Elementary kinetics of nitrogen electroreduction to ammonia on late transition metals
- University of North Carolina, Wilmington, NC (United States)
- Pennsylvania State Univ., University Park, PA (United States)
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:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- Grant/Contract Number:
- SC0016529; ACI-1053575; DGE-1449785
- OSTI ID:
- 1612613
- Alternate ID(s):
- OSTI ID: 1484537
- Journal Information:
- Catalysis Science and Technology, Vol. 9, Issue 1; ISSN 2044-4753
- Publisher:
- Royal Society of ChemistryCopyright Statement
- Country of Publication:
- United States
- Language:
- English
Web of Science
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 NN 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 |
Similar Records
Mechanistic Insights Evaluating Ag, Pb, and Ni as Electrocatalysts for Furfural Reduction from First-Principles Methods
Unifying principles for catalytic hydrotreating processes (Final Technical Report)