Hybrid MOF Template‐Directed Construction of Hollow‐Structured In2O3@ZrO2 Heterostructure for Enhancing Hydrogenation of CO2 to Methanol

Direct hydrogenation of CO2 to methanol using green hydrogen has emerged as a promising method for carbon neutrality, but qualifying catalysts represent a grand challenge. In2O3/ZrO2 catalyst has been extensively applied in methanol synthesis due to its superior activity; however, the electronic effect by strong oxides‐support interactions between In2O3 and ZrO2 at the In2O3/ZrO2 interface is poorly understood. In this work, abundant In2O3/ZrO2 heterointerfaces are engineered in a hollow‐structured In2O3@ZrO2 heterostructure through a facile pyrolysis of a hybrid metal–organic framework precursor MIL‐68@UiO‐66. Owing to well‐defined In2O3/ZrO2 heterointerfaces, the resultant In2O3@ZrO2 exhibits superior activity and stability toward CO2 hydrogenation to methanol, which can afford a high methanol selectivity of 84.6% at a conversion of 10.4% at 290 °C, and 3.0 MPa with a methanol space‐time yield of up to 0.29 gMeOH gcat−1 h−1. Extensive characterization demonstrates that there is a strong correlation between the strong electronic In2O3–ZrO2 interaction and catalytic selectivity. At In2O3/ZrO2 heterointerfaces, the electron tends to transfer from ZrO2 to In2O3 surface, which facilitates H2 dissociation and the hydrogenation of formate (HCOO*) and methoxy (CH3O*) species to methanol. This study provides an insight into the In2O3‐based catalysts and offers appealing opportunities for developing heterostructured CO2 hydrogenation catalysts with excellent activity.