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Catalytic upgrading of CO₂ to value-added chemicals is an important challenge within the chemical sciences. Of particular interest are catalysts which are both active and selective for the hydrogenation of CO₂ to methanol. PdZn alloy nanoparticles supported on TiO₂ via a solvent-free chemical vapour impregnation method are shown to be effective for this reaction. This synthesis technique is shown to minimise surface contaminants, which are detrimental to catalyst activity. The effect of reductive heat treatments on both structural properties of PdZn/TiO₂ catalysts and rates of catalytic CO₂ hydrogenation are investigated. PdZn nanoparticles formed upon reduction showed high stability towards particle sintering at high reduction temperature with average diameter of 3–6 nm to give 1710 mmol kg⁻¹ h of methanol. Reductive treatment at high temperature results in the formation of ZnTiO₃ as well as PdZn …