Payra, S.Devaraj, N.Tarafder, K.Roy, S.2026-02-042022ACS Applied Energy Materials, 2022, 5, 4, pp. 4945-4955https://doi.org/10.1021/acsaem.2c00330https://idr.nitk.ac.in/handle/123456789/22594Designing suitable catalysts for efficient and selective electrocatalytic reduction of CO<inf>2</inf> is a need of the hour, and in this regard, the well-defined, highly dispersed active metal centers can be a trendsetting research endeavor toward CO<inf>2</inf> electroreduction due to the maximum atom utilization and unique electronic structure. This study describes the synthesis and electrocatalytic CO<inf>2</inf> reduction activity of atomistically dispersed Cu/C and Ni/C and the intermetallic nano-alloy Cu<inf>0.85</inf> Ni<inf>0.15</inf> /C. The catalysts were synthesized from the corresponding MOF precursors. The successful synthesis of the monometallic and intermetallic nano-alloys was established from structural, surface morphological, and electronic properties. Cu<inf>0.85</inf> Ni<inf>0.15</inf> /C exhibited an unprecedented electrocatalytic reduction of CO<inf>2</inf> with a high selectivity and high faradaic efficiency toward CH<inf>3</inf> OH. The kinetic studies and the first-principles calculations elucidated the intricate mechanism and the superior activity of electrocatalytic reduction of CO<inf>2</inf> over the intermetallic Cu<inf>0.85</inf> Ni<inf>0.15</inf> /C catalyst. © 2022 American Chemical Society. All rights reserved.CalculationsElectrolytic reductionElectronic propertiesElectronic structureMetal-Organic FrameworksMetalsReaction kineticsCO reductionElectrocatalyticElectrocatalytic CO2reductionElectrocatalytic reductionIntermetallic nano-alloyMetalorganic frameworks (MOFs)Nano-alloysProduct selectivitiesReaction mechanism]+ catalystIntermetallics