Synergistic Cu–Zr and Cu–Mn Dual-Interfaces Boost CO 2 Hydrogenation to Methanol

Designing highly active and stable Cu-based catalysts for CO2 hydrogenation to methanol is challenging due to an insufficient understanding of the critical role of interfacial sites. In this work, we construct a high-performance CuZrMn catalyst with abundant Cu-Zr/Cu-Mn dual interfaces. The optimized CZM-3 catalyst exhibits a CO2 conversion of 23.9% and a high methanol space-time yield of 857 g kgcat-1 h-1 under conditions of 4.5 MPa and 260 °C. By integrating in situ DRIFTS, TPSR-MS, and transient pulse experiments, we reveal a synergistic dual-channel mechanism involving *HOCO/*CO and *HCOO intermediates: Cu-Zr interfaces stabilize and hydrogenate *HCOO to methanol, while Cu-Mn interfaces promote CO2 activation, generating substantial *HOCO/*CO species. This synergy ensures efficient CO2 activation and high methanol productivity. This work provides a molecular-level understanding of interfacial synergy and establishes a design principle for high-performance CO2 hydrogenation catalysts.