Spin regulation for efficient electrocatalytic N2 reduction over diatomic Fe-Mo catalyst

Shuaishuai Gao; Xiaojing Liu; Zhiwei Wang; Yantong Lu; Rongjian Sa; Qiaohong Li; Chenghua Sun; Xin Chen; Zuju Ma

doi:10.1016/j.jcis.2022.10.099

Spin regulation for efficient electrocatalytic N₂ reduction over diatomic Fe-Mo catalyst

J Colloid Interface Sci. 2023 Jan 15;630(Pt B):215-223. doi: 10.1016/j.jcis.2022.10.099. Epub 2022 Oct 25.

Authors

Shuaishuai Gao¹, Xiaojing Liu¹, Zhiwei Wang¹, Yantong Lu¹, Rongjian Sa², Qiaohong Li³, Chenghua Sun⁴, Xin Chen⁵, Zuju Ma⁶

Affiliations

¹ School of Environmental and Materials Engineering, Yantai University, Yantai 264005, China.
² Institute of Oceanography, Ocean College, Minjiang University, Fuzhou 350108, 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 Department of Chemistry and Biotechnology, Faculty of Science, Engineering & Technology, Swinburne University of Technology, Hawthorn, VIC 3122, Australia. Electronic address: chenghuasun@swin.edu.au.
⁵ School of Computer and Control Engineering, Yantai University, Yantai 264005, China. Electronic address: xchen@ytu.edu.cn.
⁶ School of Environmental and Materials Engineering, Yantai University, Yantai 264005, China; State Key Laboratory of Crystal Materials, Shandong University, Jinan, Shandong 250100, China. Electronic address: zjma@outlook.com.

PMID: 36327724
DOI: 10.1016/j.jcis.2022.10.099

Abstract

Electrocatalytic nitrogen reduction reaction (eNRR) is a promising method for the sustainable production of ammonia as an alternative to the traditional energy-intensive Haber-Bosch process. In this work, an efficient strategy by atomic spin regulation to promote NRR through Fe-transition metal (TM) hybrid heteronuclear dual-atom catalysts has been studied. By means of DFT computations, the stability, activity, and selectivity of 30 kinds of Fe-based dual-atoms anchored on N-doped porous graphene are systematically investigated to evaluate their catalytic performance. Fe/MoNC is screened as an excellent NRR catalyst with the limiting potentials of 0.63 V, and also suppresses HER. In the Fe/MoNC, the neighboring Fe atom regulates the spin state of the Mo center in MoN₄ from high-spin state (2.63 μ_B) to medium-spin state (0.74 μ_B), which can effectively relieve the strong overlapping between Mo 4d orbital with the N_xH_y intermediates, promote the desorption of reaction product, and eventually achieve a lower limiting potential. Interestingly, the archetype of the active center of nitrogenase is also a FeMo-cofactor, which is consistent with our screening results. The work may provide new insight into the mechanism of nitrogenase, and promote the rational design of efficient NRR catalysts by atomic spin regulation.

MeSH terms

Ammonia
Catalysis
Diatoms*
Nitrogen
Nitrogenase

Substances

Nitrogen
Ammonia
Nitrogenase