In situ growth of co-catalysts on BiVO_(4)(BVO)to enhance photoelectrochemical(PEC)water splitting performance has been extensively reported.However,the understanding of the synergistic effects among various elements,...In situ growth of co-catalysts on BiVO_(4)(BVO)to enhance photoelectrochemical(PEC)water splitting performance has been extensively reported.However,the understanding of the synergistic effects among various elements,especially at the interface between the semiconductor and cocatalyst,has received insufficient attention.In this study,we report a Co,Ni and Mn trimetallic fluoride-modified BVO photoanode featuring a unique interfacial chemical bond(V-F).Under AM 1.5 G illumination,an exciting photocurrent density of 6.05 mA cm^(-2)was achieved at 1.23 V vs.RHE by the integrated BVO/CoNi_(0.18)Mn_(0.12)(OH)_(x)F photoanode and over 98%of the initial photocurrent was maintained after 10 h of photoelectrolysis.Control experiments and theoretical calculations demonstrate that the V-F interfacial bond stabilizes the Co^(2+)active sites.It serves as a transmission gear,interlinking the migration of interfacial charge and the regeneration of cocatalyst,endowing the photoanode with significant activity and stability.Furthermore,we have systematically elucidated the role of the individual Co,Ni,and Mn components in the synergistic cocatalyst layer.The interfacial modification provides novel insights into developing advanced photoanodes towards PEC water splitting.展开更多
Multi-metal porous crystalline materials(MPCM),integrating the functions of both multi-metal centres and porous crystalline materials(e.g.,metal-organic frameworks(MOFs)and covalent organic frameworks(COFs)),are an ex...Multi-metal porous crystalline materials(MPCM),integrating the functions of both multi-metal centres and porous crystalline materials(e.g.,metal-organic frameworks(MOFs)and covalent organic frameworks(COFs)),are an extended class of porous materials that have attracted much attention for a broad range of applications.Owing to the advantages of these materials,they generally display high porosity,multimetal active sites,well-tuned functions,and pre-designable structures,etc.,serving as desired platforms for the study of structure-property relationships.In view of the clean and sustainable target,a series of MPCM have been explored as electrocatalysts for electrocatalytic reactions like hydrogen evolution reaction,oxygen evolution reaction and electrocatalytic CO_(2)reduction reaction.Concerning the progress achieved for MPCM in electrocatalytic field during past years,this review will provide a brief introduction on the recent breakthrough of MPCM based electrocatalysts including their synthesis methods,structure design,component/morphology tuning,electrocatalytic property and structure-property relationship,etc.Besides,it will also conclude the current challenges and present perspectives for the MPCM based electrocatalysts,which might promote the development of porous crystalline materials in electrocatalysis and hope to provide new insights for scientists in related fields.展开更多
Strategic design and synergistic interactions between the electrodes and electroactive materials profoundly influence the energy storage efficiency of supercapacitor devices. Herein, we present the interfacial enginee...Strategic design and synergistic interactions between the electrodes and electroactive materials profoundly influence the energy storage efficiency of supercapacitor devices. Herein, we present the interfacial engineering of CoMoS_(4)-NiS_(2) with a well-defined construction of amorphous/crystalline hetero-phases deposited on carbon cloth using a hydrothermal technique. The optimal in-situ growth of CoMoS_(4)-NiS_(2)@CFC boasts an impressive areal capacity of 1341 mC cm^(-2) and retains ∼91 % capacity after 5000 cycles, attributed to the synergy effect and improved conductivity of multi-metallic sulfide ions over the CFC substrate. Density functional theory (DFT) reveals the metallic nature of CoMoS_(4)-NiS_(2)@CFC and favorable OH- ion adsorption energy of -4.35 eV, enhancing its charge storage capabilities. Furthermore, a hybrid supercapacitor (HSC) and Pouch HSC are assembled utilizing the CoMoS_(4)-NiS_(2)@CFC as a positrode and marine waste jellyfish-derived AC as a negatrode with an aqueous electrolyte. The HSC and PHSC demonstrate superior specific energies of 51.99 and 58.4 W h kg^(-1), respectively, along with corresponding specific powers of 800 and 780 W kg^(-1), maintaining robust stability of ∼90 % stability over 10000 cycles. Additionally, the HSC and PHSC have successfully illuminated several light-emitting diodes (LEDs) demonstrating superior energy storage performance. This work advances the design of hetero-phase multi-metal sulfides, paving the way for high-performance supercapacitor devices.展开更多
Laser additive manufacturing(LAM)is promising for fabricating multi-metallic component,but the mechanism of microstructural evolution at the interface of two metals is still needed to research further.In this study,a ...Laser additive manufacturing(LAM)is promising for fabricating multi-metallic component,but the mechanism of microstructural evolution at the interface of two metals is still needed to research further.In this study,a 316L stainless steel/Ti6Al4V alloy multi-metal was fabricated by LAM,and the mechanism of intermetallic phase transformation was deeply investigated.Results show that a strong reaction zone(SRZ)can be induced at the interface of the multi-metal.The phase constituents at the SRZ vary fromχ(Ti_(5)Fe_(17)Cr_(5))+Fe_(2)Ti+α′-Ti+β-Ti or FeTi to Fe_(2)Ti+χwhen the laser power is increased.When the scanning speed is further decreased,the thickness of the SRZ is significantly increased,andα′-Ti phase is also formed at this region besides Fe_(2)Ti andχphases.Moreover,the micro-hardness at the SRZ is increased,caused by the intermetallic phase transformation and elemental interdiffusion at the interface.展开更多
Two new isostructural multi-metal beryllium borates, m^3 Li Na4Be4B10O24F（M = Sr（1）, Cd（2））, have been synthesized by spontaneous crystallization. The structures were verified by single-crystal X-ray crystallogr...Two new isostructural multi-metal beryllium borates, m^3 Li Na4Be4B10O24F（M = Sr（1）, Cd（2））, have been synthesized by spontaneous crystallization. The structures were verified by single-crystal X-ray crystallography. The compounds crystallize in the trigonal space group R 3, with a = b = 9.4645（1） A, c = 38.842（8） A, V = 3013.2（6） A3, Z = 6, F（000） = 2568, Dc = 3.005 g/cm^3, Mr = 908.9, R = 0.0327, w R = 0.0678, μ = 8.160 mm-1 for Sr3 Li Na4Be4B10O24F and a = b = 9.3019（8） A, c = 37.782（7） A, V = 2831.12（9） A3, Z = 6, F（000） = 2748, Dc = 3.459 g/cm^3, Mr = 983.24, R = 0.0158, w R = 0.0455, μ = 3.586 mm-1 for Cd3 Li Na4Be4B10O24F. The structures are characterized by an infinite two-dimensional [Be8B16O40F2]∞ double layer bridged by [B12O24] groups like a sandwich structure, while the cations reside in tunnels along different directions. UV-vis-IR diffuse reflectance spectroscopy demonstrates that their cut-off edges are below 200 nm. Thermal analysis shows that they melt incongruently and their melting points are around 740-770 ℃.展开更多
Bioinspired Multi-Metal Structures(MMSs)combine distinct properties of multiple materials,benefiting from improved properties and providing superior designs.Additive Manufacturing(AM)exhibits enormous advantages in ap...Bioinspired Multi-Metal Structures(MMSs)combine distinct properties of multiple materials,benefiting from improved properties and providing superior designs.Additive Manufacturing(AM)exhibits enormous advantages in applying different materials and geometries according to the desired functions at specific locations of the structure,having great potential in fabricating multi-materials structures.However,current AM techniques have difficulty manufacturing 3D MMSs without material cross-contamination flexibly and reliably.This study demonstrates a reliable,fast,and flexible direct ink writing method to fabricate 3D MMSs.The in-situ material-switching system enables the deposition of multiple metallic materials across different layers and within the same layer.3D Fe-Cu MMSs with complex geometries and fine details are fabricated as proof of concept.The microstructures,chemical and phase compositions,and tensile fracture surfaces of the Fe-Cu interfaces indicate a well-bonded interface without cracks,delamination,or material cross-contamination.We envision this novel method making other metallic combinations and even metal-ceramic components.It paves the way for manufacturing 3D MMSs using AM and establishes the possibilities of numerous MMSs applications in engineering fields.展开更多
Morphology of zinc alloy layer,from zincate solution with zinc sulfate and zinc oxide respectively,together with the consequent deposit was observed with SEM and back scattering electron image.EDS was applied to analy...Morphology of zinc alloy layer,from zincate solution with zinc sulfate and zinc oxide respectively,together with the consequent deposit was observed with SEM and back scattering electron image.EDS was applied to analyze the components of zinc alloy layer and the interface of high-Si aluminum alloy substrate-zinc alloy-deposit.Besides,the surface morphology of the zincated aluminum alloy after immersing in 3.5%NaCl solution for 7 d,is observed and the corrosion rate was calculate.Finally,tension test is conducted to quantify the adhesion between high-Si aluminum cast substrate and the deposit.The results show that,the zinc oxide contained zincating solution with sodium potassium tartrate and sodium citrate is a better one in multi-metal zincating solutions.The zinc alloy layer from this one gets stable performance,perfect adhesion with deposit,and good corrosion resistance.展开更多
A kinetic study on the sulfuric acid leaching of multi-metal oxide, which is the product of multi-metal copper alloy with iron trioxide roasted in oxygen, was carried out. The effects of leaching time, stirring speed,...A kinetic study on the sulfuric acid leaching of multi-metal oxide, which is the product of multi-metal copper alloy with iron trioxide roasted in oxygen, was carried out. The effects of leaching time, stirring speed, sulfuric acid concentration, reaction temperature, and particle size of the multi-metal oxide on the kinetics and mechanism of copper extraction were studied. It was found that the reaction kinetic model about the copper extraction from multi-metal oxide follows the mixed kinetic shrinking core mode： 1/31n（1-X）＋（1-X）-l/3-1=680.5C（H2SO4）0.4297dp0.75115exp（-Ea/RT）t.展开更多
Herein,we report the multi-metal atomic catalysts for solid-state dehydrogenation of MgH_(2).It aims to reveal the multi-element synergy in catalysts for solid-state hydrogen storage.The kinetic measurements and fitti...Herein,we report the multi-metal atomic catalysts for solid-state dehydrogenation of MgH_(2).It aims to reveal the multi-element synergy in catalysts for solid-state hydrogen storage.The kinetic measurements and fitting reveal two mechanisms:one shows a maximum rate at the early stage,such as V and Cr;the other needs a temperature-sensitive preparation time for its maximum rate,such as Ni.The combina-tion of two catalyst components demonstrates the best kinetics:V and Cr boost the initial dehydrogena-tion,and Ni benefits the further hydrogen transfer which alleviates the rate of decay.This work provides guidelines for the design of multi-element doped catalysts for MgH_(2) dehydrogenation.展开更多
文摘In situ growth of co-catalysts on BiVO_(4)(BVO)to enhance photoelectrochemical(PEC)water splitting performance has been extensively reported.However,the understanding of the synergistic effects among various elements,especially at the interface between the semiconductor and cocatalyst,has received insufficient attention.In this study,we report a Co,Ni and Mn trimetallic fluoride-modified BVO photoanode featuring a unique interfacial chemical bond(V-F).Under AM 1.5 G illumination,an exciting photocurrent density of 6.05 mA cm^(-2)was achieved at 1.23 V vs.RHE by the integrated BVO/CoNi_(0.18)Mn_(0.12)(OH)_(x)F photoanode and over 98%of the initial photocurrent was maintained after 10 h of photoelectrolysis.Control experiments and theoretical calculations demonstrate that the V-F interfacial bond stabilizes the Co^(2+)active sites.It serves as a transmission gear,interlinking the migration of interfacial charge and the regeneration of cocatalyst,endowing the photoanode with significant activity and stability.Furthermore,we have systematically elucidated the role of the individual Co,Ni,and Mn components in the synergistic cocatalyst layer.The interfacial modification provides novel insights into developing advanced photoanodes towards PEC water splitting.
基金supported by the National Key R&D Program of China(No.2023YFA1507204)the National Natural Science Foundation of China(Nos.22171139,22225109,22309054,22071109,22371080,21775048)+2 种基金Natural Science Foundation of Guangdong Province(No.2023B1515020076)China Postdoctoral Science Foundation(No.2023M731154)China National Postdoctoral Program for Innovative Talents(No.BX20220116)。
文摘Multi-metal porous crystalline materials(MPCM),integrating the functions of both multi-metal centres and porous crystalline materials(e.g.,metal-organic frameworks(MOFs)and covalent organic frameworks(COFs)),are an extended class of porous materials that have attracted much attention for a broad range of applications.Owing to the advantages of these materials,they generally display high porosity,multimetal active sites,well-tuned functions,and pre-designable structures,etc.,serving as desired platforms for the study of structure-property relationships.In view of the clean and sustainable target,a series of MPCM have been explored as electrocatalysts for electrocatalytic reactions like hydrogen evolution reaction,oxygen evolution reaction and electrocatalytic CO_(2)reduction reaction.Concerning the progress achieved for MPCM in electrocatalytic field during past years,this review will provide a brief introduction on the recent breakthrough of MPCM based electrocatalysts including their synthesis methods,structure design,component/morphology tuning,electrocatalytic property and structure-property relationship,etc.Besides,it will also conclude the current challenges and present perspectives for the MPCM based electrocatalysts,which might promote the development of porous crystalline materials in electrocatalysis and hope to provide new insights for scientists in related fields.
基金supported by the Technology Devel-opment Program(No.S3218794)funded by the Ministry of SMEs and Startups(MSS,Korea)supported by the Nano&Material Technology Development Program through the National Research Foundation of Korea(NRF)funded by the Min-istry of Science and ICT(No.RS-2024-00446825).
文摘Strategic design and synergistic interactions between the electrodes and electroactive materials profoundly influence the energy storage efficiency of supercapacitor devices. Herein, we present the interfacial engineering of CoMoS_(4)-NiS_(2) with a well-defined construction of amorphous/crystalline hetero-phases deposited on carbon cloth using a hydrothermal technique. The optimal in-situ growth of CoMoS_(4)-NiS_(2)@CFC boasts an impressive areal capacity of 1341 mC cm^(-2) and retains ∼91 % capacity after 5000 cycles, attributed to the synergy effect and improved conductivity of multi-metallic sulfide ions over the CFC substrate. Density functional theory (DFT) reveals the metallic nature of CoMoS_(4)-NiS_(2)@CFC and favorable OH- ion adsorption energy of -4.35 eV, enhancing its charge storage capabilities. Furthermore, a hybrid supercapacitor (HSC) and Pouch HSC are assembled utilizing the CoMoS_(4)-NiS_(2)@CFC as a positrode and marine waste jellyfish-derived AC as a negatrode with an aqueous electrolyte. The HSC and PHSC demonstrate superior specific energies of 51.99 and 58.4 W h kg^(-1), respectively, along with corresponding specific powers of 800 and 780 W kg^(-1), maintaining robust stability of ∼90 % stability over 10000 cycles. Additionally, the HSC and PHSC have successfully illuminated several light-emitting diodes (LEDs) demonstrating superior energy storage performance. This work advances the design of hetero-phase multi-metal sulfides, paving the way for high-performance supercapacitor devices.
基金supported by the Key Research and Develop Program of Anhui Province(No.202004b11020030)the China Postdoctoral Science Foundation(No.2020M680292)。
文摘Laser additive manufacturing(LAM)is promising for fabricating multi-metallic component,but the mechanism of microstructural evolution at the interface of two metals is still needed to research further.In this study,a 316L stainless steel/Ti6Al4V alloy multi-metal was fabricated by LAM,and the mechanism of intermetallic phase transformation was deeply investigated.Results show that a strong reaction zone(SRZ)can be induced at the interface of the multi-metal.The phase constituents at the SRZ vary fromχ(Ti_(5)Fe_(17)Cr_(5))+Fe_(2)Ti+α′-Ti+β-Ti or FeTi to Fe_(2)Ti+χwhen the laser power is increased.When the scanning speed is further decreased,the thickness of the SRZ is significantly increased,andα′-Ti phase is also formed at this region besides Fe_(2)Ti andχphases.Moreover,the micro-hardness at the SRZ is increased,caused by the intermetallic phase transformation and elemental interdiffusion at the interface.
基金supported by the National Natural Science Foundation of China(No.50972149,61138004,51402316)the National Instrumentation Program(No.2012YQ120048)
文摘Two new isostructural multi-metal beryllium borates, m^3 Li Na4Be4B10O24F（M = Sr（1）, Cd（2））, have been synthesized by spontaneous crystallization. The structures were verified by single-crystal X-ray crystallography. The compounds crystallize in the trigonal space group R 3, with a = b = 9.4645（1） A, c = 38.842（8） A, V = 3013.2（6） A3, Z = 6, F（000） = 2568, Dc = 3.005 g/cm^3, Mr = 908.9, R = 0.0327, w R = 0.0678, μ = 8.160 mm-1 for Sr3 Li Na4Be4B10O24F and a = b = 9.3019（8） A, c = 37.782（7） A, V = 2831.12（9） A3, Z = 6, F（000） = 2748, Dc = 3.459 g/cm^3, Mr = 983.24, R = 0.0158, w R = 0.0455, μ = 3.586 mm-1 for Cd3 Li Na4Be4B10O24F. The structures are characterized by an infinite two-dimensional [Be8B16O40F2]∞ double layer bridged by [B12O24] groups like a sandwich structure, while the cations reside in tunnels along different directions. UV-vis-IR diffuse reflectance spectroscopy demonstrates that their cut-off edges are below 200 nm. Thermal analysis shows that they melt incongruently and their melting points are around 740-770 ℃.
基金National Natural Science Foundation of China,China(Grant ID:52105343 and 52021003)China Postdoctoral Science Foundation,China(Grant ID:2021M701387 and 2022T150259)Department of Science and Technology of Jilin Province,China(Grant ID:2020122214JC).
文摘Bioinspired Multi-Metal Structures(MMSs)combine distinct properties of multiple materials,benefiting from improved properties and providing superior designs.Additive Manufacturing(AM)exhibits enormous advantages in applying different materials and geometries according to the desired functions at specific locations of the structure,having great potential in fabricating multi-materials structures.However,current AM techniques have difficulty manufacturing 3D MMSs without material cross-contamination flexibly and reliably.This study demonstrates a reliable,fast,and flexible direct ink writing method to fabricate 3D MMSs.The in-situ material-switching system enables the deposition of multiple metallic materials across different layers and within the same layer.3D Fe-Cu MMSs with complex geometries and fine details are fabricated as proof of concept.The microstructures,chemical and phase compositions,and tensile fracture surfaces of the Fe-Cu interfaces indicate a well-bonded interface without cracks,delamination,or material cross-contamination.We envision this novel method making other metallic combinations and even metal-ceramic components.It paves the way for manufacturing 3D MMSs using AM and establishes the possibilities of numerous MMSs applications in engineering fields.
基金This work is financially supported by the Foundation of Basic Research of Harbin Engineering Universi-ty(HEUFT06030)
文摘Morphology of zinc alloy layer,from zincate solution with zinc sulfate and zinc oxide respectively,together with the consequent deposit was observed with SEM and back scattering electron image.EDS was applied to analyze the components of zinc alloy layer and the interface of high-Si aluminum alloy substrate-zinc alloy-deposit.Besides,the surface morphology of the zincated aluminum alloy after immersing in 3.5%NaCl solution for 7 d,is observed and the corrosion rate was calculate.Finally,tension test is conducted to quantify the adhesion between high-Si aluminum cast substrate and the deposit.The results show that,the zinc oxide contained zincating solution with sodium potassium tartrate and sodium citrate is a better one in multi-metal zincating solutions.The zinc alloy layer from this one gets stable performance,perfect adhesion with deposit,and good corrosion resistance.
基金Project(2011AA061003)supported by Hi-Tech Research and Development Program of China
文摘A kinetic study on the sulfuric acid leaching of multi-metal oxide, which is the product of multi-metal copper alloy with iron trioxide roasted in oxygen, was carried out. The effects of leaching time, stirring speed, sulfuric acid concentration, reaction temperature, and particle size of the multi-metal oxide on the kinetics and mechanism of copper extraction were studied. It was found that the reaction kinetic model about the copper extraction from multi-metal oxide follows the mixed kinetic shrinking core mode： 1/31n（1-X）＋（1-X）-l/3-1=680.5C（H2SO4）0.4297dp0.75115exp（-Ea/RT）t.
基金Yijing Wang acknowledges the funding support of the National Key Research and Development Program of China(No.2021YFB4000604)the National Natural Science Foundation of China(No.52271220)+6 种基金the Higher Education Discipline Innovation Project(No.B12015)“the Fundamental Research Funds for the Central Universities”Huaiyu Shao acknowledges the funding support of the Multi-Year Research Grant(MYRG)from the University of Macao(No.MYRG2022-00105-IAPME)the Joint Scientific Research Project Funding by the National Natural Science Foundation of China and the Macao Science and Technology Development Fund(No.0090/2022/AFJ)the Macao Science and Technology Development Fund(FDCT)for funding No.006/2022/ALC of the Macao Centre for Research and Development in Advanced Materials(No.2022-2024)the Natural Science Foundation of Guangdong Province(Grant No.2023A1515010765)the Shenzhen-Hong Kong-Macao Science and Technology Innovation Project(Category C).
文摘Herein,we report the multi-metal atomic catalysts for solid-state dehydrogenation of MgH_(2).It aims to reveal the multi-element synergy in catalysts for solid-state hydrogen storage.The kinetic measurements and fitting reveal two mechanisms:one shows a maximum rate at the early stage,such as V and Cr;the other needs a temperature-sensitive preparation time for its maximum rate,such as Ni.The combina-tion of two catalyst components demonstrates the best kinetics:V and Cr boost the initial dehydrogena-tion,and Ni benefits the further hydrogen transfer which alleviates the rate of decay.This work provides guidelines for the design of multi-element doped catalysts for MgH_(2) dehydrogenation.
