The electronic structures and properties of electrocatalysts,which depend on the physicochemical structure and metallic element components,could significantly affect their electrocatalytic performance and their future...The electronic structures and properties of electrocatalysts,which depend on the physicochemical structure and metallic element components,could significantly affect their electrocatalytic performance and their future applications in Zn-air battery(ZAB)and overall water splitting(OWS).Here,by combining vacancies and heterogeneous interfacial engineering,three-dimensional(3D)core-shell NiCoP/NiO heterostructures with dominated oxygen vacancies have been controllably in-situ grown on carbon cloth for using as highly efficient electrocatalysts toward hydrogen and oxygen electrochemical reactions.Theoretical calculation and electrochemical results manifest that the hybridization of NiCoP core with NiO shell produces a strong synergistic electronic coupling effect.The oxygen vacancy can enable the emergence of new electronic states within the band gap,crossing the Fermi levels of the two spin components and optimizing the local electronic structure.Besides,the hierarchical core-shell NiCoP/NiO nanoarrays also endow the catalysts with multiple exposed active sites,faster mass transfer behavior,optimized electronic strutures and improved electrochemical performance during ZAB and OWS applications.展开更多
We have previously developed a new process of highly efficient conversion of COand water into formic acid with metallic Zn without the addition of catalyst, however, its mechanism is not clear, particularly in the cat...We have previously developed a new process of highly efficient conversion of COand water into formic acid with metallic Zn without the addition of catalyst, however, its mechanism is not clear, particularly in the catalytic role of Zn/ZnO interface. Herein, the autocatalytic role of Zn/ZnO interface formed in situ during the reduction of COinto formic acid with Zn in water was studied by combining high resolution transmission electron microscopy（HRTEM）, X-ray diffraction（XRD） and X-ray photoelectron spectroscopy（XPS） techniques and experimental data. The electron microscope results show that possible defects or dislocations formed on Zn/ZnO interface, in which plays a key role for Zn H-formation. Further XPS analyses indicate that oxygen vacancies on Zn/ZnO interface increased at short reaction times（less than 10 min）. These analyses and experimental results suggest that a highly efficient and rapid conversion of COand water into formic acid should involve an autocatalytic role of the Zn/ZnO interface formed in situ, particularly at the beginning of the reaction.展开更多
Zinc-air batteries(ZABs)offer tremendous potential in various industries and daily life due to their excellent energy density,safety and affordability.However,the practical application of ZABs has been severely hinder...Zinc-air batteries(ZABs)offer tremendous potential in various industries and daily life due to their excellent energy density,safety and affordability.However,the practical application of ZABs has been severely hindered by challenges such as high low round-trip efficiencies and overpotential,primarily attributed to the inherent sluggish kinetics in the oxygen evolution reaction(OER)of air electrocatalysts.To address these issues effectively and economically,heterojunction engineering accompanied by interfacial chemistry emerges as an ideal approach to designing efficient OER electrocatalysts.Herein,a novel heterogeneous interfacial chemical structure,namely NiCoP/NiFe LDH(layered double hydroxide),needle-like NiCoP and NiFe LDH nanosheets were assembled from cores and shells,respectively.Remarkably,the NiCoP/NiFe LDH-based ZABs have an exceptionally long cycle life of 238 h,far superior to Pt/C+Ir/C batteries(~97 h).Theoretical calculations and experimental results demonstrate that NiCoP/NiFe LDH possesses tunable interfacial chemistry,demonstrating significant electronic,coordination,geometric and synergistic effects.These enhancements dramatically improve the active site density,intrinsic activity and electrochemical durability of the catalyst.In summary,this work provides a solid foundation for the development of costeffective OER electrocatalysts for electrochemical energy devices.展开更多
Large-scale applications of resource-enriched sodium-ion batteries(SIBs)suffer serious obstacles on the hard carbon(HC)anode due to large interface resistance and continuous electrolyte consumption induced poor cyclin...Large-scale applications of resource-enriched sodium-ion batteries(SIBs)suffer serious obstacles on the hard carbon(HC)anode due to large interface resistance and continuous electrolyte consumption induced poor cycling stability.Herein,we reported a metal-organic coordination interface(2-mercaptobenzothiazole-Cu)on the HC anode and particles(HC@MBT-Cu)to obtain the desired solid electrolyte interphase(SEI)and reduce the polarization of plateau-region sodium storage for durable SIBs.In the metal-organic coordination interface,Cu cations as catalytic centers coordinated with PF6-for easier breakage of P-F bonds to form CuF_(2)and NaF into SEI.Cu and Na cations coordinate with exocyclic S groups of the decoration interface,promoting the breakage of C-S bonds and obtaining Na2S and CuS in SEI.Meanwhile,N,S rigid-ring groups contribute to the SEI's elasticity.Ultimately,thin elastic(Cu-F/S,Na-F/S)-rich SEI(14-18 nm,Cryo-TEM)was constructed with less electrolyte consumption and significantly reduced gas production.As a result,the polarization voltage of HC greatly decreased.The assembled HC@MBT-Cu||Na_(3)V_(2)(PO_(4))_(3)full cells exhibited 86.4%after 600 cycles and pouch cells had a high-energy density of 175.1 Wh kg^(-1).This work not only provides new insight into interface engineering but also offers a strategy to enhance the stability of HC particles and anodes,which might promote the development process of SIBs.展开更多
Oxide nanostructures grown on noble metal surfaces are often highly active in many reactions,in which the oxide/metal interfaces play an important role.In the present work,we studied the surface structures of Fe Ox-on...Oxide nanostructures grown on noble metal surfaces are often highly active in many reactions,in which the oxide/metal interfaces play an important role.In the present work,we studied the surface structures of Fe Ox-on-Pt and Ni Ox-on-Pt catalysts and their activity to CO oxidation reactions using both model catalysts and supported nanocatalysts.Although the active Fe O1x structure is stabilized on the Pt surface in a reductive reaction atmosphere,it is prone to change to an Fe O2x structure in oxidative reaction gases and becomes deactivated.In contrast,a Ni O1x surface structure supported on Pt is stable in both reductive and oxidative CO oxidation atmospheres.Consequently,CO oxidation over the Ni O1x-on-Pt catalyst is further enhanced in the CO oxidation atmosphere with an excess of O2.The present results demonstrate that the stability of the active oxide surface phases depends on the stabilization effect of the substrate surface and is also related to whether the oxide exhibits a variable oxidation state.展开更多
Exploring cost-effective catalysts with high catalytic performance and long-term stability has always been a general concern for environment protection and energy conversion.Here,Au nanoparticles(NPs)embedded CuOx-CeO...Exploring cost-effective catalysts with high catalytic performance and long-term stability has always been a general concern for environment protection and energy conversion.Here,Au nanoparticles(NPs)embedded CuOx-CeO2 core/shell nanospheres(Au@CuOx-CeO2 CSNs)have been successfully prepared through a versatile one-pot method at ambient conditions.The spontaneous auto-redox reaction between HAuCl4 and Ce(OH)3 in aqueous solution triggered the self-assembly growth of micro-/nanostructural Au@CuOx-CeO2 CSNs.Meanwhile,the CuOx clusters in Au@CuOx-CeO2 CSNs are capable of improving the anti-sintering ability of Au NPs and providing synergistic catalysis benefits.As a result,the confined Au NPs exhibited extraordinary thermal stability even at a harsh thermal condition up to 700℃.In addition,before and after the severe calcination process,Au@CuOx-CeO2 CSNs can exhibit enhanced catalytic activity and excellent recyclability towards the hydrogenation of p-nitrophenol compared to previously reported nanocatalysts.The synergistic catalysis path between Au/CuOx/CeO2 triphasic interfaces was revealed by density functional theory(DFT)calculations.The CuOx clusters around the embedded Au NPs can provide moderate adsorption strength of p-nitrophenol,while the adjacent CeO2-supported Au NPs can facilitate the hydrogen dissociation to form H*species,which contributes to achieve the efficient reduction of p-nitrophenol.This study opens up new possibilities for developing high-efficient and sintering-resistant micro-/nanostructural nanocatalysts by exploiting multiphasic systems.展开更多
基金financially supported by the National Natural Science Foundation of China(No.22179014,21603019)program for the Hundred Talents Program of Chongqing University。
文摘The electronic structures and properties of electrocatalysts,which depend on the physicochemical structure and metallic element components,could significantly affect their electrocatalytic performance and their future applications in Zn-air battery(ZAB)and overall water splitting(OWS).Here,by combining vacancies and heterogeneous interfacial engineering,three-dimensional(3D)core-shell NiCoP/NiO heterostructures with dominated oxygen vacancies have been controllably in-situ grown on carbon cloth for using as highly efficient electrocatalysts toward hydrogen and oxygen electrochemical reactions.Theoretical calculation and electrochemical results manifest that the hybridization of NiCoP core with NiO shell produces a strong synergistic electronic coupling effect.The oxygen vacancy can enable the emergence of new electronic states within the band gap,crossing the Fermi levels of the two spin components and optimizing the local electronic structure.Besides,the hierarchical core-shell NiCoP/NiO nanoarrays also endow the catalysts with multiple exposed active sites,faster mass transfer behavior,optimized electronic strutures and improved electrochemical performance during ZAB and OWS applications.
基金the financial support of the National Natural Science Foundation of China (No. 21277091 & 51472159)the State Key Program of National Natural Science Foundation of China (No. 21436007)+1 种基金the Key Basic Research Projects of Science and Technology Commission of Shanghai (No. 14JC1403100)the Chenxing-SMG Young Scholar Project of Shanghai Jiao Tong University
文摘We have previously developed a new process of highly efficient conversion of COand water into formic acid with metallic Zn without the addition of catalyst, however, its mechanism is not clear, particularly in the catalytic role of Zn/ZnO interface. Herein, the autocatalytic role of Zn/ZnO interface formed in situ during the reduction of COinto formic acid with Zn in water was studied by combining high resolution transmission electron microscopy（HRTEM）, X-ray diffraction（XRD） and X-ray photoelectron spectroscopy（XPS） techniques and experimental data. The electron microscope results show that possible defects or dislocations formed on Zn/ZnO interface, in which plays a key role for Zn H-formation. Further XPS analyses indicate that oxygen vacancies on Zn/ZnO interface increased at short reaction times（less than 10 min）. These analyses and experimental results suggest that a highly efficient and rapid conversion of COand water into formic acid should involve an autocatalytic role of the Zn/ZnO interface formed in situ, particularly at the beginning of the reaction.
基金financially supported by the National Natural Science Foundation of China(Nos.22309023 and22179014)China Postdoctoral Science Foundation(No.2022M720593)+3 种基金the Scientific Research Foundation of Chongqing University of Technology(Nos.2022ZDZ011 and 2022PYZ026)the Youth Project of Science and Technology Research Program of Chongqing Municipal Education Commission of China(No.KJQN202201127)the Natural Science Foundation of Chongqing(No.CSTB2022NSCQ-MSX0270)the Special Funding for Research Projects of Chongqing Human Resources and Social Security Bureau(No.2022CQBSHTB1023)。
文摘Zinc-air batteries(ZABs)offer tremendous potential in various industries and daily life due to their excellent energy density,safety and affordability.However,the practical application of ZABs has been severely hindered by challenges such as high low round-trip efficiencies and overpotential,primarily attributed to the inherent sluggish kinetics in the oxygen evolution reaction(OER)of air electrocatalysts.To address these issues effectively and economically,heterojunction engineering accompanied by interfacial chemistry emerges as an ideal approach to designing efficient OER electrocatalysts.Herein,a novel heterogeneous interfacial chemical structure,namely NiCoP/NiFe LDH(layered double hydroxide),needle-like NiCoP and NiFe LDH nanosheets were assembled from cores and shells,respectively.Remarkably,the NiCoP/NiFe LDH-based ZABs have an exceptionally long cycle life of 238 h,far superior to Pt/C+Ir/C batteries(~97 h).Theoretical calculations and experimental results demonstrate that NiCoP/NiFe LDH possesses tunable interfacial chemistry,demonstrating significant electronic,coordination,geometric and synergistic effects.These enhancements dramatically improve the active site density,intrinsic activity and electrochemical durability of the catalyst.In summary,this work provides a solid foundation for the development of costeffective OER electrocatalysts for electrochemical energy devices.
基金supported by the National Natural Science Foundation of China(22279121,U24A200471,22209153)the Key Research and Development Program of Henan Province(231111241400)+3 种基金the Joint Fund of Scientific and Technological Research and Development Program of Henan Province(222301420009)Zhengzhou Universitysupported by the National Supercomputing Centre in Zhengzhouthe funding of Zhengzhou University。
文摘Large-scale applications of resource-enriched sodium-ion batteries(SIBs)suffer serious obstacles on the hard carbon(HC)anode due to large interface resistance and continuous electrolyte consumption induced poor cycling stability.Herein,we reported a metal-organic coordination interface(2-mercaptobenzothiazole-Cu)on the HC anode and particles(HC@MBT-Cu)to obtain the desired solid electrolyte interphase(SEI)and reduce the polarization of plateau-region sodium storage for durable SIBs.In the metal-organic coordination interface,Cu cations as catalytic centers coordinated with PF6-for easier breakage of P-F bonds to form CuF_(2)and NaF into SEI.Cu and Na cations coordinate with exocyclic S groups of the decoration interface,promoting the breakage of C-S bonds and obtaining Na2S and CuS in SEI.Meanwhile,N,S rigid-ring groups contribute to the SEI's elasticity.Ultimately,thin elastic(Cu-F/S,Na-F/S)-rich SEI(14-18 nm,Cryo-TEM)was constructed with less electrolyte consumption and significantly reduced gas production.As a result,the polarization voltage of HC greatly decreased.The assembled HC@MBT-Cu||Na_(3)V_(2)(PO_(4))_(3)full cells exhibited 86.4%after 600 cycles and pouch cells had a high-energy density of 175.1 Wh kg^(-1).This work not only provides new insight into interface engineering but also offers a strategy to enhance the stability of HC particles and anodes,which might promote the development process of SIBs.
基金financially supported by the National Natural Science Foundation of China(21222305,11079005,20923001)the National Basic Research Program of China(2011CBA00503,2013CB933100)
文摘Oxide nanostructures grown on noble metal surfaces are often highly active in many reactions,in which the oxide/metal interfaces play an important role.In the present work,we studied the surface structures of Fe Ox-on-Pt and Ni Ox-on-Pt catalysts and their activity to CO oxidation reactions using both model catalysts and supported nanocatalysts.Although the active Fe O1x structure is stabilized on the Pt surface in a reductive reaction atmosphere,it is prone to change to an Fe O2x structure in oxidative reaction gases and becomes deactivated.In contrast,a Ni O1x surface structure supported on Pt is stable in both reductive and oxidative CO oxidation atmospheres.Consequently,CO oxidation over the Ni O1x-on-Pt catalyst is further enhanced in the CO oxidation atmosphere with an excess of O2.The present results demonstrate that the stability of the active oxide surface phases depends on the stabilization effect of the substrate surface and is also related to whether the oxide exhibits a variable oxidation state.
基金The authors are grateful for the financial support of the National Natural Science Foundation of China(Nos.21590791,21771005,21931001,and 21927901)Ministry of Science and Technology(MOST)of China(Nos.2014CB643803,2017YFA0205101,and 2017YFA0205104)+1 种基金The computational work was supported by the High-performance Computing Platform of Peking University.K.W.specifically thanks the National Postdoctoral Program for Innovative Talents under grant No.BX20190005the China Postdoctoral Science Foundation(No.2019M660293).
文摘Exploring cost-effective catalysts with high catalytic performance and long-term stability has always been a general concern for environment protection and energy conversion.Here,Au nanoparticles(NPs)embedded CuOx-CeO2 core/shell nanospheres(Au@CuOx-CeO2 CSNs)have been successfully prepared through a versatile one-pot method at ambient conditions.The spontaneous auto-redox reaction between HAuCl4 and Ce(OH)3 in aqueous solution triggered the self-assembly growth of micro-/nanostructural Au@CuOx-CeO2 CSNs.Meanwhile,the CuOx clusters in Au@CuOx-CeO2 CSNs are capable of improving the anti-sintering ability of Au NPs and providing synergistic catalysis benefits.As a result,the confined Au NPs exhibited extraordinary thermal stability even at a harsh thermal condition up to 700℃.In addition,before and after the severe calcination process,Au@CuOx-CeO2 CSNs can exhibit enhanced catalytic activity and excellent recyclability towards the hydrogenation of p-nitrophenol compared to previously reported nanocatalysts.The synergistic catalysis path between Au/CuOx/CeO2 triphasic interfaces was revealed by density functional theory(DFT)calculations.The CuOx clusters around the embedded Au NPs can provide moderate adsorption strength of p-nitrophenol,while the adjacent CeO2-supported Au NPs can facilitate the hydrogen dissociation to form H*species,which contributes to achieve the efficient reduction of p-nitrophenol.This study opens up new possibilities for developing high-efficient and sintering-resistant micro-/nanostructural nanocatalysts by exploiting multiphasic systems.
