Selective electrochemical methanation of carbon dioxide using a sulphide derived CuZn catalyst

•Synthesized sulphide derived CuZn nanoparticles for advanced CO2 hydrogenation.•Achieved 76 ± 3 % CH4 selectivity at −0.98 V vs RHE in CO2-saturated 0.1 M KHCO3.•In situ generated partially reduced CuS species is crucial in determining product selectivity. Efficient catalysts facilitate the electrochemical reduction of CO2, enabling its conversion into fuels or chemical feedstocks through proton coupled electron transfer processes. Among these catalysts, Cu-based ones stand out for their unique ability to produce hydrocarbon products with high faradaic efficiencies. This study focuses on the use of sulphide-derived (SD)-CuxZny nanoparticle catalysts, which have been found to exhibit enhanced methane selectivity during CO2 reduction in an H-Cell with 0.10 M KHCO3 as the electrolyte. The composition of the catalysts plays a crucial role in determining their catalytic behavior. At an optimal Cu/Zn ratio of 1:1, the SD-CuZn catalyst demonstrates exceptional methane production, achieving a faradaic efficiency of 76 ± 3 % at a potential of −0.98 V vs RHE. Moreover, a partial current density of −4.5 mA cm−2 was achieved at a more negative potential of −1.09 V vs RHE. Ex situ characterization highlighted the significance of partially reduced CuS species in influencing the selectivity of hydrogenated carbon products. When CO2 reduction was performed in a flow cell equipped with a gas diffusion electrode with 1.0 M KHCO3 or 1.0 M KOH electrolytes in both anodic and cathodic compartments, the current density increased due to the enhanced mass transport rate. However, the altered conditions lead to a shift in selectivity, favoring carbon monoxide over methane. It is important to note that insights garnered from H-Cell experiments may not be directly extrapolated to flow cell setups. [Display omitted]