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Metal-organic frameworks with dinuclear metal centers for synergistically boosting CO2 photoreduction

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Science China Chemistry 2025年第1期68卷 201-208页

作者： Hui-Feng Wang Wen-Jie Shi Yu-Xin Yang Bao-Xia Dong Tong-Bu Lu Di-Chang Zhong school of Chemistry and Chemical engineering Yangzhou University Institute for New Energy materials and Low Carbon Technologies School of Materials Science and Engineering Tianjin University of Technology

Dinuclear metal synergistic catalysis （DMSC） has been proved powerful in boosting CO2reduction,while this has not been achieved in heterogeneous catalysts with long-range order *** this study,we,by introduction of metal catalytic centers into an indium-based metal-organic framework （MOF）,obtained a series of isostructural In-MOFs,including three MOFs with mononuclear metal catalytic center （M-In）,three MOFs with dinuclear homometallic catalytic centers （MM-In）,and three MOFs with dinuclear heterometallic catalytic centers (MM’-In,M/M’=Co（II）,Ni（II）,Zn（II）).It was found that all these MOFs can serve as catalysts for photochemical CO2reduction to *** with M-In,the catalytic activities of MM-In were obviously enhanced,and that of MM’-In was further significantly *** example,the CO yield of Co Zn-In reaches a record value of 12,700μmol g-1h-1,which is 4.0,8.1,9.4,and 18.6-fold higher than that of Co Co-In,Zn Zn-In,Co-In,and Zn-In,***,the catalytic activities of Co Ni-In and Ni Zn-In also show different fold increase than those of corresponding dinuclear homometallic and mononuclear metallic *** results of control experiments and theoretical calculation reveal that the higher catalytic activities of MM-In over M-In can be ascribed to the DMSC effect,and the higher catalytic activity of MM’-In over MM-In can be ascribed to the strengthened DMSC *** work reveals the relationship between DMSC effect and bimetal centers in CO2reduction,which provides new insights into the DMSC and paves a new way to design highly active catalysts for photochemical CO2reduction.

关键词： metal-organic frameworks dinuclear metal centers synergistic catalysis CO2 reduction photocatalysis

Controlled cationic ring-opening polymerization of L-lactide by organic ion pair: novel approach to isotactic-rich and crystalline polylactide

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Science China Chemistry 2025年第1期68卷 394-402页

作者： Zhiqiang Ding Mingqian Wang Zijing Zhou Bin Wang Yuesheng Li Tianjin Key Laboratory of Composite & Functional materials School of Materials Science and Engineering Tianjin University

Living/controlled cationic ring-opening polymerization （ROP） of L-lactide is a promising approach to isotactic-rich and crystalline poly（L-lactide）.In contrast with the unsubstituted lactones,L-LA can not be polymerized by organic Lewis acids or carbenium ions,and the state of the art in this field is the cationic ROP of L-LA catalyzed by Br?nsted acid/alcohol system via activated monomer ***,we reported the first example of controlled cationic ROP of L-LA by using Meerweintype ion pair[Me3O]+[B（C6F5）4]-as the catalyst.[Me3O]+[B（C6F5）4]-promoted rapid L-LA cationic polymerization in the absence of alcohol,producing isotactic-rich and crystalline PLLA without transesterification and epimerization side *** activated chain end mechanism,involving twice SN2 substitution and configuration-inversion （S→R→S） with the assistance of released Me2O,was proposed and further verified by density functional theory and control *** work expands the catalytic toolbox of isotactic-rich and crystalline polylactide *** represents a unique example of cationic-controlled polymerization of L-LA catalyzed by an organic ion pair.

关键词： organic ion pair controlled cationic ring-opening polymerization activated chain end mechanism isotactic-rich polylactide

“One stone, two birds”: Salt template enabling porosity engineering and single metal atom coordinating toward high-performance zinc-ion capacitors

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Journal of Energy Chemistry 2025年第1期100卷 637-645页

作者： Chunliu Zhu Huanyu Liang Ping Li Chenglong Qiu Jingyi Wu Jingwei Chen Weiqian Tian Yue Zhu Zhi Li Huanlei Wang school of materials Science and engineering Ocean University of China Department of Chemical and materials engineering University of Alberta

Zinc-ion hybrid capacitors （ZIHCs） have received increasing attention as energy storage devices owing to their low cost,high safety,and environmental ***,their progress has been hampered by low energy and power density,as well as unsatisfactory long-cycle stability,mainly due to the lack of suitable electrode *** this context,we have developed manganese single atoms implanted in nitrogen-doped porous carbon nanosheets （MnSAs/NCNs） using a metal salt template method as cathodes for *** metal salt serves a dual purpose in the synthesis process:It facilitates the uniform dispersion of Mn atoms within the carbon matrix and acts as an activating agent to create the porous *** applied in ZIHCs,the MnSAs/NCNs electrode demonstrates exceptional performance,including a high capacity of 203 m Ah g-1,an energy density of 138 Wh kg-1at 68 W kg-1,and excellent cycle stability with 91%retention over 10,000 *** calculations indicate that the introduced Mn atoms modulate the local charge distribution of carbon materials,thereby improving the electrochemical *** work demonstrates the significant potential of carbon materials with metal atoms in zinc-ion hybrid capacitors,not only in enhancing electrochemical performance but also in providing new insights and methods for developing high-performance energy storage devices.

关键词： Zinc ion hybrid capacitors Cathodes Carbon materials Heteroatoms Single atoms

Electrocatalytic nitrite reduction to ammonia on isolated bismuth alloyed ruthenium

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Journal of Energy Chemistry 2025年第1期100卷 369-376页

作者： Shiyao Shang Fuzhou Wang Zeyi Sun Chaofan Qiang Ke Chu school of materials Science and engineering Lanzhou Jiaotong University

Electrochemical reduction of NO2-to NH3（NO2-RR） is recognized as an appealing approach for achieving renewable NH3synthesis and waste ***,we report isolated Bi alloyed Ru （Bi1Ru） as an efficient NO2-RR *** calculations and in situ electrochemical measurements reveal the creation of Bi1-Ru dual sites which can remarkably promote NO2-activation and suppress proton adsorption,while accelerating the NO2-RR protonation energetics to render a high NO2--to-NH3conversion ***,Bi1Ru assembled in a flow cell delivers an NH3yield rate of 1901.4μmol h-1cm-2and an NH3-Faradaic efficiency of 94.3%at an industrial-level current density of 324.3 mA *** study offers new perspectives for designing and constructing p-block single-atom alloys as robust and high-current-density NO2-RR catalysts toward the ammonia electrosynthesis.

关键词： Ammonia

Thickness and sp3 bond modulation of（Ti/tetrahedral amorphous carbon）_n multilayer coatings

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Tungsten 2025年第1期7卷 152-160页

作者： Zhi-Jun Xie Jia-Lin Li Ling Gong Xiang-Li Zhong Hong-Jia Song Jin-Bin Wang National-Provincial Laboratory of Special Function Thin Film materials School of Materials Science and Engineering Xiangtan University

The durability of wear-resistant tetrahedral amorphous carbon（ta-C） coatings is intimately linked to their thickness and the concentration of *** enhance the lifespan of the coatings,we have prepared a multilayer coating consisting of alternating layers of Ti and ta-C,denoted as（Ti/ta-C）_n,using arc ion plating.A multi-layer structure in conjunction with stage cooling is employed to enhance the thickness and promote *** results indicate that the ID/IGvalue,representing the ratio of the intensity of the D peak to that of the G peak in Raman spectroscopy,decreases from 0.85 when no stage cooling is applied to 0.35 when stage cooling is employed,suggesting an enhancement in the fraction of sp3bonds within the *** obtained（Ti/ta-C）_n multilayer coating without peeling off has a maximum thickness of 1.14 μm,which is almost double that of the ta-C coating single layer *** the same time,the coating has a low coefficient of friction,down to 0.069,and maintains excellent friction properties with a wear rate of 3.4×10-6mm3·N-1·*** results conclusively show that the preparation technology can enhance both thickness and sp3bonding in ta-C coatings,significantly expanding their utility across tools,molds,and precision engineering components.

关键词： Arc ion plating Multilayer structure sp3 bond Ta-C coating Wear resistance

Nano high-entropy oxide cathode with enhanced stability for direct borohydride fuel cells

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Journal of Energy Chemistry 2025年第1期100卷 309-316页

作者： Lei Zhang Lingfeng Kuang Lianke Zhang Wen Chu Haiying Qin Jing Zhang Junjing He Hualiang Ni Hongzhong Chi New Energy materials Research Center College of Materials and Environmental Engineering Hangzhou Dianzi University school of materials Science and engineering Zhejiang University Key Laboratory of MEMS of Ministry of Education School of Integrated Circuits Southeast University

High-entropy materials have become high-activity electrocatalysis owing to their high-entropy effect and multiple active ***,we synthesize a series of carbon-supported nano high-entropy oxides（HEOs/C）,specifically （PtFeCoNiCu）O/C,using a carbothermal shock （CTS） method for application as a cathode catalyst in direct borohydride fuel cells （DBFCs）.The microstructure of the prepared catalysts was characterized by X-ray photoelectron spectroscopy,X-ray absorption fine structure,and transmission electron *** prepared （PtFeCoNiCu）O/C,with particle sizes ranging from 2 to 4 nm,demonstrates 3.94 transferred electrons towards the oxygen reduction reaction in an alkaline environment,resulting in a minimal H2O2yield of 2.6%.Additionally,it exhibits a Tafel slope of 61 mV dec-1,surpassing that of commercial Pt/C (82 mV dec-1).Furthermore,after 40,000 cycles of cyclic voltammetry（CV） testing,the half-wave potential of （PtFeCoNiCu）O/C shows a positive shift of 3 mV,with no notable decline in the limiting current *** （PtFeCoNiCu）O/C is used as a cathode catalyst in DBFCs,the DBFC achieves a maximum power density of 441 mW cm-2at 60°C and sustains a cell voltage of approximately 0.73 V after 52 h at 30°*** findings confirm that HEO/C is a promising cathode catalyst for DBFCs.

关键词： Direct borohydride fuel cells (DBFC)

Preparation of Modified Composite Nanofiltration Membrane Synergistically Using Carboxylic Multi- walled Carbon Nanotube and β-cyclodextrin

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Journal of Wuhan University of Technology(materials Science) 2025年第1期40卷 232-239页

作者： LIU Peng MAO Junpeng FANG Yanfeng YU Yunwu CHEN Changxiu TANG Ning WAN Ye GU Yaxin LIU Yunxue WANG Lihua school of materials Science and engineering Shenyang Jianzhu UniversityShenyang 110168China

A new modified blend ultrafiltration(UF)membrane with good hydrophilicity,high porosity and excellent anti-fouling performance was developed by using carboxylic multi-walled carbon nanotube(CMWCNT)as casting solution ***,a composite nanofiltration(NF)membrane with large water flux and good retention rate was fabricated by using the PVDF/CMWCNT blend UF membrane as the substrate,and polyvinyl alcohol(PVA),β-cyclodextrin(β-CD)and polyethylenimine(PEI)as the coating *** results show that with the appropriate addition of CMWCNT in the casting solution,the surface roughness,porosity and recovery rate of the PVDF/CMWCNT blend UF membrane is obviously *** water flux of blend UF membrane is significantly improved when the CMWCNT content increases from 0 wt%to 0.2 wt%.The water flux of blend UF membrane with 0.2 wt%CMWCNT is 162.7 L/(m^(2)·h),which is 44.3%higher than that of the pure PVDF ***β-CD content is 0.8 wt%,the retention rate of Congo red by PVDF/CMWCNT/β-CD composite NF membrane reaches 98.7%,which is 28.3%higher than that of single PVA/PEI modified *** research will provide a new idea and simple method for developing novel high-performance composite NF membranes.

关键词： CMWCNT cyclodextrin nanofiltration membrane

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A comprehensive investigation on nonlinear vibration and bending characteristics of bio-inspired helicoidal laminated composite structures

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Applied Mathematics and Mechanics(English Edition) 2025年第1期46卷 81-100页

作者： S.SAURABH R.KIRAN D.SINGH R.VAISH V.S.CHAUHAN school of Mechanical and materials engineering Indian Institute of Technology Mandi

Bio-inspired helicoidal composite laminates, inspired by the intricate helical structures found in nature, present a promising frontier for enhancing the mechanical properties of structural designs. Hence, this study provides a comprehensive investigation into the nonlinear free vibration and nonlinear bending behavior of bio-inspired composite plates. The inverse hyperbolic shear deformation theory(IHSDT) of plates is employed to characterize the displacement field, with the incorporation of Green-Lagrange nonlinearity. The problem is modeled using the C0finite element method(FEM), and an in-house code is developed in the MATLAB environment to solve it numerically. Various helicoidal layup configurations including helicoidal recursive(HR), helicoidal exponential(HE), helicoidal semi-circular(HS), linear helicoidal(LH), and Fibonacci helicoidal(FH)with different layup sequences and quasi-isotropic configurations are studied. The model is validated, and parametric studies are conducted. These studies investigate the effects of layup configurations, side-to-thickness ratio, modulus ratios, boundary conditions, and loading conditions at different load amplitudes on the nonlinear vibration and nonlinear bending behaviors of bio-inspired composite plates. The results show that the laminate sequence exerts a substantial impact on both nonlinear natural frequencies and nonlinear bending behaviors. Moreover, this influence varies across different side-to-thickness ratios and boundary conditions of the bio-inspired composite plate.

关键词： Inverse problems

Post-tunable salt gel electrolytes toward flexible supercapacitor switches

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Journal of Energy Chemistry 2025年第1期100卷 114-124页

作者： Hui Wang Shuang Chen Xuming Liu Qin Zhang Xin Liu Polymeric and Soft materials Laboratory School of Chemistry and Life Science and Advanced Institute of Materials Science Changchun University of Technology Polymeric and Soft materials Laboratory School of Chemical Engineering and Advanced Institute of Materials Science Changchun University of Technology

Convertible hydrogel supercapacitors have emerged as promising energy storage devices in switches,diodes, and transistors. However, inherent weaknesses in ionic conductivity, mechanical properties,and water retention of hydrogel electrolytes seriously hinder their development. Inspired by the hardness conversion of sea cucumber skin, a conductivity and mechanics dual-tunable salt gel electrolyte is successfully designed. The salt gel presents a reversible switching of conductors-insulators and a mechanical regulation between softness and hardness via the dissolution-crystallization transition of sodium acetate trihydrate（SAT）. Meanwhile, the salt gels spontaneously grow a layer of “armor” through saturated phase-change salt crystals effectively reducing water evaporation of hydrogel ***, this phase-change soft-rigid conversion strategy will expand the capabilities of gel-based flexible supercapacitors(area capacitance: 258.6 mF cm-2), and the capacitance retention rate could still reach 86.9% after 3000 cycles at high temperatures. Moreover, the salt gel supercapacitor is potentially used in over-heat alarm systems. It is anticipated that the strategy of conductivity and mechanics of dual-tunable salt gel would provide a new perspective on the development of energy storage devices,wearable electronics, and flexible robots.

关键词： Capacitance