Controlled syngas production by electrocatalytic CO₂ reduction on formulated Au₂₅(SR)₁₈ and PtAu₂₄(SR)₁₈ nanoclusters

Syngas, a gaseous mixture of CO and H₂, is a critical industrial feedstock for producing bulk chemicals and synthetic fuels, and its production via direct CO₂ electroreduction in aqueous media constitutes an important step toward carbon-negative technologies. Herein, we report controlled syngas production with various H₂/CO ratios via the electrochemical CO₂ reduction reaction (CO₂RR) on specifically formulated Au₂₅ and PtAu₂₄ nanoclusters (NCs) with core-atom-controlled selectivities. While CO was predominantly produced from the CO₂RR on the Au NCs, H₂ production was favored on the PtAu₂₄ NCs. Density functional theory calculations of the free energy profiles for the CO₂RR and hydrogen evolution reaction (HER) indicated that the reaction energy for the conversion of CO₂ to CO was much lower than that for the HER on the Au₂₅ NC. In contrast, the energy profiles calculated for the HER indicated that the PtAu₂₄ NCs have nearly thermoneutral binding properties; thus, H₂ production is favored over CO formation. Based on the distinctly different catalytic selectivities of Au₂₅ and PtAu₂₄ NCs, controlled syngas production with H₂/CO ratios of 1 to 4 was demonstrated at a constant applied potential by simply mixing the Au₂₅ and PtAu₂₄ NCs based on their intrinsic catalytic activities for the production of CO and H₂.