Proton exchange membrane fuel cells(PEMFCs)are considered ideal energy‐conversion devices because of their environmentally friendly nature and high theoretical energy efficiency.However,cathodic polarization,which is...Proton exchange membrane fuel cells(PEMFCs)are considered ideal energy‐conversion devices because of their environmentally friendly nature and high theoretical energy efficiency.However,cathodic polarization,which is a result of the sluggish oxygen reduction reaction(ORR)kinetics,is a significant source of energy loss and reduces fuel cell efficiency.Further,the need to use Pt in commercial Pt/C cathodes has restricted their large‐scale application in fuel cells because of its high cost and poor durability.Thus,improvements in the activity and durability of Pt‐based catalyst are required to reduce the amount of Pt required and,thus,costs,while increasing the ORR rate and fuel cell power density and promoting widespread PEMFC commercialization.In recent years,atomically ordered Pt‐based intermetallic nanocrystals have received tremendous attention owing to their excellent activity and stability for the ORR.Therefore,in this review,we first introduce the formation of intermetallic compounds from the perspective of thermodynamics and kinetics to lay a theoretical foundation for the design of these compounds.In addition,optimization strategies for Pt‐based ordered intermetallic catalysts are summarized in terms of the catalyst composition,size,and morphology.Finally,we conclude with a discussion of the current challenges and future prospects of Pt‐based ordered alloys.This review is designed to help readers gain insights into the recent developments in and rational design of Pt‐based intermetallic nanocrystals for the ORR and encourage research that will enable the commercialization of PEMFCs.展开更多
The commercialization of proton exchange membrane fuel cells(PEMFCs)could provide a cleaner energy society in the near future.However,the sluggish reaction kinetics and harsh conditions of the oxygen reduction reactio...The commercialization of proton exchange membrane fuel cells(PEMFCs)could provide a cleaner energy society in the near future.However,the sluggish reaction kinetics and harsh conditions of the oxygen reduction reaction affect the durability and cost of PEMFCs.Most previous reports on Pt-based electrocatalyst designs have focused more on improving their activity;however,with the commercialization of PEMFCs,durability has received increasing attention.In-depth insight into the structural evolution of Pt-based electrocatalysts throughout their lifecycle can contribute to further optimization of their activity and durability.The development of in situ electron microscopy and other in situ techniques has promoted the elucidation of the evolution mechanism.This mini review highlights recent advances in the structural evolution of Pt-based electrocatalysts.The mechanisms are adequately discussed,and some methods to inhibit or exploit the structural evolution of the catalysts are also briefly reviewed.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
A series of Sn‐incorporated SBA‐15materials with high specific surface areas and highly orderedmesoporous structures were synthesized by a facile one‐pot method and used as catalyst supports.A reference sample was ...A series of Sn‐incorporated SBA‐15materials with high specific surface areas and highly orderedmesoporous structures were synthesized by a facile one‐pot method and used as catalyst supports.A reference sample was also prepared using a conventional impregnation method.The catalystswere characterized using various methods,and their activities in propane dehydrogenation wereinvestigated.The incorporation of Sn into the SBA‐15matrix led to strong interactions between Snspecies and the support,and these helped to maintain the oxidation states of Sn species during thereaction.Substitution with Sn changed the interfacial properties of the Pt species and improved thefunction and effect of the Sn promoter.The catalytic activities and stabilities of the Pt catalysts supportedon Sn‐incorporated SBA‐15were better than those of the impregnated sample.However,thecatalytic performance deteriorated when an excessive amount of Sn was introduced and the interactionsamong Pt,Sn species,and the support became weaker.The Pt/0.5Sn‐SBA‐15catalyst gavethe best propene selectivity,i.e.,98.5%,with a corresponding propane conversion of about43.8%.展开更多
Efficacious regulation of the geometric and electronic structures of carbon nanomaterials via the introduction of defects and their synergy is essential to achieving good electrochemical performance.However,the guidel...Efficacious regulation of the geometric and electronic structures of carbon nanomaterials via the introduction of defects and their synergy is essential to achieving good electrochemical performance.However,the guidelines for designing hybrid materials with advantageous structures and the fundamental understanding of their electrocatalytic mechanisms remain unclear.Herein,superfine Pt and PtCu nanoparticles supported by novel S,N‐co‐doped multi‐walled CNT(MWCNTs)were prepared through the innovative pyrolysis of a poly(3,4‐ethylenedioxythiophene)/polyaniline copolymer as a source of S and N.The uniform wrapping of the copolymer around the MWCNTs provides a high density of evenly distributed defects on the surface after the pyrolysis treatment,facilitating the uniform distribution of ultrafine Pt and PtCu nanoparticles.Remarkably,the Pt_(1)Cu_(2)/SN‐MWCNTs show an obviously larger electroactive surface area and higher mass activity,stability,and CO poisoning resistance in methanol oxidation compared to Pt/SN‐MWCNTs,Pt/S‐MWCNTs,Pt/N‐MWCNTs,and commercial Pt/C.Density functional theory studies confirm that the co‐doping of S and N considerably deforms the CNTs and polarizes the adjacent C atoms.Consequently,both the adsorption of Pt1Cu2 onto the SN‐MWCNTs and the subsequent adsorption of methanol are enhanced;in addition,the catalytic activity of Pt_(1)Cu_(2)/SN‐MWCNTs for methanol oxidation is thermodynamically and kinetically more favorable than that of its CNT and N‐CNT counterparts.This work provides a novel method to fabricate high‐performance fuel cell electrocatalysts with highly dispersed and stable Pt‐based nanoparticles on a carbon substrate.展开更多
文摘Proton exchange membrane fuel cells(PEMFCs)are considered ideal energy‐conversion devices because of their environmentally friendly nature and high theoretical energy efficiency.However,cathodic polarization,which is a result of the sluggish oxygen reduction reaction(ORR)kinetics,is a significant source of energy loss and reduces fuel cell efficiency.Further,the need to use Pt in commercial Pt/C cathodes has restricted their large‐scale application in fuel cells because of its high cost and poor durability.Thus,improvements in the activity and durability of Pt‐based catalyst are required to reduce the amount of Pt required and,thus,costs,while increasing the ORR rate and fuel cell power density and promoting widespread PEMFC commercialization.In recent years,atomically ordered Pt‐based intermetallic nanocrystals have received tremendous attention owing to their excellent activity and stability for the ORR.Therefore,in this review,we first introduce the formation of intermetallic compounds from the perspective of thermodynamics and kinetics to lay a theoretical foundation for the design of these compounds.In addition,optimization strategies for Pt‐based ordered intermetallic catalysts are summarized in terms of the catalyst composition,size,and morphology.Finally,we conclude with a discussion of the current challenges and future prospects of Pt‐based ordered alloys.This review is designed to help readers gain insights into the recent developments in and rational design of Pt‐based intermetallic nanocrystals for the ORR and encourage research that will enable the commercialization of PEMFCs.
文摘The commercialization of proton exchange membrane fuel cells(PEMFCs)could provide a cleaner energy society in the near future.However,the sluggish reaction kinetics and harsh conditions of the oxygen reduction reaction affect the durability and cost of PEMFCs.Most previous reports on Pt-based electrocatalyst designs have focused more on improving their activity;however,with the commercialization of PEMFCs,durability has received increasing attention.In-depth insight into the structural evolution of Pt-based electrocatalysts throughout their lifecycle can contribute to further optimization of their activity and durability.The development of in situ electron microscopy and other in situ techniques has promoted the elucidation of the evolution mechanism.This mini review highlights recent advances in the structural evolution of Pt-based electrocatalysts.The mechanisms are adequately discussed,and some methods to inhibit or exploit the structural evolution of the catalysts are also briefly reviewed.
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 Science & Technology Support Plan Projects of Sichuan Province (2016GZ0371)National Natural Science Foun-dation of China (NNSFC,21476145,21506111)~~
文摘A series of Sn‐incorporated SBA‐15materials with high specific surface areas and highly orderedmesoporous structures were synthesized by a facile one‐pot method and used as catalyst supports.A reference sample was also prepared using a conventional impregnation method.The catalystswere characterized using various methods,and their activities in propane dehydrogenation wereinvestigated.The incorporation of Sn into the SBA‐15matrix led to strong interactions between Snspecies and the support,and these helped to maintain the oxidation states of Sn species during thereaction.Substitution with Sn changed the interfacial properties of the Pt species and improved thefunction and effect of the Sn promoter.The catalytic activities and stabilities of the Pt catalysts supportedon Sn‐incorporated SBA‐15were better than those of the impregnated sample.However,thecatalytic performance deteriorated when an excessive amount of Sn was introduced and the interactionsamong Pt,Sn species,and the support became weaker.The Pt/0.5Sn‐SBA‐15catalyst gavethe best propene selectivity,i.e.,98.5%,with a corresponding propane conversion of about43.8%.
文摘Efficacious regulation of the geometric and electronic structures of carbon nanomaterials via the introduction of defects and their synergy is essential to achieving good electrochemical performance.However,the guidelines for designing hybrid materials with advantageous structures and the fundamental understanding of their electrocatalytic mechanisms remain unclear.Herein,superfine Pt and PtCu nanoparticles supported by novel S,N‐co‐doped multi‐walled CNT(MWCNTs)were prepared through the innovative pyrolysis of a poly(3,4‐ethylenedioxythiophene)/polyaniline copolymer as a source of S and N.The uniform wrapping of the copolymer around the MWCNTs provides a high density of evenly distributed defects on the surface after the pyrolysis treatment,facilitating the uniform distribution of ultrafine Pt and PtCu nanoparticles.Remarkably,the Pt_(1)Cu_(2)/SN‐MWCNTs show an obviously larger electroactive surface area and higher mass activity,stability,and CO poisoning resistance in methanol oxidation compared to Pt/SN‐MWCNTs,Pt/S‐MWCNTs,Pt/N‐MWCNTs,and commercial Pt/C.Density functional theory studies confirm that the co‐doping of S and N considerably deforms the CNTs and polarizes the adjacent C atoms.Consequently,both the adsorption of Pt1Cu2 onto the SN‐MWCNTs and the subsequent adsorption of methanol are enhanced;in addition,the catalytic activity of Pt_(1)Cu_(2)/SN‐MWCNTs for methanol oxidation is thermodynamically and kinetically more favorable than that of its CNT and N‐CNT counterparts.This work provides a novel method to fabricate high‐performance fuel cell electrocatalysts with highly dispersed and stable Pt‐based nanoparticles on a carbon substrate.
