Tailoring ZnO x Species Confined on ZrO2 Support for Enhanced CO Hydrogenation.

ZnZrO x is a promising oxide component for direct syngas conversion via oxide-zeolite bifunctional catalysis, while rational design of active centers within the composite oxide remains limited. In this study, through ab initio thermodynamics, molecular dynamics, and microkinetic modeling, we find that diverse subnanometer ZnO x species, including single-site, single-chain, and single-layer configurations, can form on active ZrO2 surfaces under the reaction conditions. These confined ZnO x species weaken CO adsorption but enhance heterolytic H2 dissociative adsorption, favoring continuous hydrogenation of CO to methanol over direct or H-assisted CO dissociation. For single-layer ZnO x structures, a double-chain film grows on a monoclinic ZrO2 (m-ZrO2) surface while a graphene-like film emerges on tetragonal ZrO2 (t-ZrO2). These single-layer ZnO x species exhibit higher methanol formation activity than their single-chain or single-site counterparts, which benefit from sufficient sites for adsorption of intermediates and a suitable space for bonding of H with C in CHO. Furthermore, the double-chain ZnO x film confined on m-ZrO2 exposes octahedral Znoct sites, which are more reactive than the triangular Zntri sites in the graphene-like ZnO x on t-ZrO2, despite both sites being nominally three-coordinate. These findings provide insights for the precise design of composite oxide/oxide catalysts through fine-tuning overlayer coverage and/or support surface properties.