Hybrid MOF Template-Directed Construction of Hollow-Structured In O @ZrO Heterostructure for Enhancing Hydrogenation of CO to Methanol.

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