La-Doped Cu/ZnO/Al ₂ O ₃ Catalysts with Cu–Zn Coordination: Boosting CO ₂ Hydrogenation to Methanol via High-Density Cu–ZnO _{1– <i>x</i>} Interfaces and Cu ⁰ /Cu ⁺ Regulation

Cu/ZnO/Al 2 O 3 (CZA) catalyst remains the benchmark for methanol synthesis but suffers from active-site sintering and insufficient CO 2 activation. In this study, we proposed a dual strategy to enhance and regulate the active sites of CZA: hydrothermal treatment induces Cu–Zn coordination to create high-density Cu–ZnO 1– x interfaces that promote CO 2 conversion, while subsequent La doping regulates Cu 0 /Cu + species to favor methanol selectivity. As a result, the maximum space-time yield (STY) of methanol over the designed CZA&5%La-LRCP (prepared by the ligand-regulated coprecipitation method) catalyst improved significantly from 283.0 g MeOH ·kg cat –1 ·h –1 for the conventional coprecipitation-prepared CZA to 400.4 g MeOH ·kg cat –1 ·h –1 under the tested conditions, surpassing most literature reports on La-doped Cu-based catalysts. Comprehensive characterizations and kinetic studies revealed that high-density Cu–ZnO 1– x interfaces enhance CO 2 adsorption and activation, while uniformly distributed electron-enriched Cu 0 /Cu + species promote H 2 dissociation and facilitate formate formation and transformation, together establishing an efficient pathway for CO 2 activation and hydrogenation. This study demonstrates a promising strategy for the rational design of CO 2 hydrogenation catalysts through the synergistic modulation of interfacial structure and electronic properties.