Single-Boron Catalysts for Nitrogen Reduction Reaction

Chuangwei Liu; Qinye Li; Chengzhang Wu; Jie Zhang; Yonggang Jin; Douglas R MacFarlane; Chenghua Sun

doi:10.1021/jacs.8b13165

Single-Boron Catalysts for Nitrogen Reduction Reaction

J Am Chem Soc. 2019 Feb 20;141(7):2884-2888. doi: 10.1021/jacs.8b13165. Epub 2019 Feb 6.

Authors

Chuangwei Liu¹, Qinye Li², Chengzhang Wu³, Jie Zhang¹, Yonggang Jin⁴, Douglas R MacFarlane¹, Chenghua Sun⁵

Affiliations

¹ School of Chemistry, Faculty of Science , Monash University , Clayton , Victoria 3800 , Australia.
² School of Chemical Engineering , Monash University , Clayton , Victoria 3800 , Australia.
³ Key Laboratory of Advanced Special Steel, Shanghai Key Laboratory of Advanced Ferrometallurgy, School of Materials Science and Engineering , Shanghai University , Shanghai 200072 , China.
⁴ CSIRO Energy , 1 Technology Court , Pullenvale , Queensland 4069 , Australia.
⁵ Department of Chemistry and Biotechnology, Faculty of Science, Engineering & Technology , Swinburne University of Technology , Hawthorn , Victoria 3122 , Australia.

PMID: 30719913
DOI: 10.1021/jacs.8b13165

Abstract

Boron has been explored as p-block catalysts for nitrogen reduction reaction (NRR) by density functional theory. Unlike transition metals, on which the active centers need empty d orbitals to accept the lone-pair electrons of the nitrogen molecule, the sp³ hybrid orbital of the boron atom can form B-to-N π-back bonding. This results in the population of the N-N π* orbital and the concomitant decrease of the N-N bond order. We demonstrate that the catalytic activity of boron is highly correlated with the degree of charge transfer between the boron atom and the substrate. Among the 21 concept-catalysts, single boron atoms supported on graphene and substituted into h-MoS₂ are identified as the most promising NRR catalysts, offering excellent energy efficiency and selectivity against hydrogen evolution reaction.