Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 58, Issue 39, Pages 13768-13772Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201906449
Keywords
ammonia synthesis; density functional theory; electrochemical nitrogen reduction; isotopic labeling; vanadium nitride
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Funding
- U.S. Department of Energy [DE-FG02-13ER16381, DE-AC02-06CH11357, DE-SC0016537]
- U.S. Department of Energy (DOE) [DE-SC0016537] Funding Source: U.S. Department of Energy (DOE)
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Despite recent intense interest in the development of catalysts for the electrochemical nitrogen reduction reaction (ENRR), mechanistic understanding and catalyst design principles remain lacking. In this work, we develop a strategy to determine the density of initial and steady-state active sites on ENRR catalysts that follow the Mars-van Krevelen mechanism via quantitative isotope-exchange experiments. This method allows the comparison of intrinsic activities of active sites and facilitates the identification and improvement of active-site structures for ENRR. Combined with detailed density functional theory calculations, we show that the rate-limiting step in the ENRR is likely the initial N equivalent to N bond activation via the addition of a proton and an electron to the adsorbed N-2 on the N vacancies to form N2H. The methodology developed and mechanistic insights gained in this work could guide the rational catalyst design in the ENRR.
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