Disclosing Support‐Size‐Dependent Effect on Ambient Light‐Driven Photothermal CO2 Hydrogenation over Nickel/Titanium Dioxide

Abstract The size of support in heterogeneous catalysts can strongly affect the catalytic property but is rarely explored in light‐driven catalysis. Herein, we demonstrate the size of TiO 2 support governs the selectivity in photothermal CO 2 hydrogenation by tuning the metal‐support interactions (MSI). Small‐size TiO 2 loading nickel (Ni/TiO 2 ‐25) with enhanced MSI promotes photo‐induced electrons of TiO 2 migrating to Ni nanoparticles, thus favoring the H 2 cleavage and accelerating the CH 4 formation (227.7 mmol g −1 h −1 ) under xenon light‐induced temperature of 360 °C. Conversely, Ni/TiO 2 ‐100 with large TiO 2 prefers yielding CO (94.2 mmol g −1 h −1 ) due to weak MSI, inefficient charge separation, and inadequate supply of activated hydrogen. Under ambient solar irradiation, Ni/TiO 2 ‐25 achieves the optimized CH 4 rate (63.0 mmol g −1 h −1 ) with selectivity of 99.8 %, while Ni/TiO 2 ‐100 exhibits the CO selectivity of 90.0 % with rate of 30.0 mmol g −1 h −1 . This work offers a novel approach to tailoring light‐driven catalytic properties by support size effect.