Non-Noble CoO _<i>x</i> /In ₂ O ₃ Catalyst with Record-Breaking Methanol Space-Time Yield via Electron-Channel-Directed Dual-Site Regulation

In this work, we report a noble-metal-free CoOx/In2O3 catalyst (0 < x < 1) with stable Co–O–In bonds synthesized via hydrothermal method, achieving a breakthrough methanol space-time yield of 0.67 gCH3OH.gcat–1·h–1 at 3 MPa (>300 h stability) and 0.91 gCH3OH.gcat–1·h–1 at 5 MPa─surpassing non-noble references (e.g., CoIn-BP-1:0.43 gCH3OH.gcat–1·h–1) and rivaling Pd/In2O3 (0.89 gCH3OH.gcat–1·h–1). XANES/EXAFS/XPS studies confirm Co–O–In bonds act as electron-transfer channels that dynamically regulate dual active sites: at optimal reduction temperature (340 °C), balanced Co0 sites (x = 0.95, for H2 dissociation) and oxygen vacancies (44%, for CO2 adsorption) synergistically accelerate methanol formation via the HCOO* → H3CO* pathway, while Co0 deficiency (x > 0.95) causes incomplete H2 dissociation and CO formation, and Co0 excess (x < 0.95) triggers CO2 over-reduction. In situ DRIFTS verifies rapid intermediate conversion under optimal conditions. The catalyst maintains high activity across industrially relevant pressures (3–5 MPa) and space velocities (18.000 mL·gcat–1·h–1), establishing a new paradigm for sustainable methanol synthesis.