Mechanistic Insights into Electrochemical Nitrogen Reduction Reaction on Vanadium Nitride Nanoparticles

Yang, Xuan; Nash, Jared; Anibal, Jacob; Dunwell, Marco; Kattel, Shyam; Stavitski, Eli; Attenkofer, Klaus; Chen, Jingguang G.; Yan, Yushan; Xu, Bingjun

doi:10.1021/jacs.8b08379

Title: Mechanistic Insights into Electrochemical Nitrogen Reduction Reaction on Vanadium Nitride Nanoparticles

Journal Article · 23 September 2018 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.8b08379 · OSTI ID:1484883

^[1]; Nash, Jared ^[1]; Anibal, Jacob ^[1]; Dunwell, Marco ^[1]; Kattel, Shyam ^[2]; Stavitski, Eli ^[3]; Attenkofer, Klaus ^[3]; Chen, Jingguang G. ^[2];

^[1];

^[1]

Univ. of Delaware, Newark, DE (United States). Center for Catalytic Science and Technology, Dept. of Chemical and Biomolecular Engineering
Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division; Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Renewable production of ammonia, a building block for most fertilizers, via the electrochemical nitrogen reduction reaction (ENRR) is desirable; however, a selective electrocatalyst is lacking. Here we show that vanadium nitride (VN) nanoparticles are active, selective, and stable ENRR catalysts with an ENRR rate and a Faradaic efficiency (FE) of 3.3 × 10^–10 mol s^–1 cm^–2 and 6.0% at -0.1 V within 1 h, respectively. ENRR with ¹⁵N₂ as the feed produces both ¹⁴NH₃ and ¹⁵NH₃, which indicates that the reaction follows a Mars–van Krevelen mechanism. Ex situ X-ray photoelectron spectroscopy characterization of fresh and spent catalysts reveals that multiple vanadium oxide, oxynitride, and nitride species are present on the surface and identified VN0.7O0.45 as the active phase in the ENRR. Operando X-ray absorption spectroscopy and catalyst durability test results corroborate this hypothesis and indicate that the conversion of VN_0.7O0.45 to the VN phase leads to catalyst deactivation. We hypothesize that only the surface N sites adjacent to a surface O are active in the ENRR. Finally, an ammonia production rate of 1.1 × 10^–10 mol s^–1 cm^–2 can be maintained for 116 h, with a steady-state turnover number of 431.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704

OSTI ID:: 1484883

Report Number(s):: BNL-209653-2018-JAAM

Journal Information:: Journal of the American Chemical Society, Vol. 140, Issue 41; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 381 works

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Anomalous hydrogen evolution behavior in high-pH environment induced by locally generated hydronium ions Wang, Xuesi; Xu, Chaochen; Jaroniec, Mietek Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-12773-7	journal	October 2019