A g−1). Symmetric supercapacitor devices that using WCs derived HACFs as electrodes deliver a maximum energy density of ∼8.8 Wh kg−1 at power density of 50 W kg−1 and good cycling performance with 95.5% retention over 3000 cycles at 5 A g−1 in 6 M KOH aqueous electrolytes.

Herein, Ni/SiO2 and bimetallic NixGa/SiO2 (Ni/Ga atomic ratio x = 6 and 3) catalysts were prepared by the impregnation method followed by reduction at 550 °C and tested in the vapor hydrodeoxygenation of anisole at 0.1 MPa and 300 °C. Ni-Ga alloy and Ni3Ga intermetallic compound (IMC) formed in Ni6Ga/SiO2 and Ni3Ga/SiO2, respectively, where the Ga atoms break contiguous Ni ones reducing the ensembles of Ni atoms and the H2 uptakes. Also, a charge transfer from Ga to Ni increased the electron density of Ni, and hydrogen spill-over occurred on NixGa/SiO2. In contrast to Ni/SiO2, NixGa/SiO2 improved not only the hydrodeoxygenation activity but also the selectivity to benzene. At the similar anisole conversion (˜31%), the selectivity to benzene was 75.2%, 83.0% and 92.6% on Ni/SiO2, Ni6Ga/SiO2 and Ni3Ga/SiO2, respectively. Reactivity evaluation, anisole-TPD and TPSR results show that the direct CArOCH3 bond cleavage (CAr represents the carbon in benzene ring) to benzene was more preferential on NixGa/SiO2 than on Ni/SiO2. Isotope tracing experiment indicates that the spilt-over hydrogen at the interface between the Ni3Ga particles and support participated in the reaction. We suggest that the synergetic effect between Ni and Ga facilitated the direct CArO bond cleavage. Moreover, NixGa/SiO2 were less active for benzene hydrogenation and CC bond hydrogenolysis than Ni/SiO2, contributing to higher selectivity to benzene. Significantly, methanol, derived from the direct the CArOCH3 bond cleavage, dominatingly decomposed to CO and H2 and methanation scarcely occurred on NixGa/SiO2, however, it was mainly converted to methane on Ni/SiO2. Low activities for benzene hydrogenation, CC bond hydrogenolysis and methanation on NixGa/SiO2 (especially Ni3Ga/SiO2) are attributed to the geometric and electronic effects of Ga in alloy and IMC. The finding is significant in rationally designing the catalyst with high benzene yield and low H2 consumption.

A series of metal-organic frameworks MOF-808-X (6-connected) were synthesized by regulating the ZrOCl2·8H2O/1,3,5-benzenetricarboxylic acid (BTC) molar ratio (X) and tested for the direct synthesis of dimethyl carbonate (DMC) from CO2 and CH3OH with 1,1,1-trimethoxymethane (TMM) as a dehydrating agent. The effect of the ZrOCl2·8H2O/BTC molar ratio on the physicochemical properties and catalytic performance of MOF-808-X was investigated. Results showed that a proper ZrOCl2·8H2O/BTC molar ratio during MOF-808-X synthesis was fairly important to reduce the redundant BTC or zirconium clusters trapped in the micropores of MOF-808-X. MOF-808-4, with almost no redundant BTC or zirconium clusters trapped in the micropores, exhibited the largest surface area, micropore size, and the number of acidic-basic sites, and consequently showed the best activity among all MOF-808-X, with the highest DMC yield of 21.5% under the optimal reaction conditions. Moreover, benefiting from the larger micropore size, MOF-808-4 outperformed our previously reported UiO-66-24 (12-connected), which had even more acidic-basic sites and larger surface area than MOF-808-4, mainly because the larger micropore size of MOF-808-4 provided higher accessibility for the reactant to the active sites located in the micropores. Furthermore, a possible reaction mechanism over MOF-808-4 was proposed based on the in situ FT-IR results. The effects of different reaction parameters on DMC formation and the reusability of MOF-808-X were also studied.

Garnets are promising solid electrolytes for developing solid state Li batteries, owing to their features of relatively high conductivity and stability against lithium metal. However, they show shortcoming of Li penetration through garnets during Li plating and stripping, which limits their practice application. Herein, we present a strategy to solve such problem by coating SnO2 films on the surfaces of the Li6·4La3Zr1·4Ta0·6O12 pellets. Through conversion reaction of SnO2 with Li at 200 °C, the nanocomposite layers consisting of crosslinked LixSn and Li2O are formed between the Li and the Li6·4La3Zr1·4Ta0·6O12 electrolytes. This leads to transition from lithiophobicity to lithiophilicity, thus greatly reducing interfacial resistance from 1100 Ω cm2 to 25 Ω cm2. Furthermore, taking advantage of suppressing volume change of LixSn alloy which is about 260%, the intermediate layers maintain integrity under the current densities of 0.2 mA cm−2 for 650 h cycles. In addition, the critical current density of Li/SnO2-Li6.4La3Zr1·4Ta0·6O12-SnO2/Li can be as high as 1.15 mA cm−2. As a proof-of-concept, this effective interface modification based on conversion reaction method contributes to a useful way of solving the Li/garnet interface problem and promoting the solid state Li batteries development.

Garnet-type solid-state electrolytes (SSEs) are promising for the realization of next-generation high-energy-density Li metal batteries. However, a critical issue associated with the garnet electrolytes is the poor physical contact between the Li anode and the garnet SSE and the resultant high interfacial resistance. Here, it is reported that the Li|garnet interface challenge can be addressed by using Li metal doped with 0.5 wt% Na (denoted as Li*) and melt-casting the Li* onto the garnet SSE surface. A mechanistic study, using Li6.4 La3 Zr1.4 Ta0.6 O12 (LLZTO) as a model SSE, reveals that Li2 CO3 resides within the grain boundaries of newly polished LLZTO pellet, which is difficult to remove and hinders the wetting process. The Li* melt can phase-transfer the Li2 CO3 from the LLZTO grain boundary to the Li*'s top surface, and therefore facilitates the wetting process. The obtained Li*|LLZTO demonstrates a low interfacial resistance, high rate capability, and long cycle life, and can find applications in future all-solid-state batteries (e.g., Li*|LLZTO|LiFePO4 ).

A stable Z-scheme with well-defined architecture by in situ growth of COFs on CdS for photocatalytic water splitting is constructed. The T-COF shell can protect the catalytic center of CdS from deactivation and photocorrosion.

The CO2-induced plasticization effects impose detrimental effects on polymeric membranes separation performance. To address this issue, a high-performance crosslinked brominated 6FDA-based polyimide (BMPI) is developed in this work, exhibiting highly suppressed plasticizing effects. The permeability and selectivity of polyimide precursor membranes are tuned by introducing bromine atoms into the polyimide structure, creating a best performing membrane with bromination degree of 60%. The membrane CO2 permeability reaches 395 Barrer, and the selectivity of CO2/CH4 increases from 22.0 for a non-brominated analogue to 26.0. The debromination induced crosslinked BMPI membranes are achieved upon thermal treatment within the temperature range of 150 °C–350 °C with varied crosslinking degree, resulting in large differences for the membrane separation performance. The completely crosslinked BMPI treated at 350 °C for 10 h demonstrates high CO2 permeability of 483.6 Barrer and the CO2/CH4 selectivity of 26.0. Most importantly, the crosslinking reaction greatly stabilizes the membrane performance against plasticization under high CO2 feed pressure. Compared with the non-crosslinked membranes with a plasticizing pressure of 150 psia, the plasticization for the crosslinked membrane occurs at high CO2 pressure of 600 psia. This study provides a facile approach for the preparation of high-performance gas separation polymeric membranes with enhanced plasticization resistance.

Three-dimensional (3D) printing is becoming a revolutionary technique across various fields. Especially, digital light processing (DLP) 3D printing shows advantages of high resolution and high efficiency. However, multifunctional monomers are commonly used to meet the rapid liquid-to-solid transformation during DLP printing, and the extensive production of unreprocessable thermosets will lead to resource waste and environmental problems. Here, we report a family of dynamic polymers with highly tailorable mechanical properties for DLP printing. The dynamic polymers cross-linked by ionic bonding and hydrogen bonding endow printed objects with excellent self-healing and recycling ability. The mechanical properties of printed objects can be easily tailored from soft elastomers to rigid plastics to satisfy practical applications. Taking advantage of the dynamic cross-linking, various assembling categories, including 2D to 3D, small to large 3D structures, and same to different materials assembly, and functional devices with a self-healing capacity can be realized. This study not only helps to address environmental issues caused by traditional DLP-printed thermosets but also realizes the on-demand fabrication of complex structures.

ENERGY & ENVIRONMENTAL MATERIALSVolume 5, Issue 2 p. 524-532 Research ArticleFree Access In situ Observation of Li Deposition-Induced Cracking in Garnet Solid Electrolytes Jun Zhao, Jun Zhao Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004 ChinaSearch for more papers by this authorYongfu Tang, Yongfu Tang Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004 China Hebei Key Laboratory of Applied Chemistry, School of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao, 066004 ChinaSearch for more papers by this authorQiushi Dai, Qiushi Dai Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004 ChinaSearch for more papers by this authorCongcong Du, Congcong Du Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004 ChinaSearch for more papers by this authorYin Zhang, Yin Zhang Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, Georgia, 30332 USASearch for more papers by this authorDingchuan Xue, Dingchuan Xue Department of Engineering Science and Mechanics, The Pennsylvania State University, University Park, PA, 16802 USASearch for more papers by this authorTianwu Chen, Tianwu Chen Department of Engineering Science and Mechanics, The Pennsylvania State University, University Park, PA, 16802 USASearch for more papers by this authorJingzhao Chen, Jingzhao Chen Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004 ChinaSearch for more papers by this authorBo Wang, Bo Wang Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004 ChinaSearch for more papers by this authorJingming Yao, Jingming Yao Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004 ChinaSearch for more papers by this authorNing Zhao, Ning Zhao College of Physics, Qingdao University, Qingdao, 266071 ChinaSearch for more papers by this authorYanshuai Li, Yanshuai Li Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004 ChinaSearch for more papers by this authorShuman Xia, Shuman Xia Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, Georgia, 30332 USASearch for more papers by this authorXiangxin Guo, Xiangxin Guo College of Physics, Qingdao University, Qingdao, 266071 ChinaSearch for more papers by this authorStephen J. Harris, Stephen J. Harris Energy Storage Division, Lawrence Berkeley, National Laboratory, Berkeley, CA, 94720 USASearch for more papers by this authorLiqiang Zhang, Corresponding Author Liqiang Zhang [email protected] Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004 ChinaSearch for more papers by this authorSulin Zhang, Corresponding Author Sulin Zhang [email protected] Department of Engineering Science and Mechanics, The Pennsylvania State University, University Park, PA, 16802 USASearch for more papers by this authorTing Zhu, Corresponding Author Ting Zhu [email protected] Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, Georgia, 30332 USASearch for more papers by this authorJianyu Huang, Corresponding Author Jianyu Huang [email protected] orcid.org/0000-0002-8424-5368 Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004 China School of Materials Science and Engineering, Xiangtan University, Xiangtan, 411105 ChinaSearch for more papers by this author Jun Zhao, Jun Zhao Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004 ChinaSearch for more papers by this authorYongfu Tang, Yongfu Tang Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004 China Hebei Key Laboratory of Applied Chemistry, School of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao, 066004 ChinaSearch for more papers by this authorQiushi Dai, Qiushi Dai Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004 ChinaSearch for more papers by this authorCongcong Du, Congcong Du Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004 ChinaSearch for more papers by this authorYin Zhang, Yin Zhang Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, Georgia, 30332 USASearch for more papers by this authorDingchuan Xue, Dingchuan Xue Department of Engineering Science and Mechanics, The Pennsylvania State University, University Park, PA, 16802 USASearch for more papers by this authorTianwu Chen, Tianwu Chen Department of Engineering Science and Mechanics, The Pennsylvania State University, University Park, PA, 16802 USASearch for more papers by this authorJingzhao Chen, Jingzhao Chen Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004 ChinaSearch for more papers by this authorBo Wang, Bo Wang Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004 ChinaSearch for more papers by this authorJingming Yao, Jingming Yao Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004 ChinaSearch for more papers by this authorNing Zhao, Ning Zhao College of Physics, Qingdao University, Qingdao, 266071 ChinaSearch for more papers by this authorYanshuai Li, Yanshuai Li Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004 ChinaSearch for more papers by this authorShuman Xia, Shuman Xia Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, Georgia, 30332 USASearch for more papers by this authorXiangxin Guo, Xiangxin Guo College of Physics, Qingdao University, Qingdao, 266071 ChinaSearch for more papers by this authorStephen J. Harris, Stephen J. Harris Energy Storage Division, Lawrence Berkeley, National Laboratory, Berkeley, CA, 94720 USASearch for more papers by this authorLiqiang Zhang, Corresponding Author Liqiang Zhang [email protected] Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004 ChinaSearch for more papers by this authorSulin Zhang, Corresponding Author Sulin Zhang [email protected] Department of Engineering Science and Mechanics, The Pennsylvania State University, University Park, PA, 16802 USASearch for more papers by this authorTing Zhu, Corresponding Author Ting Zhu [email protected] Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, Georgia, 30332 USASearch for more papers by this authorJianyu Huang, Corresponding Author Jianyu Huang [email protected] orcid.org/0000-0002-8424-5368 Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004 China School of Materials Science and Engineering, Xiangtan University, Xiangtan, 411105 ChinaSearch for more papers by this author First published: 15 August 2021 https://doi.org/10.1002/eem2.12261Citations: 6AboutSectionsPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Abstract Lithium (Li) penetration through solid electrolytes (SEs) induces short circuits in Li solid-state batteries (SSBs), which is a critical issue that hinders the development of high energy density SSBs. While cracking in ceramic SEs has been often shown to accompany Li penetration, the interplay between Li deposition and cracking remains elusive. Here, we constructed a mesoscale SSB inside a focused ion beam-scanning electron microscope (FIB-SEM) for in situ observation of Li deposition-induced cracking in SEs at nanometer resolution. Our results revealed that Li propagated predominantly along transgranular cracks in a garnet Li6.4La3Zr1.4Ta0.6O12 (LLZTO). Cracks appeared to initiate from the interior of LLZTO beneath the electrode surface and then propagated by curving toward the LLZTO surface. The resulting bowl-shaped cracks resemble those from hydraulic fracture caused by high fluid pressure on the surface of internal cracks, suggesting that the Li deposition-induced pressure is the major driving force of crack initiation and propagation. The high pressure generated by Li deposition is further supported by in situ observation of the flow of filled Li between the crack flanks, causing crack widening and propagation. This work unveils the dynamic interplay between Li deposition and cracking in SEs and provides insight into the mitigation of Li dendrite penetration in SSBs. 1 Introduction Solid-state batteries (SSBs) have great potential as high energy density Li battery systems for electrical vehicle and grid energy storage applications.[1-9] However, the applications of SSBs are plagued by Li penetration-induced short circuits,[10-13] mechanisms of which remain unclear.[9, 12, 14-20] Ceramic solid electrolytes (SEs) are often used as the ion conduction media in SSBs, because they have high mechanical strength that may block dendrite growth and thus offer better safety and longer lifetime than liquid electrolyte Li-ion batteries (LIBs).[21-24] However, Li dendrites can grow even more readily in SSBs than in liquid electrolyte LIBs. The mechanisms for Li penetrating through SEs are still under debate. It is generally thought that Li deposits and propagates preferentially along grain boundaries in SEs, causing short circuits of SSBs.[10, 13, 20, 25, 26] Cheng et al. observed a honeycomb Li structure on the fractured surface of cycled garnet SEs, and the feature size of the hexagonal web structure was similar to the grain size of the SE.[13] Based on this observation, they suggested that Li was plated along grain boundaries and proposed to increase the grain size of the SE and thus reduce its grain boundary fraction for mitigating Li penetration.[27] In situ experiments by electron beam demonstrated that defects on the garnet surface, such as surface ledges and grain boundaries, are preferable locations for Li nucleation.[25, 28] Kazyak et al. observed different Li penetration morphologies with straight, branching, spalling, and diffuse types in LLZTO SEs. They found that at relatively high current densities, Li filaments propagate by a mechanical crack-opening mechanism, where the rate of propagation was proportional to the current density.[18] Significant progress has been made in recent optical microscopy observations of dendrite growth in SEs.[18, 25, 29] However, the resolution of optical microscopy is limited by the wavelength of light. Also optical microscopy does not permit visualization of buried interfaces unless the SE is transparent.[12] Recently Ning et al. visualized crack propagation in Li6PS5Cl SE using in situ X-ray computed tomography (XRCT) coupled with spatially mapped X-ray diffraction.[30] They observed that cracking initiates with spallation, with conical “pothole”-like cracks forming near the surface of the plated electrode. Transverse cracks then propagated from the near-surface spallation sites across the electrolyte to the stripped electrode. Li deposition drove crack propagation and widening from the rear of the cracks until short circuit occurred. Using in situ XRCT, Hao et al. revealed the formation of thin-sheet cracks penetrating Li3PS4 SE without immediate short-circuiting of the cell.[31] They found that Li only partially filled the cracks, so that the cracks near the stripped side were largely hollow and the cell could continue to operate. These studies significantly advanced our understanding of Li penetration mechanisms in SSBs. However, the spatial resolution of XRCT was limited to the micrometer scale, and grain boundaries and individual grains in SEs were not resolved. The time resolution is also not sufficiently high for resolving the dynamic cracking process near the SE surface, which is crucial for unraveling the initiation of Li deposition-induced damage in SEs. Until now, it remains unclear whether Li deposition leads to intergranular or transgranular cracking and whether Li deposition-induced cracking initiates from the surface or sub-surface of SEs. It is essential to clarify these questions toward a deeper understanding of Li penetration mechanisms in SEs, therefore providing a scientific basis for finding the effective means of mitigating Li dendrite growth in SSBs. In this work, we design a novel mesoscale electrochemical device in a focused ion beam-scanning electron microscopy (FIB-SEM) system, which enables real-time observations of Li deposition and cracking in LLZTO SEs at nanometer resolution. Meanwhile, we can verify the internal structural changes of LLZTO SEs by FIB-SEM tomography.[32, 33] We show that Li deposition induces predominantly transgranular cracking rather than intergranular cracking in ceramic LLZTO. Chunks of LLZTO are lifted out by the formation of near-surface bowl-shaped cracks, which resemble those from “hydraulic fracture” caused by highly pressurized fluids within the cracks[34, 35] and thus suggest the Li deposition-induced internal pressure as the major driving force of crack initiation and propagation. Our in situ observations also reveal detailed dynamic interplay between Li deposition and crack propagation and multiplication. These results advance our understanding of Li penetration mechanisms in SEs. 2 Results and Discussion Our experiments were conducted in an FIB-SEM system, where a two-terminal electrochemical device was constructed to enable in situ testing of a mesoscale battery. LLZTO with the cubic crystal structure (Figure S1, Supporting Information) was synthesized via hot pressing at a pressure of 20 MPa and a temperature of 1150 °C for 1 h under Ar atmosphere. An LLZTO disk with a diameter of 12 mm and thickness of 1 mm was placed on a Li metal electrode supported by an SEM sample stub, which was connected to one terminal of an external power supply (Figure 1a). On the top surface of the LLZTO disk, a Pt electrode pad of 10 µm × 10 µm was deposited using electron beam. A W tip was manipulated to contact the Pt electrode, and it was connected to the other terminal of the potentiostat, thus completing the mesoscale battery setup. This mesoscale battery was used for in situ observation of Li deposition and cracking in LLZTO. Similar results were obtained when the Li metal electrode was replaced by a layer of InGaAg liquid metal. Figure 1Open in figure viewerPowerPoint In situ observation of Li deposition and cracking in SEs by a mesoscale FIB-SEM-based SSB, showing two sets of time sequence images in (a-e) and (f-k) for the formation of bowl-shaped cracks followed by Li filling in cracks. a) Schematic of the in situ battery testing, resulting in the formation of a bowl-shaped crack. A Pt electrode was deposited on the top surface of the LLZTO SE. Li or liquid GaInAg metal was used as the counter electrode. b, c) SEM images showing the formation of a bowl-shaped crack in the LLZTO SE. c) is the same as b), except that the colored grains around the bowl-shaped crack line on the LLZTO surface are sketched and overlaid on the real grains, showing the crack path through grain interiors. d) A cross-sectional view of the bowl-shaped crack, where the yellow and red dotted lines outline the bowl-shaped crack on the top surface and cross section, respectively. e) Magnified view of the bowl-shaped crack on the cross section from FIB milling, corresponding to the region boxed by green dotted lines in (d). f–k) In situ observation of the dynamic formation of a bowl-shaped crack and Li filling. f) A full view of the bowl-shaped crack, showing the crack contour on both the top surface and cross section. Li dendrites formed at the Pt electrode pad before the occurrence of LLZTO cracking. g) Schematic of the Li dendrites, bowl-shaped crack, and filled Li in the crack. h) LLZTO was milled by FIB to expose its side surface. h–k) Time-lapse images showing the formation of a bowl-shaped crack. A dendrite appeared near the Pt electrode (i) and then grew (j); the formation of two bowl-shaped cracks is shown in (j, k). The growth of dendrites appeared to cease once the bowl-shaped crack emerged by comparing (j) and (k). As a negative potential was applied to the Pt electrode, a fine-line crack with a closed-loop contour appeared on the top surface of the LLZTO disk (Figure 1b–d; Figure S2, Supporting Information). With the passage of time, Li metal emerged along the crack line and was then extruded out at the LLZTO surface (Figure 1b; Figure S2, Supporting Information). The crack line was widened as more Li extruded until a Li ring was formed on the top surface of the LLZTO disk (Figure 1b-d; Figure S2, Supporting Information). Before battery testing, the grain boundary contours on the LLZTO surface were made visible (Experimental Section), permitting the identification of individual grains (Figure 1b, c; Figure S2, Supporting Information). Interestingly, we found that the cracks were predominantly transgranular (through grains) rather than intergranular (along grain boundaries) (Figure 1c; Figure S2, Supporting Information). Moreover, the entire Li ring was lifted up the LLZTO surface (Figure 1b-d; Figure S2, Movie S1, Supporting Information). To reveal how deep the surface crack ran, a trench perpendicular to the LLZTO top surface was milled out by FIB (Figure 1d, e). To our surprise, a "bowl-shaped" crack was formed underneath the Pt electrode (Figure 1d, e), and such kind of three-dimensional (3D), near-surface crack geometry was highly reproducible. Apparently, the "bowl" was spalled off the LLZTO matrix, as it was entirely lifted up from the LLZTO surface presumably by deposited Li. To reveal the dynamic formation of the bowl-shaped crack, we pre-milled a trench near the Pt electrode to expose one side surface of the trench (Figure 1f, g). Upon applying a negative potential to the Pt electrode, Li dendrites initially grew at the Pt electrode pad on the LLZTO surface (Figure 1h, i). With increasing potential, a few crack segments emerged and extended on the exposed side surface of the trench (Figure 1g; Movie S2, Supporting Information). By monitoring the evolution of the 3D morphology of two bowl-shaped cracks involved (Figure 1f), we understood the growth processes of these crack segments as follows. At 68 s (Figure 1j), the tip of one bowl-shaped crack (outlined by a blue dotted line) extended into the exposed side surface of the trench and continued to propagate toward its upper left; meanwhile, a branch of another bowl-shaped crack (outlined by a yellow dotted line) emerged near the LLZTO surface. At 212 s (Figure 1k), the first bowl-shaped crack grew longer toward its upper left to merge with the second bowl-shaped crack (Movie S2, Supporting Information). These in situ observations provide evidence of the growth of the bowl-shaped crack from the interior to the top surface of LLZTO. During this process, the crack contour lines on the top surface of the LLZTO disk were widened due to filling of Li metal between the crack flanks (Figure 1j), eventually forming two overlapped Li rings on the LLZTO surface (Figure 1k). Figure S3, Supporting Information provides one more example of the formation of a bowl-shaped crack underneath the Pt electrode. It appears that only a segment of the bowl-shaped crack (Figure S3b, c, left, yellow dotted lines, Supporting Information) reached the LLZTO surface. Once the crack reached the surface, Li was immediately extruded out of the surface from the crack (Figure S3b–d, Supporting Information). The cross-sectional view confirms that only the left segment of the bowl crack reached the surface (Figure S3e, f, Supporting Information). Voids filled with Li near the crack were present on the exposed side surface of LLZTO (Figure S3e, f, Supporting Information). Li filling of the cracks was observed in real time (Figure 2; Movie S3, Supporting Information). Figure 2a shows an FIB-milled cross section with two crossing crack segments (denoted as crack 1 and 2). The full profile of the bowl-shaped crack is shown in Figure S4, Supporting Information. With the passage of time, crack 4 extended into the cross section, propagated from the lower right toward the upper left, and merged with crack 1. Subsequently, crack 4 widened (Figure 2b–d, g–n; Movie S3, Supporting Information) as Li was filled in the space between the crack flanks. The Li filling front is marked by a moving green arrowhead in Figure 2i–n. Since crack 1 and 4 were connected, the widening of crack 4 by Li filling also led to the widening of crack 1. As a result, a small crack formed near crack 1 at the upper left corner of the cross section, and this newly formed crack is indicated by an arrowhead and marked as crack 3 in Figure 2b. Interestingly, as crack 1 and 4 were connected and widened (Figure 2g–n), the lower right segment of crack 1 was closed (marked by a down pointed arrowhead in Figure 2n), likely due to compression caused by the widening of crack 4. The above in situ observations demonstrate that the filled Li between crack flanks can flow and, more importantly, produce sufficiently high internal pressure to cause the formation, widening, and closing of cracks. Upon a reverse potential, crack 1 was closed (Figure 2e, o; Figure S5, Supporting Information). Dendrites that break off will lost contact with the lithium metal anodes and become dead lithium as shown in Figure S6, Supporting Information resulting in the cracks being unable to be healed completely. Figure 2Open in figure viewerPowerPoint In situ observation of the dynamic interplay between crack opening and Li filling in the bowl-shaped crack. a–e) Sequential SEM images showing the dynamic processes of Li filling in a segment of the bowl-shaped crack. f–o) High-magnification SEM images showing Li filling and extracting from the bowl-shaped crack. Note that the crack was widened when Li was filled in between the crack flanks (a–d, f–n), and the crack was closed when Li was extracted (e, o). "1"-"4" mark four different cracks. A green arrowhead indicates the Li moving front in (i–n). By SEM imaging at higher magnification, Li deposition along transgranular cracks became clearly visible (Figure 3). Figure 3a shows the top view of the LLZTO surface where a bowl-shaped crack emerges as a closed-loop crack line (traced by yellow dotted lines) that intersects with another emerging crack line (traced by blue dotted lines) from a different bowl-shaped crack. High-magnification images of the boxed regions in Figure 3a show clearly the surface cracks crossing the interior of a series of grains (Figure 3b–f). The FIB-milled cross section reveals that the surface transgranular crack penetrated into the interior of the LLZTO disk (Figure 3f). The original image of Figure 3 is shown in Figure S7, Supporting Information. Figure 3Open in figure viewerPowerPoint SEM images showing Li transpassing LLZTO grains. a–d) Plan view of cracks transpassing grain interiors. a) A full view of the bowl-shaped crack line (outlined by yellow dotted lines) on the top surface of LLZTO. Blue dotted lines outline segments of another bowl-shaped crack. b–f) Magnified view of crack transpassing grain interiors. The false color outlines grains, showing cracks transpassing grain interiors. To investigate the transgranular fracture induced by Li deposition, we show that cracks can nucleate and propagate in single-crystal LLZTO grains (Figure 4 and Movies S4, S5, Supporting Information). A single-crystal grain was sliced by FIB milling so that a flat side surface was exposed (Figure 4a). Then, the W tip was manipulated to contact this side surface (Figure 4a). When a negative potential was applied to the W tip, a Li dendrite initially grew out under the W tip (Figure 4b). With continued dendrite growth, a slanted crack emerged in the center of the particle (Figure 4b–d, yellow dotted lines), and then, the crack propagated toward the upper-right direction until the grain broke into two parts (Figure 4b–d, Movie S4, Supporting Information). Consecutive FIB slicing along the side surface indicates that the crack crossed through the entire grain (Figure 4e–i, Movie S5, Supporting Information). Figure 4Open in figure viewerPowerPoint Time-lapse SEM images showing crack nucleation and propagation in a single LLZTO grain. a) The initial LLZTO grain with side surface being exposed. b–d) A dendrite and a slanted crack emerged from the LLZTO grain (traced by yellow dotted lines). e–i) Consecutive FIB slicing of the grain showing the crack running from the top to the bottom section of the entire grain, breaking the grain into two pieces. i) Schematic of the slicing process. We further show that a crack can cross through two neighboring grains continuously in a multi-grained LLZTO particle (Figure 5a–i). The particle comprised at least three grains with grain boundaries and cavities (Figure 5a–i). We made a Pt electrode pad on top of the particle (Figure 5a). Upon applying a negative potential to the Pt electrode, three Li dendrites appeared at the edge of the contact pad (indicated by three green arrowheads in Figure 5f). At 283 s, another slim dendrite emerged accompanying the formation of a microcrack in grain 1 (Figure 5c, g). The crack was neither stopped nor deflected by the grain boundaries; instead, it crossed directly into grain 2 and then propagated downward through grain 2 (Figure 5c–e, g–i, Movie S6, Supporting Information). We milled the particle to expose its side surface, which showed that the crack ran through the entire particle, breaking the particle into two parts (Figure 5j–l; Movie S7, Supporting Information). Figure 5Open in figure viewerPowerPoint Time-lapse SEM images showing crack nucleation and propagation in an LLZTO particle comprising multiple grains. a) The initial LLZTO grain. b–e) Nucleation and propagation of a crack. f–i) Magnified view of the corresponding image in (b-e) enclosed by the box of same color, showing the crack propagation. Three grains are marked by 1-3 in (f). The crack transpassing grains 1-3 is indicated by a yellow dotted line and the crack tip by a yellow arrowhead. j–l) FIB slicing showing the crack transverse from the top to bottom of the grain. l) Schematic showing cracking of the LLZTO grain. Based on the above in situ observations, we envision the following mechanisms of Li deposition-induced nucleation and growth of bowl-shaped cracks (Figure 6a–f). As a sufficiently large negative potential was applied to the Pt electrode, significant Li deposition took place underneath the Pt electrode pad, presumably at favored internal defects such as voids or grain boundaries (Figure 6a, b). These voids may include intragranular voids, not just those between grains. We used FIB to slice single-crystal LLZTO grains and found that almost all of them contain microscale voids (Figure S8; Movie S8, Supporting Information). Electrons needed for the reduction of Li ions are likely available due to the small, but finite electrical conductivity of LLZTO.[14] Li deposition could be enhanced by the elevated electric field near the Pt electrode that promoted electron flow. Li deposition was self-amplified due to increased electronic conductivity at these Li deposition sites. Under the mechanical confinement of the surrounding LLZTO, continued Li deposition leads to the buildup of large internal pressure, triggering the nucleation of an internal crack through the expansion of a Li-filled defect. Figure 6Open in figure viewerPowerPoint Schematic illustration of the formation mechanism of the bowl-shaped crack. a–c) Li deposition initiates at internal defects such as voids (a, b), generating high pressure in Li-filled defects, causing crack nucleation and propagation and then continued Li filling in between the crack flanks behind the running crack front (b-c). The filled Li is constrained by the crack flanks, producing wedging stresses to drive the crack propagation (d). Due to surface attraction, the running crack curves toward the free surface, resulting in a bowl-shaped crack (d, e), and a chunk of LLZTO spalled off and was lifted up by filled Li in the bowl-shaped crack (f). The observed formation of bowl-shaped cracks provides crucial insights into the dynamic interplay of Li deposition and crack growth in SEs. The characteristic bowl-shaped cracks have been previously reported in the study of hydraulic fracture in geomaterials and civil engineering applications.[34, 35] Hydraulic fracture is usually caused by high fluid pr

Tuning the relationship between the microporous structure of carbon molecular sieve (CMS) membranes and the corresponding gas permeability performance enables optimization for gas separation applications. The pre-crosslinked structure of the precursor plays a key role in improving the performance of the CMS membrane. Herein, the thermally crosslinkable brominated 6FDA-based polyimide (BMPI) by debromination is prepared and selected as the precursor to fabricate high performance CMS gas separation membranes. By heat-treating the BMPI membrane at 350 °C for 10 h, the debromination-induced crosslinking exhibited higher permeability over the uncrosslinked precursors, as it forms a pre-crosslinked structure that is more stable at 550 °C. A representative BMPI-350/10h-550 °C CMS membranes pyrolyzed at 550 °C had CO2 and O2 permeabilities of 11169 and 2182 Barrer with a CO2/CH4 and O2/N2 ideal selectivity of 26.5 and 5.4. These values are much higher than that of the un-crosslinkable precursor (6FDA-DAM) derived CMS membrane (PCO2 = 3465, αCO2/CH4 = 21.1). Even at the high carbonization temperature of 800 °C, the as-obtained CMS membrane still show a promising CO2 permeability of 1119 Barrer and a CO2/CH4 ideal gas selectivity of 41.2. Importantly, the excellent gas separation performance of CMS membranes obtained in this work exceeds the Robeson's upper-bound. This work outlines a new protocol to tailor CMS membrane microstructures to meet high permeability performance needs. These CMS membrane materials hold great potential in corrosive natural gas purification applications.

Z-scheme heterostructure consisting of covalent organic frameworks (COF) and inorganic semiconductor possesses tremendous potential for achieving efficient photoreduction of CO2. However, the precise design and rationalization of the interaction between COF and inorganic semiconductors remains a great challenge. Herein, the interaction of different N-sites on T−COF framework with defect TiO2 and stoichiometric TiO2 is investigated by density functional theory. The theoretical analysis suggests that the amine group of T−COF could provide an energetically favored binding site towards defect TiO2. Accordingly, a stable Z-scheme heterostructure with well-defined chemical bonding between Ti3+ and −NH2, and well-engineered geometry configuration through in situ anchoring defect TiO2 on the surface of amine-functionalized T−COF sphere is designed. The obtained heterostructure exhibits a high CO2-to-CO conversion efficiency, with nearly 100 % CO selectivity and an apparent quantum efficiency of 6.81 % at 365 nm. This work could provide guidance for the rational design of Z-scheme heterostructure photocatalysts for photocatalytic applications in high efficiency.

Due to the low valence band maximum value, Co3O4 is an outstanding catalyst, but its utilization in adsorption needs to be addressed. In this study, we proposed a novel method for loading aggregation-prone Co3O4 onto sepiolite (Sep) to facilitate tetracycline (TC) adsorption. The XRD, TEM, and FTIR analyses demonstrated that the highly dispersed Co3O4 was successfully anchored on the sepiolite grooves via the Si-OH on the sepiolite surface’s grooves to the cobalt site in Co3O4. We firstly proposed a view of how metal oxide aggregates are confined to the grooves on the surface of sepiolite (via Si-OH at the edges of the grooves on the sepiolite surface). The ultra-high sorption capacity of Co3O4-Sep is 219.53 mg/g for TC, which is three times that of Sep (70.75 mg/g) and Co3O4 (85.29 mg/g). The kinetic and isotherm results fitting suggested that the adsorption of TC on Co3O4-Sep mainly contributed to the multilayer chemisorption adsorption process. Thermodynamic investigations revealed the spontaneous endothermic reaction of TC adsorption on Co3O4-Sep. Co3O4 strengthened the complexation between the composite and functional groups of TC, significantly increasing TC adsorption capacity. In addition, the Co3O4-Sep retained an extraordinary adsorption capacity with the presence of competing ions, at strongly acidic and alkaline pH values and after three cycles. Therefore, this study offers new perspectives on applying cobalt-based materials and demonstrates the potential for antibiotic adsorption in the prepared composites.

Intelligently responsive nanoparticles can improve insecticidal activity against target organisms and reduce the use of pesticides in agriculture. In this study, enzymatic hydrolysis lignin (EHL) nanocarriers with enzyme responsiveness were successfully prepared by electrostatic interaction, and abamectin (Abm)-loaded EHL-based nanoparticles (Abm@L-CL) were investigated. The release behavior of Abm@L-CL nanoparticles showed that Abm was released rapidly in the presence of cellulase and pectinase but slowly under natural conditions. The insecticidal activity of Abm@L-CL treatment (LC50 = 0.68 μg/mL) against nematodes (Meloidogyne incognita) was significantly more effective than that of original Abm treatment (LC50 = 1.32 μg/mL). The mortality rate of Abm@L-CL was more than 90% by applying the same dose of Abm after 12 h. The bioactivity of Abm@L-CL against root-knot nematodes was 1.7-fold greater than that of Abm. The result of fluorescence indicated that nanoparticles could enter the intestinal tract through the oral cavity of nematodes and achieve obvious gastric toxicity. Furthermore, the enzyme-controlled lignin-based Abm nanocarriers could penetrate the tomato root near the elongation zone. This study provided intelligent enzyme-responsive nanocarriers for efficient management of soil-borne diseases and pests in green agricultural inputs.

Metaverse sector growth supports energy conservation, boosts renewable energy penetration, lessens fossil fuel dependency, and reduces anthropogenic emissions, such as greenhouse gases and aerosol precursors, thereby aiding climate change mitigation.

The catalytic conversion of the biomass platform compound sorbitol to isosorbide is an important reaction for the production of relevant renewable chemicals. The development of highly efficient heterogeneous catalyst materials offers promising perspectives for the sorbitol dehydration reaction. The complex competitive reactions, such as degradation and polymerization, are still a major challenge to obtain isosorbide in high yield. In this work, a series of ionic liquid functionalized polymer catalysts, P-[C3/4R]-SF, were successfully prepared by hydrothermal synthesis, which has a high surface area and strong acidity. And the catalysts were fully characterized by the N2 sorption–desorption isotherms, elemental analysis, water adsorption isotherms, FT-IR, TGA and 31P NMR, etc. As a result, the as-prepared P-[C3/4R]-SF catalysts exhibited excellent catalytic activity and stability under mild reaction condition (140 °C, 6 h). The yield of isosorbide is up to 75 %, and it still has good catalytic activity after five cycles. This work provides a synthesis method of ionic liquid functionalized polymer catalyst and its application in sorbitol dehydration reaction.

The development of superior electrode materials using biomass as sustainable carbon sources is of great significance in promoting the practical application of supercapacitors. Herein, we prepared a N, O co-doped hierarchical porous carbon (GPC-0.9 N) with an ultra-high specific surface area of 2808.65 m2 g−1 and abundant microporous, mesoporous and macroporous structures through the straightforward pre-carbonization method using garlic peels combined with KHCO3/melamine activation. Additionally, the relatively high nitrogen (3.81%) and oxygen content (4.79%) can enhance the wettability of the carbon materials and introduce additional pseudocapacitance. As a result, the electrode material achieved a high specific capacitance of 396.25 F g−1 at 1 A g−1 and outstanding rate capability of 283.13 F g−1 at 25 A g−1 in 6 M KOH electrolyte in a three-electrode system. Meanwhile, the symmetrical supercapacitor based on the GPC-0.9 N electrode material showed a high energy density of 9.07 Wh kg−1 at the power density of 309.2 W kg−1. Furthermore, it exhibited excellent cycling stability, with 92.5% of the capacitance retained after 10000 cycles at 10 A g−1. This research provides insights for the rational design of a green, renewable and eco-friendly biomass-derived porous carbon that can be widely used as supercapacitor electrode materials in the future.

Ascribing to the abundance of Ti element, exceptional electrical conductivity, and electrocatalytic performance, titanium carbide MXene (Ti 3 C 2 T x , MX) is considered as an ideal conductive matrix and employed for in situ preparation of promising TiO 2 NPs@MX/reduced graphene oxide (rGO) heterojunction electrodes for uric acid (UA) detection. However, the incapability of achieving the controllable growth and synthesis of TiO 2 nanoparticles (NPs) on MX nanosheets is a bottleneck in fabricating optimal and controllable TiO 2 NPs@MX hybrid. Herein, an “on‐site transformation strategy” is developed to synthetize TiO 2 NPs@MX/rGO heterojunction platform controllably by in situ electrochemical oxidizing MX nanosheets at various treatment times. The proposed approach allows for the greater operability to controllably grow and synthetize TiO 2 NPs on the surface of MX nanosheets. The heterojunction electrodes present a linear voltammetric response toward UA in the concentration range of 0.003–0.3 and 0.3–300 μ m and a low detection limit of 0.78 n m ( S / N = 3). Additionally, a handheld electrochemical system with a smartphone readout is developed for point‐of‐care health monitoring, enabling fast, precise, and specific recognition of UA in real urine samples. The study provides a facile and controllable approach to fabricate TiO 2 NPs@MX/rGO heterojunction platform for future use in other biomolecules' detection.

ZrO2-doped CuZnO catalyst prepared by successive-precipitation method was investigated by ICP-AES, BET, TEM, XRD, EXAFS, H2-TPR and CO/CO2 hydrogenation. The active phase of copper in CuZnO catalyst prepared by co-precipitation method was well-crystallized. The presence of ZrO2 led to a high copper dispersion, which was distinctive from CuZnO. Though the activity for carbon monoxide hydrogenation was little lower than that of CuZnO catalyst, ZrO2-doped CuZnO catalyst showed much higher activity and selectivity towards methanol synthesis from carbon dioxide hydrogenation. Moreover, ZrO2-doped CuZnO catalyst showed high performance for methanol synthesis from CO2-rich syngas.

Several metal oxides were used for synthesis of ethylene carbonate from urea and ethylene glycol. ZnO showed high activity towards the reaction. TPD, FTIR and reaction test indicated that the catalysts with appropriate acid and base properties were favorable to the synthesis of cyclic carbonate. Furthermore, the reaction of urea with various diols revealed that the selectivity of five-membered cyclic carbonates was higher than that of six-membered cyclic carbonates.

Segmented polyether−polyurethane (PU)/montmorillonite nanocomposites have been synthesized with poly(tetramethylene glycol), 4,4-diphenylmethane diisocyanate, propylenediamine, and montmorillonite. The nanoscale silicate layers are intercalated or exfoliated in the PU matrix, which are characterized by X-ray diffraction pattern and transmission electron microscopy. The PU/montmorillonite composites have been investigated by FT-IR dichroism during the stretching process in order to study the hard and soft chain orientation, hydrogen bonding, and strain induced by crystallization of the soft segment chains in PU. DSC experiment indicates that the soft phase Tg increases with the montmorillonite content. The mechanical analysis showed that tensile strength,Young's modulus, and elongation at break increase markedly, 1700% elongation at break for the composite containing 2.0 wt % montmorillonite.

ChemPhysChemVolume 7, Issue 4 p. 824-827 Communication A Lotus-Leaf-Like Superhydrophobic Surface Prepared by Solvent-Induced Crystallization Ning Zhao, Ning Zhao State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P. R. China, Fax: (+86) 10-8261-9667 Graduate School of the Chinese Academy of Sciences, Beijing 100080, P. R. ChinaSearch for more papers by this authorLihui Weng Dr., Lihui Weng Dr. State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P. R. China, Fax: (+86) 10-8261-9667Search for more papers by this authorXiaoyan Zhang, Xiaoyan Zhang State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P. R. China, Fax: (+86) 10-8261-9667 Graduate School of the Chinese Academy of Sciences, Beijing 100080, P. R. ChinaSearch for more papers by this authorQiongdan Xie, Qiongdan Xie State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P. R. China, Fax: (+86) 10-8261-9667Search for more papers by this authorXiaoli Zhang, Xiaoli Zhang State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P. R. China, Fax: (+86) 10-8261-9667Search for more papers by this authorJian Xu Prof., Jian Xu Prof. [email protected] State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P. R. China, Fax: (+86) 10-8261-9667Search for more papers by this author Ning Zhao, Ning Zhao State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P. R. China, Fax: (+86) 10-8261-9667 Graduate School of the Chinese Academy of Sciences, Beijing 100080, P. R. ChinaSearch for more papers by this authorLihui Weng Dr., Lihui Weng Dr. State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P. R. China, Fax: (+86) 10-8261-9667Search for more papers by this authorXiaoyan Zhang, Xiaoyan Zhang State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P. R. China, Fax: (+86) 10-8261-9667 Graduate School of the Chinese Academy of Sciences, Beijing 100080, P. R. ChinaSearch for more papers by this authorQiongdan Xie, Qiongdan Xie State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P. R. China, Fax: (+86) 10-8261-9667Search for more papers by this authorXiaoli Zhang, Xiaoli Zhang State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P. R. China, Fax: (+86) 10-8261-9667Search for more papers by this authorJian Xu Prof., Jian Xu Prof. [email protected] State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P. R. China, Fax: (+86) 10-8261-9667Search for more papers by this author First published: 04 April 2006 https://doi.org/10.1002/cphc.200500698Citations: 95Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Graphical Abstract Natural inspiration: A lotus-leaf-like hierarchical structure is formed on a polycarbonate plate under mild conditions by successive plasticization and coagulation of the polymer surface. The resultant micron- and nanoscale rough structure, shown in the figure allows the common plastic to be superhydrophobic with a large water contact angle and less contact angle hysteresis. Supporting Information Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2267/2006/z500698_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article. References 1S. Mann, Biomineralization, Principles and Concepts in Bioinorganic Materials Chemistry, Oxford Uniersity Press, 2001. 2See, for example, 2a Z. Gu, H. Wei, R. Zhang, G. Han, C. Pan, H. Zhang, X. Tian, Z. Chen, Appl. Phys. Lett. 2005, 86, 201915; 2bA. K. Geim, S. V. Dubonos, I. V. Grigorieva, K. S. Novoselov, A. A. Zhukov, S. Y. Shapoval, Nat. Mater. 2003, 2, 461; 2cL. Feng, S. Li, Y. Li, H. Li, L. Zhang, J. Zhai, Y. Song, B. Liu, L. Jiang, D. Zhu, Adv. Mater. 2002, 14, 1857. 3C. Neinhuis, W. Barthlott, Ann. Bot. 1997, 79, 667. 4 4aR. N. Wenzel, Ind. Eng. Chem. 1936, 28, 988; 4bA. B. D. Cassie, S. Baxter, Trans. Faraday Soc. 1944, 40, 546; 4cS. Herminghaus, Europhys. Lett. 2000, 52, 165. 5 5aA. Nakajima, K. Hashimoto, T. Watanabe, Monatsh. Chem. 2001, 132, 31; 5bR. Blossey, Nat. Mater. 2003, 2, 301; 5cT. Sun, L. Feng, X. Gao, L. Jiang, Acc. Chem. Res. 2005, 38, 644; 5dM. Callies, D. Quéré, Soft Matter, 2005, 1, 55. 6 6aS. Shibuichi, T. Onda, N. Satoh, K. Tsujii, J. Phys. Chem. 1996, 100, 19512; 6bA. Nakajima, K. Hashimoto, T. Watanabe, K. Takai, G. Yamauchi, A. Fujishima, Langmuir 2000, 16, 7044; 6cL. Feng, S. Li, H. Li, J. Zhai, Y. Song, L. Jiang, D. Zhu, Angew. Chem. 2002, 114, 1269; Angew. Chem. Int. Ed. 2002, 41, 1221; 6dM. L. Ma, R. M. Hill, J. L. Lowery, S. V. Fridrikh, G. C. Rutledge, Langmuir 2005, 21, 5549; 6eJ. T. Han, D. H. Lee, C. Y. Ryu, K. Cho, J. Am. Chem. Soc. 2004, 126, 4796; 6fK. Tadanaga, K. Kitamuro, A. Matsuda, T. Minami, J. Sol-Gel. Sci. Technol. 2003, 26, 705; 6gJ. Y. Shiu, C. W. Kuo, P. Chen, C. Y. Mou, Chem. Mater. 2004, 16, 561; 6hX. Zhang, F. Shi, X. Yu, H. Liu, Y. Fu, Z. Wang, L. Jiang, X. Li, J. Am. Chem. Soc. 2004, 126, 3064; 6iJ. Bico, C. Marzolin, D. Quéré, Europhys. Lett. 1999, 47, 220; 6jN. Zhao, Q. Xie, L. Weng, S. Wang, X. Zhang, J. Xu, Macromolecules 2005, 38, 8996; 6kK. K. S. Lau, J. Bico, K. B. K. Teo, M. Chhowalla, G. A. J. Amaratunga, W. I. Milne, G. H. McKinley, K. K. Gleason, Nano Lett. 2003, 3, 1701; 6lR. M. Jisr, H. H. Rmaile, J. B. Schlenoff, Angew. Chem. 2005, 117, 792; Angew. Chem. Int. Ed. 2005, 44, 782; 6mN. J. Shirtcliffe, G. McHale, M. I. Newton, C. C. Perry, P. Roach, Chem. Commun. 2005, 25, 3135; 6nN. J. Shirtcliffe, G. McHale, M. I. Newton, G. Chabrol, C. C. Perry, Adv. Mater. 2004, 16, 1929; 6oK. Acatay, E. Simsek, C. Ow-Yang, Y. Z. Menceloglu, Angew. Chem. 2004, 116, 5322; Angew. Chem. Int. Ed. 2004, 43, 5210; 6pG. Grundmeier, P. Thiemann, J. Carpentier, N. Shirtcliffe, M. Stratmann, Thin Solid Films, 2004, 446, 61; 6qH. Yabu, M. Takebayashi, M. Tanaka, M. Shimomura, Langmuir, 2005, 21, 3235; 6rX. Feng, L. Feng, J. Zhai, L. Jiang, D. Zhu, J. Am. Chem. Soc. 2004, 126, 62. 7 7aA. Marmur, Langmuir 2004, 20, 3517; 7bN. A. Patankar, Langmuir 2004, 20, 8209; 7cA. Otten, S. Herminghuas, Langmuir 2004, 20, 2405. 8 8aH. Y. Erbil, A. L. Demirel, Y. Avci, O. Mert, Science 2003, 299, 1377; 8bX. Lu, C. Zhang, Y. Han, Macromol. Rapid Commun. 2004, 25, 1606; 8cN. Zhao, J. Xu, Q. Xie, L. Weng, X. Guo, X. Zhang, L. Shi, Macromol. Rapid Commun. 2005, 26, 1075; 8dQ. Xie, J. Xu, L. Feng, L. Jiang, W. Tang, X. Luo, C. C. Han, Adv. Mater. 2004, 16, 302; 8eL. Zhai, F. C. Cebeci, R. E. Cohen, M. F. Rubner, Nano Lett. 2004, 4, 1349; 8fQ. Xie, G. Fan, N. Zhao, X. Guo, J. Xu, J. Dong, L. Zhang, Y. Zhang, C. C. Han, Adv. Mater. 2004, 16, 1830; 8gL. Jiang, Y. Zhao, J. Zhai, Angew. Chem. 2004, 116, 4438; Angew. Chem. Int. Ed. 2004, 43, 4338; 8hR. Furstner, W. Barthlott, C. Neinhuis, P. Walzel, Langmuir, 2005, 21, 956. 9H. R. Harron, R. G. Pritchard, B. C. Cope, D. T. Goddard, J. Polym. Sci. B: Polym. Phys. 1996, 34, 173. 10E. Turska, H. Janeczek, Polymer 1979, 20, 855. 11C. Guo, L. Feng, J. Zhai, G. Wang, Y. Song, L. Jiang, D. Zhu, ChemPhysChem 2004, 5, 750. 12 12aW. Chen, A. Y. Fadeev, M. C. Hsieh, D. Öner, J. Youngblood, T. J. McCarthy, Langmuir, 1999, 15, 3395; 12bD. Öner, T. J. McCarthy, Langmuir 2000, 16, 7777; 12cM. Miwa, A. Nakajima, A. Fujishima, K. Hashimoto, T. Watanabe, Langmuir 2000, 16, 5754; 12dA. Lafuma, D. Quéré, Nat. Mater. 2003, 2, 457. Citing Literature Volume7, Issue4April 10, 2006Pages 824-827 ReferencesRelatedInformation

Amine-functionalized silica catalysts (NH2/SiO2, NH(CH2)2NH2/SiO2 and 1,5,7-triazabicyclo[4,4,0]dec-5-ene/SiO2 (TBD/SiO2)), which were characterized by 29Si NMR, elemental analysis, N2 adsorption–desorption method and indicator dye adsorption, were prepared by ultrasonic technique under mild conditions. Such hybrid solid bases showed high catalytic activity towards CO2 coupling with epoxide. However, it was found that the reaction conditions had a great influence on the performance. Furthermore, silanols on the surface played an important role in the chemical fixation of CO2. Based on these, the possible reaction mechanism was proposed for CO2 coupling with epoxide over such type of catalysts.

Here, we have introduced a novel and facile method to prepare porous hollow CuO nanofibers and Cu nanofibers via single-spinneret electrospinning of polyvinyl pyrrolidone (PVP)/copper acetate (Cu(CH3COO)2) solution followed by annealing and reduction. In this approach, the diameter and the shell thickness of the fibers can be simply adjusted by the concentration of PVP and the ratio of PVP to Cu(CH3COO)2. A possible mechanism is proposed to explain the formation of porous hollow CuO and Cu nanofiber. This method provides an new idea to prepare metal-oxide and metal fibers with a long continuous porous hollow morphology.

Ni–CaO–ZrO2 catalysts for CO2 reforming of CH4 were prepared by either co-precipitation or impregnation and characterized by means of N2 adsorption–desorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and temperature programmed (TP) techniques. It was found that the preparation procedure greatly influenced the physicochemical properties of catalysts, such as morphology, phase and surface structure. As a result, their activity in CO2 reforming of CH4 was determined by the dispersion of Ni and the co-precipitated catalysts showed a better stability. Furthermore, CO2-TPD and transient pulse experiments suggested that the carbon formed over two co-precipitated catalysts was eliminated by different mechanisms, and redox properties and strong basicity were believed to be the key factor for the stability, respectively.

Superhydrophilic silica film with antifogging and antireflective properties was prepared by dip-coating the glass in SiO2 nanoparticles sol. The transparent superhydrophilic film was composed of silica nanoparticles of about 20–30 nm in diameter. The combination of hydrophilic SiOH on the surface and nanoporous surface topography was believed to be responsible for the antifogging property. The nanopores also effectively reduced the refractive index of the film and resulted in the antireflective property. By sintering the multifunctional silica film, a pencil hardness of 2H could be obtained. Application of the functional film in full-sized photovoltaic modules (1580 × 808 × 35 mm) demonstrated an increase of the power output of about 2%, 5% and 8%, respectively, at incidence angles of 0°, 30° and 60°.