TM3(TM=V,Fe,Mo,W)single-cluster catalyst confined on porous BN for electrocatalytic nitrogen reduction

Shuaishuai Gao ¹Zuju Ma ¹Chengwei Xiao ²Zhitao Cui ²Wei Du ¹Xueqin Sun ¹Qiaohong Li ³Rongjian Sa ⁴Chenghua Sun⁵

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作者信息

1. School of Environmental and Materials Engineering,Yantai University,Yantai 264005,China
2. School of Materials Science and Engineering,Anhui University of Technology,Maanshan 243002,China
3. State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China
4. Institute of Oceanography,Ocean College,Minjiang University,Fuzhou 350108,China
5. 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
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Abstract

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.

Key words

Electrocatalytic N2 reduction/Density functional theory/Single-cluster/Porous boron nitride

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基金项目

This work was financially supported by the National Natu-ral Science Foundation of China(Nos.21771182)

This work was financially supported by the National Natu-ral Science Foundation of China(21501177)

This work was financially supported by the National Natu-ral Science Foundation of China(21673240)

Guangdong Innovation Research Team for Higher Education(2017KCXTD030)

High-level Talents Project of Dongguan University of Technology(KCYKYQD2017017)

and the Open Project Program of the State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure o(20200006)

出版年

2022

材料科学技术(英文版)

中国金属学会中国材料研究学会中国科学院金属研究所

材料科学技术(英文版)

CSTPCDCSCDSCI

影响因子：0.657

ISSN：1005-0302

参考文献量59

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