Lewis Acid Strength of Interfacial Metal Sites Drives CH3OH Selectivity and Formation Rates on Cu‐Based CO2 Hydrogenation Catalysts

CH3OH formation rates in CO2 hydrogenation on Cu‐based catalysts sensitively depend on the nature of the support and the presence of promoters. In this context, Cu nanoparticles supported on tailored supports (highly dispersed M on SiO2; M=Ti, Zr, Hf, Nb, Ta) were prepared via surface organometallic chemistry, and their catalytic performance was systematically investigated for CO2 hydrogenation to CH3OH. The presence of Lewis acid sites enhances CH3OH formation rate, likely originating from stabilization of formate and methoxy surface intermediates at the periphery of Cu nanoparticles, as evidenced by metrics of Lewis acid strength and detection of surface intermediates. The stabilization of surface intermediates depends on the strength of Lewis acid M sites, described by pyridine adsorption enthalpies and 13C chemical shifts of ‐OCH3 coordinated to M; these chemical shifts are demonstrated here to be a molecular descriptor for Lewis acid strength and reactivity in CO2 hydrogenation. Cu nanoparticles, dispersed on supports decorated with isolated group IV and V metal centers on SiO2, catalyze the selective hydrogenation of CO2 to CH3OH. The promotion of CH3OH formation rates and selectivity correlates with the Lewis acid strength of the group IV and V dopants, which stabilize surface intermediates at the periphery of Cu nanoparticles.