Oxygen-deficient metal oxides supported nano-intermetallic InNi(3)C(0.5) toward efficient CO(2) hydrogenation to methanol

Direct CO(2) 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 InNi(3)C(0.5)/ZrO(2) catalyst by tuning the performance-relevant electronic metal-support interaction (EMSI), which is tightly linked with the ZrO(2) type–dependent oxygen deficiency. Highly oxygen-deficient monoclinic-ZrO(2) support imparts high electron density to InNi(3)C(0.5) because of the considerably enhanced EMSI, thereby enabling InNi(3)C(0.5)/monoclinic-ZrO(2) with an intrinsic activity three or two times as high as that of InNi(3)C(0.5)/amorphous-ZrO(2) or InNi(3)C(0.5)/tetragonal-ZrO(2). The EMSI-governed catalysis observed in the InNi(3)C(0.5)/ZrO(2) system is extendable to other oxygen-deficient metal oxides, in particular InNi(3)C(0.5)/Fe(3)O(4), achieving 25.7% CO(2) conversion with 90.2% methanol selectivity at 325°C, 6.0 MPa, 36,000 ml g(cat)(−1) hour(−1), and H(2)/CO(2) = 10:1. This affordable catalyst is stable for at least 500 hours and is also highly resistant to sulfur poisoning.