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

Abstract

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 VN0.7O0.45 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.

Authors:
ORCiD logo [1];  [1];  [1];  [1];  [2];  [3];  [3];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Delaware, Newark, DE (United States). Center for Catalytic Science and Technology, Dept. of Chemical and Biomolecular Engineering
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division; Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1484883
Report Number(s):
BNL-209653-2018-JAAM
Journal ID: ISSN 0002-7863
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 41; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats

Yang, Xuan, Nash, Jared, Anibal, Jacob, Dunwell, Marco, Kattel, Shyam, Stavitski, Eli, Attenkofer, Klaus, Chen, Jingguang G., Yan, Yushan, and Xu, Bingjun. Mechanistic Insights into Electrochemical Nitrogen Reduction Reaction on Vanadium Nitride Nanoparticles. United States: N. p., 2018. Web. https://doi.org/10.1021/jacs.8b08379.
Yang, Xuan, Nash, Jared, Anibal, Jacob, Dunwell, Marco, Kattel, Shyam, Stavitski, Eli, Attenkofer, Klaus, Chen, Jingguang G., Yan, Yushan, & Xu, Bingjun. Mechanistic Insights into Electrochemical Nitrogen Reduction Reaction on Vanadium Nitride Nanoparticles. United States. https://doi.org/10.1021/jacs.8b08379
Yang, Xuan, Nash, Jared, Anibal, Jacob, Dunwell, Marco, Kattel, Shyam, Stavitski, Eli, Attenkofer, Klaus, Chen, Jingguang G., Yan, Yushan, and Xu, Bingjun. Sun . "Mechanistic Insights into Electrochemical Nitrogen Reduction Reaction on Vanadium Nitride Nanoparticles". United States. https://doi.org/10.1021/jacs.8b08379. https://www.osti.gov/servlets/purl/1484883.
@article{osti_1484883,
title = {Mechanistic Insights into Electrochemical Nitrogen Reduction Reaction on Vanadium Nitride Nanoparticles},
author = {Yang, Xuan and Nash, Jared and Anibal, Jacob and Dunwell, Marco and Kattel, Shyam and Stavitski, Eli and Attenkofer, Klaus and Chen, Jingguang G. and Yan, Yushan and Xu, Bingjun},
abstractNote = {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 VN0.7O0.45 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.},
doi = {10.1021/jacs.8b08379},
journal = {Journal of the American Chemical Society},
number = 41,
volume = 140,
place = {United States},
year = {2018},
month = {9}
}

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Figures / Tables:

Figure S1-1 Figure S1-1: Nitrogen adsorption isotherm for VN nanoparticles. The Brunauer−Emmett−Teller (BET) surface area is 177 m2 g−1.

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