Tuning the CO₂ hydrogenation activity and selectivity of TiO₂ nanorods supported Rh catalyst via secondary‐metals addition

Secondary‐metals promotion is key to tune the CO 2 hydrogenation performance of Rh‐based catalyst. We describe the addition of Cu or Co in TiO 2 nanorods supported Rh catalyst (viz., RhM x /TiO 2 ), showing significant impact on the CO 2 hydrogenation activity and productivity. Cu addition can promote the partial hydrogenation to alcohols (methanol and ethanol), whereas Co led to the deep hydrogenation to alkanes (CH 4 , C 2 H 6 ). Comparative time‐resolved in situ DRIFTS studies with H 2 /D 2 isotopic exchange further reveal that both surface adsorbed CO* and formates could be the key reaction intermediates during the CO 2 hydrogenation over RhM x /TiO 2 (especially the RhCu 2.5 /TiO 2 ), in which the interaction strength of CO* regulated by secondary‐metals addition was key to tune the reaction pathways and productivity. The findings suggested that rational design of active metal sites, for example the synergy between Rh and secondary‐metals, is highly needed to promote the CO insertion and CC coupling to produce ethanol.