Heteronuclear interactions of Pd-M (M = Ni, Cu, Fe, In) bimetallic on hollow dodecahedron nickel cobalt oxide for enhanced low-temperature CO2 hydrogenation to formate

Amidst the global energy crisis and escalating CO₂ levels, developing efficient catalysts for converting CO₂ into sustainable energy sources is paramount. Here, we focus on Pd-M (M = Ni, Cu, Fe, In) bimetallic catalysts supported on hollow dodecahedron nickel cobalt oxide (h-NCO) for low-temperature CO₂ hydrogenation to formate. The catalytic evaluation of Pd_xM_y/h-NCO samples emphasized formate production, demonstrating significant enhancement from heteronuclear interactions between Pd and secondary metal species. Notably, Pd₈Ni₂/h-NCO achieved the highest formate production rate (187.07 mol_formate mol_Pd⁻¹h⁻¹) at relatively low temperatures (333 K). Experimental and density functional theory calculations unveiled that heteronuclear interactions induced charge polarization, reducing the reaction energy and facilitating CO₂ hydrogenation to formate. Additionally, the unique hollow dodecahedron NCO structure offered a substantial surface area and facilitated the effective dispersion of metal species, contributing to the enhanced catalytic performance. This work highlights the significance of heteronuclear interactions in bimetallic catalysts for CO₂ conversion, offering insights for catalyst system advancement.