Au on in 2 O 3‐x /TiO 2 (110): A Highly Active and Selective Catalyst for the Conversion of CO 2 to Methanol

Methanol production by carbon dioxide hydrogenation is a promising route for supplying industrial fuel demands, but achieving high methanol selectivity remains challenging due to competing favorable reactions. Here, we investigate model Au/In 2 O 3‐x /TiO 2 (110) catalysts to elucidate the roles of metal‐oxide and oxide‐oxide interactions in CO 2 conversion. Using a combination of ambient‐pressure X‐ray photoelectron spectroscopy (AP‐XPS), temperature‐programmed desorption (TPD), and catalytic measurements, we show that small coverages of Au (<0.15 monolayer) dispersed on In 2 O 3‐x /TiO 2 (110) significantly enhance both CO 2 and H 2 activation at low temperatures (300–400 K). The Au/In 2 O 3‐x /TiO 2 (110) systems exhibit superior catalytic performance, with the highest methanol selectivity (∼80–85%) and increased conversion rates compared to In 2 O 3‐x /TiO 2 (110) and Au/TiO 2 (110). Spectroscopic results showed that Au nanoparticles promote the formation of oxygen vacancies and enhance CO 2 activation, without inducing the dissociation of methoxy and methanol. Reaction studies support a formate‐mediated reaction pathway, distinct from the CO‐mediated route observed on Au/TiO 2 catalysts that leads to very low methanol selectivity. Oxide‐oxide interactions stabilized the partially reduced In 2 O 3‐x , and prevented Au‐In alloy formation under CO 2 +H 2 conditions, preserving methanol selectivity. These findings highlight the importance of synergistic metal↔oxide‐oxide interactions when designing efficient catalysts for selective hydrogenation of CO 2 to methanol while minimizing the content of Au and In 2 O 3‐x .