Interfacial engineering of Pd/ZrO2 catalysts by atomic layer depositing ZnO for pathway-switchable CO2 hydrogenation to methanol

The selective hydrogenation of CO 2 to methanol demands precise control of both catalyst architecture and reaction pathways. ​Here, we design an atomic layer deposition (ALD)-engineered Pd/ZnO/ZrO 2 ternary catalyst with atomic-scale ZnO interlayers to ​decouple and reconfigure active sites at dual interfaces (Pd-ZnO and ZnO-ZrO 2 ). ​This interfacial engineering drives a 7-fold enhancement in methanol space–time yield (0.584 vs. 0.084 g MeOH g cat −1 h −1 ) ​and switches the dominant reaction pathway from CO-mediated to formate-driven selectivity (methanol selectivity remarkably surges from 6 % to 64 %). ​Multimodal characterization and theoretical calculations reveal that ZnO interlayers ​orchestrate bifunctional cooperation: activating CO 2 /CO adsorption while suppressing CO/CH 4 formation through electronic effects. Long-term stability study uncovers a dynamic restructuring mechanism, where Pd-ZnO interfaces gradually evolve into PdZn β alloy phases under the reaction conditions. ​This work establishes ALD-mediated interface design as a generalizable strategy to manipulate reaction networks and methanol selectivity in catalytic CO 2 hydrogenation systems.