Oxygen-deficient metal oxides supported nano-intermetallic InNi₃C_0.5 toward efficient CO₂ hydrogenation to methanol

Direct CO₂ hydrogenation to methanol using renewable energy–generated hydrogen is attracting intensive attention, but qualifying catalysts represents a grand challenge. Pure-/multi-metallic systems used for this task usually have low catalytic activity. Here, we tailored a highly active and selective InNi₃C_0.5/ZrO₂ catalyst by tuning the performance-relevant electronic metal-support interaction (EMSI), which is tightly linked with the ZrO₂ type–dependent oxygen deficiency. Highly oxygen-deficient monoclinic-ZrO₂ support imparts high electron density to InNi₃C_0.5 because of the considerably enhanced EMSI, thereby enabling InNi₃C_0.5/monoclinic-ZrO₂ with an intrinsic activity three or two times as high as that of InNi₃C_0.5/amorphous-ZrO₂ or InNi₃C_0.5/tetragonal-ZrO₂. The EMSI-governed catalysis observed in the InNi₃C_0.5/ZrO₂ system is extendable to other oxygen-deficient metal oxides, in particular InNi₃C_0.5/Fe₃O₄, achieving 25.7% CO₂ conversion with 90.2% methanol selectivity at 325°C, 6.0 MPa, 36,000 ml g_cat⁻¹ hour⁻¹, and H₂/CO₂ = 10:1. This affordable catalyst is stable for at least 500 hours and is also highly resistant to sulfur poisoning.