Liquid–Metal-Induced Metal–Support Interactions for CO2 Hydrogenation

Abstract

Abstract Metal–support interaction (MSI) is central to numerous industrial heterogeneous catalytic processes yet its classical realization typically requires high-temperature treatment (typically >500 °C), which often induces metal sintering and excessive encapsulation. Herein, we demonstrate that metals in liquid state can enable MSI on reducible transition-metal oxides at room temperature and down to −41 °C. In an In/NiO model system, room-temperature contact with metallic In extracts lattice oxygen from NiO, generating oxygen-deficient interfacial Ni sites that enhance CO2 activation and further fundamentally alter the reaction pathway of CO2 hydrogenation. Instead of methane formation typically observed on Ni-based oxides, the liquid–metal-derived interface selectively promotes CO formation with over 99% selectivity and a 5-fold higher CO yield at 350 °C. Comparable behavior is observed across a range of liquid-metal/oxide combinations (In/[Fe2O3, Co3O4, CuO, ZnO], [Sn, Bi]/NiO), indicating that the effect is chemically transferable. The catalytic activity exceeds that of benchmark commercial catalysts and reported noble-metal-based catalysts. This liquid–metal-induced low-temperature MSI reveals a new regime of oxide–metal interfacial chemistry.