Mapping the Binary Covalent Alloy Space to Pursue Superior Nitrogen Reduction Reaction Catalysts

Tezak, Cooper R.; Gerits, Sophie; Rich, Benjamin; Sutton, Christopher; Singstock, Nicholas; Musgrave, Charles B.

doi:10.1002/aenm.202304559

Title: Mapping the Binary Covalent Alloy Space to Pursue Superior Nitrogen Reduction Reaction Catalysts

Journal Article · 04 May 2024 · Advanced Energy Materials

DOI: https://doi.org/10.1002/aenm.202304559 · OSTI ID:2361132

^[1]; Gerits, Sophie ^[2]; Rich, Benjamin ^[2];

^[3];

^[2];

^[2]

University of Colorado, Boulder, CO (United States); University of Colorado, Boulder
University of Colorado, Boulder, CO (United States)
University of South Carolina, Columbia, SC (United States)

The electrochemical nitrogen reduction reaction (NRR) has the potential to decarbonize industrial ammonia production. However, NRR has poor activity and selectivity versus the competing hydrogen evolution reaction for catalysts that adhere to scaling relations. Overcoming the limitations imposed by scaling relations requires more complex catalyst materials, however, evaluating materials beyond simple metal systems is a large combinatorial problem that requires an improved understanding of the electrocatalyst surface to rationally guide the discovery of superior catalysts. The study uses grand canonical density functional theory to uncover NRR trends on a large and disparate set of binary covalent alloys (BCA) with variable compositions and active-site geometries. The studied BCAs generally follow scaling relations, albeit with larger variance and several systems that significantly break scaling. BCAs with early- to mid-transition metals tend to lie near the volcano peak and activate the N₂ triple bond via a side-on binding configuration. Trends in the BCA space cannot be readily predicted using simple electronic descriptors, which is ascribed to the large geometric variability of the BCA surfaces. Furthermore, it is anticipated that these findings will provide a foundation for the rational design of superior NRR electrocatalysts with increasing material complexity.

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Research Organization:: University of Colorado, Boulder, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0022247

OSTI ID:: 2361132

Alternate ID(s):: OSTI ID: 2345942

Journal Information:: Advanced Energy Materials, Journal Name: Advanced Energy Materials Journal Issue: 28 Vol. 14; ISSN 1614-6832

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Mapping the Binary Covalent Alloy Space to Pursue Superior Nitrogen Reduction Reaction Catalysts

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