Silica-Supported PdGa Nanoparticles: Metal Synergy for Highly Active and Selective CO₂-to-CH₃OH Hydrogenation

The direct conversion of CO₂ to CH₃OH represents an appealing strategy for the mitigation of anthropogenic CO₂ emissions. Here, we report that small, narrowly distributed alloyed PdGa nanoparticles, prepared via surface organometallic chemistry from silica-supported Ga^III isolated sites, selectively catalyze the hydrogenation of CO₂ to CH₃OH. At 230 °C and 25 bar, high activity (22.3 mol_MeOH mol_Pd ^-1 h^-1) and selectivity for CH₃OH/DME (81%) are observed, while the corresponding silica-supported Pd nanoparticles show low activity and selectivity. X-ray absorption spectroscopy (XAS), IR, NMR, and scanning transmission electron microscopy-energy-dispersive X-ray provide evidence for alloying in the as-synthesized material. In situ XAS reveals that there is a dynamic dealloying/realloying process, through Ga redox, while operando diffuse reflectance infrared Fourier transform spectroscopy demonstrates that, while both methoxy and formate species are observed in reaction conditions, the relative concentrations are inversely proportional, as the chemical potential of the gas phase is modulated. High CH₃OH selectivities, across a broad range of conversions, are observed, showing that CO formation is suppressed for this catalyst, in contrast to reported Pd catalysts.