Shapeshifting Nanocatalyst for CO₂ Conversion

The conversion of CO₂ into high-value chemicals through a photoreduction reaction in water is a promising route to reduce the dependence on fossil fuels. Enhancing selectivity toward hydrocarbons or alcohols can be achieved by Ag-Cu alloys. However, the stabilized surface state created by Ag-Cu interactions is still poorly understood. In this work, multi-modal in situ X-ray experiments reveals underlying mechanisms and the evolution of Ag-Cu nanoparticles under CO₂ reduction reaction (CO₂RR) conditions. Both morphological and chemical changes of Ag and Cu species induced by diffusion mechanics are tracked during nanocatalyst operation. The initial spheroid Ag-Cu nanoparticles are composed of a Cu-rich shell and Ag-rich core. The reduction treatment promotes Ag migration toward the surface. During photocatalytic CO₂ reduction reaction, Cu atoms migrate back to the surface, forming Ag-Cu-O species. The study observes the surface oxidation of Cu(0) to Cu⁺ and the presence of Ag at the sub-surface region. Furthermore, nanoparticles change their shape, decreasing their specific surface area, driven by Cu diffusion during the CO₂ photoreduction reaction. The results provide invaluable insights into the dynamic restructuring of the catalyst under reaction conditions and into the active species responsible for CO₂ conversion.