Revised Nitrogen Reduction Scaling Relations from Potential-Dependent Modeling of Chemical and Electrochemical Steps

Tezak, Cooper R.; Singstock, Nicholas R.; Alherz, Abdulaziz W.; Vigil-Fowler, Derek; Sutton, Christopher A.; Sundararaman, Ravishankar; Musgrave, Charles B.

doi:10.1021/acscatal.3c01978

Revised Nitrogen Reduction Scaling Relations from Potential-Dependent Modeling of Chemical and Electrochemical Steps

Journal Article · Tue Sep 19 04:00:00 EDT 2023 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.3c01978· OSTI ID:2222426

Tezak, Cooper R.; Singstock, Nicholas R.; Alherz, Abdulaziz W.; Vigil-Fowler, Derek; Sutton, Christopher A.; Sundararaman, Ravishankar; Musgrave, Charles B.

The electrochemical nitrogen reduction reaction (NRR) is a promising route to enable carbon-free ammonia production. However, this reaction is limited by the poor activity and selectivity of current catalysts. The rational design of superior NRR electrocatalysts requires a detailed mechanistic understanding of current material limitations to inform how these might be overcome. The current understanding of how scaling limits NRR on metal catalysts is predicated on a simplified reaction pathway that considers only proton-coupled electron transfer (PCET) steps. Here, we apply grand-canonical density functional theory to investigate a more comprehensive NRR mechanism that includes both electrochemical and chemical steps on 30 metal surfaces in solvent under an applied potential. We applied ..phi..max, a grand-canonical adaptation of the Gmax thermodynamic descriptor, to evaluate trends in catalyst activity. This approach produces a ..phi..max "volcano" diagram for NRR activity scaling on metals that qualitatively differs from the scaling relations identified when only PCET steps are considered. NH3* desorption was found to limit the NRR activity for materials at the top of the volcano and truncate the volcano's peak at increasingly reducing potentials. These revised scaling relations may inform the rational design of superior NRR electrocatalysts. This approach is transferable to study other materials and reaction chemistries where both electrochemical and chemical steps are modeled under an applied potential.

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE)

DOE Contract Number:: AC36-08GO28308

OSTI ID:: 2222426

Report Number(s):: NREL/JA-2C00-88154; MainId:88929; UUID:4e12b06f-afef-4813-bea8-ac3436f10414; MainAdminID:71150

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 19 Vol. 13

Country of Publication:: United States

Language:: English

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