Electrochemical nitrogen reduction reaction(ENRR)is emerging as a favorable option to the power-intensive Haber-Bosch process for ammonia synthesis.However,obstacles such as poor selectivity,low production rates,and c...Electrochemical nitrogen reduction reaction(ENRR)is emerging as a favorable option to the power-intensive Haber-Bosch process for ammonia synthesis.However,obstacles such as poor selectivity,low production rates,and competition against the hydrogen evolution reaction hinder its practical implementation.To address these,the design of highly active catalysts is critical.Single-atom catalysts(SACs)have shown great potential because of their maximized atom utilization,but their limited stability and low metal loading restrict their performances.On the other hand,dual-atom catalysts(DACs)are atomic catalysts with two metal atoms nearby and offer enhanced electrocatalytic performances by aligning with the N≡N bond to enhance N2 reduction efficiency,potentially overcoming the limitations of SAC.This review discusses recent advances in SACs and more importantly DACs for ENRR,highlighting their advantages,limitations,and the need for advanced characterization techniques to better understand catalyst behavior.The review concludes by underscoring the importance of research to optimize these catalysts for efficient and sustainable nitrogen fixation.展开更多
Recent studies have shown that single-or few-atom catalysts,with local states near the Fermi level,can promote nitrogen activation and the entire electrocatalytic nitrogen reduction reaction(eNRR)process,but are facin...Recent studies have shown that single-or few-atom catalysts,with local states near the Fermi level,can promote nitrogen activation and the entire electrocatalytic nitrogen reduction reaction(eNRR)process,but are facing limitations in loading densities and stability.Here,we conceptualize that the Kagome metals featuring naturally abundant surface sites and flat bands are promising candidates to catalyze eNRR.Using first-principles calculations,we first show that the Kagome termination of the prototypical FeSn is accompanied by the presence of flat bands from the Fe-d_(z)^(2)and d_(xz)/d_(yz)orbitals,and the exposed surface can strongly chemisorb N_(2)with an adsorption energy of~−0.7 eV.The limiting potential of 0.31 V indicates superior eNRR catalytic activity.The mutual independence between neighboring reactive sites also ensures an exceptionally high 25%atomic utilization within the Kagome layer,with each active site possessing high selectivity of eNRR.Our detailed analysis further reveals the critical role of the flat bands in boosting catalytic activity,which is also generalized to the isostructural CoSn and FeGe Kagome systems.Collectively,this work not only enhances the functionalities of Kagome materials for applications but also integrates flat band physics with single-atom catalysis,offering new opportunities in catalyst design.展开更多
基金supported by the National Research Foundation of Korea(2022R1C1C2005786,RS-2023-00256106,RS-2023-00207831,RS-2024-00346153).
文摘Electrochemical nitrogen reduction reaction(ENRR)is emerging as a favorable option to the power-intensive Haber-Bosch process for ammonia synthesis.However,obstacles such as poor selectivity,low production rates,and competition against the hydrogen evolution reaction hinder its practical implementation.To address these,the design of highly active catalysts is critical.Single-atom catalysts(SACs)have shown great potential because of their maximized atom utilization,but their limited stability and low metal loading restrict their performances.On the other hand,dual-atom catalysts(DACs)are atomic catalysts with two metal atoms nearby and offer enhanced electrocatalytic performances by aligning with the N≡N bond to enhance N2 reduction efficiency,potentially overcoming the limitations of SAC.This review discusses recent advances in SACs and more importantly DACs for ENRR,highlighting their advantages,limitations,and the need for advanced characterization techniques to better understand catalyst behavior.The review concludes by underscoring the importance of research to optimize these catalysts for efficient and sustainable nitrogen fixation.
基金supported by National Natural Science Foundation of China(Grants Nos.12374458,12488101,and 11974323)the Innovation Program for Quantum Science and Technology(Grant No.2021ZD0302800)the Strategic Priority Research Program of Chinese Academy of Sciences(Grant No.XDB0510200).
文摘Recent studies have shown that single-or few-atom catalysts,with local states near the Fermi level,can promote nitrogen activation and the entire electrocatalytic nitrogen reduction reaction(eNRR)process,but are facing limitations in loading densities and stability.Here,we conceptualize that the Kagome metals featuring naturally abundant surface sites and flat bands are promising candidates to catalyze eNRR.Using first-principles calculations,we first show that the Kagome termination of the prototypical FeSn is accompanied by the presence of flat bands from the Fe-d_(z)^(2)and d_(xz)/d_(yz)orbitals,and the exposed surface can strongly chemisorb N_(2)with an adsorption energy of~−0.7 eV.The limiting potential of 0.31 V indicates superior eNRR catalytic activity.The mutual independence between neighboring reactive sites also ensures an exceptionally high 25%atomic utilization within the Kagome layer,with each active site possessing high selectivity of eNRR.Our detailed analysis further reveals the critical role of the flat bands in boosting catalytic activity,which is also generalized to the isostructural CoSn and FeGe Kagome systems.Collectively,this work not only enhances the functionalities of Kagome materials for applications but also integrates flat band physics with single-atom catalysis,offering new opportunities in catalyst design.
