Confined metal clusters as sub-nanometer reactors for electrocatalytic N2 reduction reaction(eNRR)have received increasing attention due to the unique metal-metal interaction and higher activity than single-atom catalysts.Herein,the inspiration of the superior capacitance and unique microenvironment with regular surface cavities of the porous boron nitride(p-BN)nanosheets,we systematically studied the catalytic activity for NRR of transition-metal single-clusters in the triplet form(V3,Fe3,Mo3 and W3)confined in the surface cavities of the p-BN sheets by spin-polarized density functional theory(DFT)calculations.After a two-step screening strategy,Mo3@p-BN was found to have high catalytic activity and selectivity with a rather low limiting potential(-0.34 V)for the NRR.The anchored Mo3 single-cluster can be stably embedded on the surface cavities of the substrate preventing the diffusion of the active Mo atoms.More importantly,the Mo atoms in the Mo3 single-cluster would act as"cache"to accelerate electron transfer between active metal centers and nitrogen-containing intermediates via the intimate Mo-Mo interactions.The cooperation of Mo atoms can also provide a large number of occupied and unoccupied d orbitals to make the"donation-backdonation"mechanism more effective.This work not only provides a quite promising electrocatalyst for NRR,but also brings new insights into the rational design of triple-atom NRR catalysts.

Shuaishuai Gao;Zuju Ma;Chengwei Xiao;Zhitao Cui;Wei Du;Xueqin Sun;Qiaohong Li;Rongjian Sa;Chenghua Sun

School of Environmental and Materials Engineering,Yantai University,Yantai 264005,China;School of Materials Science and Engineering,Anhui University of Technology,Maanshan 243002,China;State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China;Institute of Oceanography,Ocean College,Minjiang University,Fuzhou 350108,China;College of Chemical Engineering and Energy Technology,Dongguan University of Technology,Dongguan 523808,China;Department of Chemistry and Biotechnology,Faculty of Science,Engineering&Technology,Swinburne University of Technology,Hawthorn,VIC 3122,Australia

材料科学技术（英文版）

[1]Shuaishuai Gao;Zuju Ma;Chengwei Xiao;Zhitao Cui;Wei Du;Xueqin Sun;Qiaohong Li;Rongjian Sa;Chenghua Sun-.TM3(TM=V,Fe,Mo,W)single-cluster catalyst confined on porous BN for electrocatalytic nitrogen reduction)[J].材料科学技术（英文版）,2022(13):46-53

backdonation

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