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

Abstract

Abstract Direct hydrogenation of CO 2 to methanol using green hydrogen has emerged as a promising method for carbon neutrality, but qualifying catalysts represent a grand challenge. In 2 O 3 /ZrO 2 catalyst has been extensively applied in methanol synthesis due to its superior activity; however, the electronic effect by strong oxides‐support interactions between In 2 O 3 and ZrO 2 at the In 2 O 3 /ZrO 2 interface is poorly understood. In this work, abundant In 2 O 3 /ZrO 2 heterointerfaces are engineered in a hollow‐structured In 2 O 3 @ZrO 2 heterostructure through a facile pyrolysis of a hybrid metal–organic framework precursor MIL‐68@UiO‐66. Owing to well‐defined In 2 O 3 /ZrO 2 heterointerfaces, the resultant In 2 O 3 @ZrO 2 exhibits superior activity and stability toward CO 2 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 g MeOH g cat −1 h −1 . Extensive characterization demonstrates that there is a strong correlation between the strong electronic In 2 O 3 –ZrO 2 interaction and catalytic selectivity. At In 2 O 3 /ZrO 2 heterointerfaces, the electron tends to transfer from ZrO 2 to In 2 O 3 surface, which facilitates H 2 dissociation and the hydrogenation of formate (HCOO*) and methoxy (CH 3 O*) species to methanol. This study provides an insight into the In 2 O 3 ‐based catalysts and offers appealing opportunities for developing heterostructured CO 2 hydrogenation catalysts with excellent activity.