比较了甲醇对 Pt/C和炭载四羧基酞菁钴 (Co Pc Tc/C)催化氧还原性能的影响 .结果表明 ,甲醇使Pt/C催化氧还原的性能严重降低 ,而对经 80 0℃热处理的 Co Pc Tc/C(Co Pc Tc/C-80 0 )基本没有影响 ;并且Co Pc Tc/C-80 0催化氧还原的性能...比较了甲醇对 Pt/C和炭载四羧基酞菁钴 (Co Pc Tc/C)催化氧还原性能的影响 .结果表明 ,甲醇使Pt/C催化氧还原的性能严重降低 ,而对经 80 0℃热处理的 Co Pc Tc/C(Co Pc Tc/C-80 0 )基本没有影响 ;并且Co Pc Tc/C-80 0催化氧还原的性能优于经其它温度热处理的 Co Pc Tc/C,Co Pc Tc/C-80 0是一种较好的直接甲醇燃料电池的耐甲醇阴极电催化剂 .XPS结果表明 ,Co Pc Tc/C-80 0的活性位可能是含 Co N4结构的物质和零价 Co的混合物 .展开更多
Today,Pt/C catalysts are widely used in proton exchange membrane fuel cells(PEMFCs).The practical applications of PEMFCs still face many limitations in the preparation of advanced Pt‐based catalysts,including high co...Today,Pt/C catalysts are widely used in proton exchange membrane fuel cells(PEMFCs).The practical applications of PEMFCs still face many limitations in the preparation of advanced Pt‐based catalysts,including high cost,limited life‐time,and insufficient power density.A kinetically sluggish oxygen reduction reaction(ORR)is primarily responsible for these issues.The development of advanced Pt‐based catalysts is crucial for solving these pro-blems when the large‐scale application of PEMFCs is to be realized.Herein,we demonstrate the design principle of advanced Pt‐based catalysts with an emphasis on theoretical understandings to practical applications.Generally,three main strategies(including strain effect,electronic effect,and ensemble effect)that governing the initial activity of Pt‐based electrocatalysts are ela-borated in detail in this review.Recent advanced Pt‐based ORR catalysts are summarized and we present representative achievements to further reveal the relationship of excellent ORR performance based on theoretical mechanisms.Then we focus on the preparation standards of membrane electrode assembles and testing protocols in practice.Finally,we predict the remaining challenges and present our perspectives with regards to design strategies for improving ORR performance of Pt‐based catalysts in the future.展开更多
Nanocarbons are of progressively increasing importance in energy electrocatalysis, including oxygen reduction, oxygen evolution, hydrogen evolution, COreduction, etc. Precious-metal-free or metal-free nanocarbon-based...Nanocarbons are of progressively increasing importance in energy electrocatalysis, including oxygen reduction, oxygen evolution, hydrogen evolution, COreduction, etc. Precious-metal-free or metal-free nanocarbon-based electrocatalysts have been revealed to potentially have effective activity and remarkable durability, which is promising to replace precious metals in some important energy technologies,such as fuel cells, metal–air batteries, and water splitting. In this review, rather than overviewing recent progress completely, we aim to give an in-depth digestion of present achievements, focusing on the different roles of nanocarbons and material design principles. The multifunctionalities of nanocarbon substrates(accelerating the electron and mass transport, regulating the incorporation of active components,manipulating electron structures, generating confinement effects, assembly into 3 D free-standing electrodes) and the intrinsic activity of nanocarbon catalysts(multi-heteroatom doping, hierarchical structure,topological defects) are discussed systematically, with perspectives on the further research in this rising research field. This review is inspiring for more insights and methodical research in mechanism understanding, material design, and device optimization, leading to a targeted and high-efficiency development of energy electrocatalysis.展开更多
Replacing Pt-based electrocatalysts for the oxygen reduction reaction (ORR) with high performance and low-cost non-precious metal catalysts is crucial for the commercialization of fuel cells.Herein,we present a highly...Replacing Pt-based electrocatalysts for the oxygen reduction reaction (ORR) with high performance and low-cost non-precious metal catalysts is crucial for the commercialization of fuel cells.Herein,we present a highly efficient Fe-N-C porous ORR electrocatalyst with FeNx moieties promoted by Fe2N nanoparticles derived from Fe-doped zeolitic imidazolate framework.The best-performing Fe-N-C/HPC-NH3 catalyst exhibits a superior ORR activity with an onset (E0) and half-wave (E1/2) potential of 0.945 and 0.803 V (RHE),respectively,which is comparable to those of the commercial Pt/C in acidic media.Probing and acid-leaching experiments prove that FeNx moieties play an important role in the ORR and the Fe2N can further improve the ORR activity.Density functional theory calculation reveals a synergistic effect that the existence of Fe2N weakens the adsorption of ORR intermediates on active sites and lowers the reaction free energy of the potential limiting step,thus facilitating the ORR.Both experimental evidence and theoretical analysis for the enhancement of ORR activity by Fe2N decoration in Fe-N-C catalyst might inspire a new strategy for rational design of high performance non-precious metal catalysts.展开更多
Proton exchange membrane fuel cells(PEMFCs) are considered a promising power source for electric vehicles and stationary residential applications. However, current PEMFCs have several problems that require solutions, ...Proton exchange membrane fuel cells(PEMFCs) are considered a promising power source for electric vehicles and stationary residential applications. However, current PEMFCs have several problems that require solutions, including high cost, insufficient power density, and limited performance durability. A kinetically sluggish oxygen reduction reaction(ORR) is primarily responsible for these issues. The development of advanced Pt-based catalysts is crucial for solving these problems if the large-scale application of PEMFCs is to be realized. In this review, we summarize the recent progress in the development of Pt M alloy(M = Fe, Co, Ni, etc.) catalysts with an emphasis on ordered Pt M intermetallic catalysts, which exhibit significantly enhanced activity and stability. In addition to exploring the intrinsic catalytic performance in traditional aqueous electrolytes via engineering nanostructures, morphologies, and crystallinity of Pt M particles, we highlight recent efforts to study catalysts under real fuel cell environments by the membrane electrode assembly(MEA).展开更多
In a seed-mediated synthesis, nanocrystal growth is often described by assuming the absence of homogeneous nucleation in the solution. Here we provide new insights into the nucleation and growth mechanisms underlying ...In a seed-mediated synthesis, nanocrystal growth is often described by assuming the absence of homogeneous nucleation in the solution. Here we provide new insights into the nucleation and growth mechanisms underlying the formation of bimetallic nanodendrites that are characterized by a dense array of Pt branches anchored to a Pd nanocrystal core. These nanostructures can be easily prepared by a one-step, seeded growth method that involves the reduction of K2PtCl4 by L-ascorbic acid in the presence of 9-nm truncated octahedral Pd seeds in an aqueous solution. Transmission electron microscopy (TEM) and high-resolution TEM analyses revealed that both homogeneous and heterogeneous nucleation of Pt occurred at the very early stages of the synthesis and the Pt branches grew through oriented attachment of small Pt particles that had been formed via homogeneous nucleation. These new findings contradict the generally accepted mechanism for seeded growth that only involves heterogeneous nucleation and simple growth via atomic addition. We have also investigated the electrocatalytic properties of the Pd-Pt nanodendrites for the oxygen reduction and formic acid oxidation reactions by conducting a comparative study with foam-like Pt nanostructures prepared in the absence of Pd seeds under otherwise identical conditions.展开更多
Catalysts of oxygen reduction reaction （ORR） play key roles in renewable energy technologies such as metal-air batteries and fuel cells. Despite tremendous ef- forts, highly active catalysts with low cost remain elu...Catalysts of oxygen reduction reaction （ORR） play key roles in renewable energy technologies such as metal-air batteries and fuel cells. Despite tremendous ef- forts, highly active catalysts with low cost remain elusive. This work used metal-organic frameworks to synthesize non-precious bimetallic carbon nanocomposites as efficient ORR catalysts. Although carbon-based Cu and Ni are good candidates, the hybrid nanocomposites take advantage of both metals to improve catalytic activity. The resulting molar ratio of Cu/Ni in the nanocomposites can be finely controlled by tuning the recipe of the precursors. Nanocom- posites with a series of molar ratios were produced, and they exhibited much better ORR catalytic performance than their monometallic counterparts in terms of limited current density, onset potential and half-wave potential. In addition, their extraordinary stability in alkaline is superior to that of commercially-available Pt-based materials, which adds to the appeal of the bimetallic carbon nanocomposites as ORR catalysts. Their improved performance can be attributed to the synergetic effects of Cu and Ni, and the enhancement of the carbon matrix.展开更多
The presence of oxygen functional groups is detrimental to the capacitive performance of porous carbon electrode in organic electrolyte. In this regards, hydrogen thermal reduction has been demonstrated effective appr...The presence of oxygen functional groups is detrimental to the capacitive performance of porous carbon electrode in organic electrolyte. In this regards, hydrogen thermal reduction has been demonstrated effective approach in removing the unstable surface oxygen while maintaining the high porosity of carbon matrix. However, the exact evolution mechanism of various oxygen species during this process, as well as the correlation with electrochemical properties, is still under development. Herein, biomass-based porous carbon is adopted as the model material to trace its structure evolution of oxygen removal under hydrogen thermal reduction process with the temperature range of 400–800 °C. The optimum microstructure with low oxygen content of 0.90% and proper pore size distribution was achieved at 700°C. XPS, TPRMS and Boehm titration results indicate that the oxygen elimination undergoes three distinctive stages(intermolecular dehydration, hydrogenation and decomposition reactions). The optimum microstructure with low oxygen content of 0.90% and proper pore size distribution was achieved at 700 °C. Benefiting from the stable electrochemical interface and the optimized porous structure, the as-obtained HAC-700 exhibit significantly suppressed self-discharge and leak current, with improved cycling stability, which is attributable to the stabilization of electrochemical interface between carbon surface and electrolyte. The result provides insights for rational design of surface chemistry for high-performance carbon electrode towards advanced energy storage.展开更多
An effective electrocatalyst being highly active in all pH range for oxygen reduction reaction(ORR)is crucial for energy conversion and storage devices.However,most of the high-efficiency ORR catalysis was reported in...An effective electrocatalyst being highly active in all pH range for oxygen reduction reaction(ORR)is crucial for energy conversion and storage devices.However,most of the high-efficiency ORR catalysis was reported in alkaline conditions.Herein,we demonstrated the preparation of atomically dispersed Fe-Zn pairs anchored on porous N-doped carbon frameworks(Fe-Zn-SA/NC),which works efficiently as ORR catalyst in the whole pH range.It achieves high half-wave potentials of 0.78,0.85 and 0.72 V in 0.1 M HClO4,0.1 M KOH and 0.1 M phosphate buffer saline(PBS)solutions,respectively,as well as respectable stability.The performances are even comparable to Pt/C.Furthermore,when assembled into a Zn-air battery,the high power density of 167.2 mWcm−2 and 120 h durability reveal the feasibility of Fe-Zn-SA/NC in real energy-related devices.Theoretical calculations demonstrate that the superior catalytic activity of Fe-Zn-SA/NC can be contributed to the lower energy barriers of ORR at the Fe-Zn-N6 centers.This work demonstrates the potential of Fe-Zn pairs as alternatives to the Pt catalysts for efficient catalytic ORR and provides new insights of dual-atom catalysts for other energy conversion related catalytic reactions.展开更多
文摘比较了甲醇对 Pt/C和炭载四羧基酞菁钴 (Co Pc Tc/C)催化氧还原性能的影响 .结果表明 ,甲醇使Pt/C催化氧还原的性能严重降低 ,而对经 80 0℃热处理的 Co Pc Tc/C(Co Pc Tc/C-80 0 )基本没有影响 ;并且Co Pc Tc/C-80 0催化氧还原的性能优于经其它温度热处理的 Co Pc Tc/C,Co Pc Tc/C-80 0是一种较好的直接甲醇燃料电池的耐甲醇阴极电催化剂 .XPS结果表明 ,Co Pc Tc/C-80 0的活性位可能是含 Co N4结构的物质和零价 Co的混合物 .
基金NSFC,Grant/Award Numbers:21871159,21890383National Key R&D Program of China,Grant/Award Numbers:2018YFA0702003,2016YFA0202801+2 种基金National Natural Science Foundation of China,Grant/Award Numbers:21890383,21671117,21871159Science and Technology Key Project of Guangdong Province of China,Grant/Award Number:2020B010188002Beijing Municipal Science&Technology Commission,Grant/Award Number:Z191100007219003。
文摘Today,Pt/C catalysts are widely used in proton exchange membrane fuel cells(PEMFCs).The practical applications of PEMFCs still face many limitations in the preparation of advanced Pt‐based catalysts,including high cost,limited life‐time,and insufficient power density.A kinetically sluggish oxygen reduction reaction(ORR)is primarily responsible for these issues.The development of advanced Pt‐based catalysts is crucial for solving these pro-blems when the large‐scale application of PEMFCs is to be realized.Herein,we demonstrate the design principle of advanced Pt‐based catalysts with an emphasis on theoretical understandings to practical applications.Generally,three main strategies(including strain effect,electronic effect,and ensemble effect)that governing the initial activity of Pt‐based electrocatalysts are ela-borated in detail in this review.Recent advanced Pt‐based ORR catalysts are summarized and we present representative achievements to further reveal the relationship of excellent ORR performance based on theoretical mechanisms.Then we focus on the preparation standards of membrane electrode assembles and testing protocols in practice.Finally,we predict the remaining challenges and present our perspectives with regards to design strategies for improving ORR performance of Pt‐based catalysts in the future.
基金supported by the National Key Research and Development Program (Nos. 2016YFA0202500 and 2016YFA0200102)the Natural Scientific Foundation of China (No. 21561130151)Royal Society for the award of a Newton Advanced Fellowship (Ref: NA140249)
文摘Nanocarbons are of progressively increasing importance in energy electrocatalysis, including oxygen reduction, oxygen evolution, hydrogen evolution, COreduction, etc. Precious-metal-free or metal-free nanocarbon-based electrocatalysts have been revealed to potentially have effective activity and remarkable durability, which is promising to replace precious metals in some important energy technologies,such as fuel cells, metal–air batteries, and water splitting. In this review, rather than overviewing recent progress completely, we aim to give an in-depth digestion of present achievements, focusing on the different roles of nanocarbons and material design principles. The multifunctionalities of nanocarbon substrates(accelerating the electron and mass transport, regulating the incorporation of active components,manipulating electron structures, generating confinement effects, assembly into 3 D free-standing electrodes) and the intrinsic activity of nanocarbon catalysts(multi-heteroatom doping, hierarchical structure,topological defects) are discussed systematically, with perspectives on the further research in this rising research field. This review is inspiring for more insights and methodical research in mechanism understanding, material design, and device optimization, leading to a targeted and high-efficiency development of energy electrocatalysis.
基金the National Key Research and Development Program of China (No.2017YFA0206500)the National Natural Science Foundation of China (Nos.21802161,21673275,and 21533005).
文摘Replacing Pt-based electrocatalysts for the oxygen reduction reaction (ORR) with high performance and low-cost non-precious metal catalysts is crucial for the commercialization of fuel cells.Herein,we present a highly efficient Fe-N-C porous ORR electrocatalyst with FeNx moieties promoted by Fe2N nanoparticles derived from Fe-doped zeolitic imidazolate framework.The best-performing Fe-N-C/HPC-NH3 catalyst exhibits a superior ORR activity with an onset (E0) and half-wave (E1/2) potential of 0.945 and 0.803 V (RHE),respectively,which is comparable to those of the commercial Pt/C in acidic media.Probing and acid-leaching experiments prove that FeNx moieties play an important role in the ORR and the Fe2N can further improve the ORR activity.Density functional theory calculation reveals a synergistic effect that the existence of Fe2N weakens the adsorption of ORR intermediates on active sites and lowers the reaction free energy of the potential limiting step,thus facilitating the ORR.Both experimental evidence and theoretical analysis for the enhancement of ORR activity by Fe2N decoration in Fe-N-C catalyst might inspire a new strategy for rational design of high performance non-precious metal catalysts.
文摘Proton exchange membrane fuel cells(PEMFCs) are considered a promising power source for electric vehicles and stationary residential applications. However, current PEMFCs have several problems that require solutions, including high cost, insufficient power density, and limited performance durability. A kinetically sluggish oxygen reduction reaction(ORR) is primarily responsible for these issues. The development of advanced Pt-based catalysts is crucial for solving these problems if the large-scale application of PEMFCs is to be realized. In this review, we summarize the recent progress in the development of Pt M alloy(M = Fe, Co, Ni, etc.) catalysts with an emphasis on ordered Pt M intermetallic catalysts, which exhibit significantly enhanced activity and stability. In addition to exploring the intrinsic catalytic performance in traditional aqueous electrolytes via engineering nanostructures, morphologies, and crystallinity of Pt M particles, we highlight recent efforts to study catalysts under real fuel cell environments by the membrane electrode assembly(MEA).
基金This work was supported in part by the National Science Foundation(NSF)(No.DMR-0804088)startup funds from Washington University in St.Louis.T.Y.was also partially supported by the National Research Foundation of Korea Grant funded by the Korean Government(No.NRF-2009-352-D00160)+1 种基金Pedro Henrique Cury Camargo(P.H.C.C.)was also partially supported by the Fulbright Program and the Brazilian Ministry of Education(CAPES).Part of the work was performed at the Nano Research Facility(NRF),a member of the National Nanotechnology Infrastructure Network(NNIN),which is supported by the National Science Foundation under award No.ECS-0335765NRF is part of the School of Engineering and Applied Science at Washington University in St.Louis.
文摘In a seed-mediated synthesis, nanocrystal growth is often described by assuming the absence of homogeneous nucleation in the solution. Here we provide new insights into the nucleation and growth mechanisms underlying the formation of bimetallic nanodendrites that are characterized by a dense array of Pt branches anchored to a Pd nanocrystal core. These nanostructures can be easily prepared by a one-step, seeded growth method that involves the reduction of K2PtCl4 by L-ascorbic acid in the presence of 9-nm truncated octahedral Pd seeds in an aqueous solution. Transmission electron microscopy (TEM) and high-resolution TEM analyses revealed that both homogeneous and heterogeneous nucleation of Pt occurred at the very early stages of the synthesis and the Pt branches grew through oriented attachment of small Pt particles that had been formed via homogeneous nucleation. These new findings contradict the generally accepted mechanism for seeded growth that only involves heterogeneous nucleation and simple growth via atomic addition. We have also investigated the electrocatalytic properties of the Pd-Pt nanodendrites for the oxygen reduction and formic acid oxidation reactions by conducting a comparative study with foam-like Pt nanostructures prepared in the absence of Pd seeds under otherwise identical conditions.
基金supported by the National Natural Science Foundation of China (21671096 and 21603094)the Natural Science Foundation of Shenzhen (JCYJ20150630145302231 and JCYJ20150331101823677)the Science and Technology Innovation Foundation for the Undergraduates of SUSTech (2014S07, 2016S10 and 2016S20)
文摘Catalysts of oxygen reduction reaction （ORR） play key roles in renewable energy technologies such as metal-air batteries and fuel cells. Despite tremendous ef- forts, highly active catalysts with low cost remain elusive. This work used metal-organic frameworks to synthesize non-precious bimetallic carbon nanocomposites as efficient ORR catalysts. Although carbon-based Cu and Ni are good candidates, the hybrid nanocomposites take advantage of both metals to improve catalytic activity. The resulting molar ratio of Cu/Ni in the nanocomposites can be finely controlled by tuning the recipe of the precursors. Nanocom- posites with a series of molar ratios were produced, and they exhibited much better ORR catalytic performance than their monometallic counterparts in terms of limited current density, onset potential and half-wave potential. In addition, their extraordinary stability in alkaline is superior to that of commercially-available Pt-based materials, which adds to the appeal of the bimetallic carbon nanocomposites as ORR catalysts. Their improved performance can be attributed to the synergetic effects of Cu and Ni, and the enhancement of the carbon matrix.
基金National Science Foundation for Excellent Young Scholars of China (21922815)Key Research and Development (R&D) Projects of Shanxi Province (201903D121007)+3 种基金Natural Science Foundations of Shanxi Province (201801D221156)DNL Cooperation Fund of CAS (DNL180308)Science and Technology Service Network Initiative of CAS (KFJ-STS-ZDTP-068)Youth Innovation Promotion Association of CAS。
文摘The presence of oxygen functional groups is detrimental to the capacitive performance of porous carbon electrode in organic electrolyte. In this regards, hydrogen thermal reduction has been demonstrated effective approach in removing the unstable surface oxygen while maintaining the high porosity of carbon matrix. However, the exact evolution mechanism of various oxygen species during this process, as well as the correlation with electrochemical properties, is still under development. Herein, biomass-based porous carbon is adopted as the model material to trace its structure evolution of oxygen removal under hydrogen thermal reduction process with the temperature range of 400–800 °C. The optimum microstructure with low oxygen content of 0.90% and proper pore size distribution was achieved at 700°C. XPS, TPRMS and Boehm titration results indicate that the oxygen elimination undergoes three distinctive stages(intermolecular dehydration, hydrogenation and decomposition reactions). The optimum microstructure with low oxygen content of 0.90% and proper pore size distribution was achieved at 700 °C. Benefiting from the stable electrochemical interface and the optimized porous structure, the as-obtained HAC-700 exhibit significantly suppressed self-discharge and leak current, with improved cycling stability, which is attributable to the stabilization of electrochemical interface between carbon surface and electrolyte. The result provides insights for rational design of surface chemistry for high-performance carbon electrode towards advanced energy storage.
基金This work was financially supported by National Key R&D Program of China(No.2017YFA0700104)the National Natural Science Foundation of China(Nos.22075211,21601136,51971157,51761165012,and 62005173)+2 种基金Project funded by China Postdoctoral Science Foundation(No.2020TQ0201)Tianjin Science Fund for Distinguished Young Scholars(No.19JCJQJC61800)The authors also acknowledge National Supercomputing Center in Shenzhen for providing the computational resources and materials studio(version 7.0,DMol3).
文摘An effective electrocatalyst being highly active in all pH range for oxygen reduction reaction(ORR)is crucial for energy conversion and storage devices.However,most of the high-efficiency ORR catalysis was reported in alkaline conditions.Herein,we demonstrated the preparation of atomically dispersed Fe-Zn pairs anchored on porous N-doped carbon frameworks(Fe-Zn-SA/NC),which works efficiently as ORR catalyst in the whole pH range.It achieves high half-wave potentials of 0.78,0.85 and 0.72 V in 0.1 M HClO4,0.1 M KOH and 0.1 M phosphate buffer saline(PBS)solutions,respectively,as well as respectable stability.The performances are even comparable to Pt/C.Furthermore,when assembled into a Zn-air battery,the high power density of 167.2 mWcm−2 and 120 h durability reveal the feasibility of Fe-Zn-SA/NC in real energy-related devices.Theoretical calculations demonstrate that the superior catalytic activity of Fe-Zn-SA/NC can be contributed to the lower energy barriers of ORR at the Fe-Zn-N6 centers.This work demonstrates the potential of Fe-Zn pairs as alternatives to the Pt catalysts for efficient catalytic ORR and provides new insights of dual-atom catalysts for other energy conversion related catalytic reactions.
