The Role of Dual-Interfaces on Structural Reconstruction of Cobalt–Zinc–Indium Catalysts for CO₂ Hydrogenation

Surface reconstruction of heterogeneous catalysts plays a critical role in determining their catalytic performance, yet controlling dynamic structural evolution remains challenging. Reconstructions are typically focused on alterations of the metal–support interactions. Herein, we reveal a dual–interface synergistic modulation strategy by introducing Co-ZnOx interfaces to stabilize Co-In2O3–x active sites in cobalt–indium catalysts for CO2 hydrogenation. Through in situ XRD, quasi-in situ XPS, and DFT simulations, it was demonstrated that this way protected the Co-In2O3–x interfaces from structural transformations to Co3InC0.75 and CoIn2, and oxygen vacancies in the support regulated the uniform distribution of dual-interface, synergistically enhancing CO2 activation and stabilizing the key intermediate HCOO*. At 280 °C, the optimized CoZnIn-P catalyst achieves a methanol space-time yield of 0.92 gmethanol gcatalyst–1 h–1, outperforming previously reported catalysts. This work provides a paradigm for designing multicomponent catalysts with controlled reconstruction dynamics, emphasizing the pivotal role of interface engineering in methanol synthesis.