The lithium-sulfur battery has attracted enormous attention as being one of the most significant energy storage technologies due to its high energy density and cost-effectiveness.However,the "shuttle effect"...The lithium-sulfur battery has attracted enormous attention as being one of the most significant energy storage technologies due to its high energy density and cost-effectiveness.However,the "shuttle effect" of polysulfide intermediates represents a formidable challenge towards its wide applications.Herein,we have designed and synthesized two-dimensional Cu,Zn and Sn-based multimetallic sulfide nanosheets to construct multi-active sites for the immobilization and entrapment of polysulfides with offering better performance in liquid Li2S6-based lithium-polysulfide batteries.Both experimental measurements and theoretical computations demonstrate that the interfacial multi-active sites of multimetallic sulfides not only accelerate the multi-chained redox reactions of highly diffusible polysulfides,but also strengthen affinities toward polysulfides.By adopting multimetallic sulfide nanosheets as the sulfur host,the liquid Li2 S6-based cell exhibits an impressive rate capability with 1200 mAh/g and retains 580 mAh/g at 0.5 mA/cm^(2) after 1000 cycles.With high sulfur mass loading conditions,the cell with 2.0 mg/cm^(2) sulfur loading delivers a cell capacity of 1068 mAh/g and maintains 480 mAh/g with 0.8 mA/cm^(2) and 500 cycles.This study provides new insights into the multifunctional material design with multi-active sites for elevated lithium-polysulfide batteries.展开更多
Due to unique electrical properties and high catalytic efficiency,transition metal nitrogen-codoped car-bide(TM-N-C)has attracted tremendous interest as a multifunctional electrocatalyst for water splitting.Unlike tra...Due to unique electrical properties and high catalytic efficiency,transition metal nitrogen-codoped car-bide(TM-N-C)has attracted tremendous interest as a multifunctional electrocatalyst for water splitting.Unlike traditional single-source modification,herein a novel pomegranate-like high-entropy(HE)elec-trocatalyst of Ni_(3)ZnC_(0.7)decorated with homogeneous multimetal(Fe,Co,Cu,and Ni)nitrogen-codoped carbon matrix(Ni_(3)ZnC_(0.7)@CoNiCuFe-NC)is reported.It can be implemented by the simple thermal an-nealing method of multimetal codoped zeolitic imidazolate framework(ZIF).Benefiting from the syn-ergistic effects of plentiful TM-N-C species,template effect of ZIF and distinct nanoporous structure,HE electrocatalyst Ni_(3)ZnC_(0.7)@CoNiCuFe-NC exhibits outstanding electrocatalytic performance.When ap-plied in strong alkaline electrolyte(1.0 M KOH),the overpotentials of Ni_(3)ZnC_(0.7)@CoNiCuFe-NC present as low as 202 and 97 mV for oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)at 10 mA cm^(−2)current density.Surprisingly as a bifunctional electrode,it can achieve the low cell voltage of 1.53 V at 10 mA cm^(−2)current density for overall water splitting,which is comparable to conventional IrO_(2)||Pt/C electrode and superior to the recently reported analogous bifunctional catalysts.Thus,the work proposes the direction for the rational design of homogeneous distribution of TM-N-C material for water splitting in the green hydrogen energy industry.展开更多
The melting mechanisms of Pt-based multimetallic nanoparticles(NPs)are important to help determine their optimal melting processes.To understand the melting and coalescence behaviors of heterogeneous NPs(Pd-Pt NPs)wit...The melting mechanisms of Pt-based multimetallic nanoparticles(NPs)are important to help determine their optimal melting processes.To understand the melting and coalescence behaviors of heterogeneous NPs(Pd-Pt NPs)with various sizes and compositions,molecular dynamics(MD)simulation was employed.The MD results for larger Pd-Pt NPs with an effective diameter of4.6-7.8 nm show that PtPd alloy can form at Pd/Pt interface before Pd NP melted completely,while for Pt-core/Pdshell NP and Pd-core/Pt-shell NP,PtPd alloy formed only after Pd portion melted completely.For smaller Pd-Pt NPs with an effective diameter of 2.5-4.0 nm,PdPt alloy is not formed until both Pd and Pt NPs melted completely.Besides,the coalescence process of Pd-Pt NPs depends on the melting temperature of Pt NP when Pt composition is higher than 20 at%.Furthermore,the melting mechanisms of Pd/Pt/Ir trimetallic NPs are investigated.A two-step melting process occurs in Pd-Pt-Ir NPs and Ir-core/Ptshell/Pd-shell NP,and the melting sequence of Pd-core/Ptshell/Ir-shell NP and Pt-core/Pd-shell/Ir-shell NP is different from Pd/Pt bimetallic NPs.展开更多
The paper expounds the metallogenic characterist ic s of Jiawula multimetals deposit in China and Uran multimetals deposit in Mongol ia. Comparative study shows that both deposits are volcanic hydrothermal mineral iza...The paper expounds the metallogenic characterist ic s of Jiawula multimetals deposit in China and Uran multimetals deposit in Mongol ia. Comparative study shows that both deposits are volcanic hydrothermal mineral ization with same epoch(Mesozoic), same source, same temperature, and same miner al assemblage, but volcanic structure are different. Therefore, both deposits ca n draw on experience of each other and supplement in future of second time ore- prospecting, and point out the new direction of ore-prospecting.展开更多
The growing demand for renewable,sustainable energy resources has spotlighted electrochemical energy conversion technologies.Due to their distinct physicochemical functionalities,multicomponent metallic nanomaterials ...The growing demand for renewable,sustainable energy resources has spotlighted electrochemical energy conversion technologies.Due to their distinct physicochemical functionalities,multicomponent metallic nanomaterials as start-of-the-art electroca-talysts lie at the heart of electrocatalysis.In the past decade,tremendous progress has been witnessed in the field of strain engineering electrocatalysts,which has been demonstrated as one of the most effective approaches to improving electrocatalytic perfor-mance.This minireview summarizes the latest advances in engineering strains for advanced elec-trocatalysis on multimetallic nanomaterials.In this paper,we start with a brief introduction on the fun-damentals and classifications of strain,followed by a comprehensive discussion of the existing synthetic toolbox and design principles for the exclusive intro-duction of strain effect in multimetallic electrocata-lysts.Next,we showcase both classical and the most recent characterizing techniques to accurately quan-tify strain magnitude,with emphasis on the emerging ones based on electron microscopy and tomography that enable atomic-level precision.Then,the under-lying mechanism behind strain-governed catalytic properties from the viewpoint of modeling studies and how it is employed to rationally design the strained electrocatalysts with boosted performances in multiple representative electrocatalysis reactions are elaborated.We conclude this minireview by out-lining the remaining challenges and opportunities in this prospering field.展开更多
The existence of multiple vacancies leads to significant changes in the local atomic structure,which can regulate the electronic structure of the surface and form unsaturated coordination geometries.However,the curren...The existence of multiple vacancies leads to significant changes in the local atomic structure,which can regulate the electronic structure of the surface and form unsaturated coordination geometries.However,the current methods employed to generate multiple vacancies in two-dimensional(2D)layered double hydroxide(LDH)materials are still difficult to achieve to some extent and are primarily limited to monolayer LDH structures.Here,we present an improved method to synthesize NiMoP/Ni_(2)P catalysts with a sponge-like porous structure.Firstly,NiO with dual defects was constructed by subjecting NiMo-LDH/Ni to air calcination.Subsequently,we performed phosphorization treatment and introduced multiple Ni vacancies and O vacancies as defect sites to tune the edge and substrate surfaces of LDH.At the same time,the electronic structure was tuned by adding P heteroatoms.The synergistic effect of porous structure,heterogeneous interfaces,vacancies,doping defects,and amorphous states can greatly enhance the electron transfer effect inside the catalysts,which significantly improves the catalytic ability of the oxygen evolution reaction(OER).Therefore,the overpotential for the oxygen evolution reaction of NiMoP/Ni_(2)P heterointerfaces reaches 270 mV at a current density of 10 mA·cm^(-2)under alkaline conditions,with the catalysts capable of sustaining high current densities even after the durability testing for 35 h.展开更多
Mo_(2)C is an excellent electrocatalyst for hydrogen evolution reaction(HER).However,Mo_(2)C is a poor electrocatalyst for oxygen evolution reaction(OER).Herein,two different elements,namely Co and Fe,are incorporated...Mo_(2)C is an excellent electrocatalyst for hydrogen evolution reaction(HER).However,Mo_(2)C is a poor electrocatalyst for oxygen evolution reaction(OER).Herein,two different elements,namely Co and Fe,are incorporated in Mo_(2)C that,therefore,has a finely tuned electronic structure,which is not achievable by incorporation of any one of the metals.Consequently,the resulting electrocatalyst Co_(0.8)Fe_(0.2)-Mo_(2)C-80 displayed excellent OER catalytic performance,which is evidenced by a low overpotential of 214.0(and 246.5)mV to attain a current density of 10(and 50)mA cm^(-2),an ultralow Tafel slope of 38.4 mV dec^(-1),and longterm stability in alkaline medium.Theoretical data demonstrates that Co_(0.8)Fe_(0.2)-Mo_(2)C-80 requires the lowest overpotential(1.00 V)for OER and Co centers to be the active sites.The ultrahigh catalytic performance of the electrocatalyst is attributed to the excellent intrinsic catalytic activity due to high Brunauer-Emmett-Teller specific surface area,large electrochemically active surface area,small Tafel slope,and low chargetransfer resistance.展开更多
基金supported by the Start-up Foundation of Nanjing Tech Universitythe National Natural Science Foundation of China (61904080, 61801210, 91833302)+3 种基金the Natural Science Foundation of Jiangsu Province (BK20190670, BK20180686)the Natural Science Foundation of Colleges and Universities in Jiangsu Province (19KJB530008)the Innovation Scientists and Technicians Team Construction Projects of Henan Province (CXTD2017002)the funding for “Distinguished professors” and “High-level talents in six industries” of Jiangsu Province and Technology Innovation Project for Overseas Scholar in Nanjing。
文摘The lithium-sulfur battery has attracted enormous attention as being one of the most significant energy storage technologies due to its high energy density and cost-effectiveness.However,the "shuttle effect" of polysulfide intermediates represents a formidable challenge towards its wide applications.Herein,we have designed and synthesized two-dimensional Cu,Zn and Sn-based multimetallic sulfide nanosheets to construct multi-active sites for the immobilization and entrapment of polysulfides with offering better performance in liquid Li2S6-based lithium-polysulfide batteries.Both experimental measurements and theoretical computations demonstrate that the interfacial multi-active sites of multimetallic sulfides not only accelerate the multi-chained redox reactions of highly diffusible polysulfides,but also strengthen affinities toward polysulfides.By adopting multimetallic sulfide nanosheets as the sulfur host,the liquid Li2 S6-based cell exhibits an impressive rate capability with 1200 mAh/g and retains 580 mAh/g at 0.5 mA/cm^(2) after 1000 cycles.With high sulfur mass loading conditions,the cell with 2.0 mg/cm^(2) sulfur loading delivers a cell capacity of 1068 mAh/g and maintains 480 mAh/g with 0.8 mA/cm^(2) and 500 cycles.This study provides new insights into the multifunctional material design with multi-active sites for elevated lithium-polysulfide batteries.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.22008180 and 21878231)the Natural Science Foundation of Tianjin(Nos.19JCQNJC05700 and 19JCZDJC37300)the Tianjin College Student Innovation and Entrepreneurship Training Program(No.202010058034).This work was also supported by the Analytical&Testing Center of Tiangong University for structural characterization tests.
文摘Due to unique electrical properties and high catalytic efficiency,transition metal nitrogen-codoped car-bide(TM-N-C)has attracted tremendous interest as a multifunctional electrocatalyst for water splitting.Unlike traditional single-source modification,herein a novel pomegranate-like high-entropy(HE)elec-trocatalyst of Ni_(3)ZnC_(0.7)decorated with homogeneous multimetal(Fe,Co,Cu,and Ni)nitrogen-codoped carbon matrix(Ni_(3)ZnC_(0.7)@CoNiCuFe-NC)is reported.It can be implemented by the simple thermal an-nealing method of multimetal codoped zeolitic imidazolate framework(ZIF).Benefiting from the syn-ergistic effects of plentiful TM-N-C species,template effect of ZIF and distinct nanoporous structure,HE electrocatalyst Ni_(3)ZnC_(0.7)@CoNiCuFe-NC exhibits outstanding electrocatalytic performance.When ap-plied in strong alkaline electrolyte(1.0 M KOH),the overpotentials of Ni_(3)ZnC_(0.7)@CoNiCuFe-NC present as low as 202 and 97 mV for oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)at 10 mA cm^(−2)current density.Surprisingly as a bifunctional electrode,it can achieve the low cell voltage of 1.53 V at 10 mA cm^(−2)current density for overall water splitting,which is comparable to conventional IrO_(2)||Pt/C electrode and superior to the recently reported analogous bifunctional catalysts.Thus,the work proposes the direction for the rational design of homogeneous distribution of TM-N-C material for water splitting in the green hydrogen energy industry.
基金funding support from the Agency for Science,Technology and Research(A*STAR,No.SERC A1983c0032)AME Individual Research Grant(IRG)the computing resources from National Supercomputing Centre Singapore。
文摘The melting mechanisms of Pt-based multimetallic nanoparticles(NPs)are important to help determine their optimal melting processes.To understand the melting and coalescence behaviors of heterogeneous NPs(Pd-Pt NPs)with various sizes and compositions,molecular dynamics(MD)simulation was employed.The MD results for larger Pd-Pt NPs with an effective diameter of4.6-7.8 nm show that PtPd alloy can form at Pd/Pt interface before Pd NP melted completely,while for Pt-core/Pdshell NP and Pd-core/Pt-shell NP,PtPd alloy formed only after Pd portion melted completely.For smaller Pd-Pt NPs with an effective diameter of 2.5-4.0 nm,PdPt alloy is not formed until both Pd and Pt NPs melted completely.Besides,the coalescence process of Pd-Pt NPs depends on the melting temperature of Pt NP when Pt composition is higher than 20 at%.Furthermore,the melting mechanisms of Pd/Pt/Ir trimetallic NPs are investigated.A two-step melting process occurs in Pd-Pt-Ir NPs and Ir-core/Ptshell/Pd-shell NP,and the melting sequence of Pd-core/Ptshell/Ir-shell NP and Pt-core/Pd-shell/Ir-shell NP is different from Pd/Pt bimetallic NPs.
文摘The paper expounds the metallogenic characterist ic s of Jiawula multimetals deposit in China and Uran multimetals deposit in Mongol ia. Comparative study shows that both deposits are volcanic hydrothermal mineral ization with same epoch(Mesozoic), same source, same temperature, and same miner al assemblage, but volcanic structure are different. Therefore, both deposits ca n draw on experience of each other and supplement in future of second time ore- prospecting, and point out the new direction of ore-prospecting.
基金supported by the National Key R&D Program of China(grant no.2021YFA1501001)the National Science Fund for Distinguished Young Scholars(grant no.52025133)+3 种基金the National Natural Science Foundation of China(grant nos.52261135633 and 52303363)the China National Petroleum Corporation-Peking University Strategic Cooperation Project of Fundamental Research,the Beijing Natural Science Foundation(grant no.Z220020)the New Cornerstone Science Foundation through the XPLORER PRIZE,China National Petroleum Corporation Innovation Found(grant no.2021DQ02-1002)the China Postdoctoral Science Foundation(grant no.2022M710200).
文摘The growing demand for renewable,sustainable energy resources has spotlighted electrochemical energy conversion technologies.Due to their distinct physicochemical functionalities,multicomponent metallic nanomaterials as start-of-the-art electroca-talysts lie at the heart of electrocatalysis.In the past decade,tremendous progress has been witnessed in the field of strain engineering electrocatalysts,which has been demonstrated as one of the most effective approaches to improving electrocatalytic perfor-mance.This minireview summarizes the latest advances in engineering strains for advanced elec-trocatalysis on multimetallic nanomaterials.In this paper,we start with a brief introduction on the fun-damentals and classifications of strain,followed by a comprehensive discussion of the existing synthetic toolbox and design principles for the exclusive intro-duction of strain effect in multimetallic electrocata-lysts.Next,we showcase both classical and the most recent characterizing techniques to accurately quan-tify strain magnitude,with emphasis on the emerging ones based on electron microscopy and tomography that enable atomic-level precision.Then,the under-lying mechanism behind strain-governed catalytic properties from the viewpoint of modeling studies and how it is employed to rationally design the strained electrocatalysts with boosted performances in multiple representative electrocatalysis reactions are elaborated.We conclude this minireview by out-lining the remaining challenges and opportunities in this prospering field.
基金supported by the National Natural Science Foundation of China(No.22269010)Jiangxi Provincial Natural Science Foundation(No.20224BAB214021)the Opening Project of National Engineering Research Center for Domestic&Building Ceramics(No.GXZX2302).
文摘The existence of multiple vacancies leads to significant changes in the local atomic structure,which can regulate the electronic structure of the surface and form unsaturated coordination geometries.However,the current methods employed to generate multiple vacancies in two-dimensional(2D)layered double hydroxide(LDH)materials are still difficult to achieve to some extent and are primarily limited to monolayer LDH structures.Here,we present an improved method to synthesize NiMoP/Ni_(2)P catalysts with a sponge-like porous structure.Firstly,NiO with dual defects was constructed by subjecting NiMo-LDH/Ni to air calcination.Subsequently,we performed phosphorization treatment and introduced multiple Ni vacancies and O vacancies as defect sites to tune the edge and substrate surfaces of LDH.At the same time,the electronic structure was tuned by adding P heteroatoms.The synergistic effect of porous structure,heterogeneous interfaces,vacancies,doping defects,and amorphous states can greatly enhance the electron transfer effect inside the catalysts,which significantly improves the catalytic ability of the oxygen evolution reaction(OER).Therefore,the overpotential for the oxygen evolution reaction of NiMoP/Ni_(2)P heterointerfaces reaches 270 mV at a current density of 10 mA·cm^(-2)under alkaline conditions,with the catalysts capable of sustaining high current densities even after the durability testing for 35 h.
基金financial support from the SERB-SURE under file number of SUR/2022/003129Jong Hyeok Park acknowledges the support of the National Research Foundation of Korea (NRF)funded by the Ministry of Science and ICT (RS-2023-00302697,RS-2023-00268523).
文摘Mo_(2)C is an excellent electrocatalyst for hydrogen evolution reaction(HER).However,Mo_(2)C is a poor electrocatalyst for oxygen evolution reaction(OER).Herein,two different elements,namely Co and Fe,are incorporated in Mo_(2)C that,therefore,has a finely tuned electronic structure,which is not achievable by incorporation of any one of the metals.Consequently,the resulting electrocatalyst Co_(0.8)Fe_(0.2)-Mo_(2)C-80 displayed excellent OER catalytic performance,which is evidenced by a low overpotential of 214.0(and 246.5)mV to attain a current density of 10(and 50)mA cm^(-2),an ultralow Tafel slope of 38.4 mV dec^(-1),and longterm stability in alkaline medium.Theoretical data demonstrates that Co_(0.8)Fe_(0.2)-Mo_(2)C-80 requires the lowest overpotential(1.00 V)for OER and Co centers to be the active sites.The ultrahigh catalytic performance of the electrocatalyst is attributed to the excellent intrinsic catalytic activity due to high Brunauer-Emmett-Teller specific surface area,large electrochemically active surface area,small Tafel slope,and low chargetransfer resistance.
