Electronic modulation of InNi₃C_0.5/Fe₃O₄ by support precursor toward efficient CO₂ hydrogenation to methanol

Carbon neutrality is spurring worldwide impetus on the exploration of CO₂ hydrogenation to methanol, but groundbreaking catalyst presents a grand challenge. An outstanding InNi₃C_0.5/Fe₃O₄ catalyst is tailored by finely tuning the electronic metal-support interaction (EMSI) that is controlled by Fe₃O₄ precursor. The one using Fe₃O₄-N (from ferric nitrate) stands out against the ones using Fe₃O₄-A (ferrous acetate) and Fe₃O₄-C (ferric chloride), achieving a turnover frequency (421.6 h⁻¹) 2.3–3.1 times as high as that of the two others. There is a correlation between the oxygen deficiency of Fe₃O₄ and the EMSI-governed activity. The EMSI effect is enhanced substantially by the highly oxygen-deficient Fe₃O₄-N. Enhanced EMSI makes InNi₃C_0.5 electron-enriched and thus enables CO₂ to be dissociated easily. The InNi₃C_0.5/Fe₃O₄-N achieves a high methanol space time yield of 2.60 g_MeOH g_cat⁻¹ h⁻¹ with 92.0% methanol selectivity at 325 °C and 6.0 MPa. This catalyst is also highly anti-sintering and anti-sulfur poisoning.