CONSPECTUS:Green electricity powered water electrolysis stands out as a promising approach for hydrogen production,which is regarded as an ideal energy carrier due to its high energy density and clean combustion.Howev...CONSPECTUS:Green electricity powered water electrolysis stands out as a promising approach for hydrogen production,which is regarded as an ideal energy carrier due to its high energy density and clean combustion.However,its large-scale application is constrained by the high cost,stemming partially from the reliance on noble-metal-based catalysts to enhance the sluggish kinetics of hydrogen and oxygen evolution reactions.To address this challenge,multiscale-coupled heterointerface catalysts(MCHCs),which integrate single atoms,clusters,and nanoparticles into one independent system,have emerged as a potential alternative.They are composed of different active components at multiple scales to achieve strong synergistic effects,where single atoms provide highly active sites with unsaturated coordination environments,clusters enable tunable electronic properties to optimize intermediate binding,and nanoparticles contribute to conductive compensation and robust architecture.Through coupling engineering,these formed heterointerfaces can regulate electronic structures and geometric configurations to break the linear scaling relationship(LSR),simultaneously facilitating H2O activation and intermediate removal.Accordingly,such synergy enables the MCHCs to overcome thermodynamic and kinetic barriers in water electrolysis,significantly boosting the catalytic performance and durability.Recent progress highlights significant advancements in MCHCs.By precisely tailoring the spatial distribution and interactions of multiscale active components,the MCHCs achieve superior reaction kinetics and long-term durability under harsh conditions of water electrolysis,which address the limitations of conventional single-component catalysts.However,the exact roles of multiscale active sites remain inadequately understood,restricting the ability to fully exploit their synergistic effects.Moreover,some key challenges,including the rational design of heterointerface structures,precise tuning of multicomponent interactions,and the development of advanced characterization techniques to elucidate structure-performance relationships,require more focused investigation.Overcoming these challenges through rational interface engineering and in-depth mechanism studies is crucial for exposing the full potential of MCHCs,which will pave a way for developing high-performance catalysts toward sustainable hydrogen production.In this Account,we focus on the emerging role of MCHCs,which integrate multiple active sites across different scales to significantly enhance the catalytic performance.We comprehensively discuss the synergistic effects,design principles,and recent advancements in multiscale-coupled heterointerfaces for water electrolysis.First,we explain the origin of the sluggish kinetics of water electrolysis,emphasizing how MCHCs overcome these limitations through the precise regulation of electronic structures and geometric configurations.By balancing the seesaw relationship between water activation and intermediate desorption,these catalysts can break the intrinsic LSR limitations.Next,we summarize the latest progress in MCHCs for applications in water electrolysis,revealing dynamic interactions and structural evolution.We finally outline the current major challenges and provide a road map for future research to fully expose the potential of MCHCs for sustainable energy conversion.展开更多
Electrocatalytic CO_(2) reduction(ECR)is a promising approach to converting CO_(2) into chemicals and fuels.Among the ECR products,C_(2) products such as ethylene,ethanol,and acetate have been extensively studied due ...Electrocatalytic CO_(2) reduction(ECR)is a promising approach to converting CO_(2) into chemicals and fuels.Among the ECR products,C_(2) products such as ethylene,ethanol,and acetate have been extensively studied due to their high industrial demands.However,the mechanistic understanding of C_(2) product formation remains unclear due to the lack of in situ or operando measurements that can observe the complex and instantaneous atomic evolutions of adsorbates at the electrode/electrolyte interface.Moreover,the sensitivity of ECR reactions to variations at the interface further widens the gap between mechanistic understanding and performance enhancement.To bridge this gap,first-principle studies provide insights into how the interface influences ECR.In this study,we present a review of mechanistic studies investigating the effects of various factors at the interface,with an emphasis on the C_(2) product formation.We begin by introducing ECR and the essential metrics.Next,we discuss the factors classified by their components at the interface,namely,electrocatalyst,electrolyte,and adsorbates,respectively,and their effects on the C_(2) product formation.Due to the interplay among these factors,we aim to deconvolute the influence of each factor and clearly demonstrate their impacts.Finally,we outline the promising directions for mechanistic studies of C_(2) products.展开更多
单原子催化剂具有原子利用率高、活性中心明确、催化中心原子配位数低等优点,有望提高电催化性能.具有相邻杂原子的双原子催化剂(DAC)有望发挥两个原子的协同作用,从而进一步提高活性.在本文中,我们报道了一种PtNi-NC催化剂,该催化剂由...单原子催化剂具有原子利用率高、活性中心明确、催化中心原子配位数低等优点,有望提高电催化性能.具有相邻杂原子的双原子催化剂(DAC)有望发挥两个原子的协同作用,从而进一步提高活性.在本文中,我们报道了一种PtNi-NC催化剂,该催化剂由固定在氮掺杂碳基底上的PtNi双原子构成,该基底采用原子层沉积技术合成.X射线吸收光谱证实了Pt–Ni双原子的存在.所制备的PtNi-NC催化剂具有优异的催化活性,在10 m A cm^(-2)的电流密度下,酸性介质中析氢反应(HER)的过电位为30 m V,与市售20 wt%Pt/C相当.特别值得注意的是,PtNi-NC具有比20 wt%Pt/C更高的质量活性,约为其21倍.密度泛函理论计算表明,Pt–Ni双原子通过调节局部电子结构和优化电荷分布产生协同效应,有助于优化吸附性能和增强电催化性能.这项工作为DAC的制备提供了新途径,揭示了它们在电催化HER等领域的应用潜力.展开更多
The development of cost-effective and highly efficient electrocatalysts to accelerate distinct electrochemical reactions is essential to help the industry to achieve a low-carbon footprint.Single-atom alloys(SAAs)with...The development of cost-effective and highly efficient electrocatalysts to accelerate distinct electrochemical reactions is essential to help the industry to achieve a low-carbon footprint.Single-atom alloys(SAAs)with the characteristics of unique electronic structures,well-defined active sites,and maximum atom utilization demonstrate promising potential to replace traditional noble metal catalysts.SAAs are expected to tailor the adsorption properties of reaction species,thus promoting electrocatalytic behaviors.Herein,representative synthetic strategies including wet chemistry,galvanic replacement,dealloying,and atomic layer deposition are introduced,followed by a summary of applications of SAAs in hydrogen evolution reaction,oxygen evolution reaction,oxygen reduction reaction,carbon dioxide reduction reaction,and ethanol electro-oxidation to provide an in-depth understanding of the structure–activity relationship.Moreover,the challenges and perspectives in this emerging field of SAAs are discussed.展开更多
基金support by the National Research Foundation,Prime Minister’s Office,Singapore under its Campus for Research Excellence and Technological Enterprise(CREATE)programme(Development of advanced catalysts for electrochemical carbon abatement),Project Code:370184872A*STAR(Agency for Science,Technology and Research)under its LCER Phase 2 Pro-gramme Hydrogen&Emerging Technologies FI,Directed Hydrogen Programme(Award No.U2305D4003)+1 种基金AISI-NUS Joint Research Initiative Fund,National Natural Science Foundation of China(No.52402039)Singapore National Research Foundation Investigatorship under Grant No.NRF-NRFI08-2022-0009.
文摘CONSPECTUS:Green electricity powered water electrolysis stands out as a promising approach for hydrogen production,which is regarded as an ideal energy carrier due to its high energy density and clean combustion.However,its large-scale application is constrained by the high cost,stemming partially from the reliance on noble-metal-based catalysts to enhance the sluggish kinetics of hydrogen and oxygen evolution reactions.To address this challenge,multiscale-coupled heterointerface catalysts(MCHCs),which integrate single atoms,clusters,and nanoparticles into one independent system,have emerged as a potential alternative.They are composed of different active components at multiple scales to achieve strong synergistic effects,where single atoms provide highly active sites with unsaturated coordination environments,clusters enable tunable electronic properties to optimize intermediate binding,and nanoparticles contribute to conductive compensation and robust architecture.Through coupling engineering,these formed heterointerfaces can regulate electronic structures and geometric configurations to break the linear scaling relationship(LSR),simultaneously facilitating H2O activation and intermediate removal.Accordingly,such synergy enables the MCHCs to overcome thermodynamic and kinetic barriers in water electrolysis,significantly boosting the catalytic performance and durability.Recent progress highlights significant advancements in MCHCs.By precisely tailoring the spatial distribution and interactions of multiscale active components,the MCHCs achieve superior reaction kinetics and long-term durability under harsh conditions of water electrolysis,which address the limitations of conventional single-component catalysts.However,the exact roles of multiscale active sites remain inadequately understood,restricting the ability to fully exploit their synergistic effects.Moreover,some key challenges,including the rational design of heterointerface structures,precise tuning of multicomponent interactions,and the development of advanced characterization techniques to elucidate structure-performance relationships,require more focused investigation.Overcoming these challenges through rational interface engineering and in-depth mechanism studies is crucial for exposing the full potential of MCHCs,which will pave a way for developing high-performance catalysts toward sustainable hydrogen production.In this Account,we focus on the emerging role of MCHCs,which integrate multiple active sites across different scales to significantly enhance the catalytic performance.We comprehensively discuss the synergistic effects,design principles,and recent advancements in multiscale-coupled heterointerfaces for water electrolysis.First,we explain the origin of the sluggish kinetics of water electrolysis,emphasizing how MCHCs overcome these limitations through the precise regulation of electronic structures and geometric configurations.By balancing the seesaw relationship between water activation and intermediate desorption,these catalysts can break the intrinsic LSR limitations.Next,we summarize the latest progress in MCHCs for applications in water electrolysis,revealing dynamic interactions and structural evolution.We finally outline the current major challenges and provide a road map for future research to fully expose the potential of MCHCs for sustainable energy conversion.
基金supported by the National Research Foundation Singapore Investigatorship Program(Grant No.NRF-NRFI08-2022-0009)A*STAR(Agency for Science,Technology and Research)LCER FI program(Award No.U2102d2002)the E-CO2RR CREATE Program.
文摘Electrocatalytic CO_(2) reduction(ECR)is a promising approach to converting CO_(2) into chemicals and fuels.Among the ECR products,C_(2) products such as ethylene,ethanol,and acetate have been extensively studied due to their high industrial demands.However,the mechanistic understanding of C_(2) product formation remains unclear due to the lack of in situ or operando measurements that can observe the complex and instantaneous atomic evolutions of adsorbates at the electrode/electrolyte interface.Moreover,the sensitivity of ECR reactions to variations at the interface further widens the gap between mechanistic understanding and performance enhancement.To bridge this gap,first-principle studies provide insights into how the interface influences ECR.In this study,we present a review of mechanistic studies investigating the effects of various factors at the interface,with an emphasis on the C_(2) product formation.We begin by introducing ECR and the essential metrics.Next,we discuss the factors classified by their components at the interface,namely,electrocatalyst,electrolyte,and adsorbates,respectively,and their effects on the C_(2) product formation.Due to the interplay among these factors,we aim to deconvolute the influence of each factor and clearly demonstrate their impacts.Finally,we outline the promising directions for mechanistic studies of C_(2) products.
基金supported by the National Natural Science Foundation of China(52122107 and 51972224)the National Research Foundation,SingaporeA*STAR under its LCER FI program Award(U2102d2002)。
文摘单原子催化剂具有原子利用率高、活性中心明确、催化中心原子配位数低等优点,有望提高电催化性能.具有相邻杂原子的双原子催化剂(DAC)有望发挥两个原子的协同作用,从而进一步提高活性.在本文中,我们报道了一种PtNi-NC催化剂,该催化剂由固定在氮掺杂碳基底上的PtNi双原子构成,该基底采用原子层沉积技术合成.X射线吸收光谱证实了Pt–Ni双原子的存在.所制备的PtNi-NC催化剂具有优异的催化活性,在10 m A cm^(-2)的电流密度下,酸性介质中析氢反应(HER)的过电位为30 m V,与市售20 wt%Pt/C相当.特别值得注意的是,PtNi-NC具有比20 wt%Pt/C更高的质量活性,约为其21倍.密度泛函理论计算表明,Pt–Ni双原子通过调节局部电子结构和优化电荷分布产生协同效应,有助于优化吸附性能和增强电催化性能.这项工作为DAC的制备提供了新途径,揭示了它们在电催化HER等领域的应用潜力.
基金National Natural Science Foundation of China,Grant/Award Numbers:51972224,52122107National Research Foundation,Singapore,and A*STAR(Agency for Science,Technology and Research)under its LCER FI program Award,Grant/Award Number:U2102d2002。
文摘The development of cost-effective and highly efficient electrocatalysts to accelerate distinct electrochemical reactions is essential to help the industry to achieve a low-carbon footprint.Single-atom alloys(SAAs)with the characteristics of unique electronic structures,well-defined active sites,and maximum atom utilization demonstrate promising potential to replace traditional noble metal catalysts.SAAs are expected to tailor the adsorption properties of reaction species,thus promoting electrocatalytic behaviors.Herein,representative synthetic strategies including wet chemistry,galvanic replacement,dealloying,and atomic layer deposition are introduced,followed by a summary of applications of SAAs in hydrogen evolution reaction,oxygen evolution reaction,oxygen reduction reaction,carbon dioxide reduction reaction,and ethanol electro-oxidation to provide an in-depth understanding of the structure–activity relationship.Moreover,the challenges and perspectives in this emerging field of SAAs are discussed.
