Single atoms of indium on hafnia enable superior CO2-based methanol synthesis.

Indium-zirconium oxides rank among the most selective and stable catalysts for CO2 hydrogenation to methanol. Yet, despite extensive research, the mechanistic origin of the exceptional role of monoclinic zirconia remains unresolved and continues to set the benchmark in the field. Here we show that monoclinic hafnia, a wide-bandgap oxide rarely explored in catalysis, can outperform this benchmark. Nanostructured indium-hafnium oxides synthesized via flame spray pyrolysis achieve up to 70% higher indium-specific methanol productivity than indium-zirconium oxides, with the largest gains observed for single atoms of indium. Experimental and theoretical analyses reveal that a combination of stable monoclinic support surfaces, flexible chemical potential of indium single atoms and the presence of a cooperative hydride-proton reservoir collectively enhance CO2 activation and intermediate hydrogenation. Crucially, the precise control of surface hydroxylation is required. These findings establish a new benchmark for green methanol synthesis and provide generalizable design principles for next-generation oxide supports in single-atom catalysis.