For advancing electrochemical CO2 reduction, it is crucial to design efficient catalysts with high activity and selectivity for a particular product. Engineering structure at the atomic level by controlled synthesis strategies can effectively tune the product selectivity by optimizing the binding energy of the key intermediates involved in the reaction. Here, we demonstrate a morphology-controlled (spherical and cubic) synthesis route for PdCu3-ordered intermetallic nanoparticles without using any external strong reducing agent. Structurally ordered cubic PdCu3 with predominantly (100) facets exhibits higher selectivity for ethanol (Faradaic efficiency (FE): 44.2%) and n-propanol (FE: 17.0%; formation rate: 39.99 mu mol h(-1) cm(-2) mg(-1)) from CO2 compared to spherical PdCu3 with (111) facets (ethanol FE: 32.7%; n-propanol FE: 9.46%). Incorporating the electrode-electrolyte interactions, the ab initio calculations highlight the key C-C coupling step enabling the formation of C2+ products. The active Pd sites, depending on their presence and absence on the surface of PdCu3 (100) facets, significantly influence the C-C coupling barrier by controlling CO* and OCCOH* binding. In contrast, this barrier remains unaffected on (111) facets due to the Pd arrangement. This further establishes the important role of alloying Pd with Cu in rationally tailored surfaces for higher alcohol synthesis.

Foreign