Lithium–oxygen battery with ultrahigh theoretical energy density is considered a highly competitive next-generation energy storage device,but its practical application is severely hindered by issues such as difficult...Lithium–oxygen battery with ultrahigh theoretical energy density is considered a highly competitive next-generation energy storage device,but its practical application is severely hindered by issues such as difficult decomposition of discharge products at present.Here,we have developed N-doped carbon anchored atomically dispersed Ru sites cathode catalyst with open hollow structure(h-RuNC)for Lithium–oxygen battery.On one hand,the abundance of atomically dispersed Ru sites can effectively catalyze the formation and decomposition of discharge products,thereby greatly enhancing the redox kinetics.On the other hand,the open hollow structure not only enhances the mass activity of atomically dispersed Ru sites but also improves the diffusion efficiency of catalytic molecules.Therefore,the excellent activity from atomically dispersed Ru sites and the enhanced diffusion from open hollow structure respectively improve the redox kinetics and cycling stability,ultimately achieving a high-performance lithium–oxygen battery.展开更多
Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utiliz...Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utilization and exceptional catalytic functionality.Furthermore,accurately controlling atomic physical properties including spin,charge,orbital,and lattice degrees of atomically dispersed catalysts can realize the optimized chemical properties including maximum atom utilization efficiency,homogenous active centers,and satisfactory catalytic performance,but remains elusive.Here,through physical and chemical insight,we review and systematically summarize the strategies to optimize atomically dispersed ORR catalysts including adjusting the atomic coordination environment,adjacent electronic orbital and site density,and the choice of dual-atom sites.Then the emphasis is on the fundamental understanding of the correlation between the physical property and the catalytic behavior for atomically dispersed catalysts.Finally,an overview of the existing challenges and prospects to illustrate the current obstacles and potential opportunities for the advancement of atomically dispersed catalysts in the realm of electrocatalytic reactions is offered.展开更多
Electrochemical carbon dioxide reduction reaction(CO_(2)RR)involves a variety of intermediates with highly correlated reaction and ad-desorption energies,hindering optimization of the catalytic activity.For example,in...Electrochemical carbon dioxide reduction reaction(CO_(2)RR)involves a variety of intermediates with highly correlated reaction and ad-desorption energies,hindering optimization of the catalytic activity.For example,increasing the binding of the*COOH to the active site will generally increase the*CO desorption energy.Breaking this relationship may be expected to dramatically improve the intrinsic activity of CO_(2)RR,but remains an unsolved challenge.Herein,we addressed this conundrum by constructing a unique atomic dispersed hetero-pair consisting of Mo-Fe di-atoms anchored on N-doped carbon carrier.This system shows an unprecedented CO_(2)RR intrinsic activity with TOF of 3336 h−1,high selectivity toward CO production,Faradaic efficiency of 95.96%at−0.60 V and excellent stability.Theoretical calculations show that the Mo-Fe diatomic sites increased the*COOH intermediate adsorption energy by bridging adsorption of*COOH intermediates.At the same time,d-d orbital coupling in the Mo-Fe di-atom results in electron delocalization and facilitates desorption of*CO intermediates.Thus,the undesirable correlation between these steps is broken.This work provides a promising approach,specifically the use of di-atoms,for breaking unfavorable relationships based on understanding of the catalytic mechanisms at the atomic scale.展开更多
基金This work was supported by National Key R&D Program of China(2021YFF0500503)National Natural Science Foundation of China(21925202,U22B2071)International Joint Mission on Climate Change and Carbon Neutrality.
文摘Lithium–oxygen battery with ultrahigh theoretical energy density is considered a highly competitive next-generation energy storage device,but its practical application is severely hindered by issues such as difficult decomposition of discharge products at present.Here,we have developed N-doped carbon anchored atomically dispersed Ru sites cathode catalyst with open hollow structure(h-RuNC)for Lithium–oxygen battery.On one hand,the abundance of atomically dispersed Ru sites can effectively catalyze the formation and decomposition of discharge products,thereby greatly enhancing the redox kinetics.On the other hand,the open hollow structure not only enhances the mass activity of atomically dispersed Ru sites but also improves the diffusion efficiency of catalytic molecules.Therefore,the excellent activity from atomically dispersed Ru sites and the enhanced diffusion from open hollow structure respectively improve the redox kinetics and cycling stability,ultimately achieving a high-performance lithium–oxygen battery.
基金supported by the National Natural Science Foundation of China(22234005,21974070)the Natural Science Foundation of Jiangsu Province(BK20222015)。
文摘Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utilization and exceptional catalytic functionality.Furthermore,accurately controlling atomic physical properties including spin,charge,orbital,and lattice degrees of atomically dispersed catalysts can realize the optimized chemical properties including maximum atom utilization efficiency,homogenous active centers,and satisfactory catalytic performance,but remains elusive.Here,through physical and chemical insight,we review and systematically summarize the strategies to optimize atomically dispersed ORR catalysts including adjusting the atomic coordination environment,adjacent electronic orbital and site density,and the choice of dual-atom sites.Then the emphasis is on the fundamental understanding of the correlation between the physical property and the catalytic behavior for atomically dispersed catalysts.Finally,an overview of the existing challenges and prospects to illustrate the current obstacles and potential opportunities for the advancement of atomically dispersed catalysts in the realm of electrocatalytic reactions is offered.
基金the National Natural Science Foundation of China(22279044,12034002,and 22202080)the Project for Self-Innovation Capability Construction of Jilin Province Development and Reform Commission(2021C026)+1 种基金Jilin Province Science and Technology Development Program(20210301009GX)the Fundamental Research Funds for the Central Universities.
文摘Electrochemical carbon dioxide reduction reaction(CO_(2)RR)involves a variety of intermediates with highly correlated reaction and ad-desorption energies,hindering optimization of the catalytic activity.For example,increasing the binding of the*COOH to the active site will generally increase the*CO desorption energy.Breaking this relationship may be expected to dramatically improve the intrinsic activity of CO_(2)RR,but remains an unsolved challenge.Herein,we addressed this conundrum by constructing a unique atomic dispersed hetero-pair consisting of Mo-Fe di-atoms anchored on N-doped carbon carrier.This system shows an unprecedented CO_(2)RR intrinsic activity with TOF of 3336 h−1,high selectivity toward CO production,Faradaic efficiency of 95.96%at−0.60 V and excellent stability.Theoretical calculations show that the Mo-Fe diatomic sites increased the*COOH intermediate adsorption energy by bridging adsorption of*COOH intermediates.At the same time,d-d orbital coupling in the Mo-Fe di-atom results in electron delocalization and facilitates desorption of*CO intermediates.Thus,the undesirable correlation between these steps is broken.This work provides a promising approach,specifically the use of di-atoms,for breaking unfavorable relationships based on understanding of the catalytic mechanisms at the atomic scale.