The direct conversion of carbon dioxide (CO 2 ) into methanol (CH 3 OH) via low-temperature hydrogenation is crucial for recycling anthropogenic CO 2 emissions and producing fuels or high value chemicals. Nevertheless, it continues to be a great challenge due to the trade-off between selectivity and catalytic activity. For CO 2 hydrogenation, In 2 O 3 catalysts are known for their high CH 3 OH selectivity. Subsequent studies explored depositing metals on In 2 O 3 to enhance CO 2 conversion. Despite extensive research on metal (M) supported In 2 O 3 catalysts, the role of In−M alloys and M/In 2 O 3 interfaces in CO 2 activation and CH 3 OH selectivity remains unclear. In this work, we have examined the behavior of In/ Au(111) alloys and InO x /Au(111) inverse systems during CO 2 hydrogenation using synchrotron-based ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and catalytic tests in a batch reactor. Indium forms alloys with Au(111) after deposition. The In−Au(111) alloys display high reactivity toward CO 2 and can dissociate the molecule at room temperature to generate InO x nanostructures. At very low coverages of In (≤0.05 ML), the InO x nanostructures are not stable under CO 2 hydrogenation conditions and the active In−Au(111) alloys produces mainly CO and little methanol. An increase in indium coverage to 0.3 ML led to stable InO x nanostructures under CO 2 hydrogenation conditions. These InO x /Au(111) catalysts displayed a high selectivity (∼80%) toward CH 3 OH production and an activity for CO 2 conversion that was at least 10 times larger than that of plain In 2 O 3 or Cu(111) and Cu/ZnO(0001̅ ) benchmark catalysts. The results of AP-XPS show that InO x /Au(111) produces methanol via methoxy intermediates. Inverse oxide/metal catalysts containing InO x open up a possibility for improving CO 2 → CH 3 OH conversion in processes associated with the control of environmental pollution and the production of high value chemicals.
