Disentangling the Role of Local Composition and Electronic Structure in NO3RR Performance of NiFe Alloys
Year: 2025
Type: preprint
Abstract: Elemental first row transition metal electrocatalysts typically exhibit a tradeoff between NO3RR Faradaic efficiency (FE) and NH4+ selectivity. Here, we find that NiFe alloys have high NO3RR FE and substantially higher NH₄⁺ selectivity than Ni or Fe. Calculations show that NO3* adsorption is promoted by Fe-rich surfaces, and its competitive adsorption with H* rationalizes trends in reaction rate order. Activation energies of subsequent reduction steps illustrate NO2* deoxygenation is promoted by Ni-rich surfaces, whereas NO* dissociation is promoted by both surface and subsurface Fe atoms. These findings suggest that NiFe alloys achieve enhanced selectivity by leveraging local site diversity.
Source: ChemRxiv
Language: English
Field: Energy
Domain: Physical Sciences
Open Access status: green
Awards: G1118031844, G1286236842, G1286251239, G1453181110, G1736462507, G1863003419, Track 4: Advanced CI Coordination Ecosystem: Monitoring and Measurement Services, G2037563265, G30714459, G3083819904, G3309974852, G3466678926, G3496119864, G3562386289, Track 1: ACCESS Resource Allocations Marketplace and Platform Services (RAMPS), G4010157413, G419881185, G42916606, G4493815120, G4501827968, ACO: An Open CI Ecosystem to Advance Scientific Discovery (OpenCI), G498139845, Track 3: COre National Ecosystem for CyberinfrasTructure (CONECT), G5367127336, G5390598945, G5464919783, G6064526139, G6261433946, G650090426, NNCI: Northwest Nanotechnology Infrastructure (NWNI), Track 2: Customized Multi-tier Assistance, Training, and Computational Help (MATCH) for End User ACCESS to CI, G969889393
OpenAlex ID: W4414088309