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Elementary kinetics of nitrogen electroreduction to ammonia on late transition metals

Journal Article · · Catalysis Science and Technology
DOI:https://doi.org/10.1039/c8cy01845f· OSTI ID:1612613
 [1];  [2];  [2]
  1. University of North Carolina, Wilmington, NC (United States); DOE/OSTI
  2. Pennsylvania State Univ., University Park, PA (United States)
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Developing small scale nitrogen to ammonia conversion devices could greatly help sustainable agriculture. The lack of effective cathode materials for reduction of nitrogen to ammonia puts a major limitation on developing small scale electrochemical ammonia production devices that can operate at low pressures and temperatures. In this study, the electrochemical nitrogen reduction reaction (NRR) mechanism is investigated over late transition metals. Activation barriers for possible rate limiting steps are calculated using density functional theory (DFT) methods and are converted to potential dependent electrochemical barriers. Associative and dissociative paths are evaluated and the associative path shows lower barriers on all metals considered at NRR potentials. Brønsted–Evans–Polanyi (BEP) relationships are evaluated for rate limiting steps and a “kinetic volcano” is demonstrated for catalyst optimization. Rhodium (Rh) and iron (Fe) appear to have the lowest kinetic barriers to convert N2 to NH3. A large over-potential, however, is required to convert nitrogen to ammonia over all the surfaces considered. Finally, the hydrogen evolution reaction (HER) has a lower activation barrier compared to NRR, demonstrating the kinetic selectivity challenge. ; A
Research Organization:
Univ. of Arkansas, Fayetteville, AR (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0016529
OSTI ID:
1612613
Alternate ID(s):
OSTI ID: 1484537
Journal Information:
Catalysis Science and Technology, Journal Name: Catalysis Science and Technology Journal Issue: 1 Vol. 9; ISSN 2044-4753
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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Liquefied Sunshine: Transforming Renewables into Fertilizers and Energy Carriers with Electromaterials journal November 2019
Atomic Modulation, Structural Design, and Systematic Optimization for Efficient Electrochemical Nitrogen Reduction journal January 2020
Activated basal planes of WS 2 by intrinsic defects as catalysts for the electrocatalytic nitrogen reduction reaction journal January 2019
Using the NN dipole as a theoretical indicator for estimating the electrocatalytic performance of active sites in the nitrogen reduction reaction: single transition metal atoms embedded in two dimensional phthalocyanine journal January 2020

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