A catalytic sites contiguity study on atomically‐dispersed <scp>ZnO</scp>‐Cu/<scp>SiO₂</scp> catalysts to improve methanol formation from <scp>CO₂</scp> hydrogenation

Abstract Cu‐ZnO‐based catalysts are commonly used in research on catalytic carbon dioxide (CO 2 ) hydrogenation for methanol (MeOH) synthesis. This work studied the catalytic sites contiguity, for example, the surface orientation or arrangement of the CO 2 and H 2 activating sites and their capability to facilitate the interaction between the adsorbed species, and its effects on the catalytic performance of MeOH formation. Cu/SiO 2 precursor was prepared by impregnating copper nitrate solution on a commercial SiO 2 gel. Controlling the exposure time and cycle numbers in atomic layer deposition (ALD), atomic‐level dispersion of ZnO (ADZn) was formed on the uncalcined and calcined Cu/SiO 2 precursors as well as on the SiO 2 gel. Characterizations allowed for identification of Cu + –Cu 0 and ADZn 2+ –Cu + /Cu 0 sites contiguity on the reduced catalyst surface. Catalytic performance tests showed that the ALD ZnO‐Cu/SiO 2 ‐C catalyst facilitated the MeOH space–time yield to 33.1 g/(kg catal ∙ h) at 240°C, three times the yield of its Cu‐only counterpart. The property–performance correlation indicated that two types of ZnO–Cu sites contiguity were responsible for MeOH and CO formation from CO 2 hydrogenation with the ADZn 2+ –Cu + /Cu 0 favouring more MeOH formation. The various contiguity of ADZn 2+ –Cu + /Cu 0 sites also influence the MeOH formation from CO 2 hydrogenation.