Pressure-induced Cu-ZnOx interfaces activate formate pathway for selective methanol synthesis from captured CO2

Solid-phase DFMs yielded 0.65 mmol g −1 CH 3 OH in ICCU at 300 °C and 30 bar. • Ga promoted methanol production by optimizing the Cu-ZnO x interface. • Cu-ZnO x promoted CO 2 migration and activation for CH 3 OH synthesis. • DFT, AIMD, and DRIFTS revealed formate hydrogenation pathways. • Cu-ZnO x interfaces enable ZnO to Cu electron transfer, lowering barriers by 0.51 eV. The development of dual functional materials (DFMs) for cyclic CO 2 capture and hydrogenation is essential for converting diluted CO 2 into valuable C 1 products, yet remains challenging due to inherent trade-off between CO 2 conversion and CH 3 OH selectivity over catalysis center. Herein, we engineered a series of copper-based materials and for selective hydrogenation of CO 2 to CH 3 OH. The highly dispersed Cu-ZnO-Ga catalyst demonstrated exceptional methanol formation activity of 0.65 mmol g −1 at 300 °C and 30 bar in 1 h hydrogenation time. Through a quantitative investigation of coordination environments, we revealed that pressure-induced conditions promote Cu 0 nanoparticle migration toward ZnO x species, generating synergistic Cu 0 -Zn δ+ interfacial sites. These interfaces facilitated CO 2 activation via a deoxygenation pathway, while carbonates remain inert during hydrogenation. Combined in situ spectroscopy and theoretical calculations demonstrated that stable formate and methoxy intermediates on Cu 0 -ZnO x facilitated heterolytic C O scission and C H bonding, significantly lowering the energy barrier for activating captured CO 2 .