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

作者：Jiandong Ling, Yuwei Hu, Xinyu Ma, Ao Zhang, Shijian Zhou, Yan Kong · 发表于：Industrial & Engineering Chemistry Research · 年份：2025 · DOI：10.1021/acs.iecr.5c03344 · 被引用次数：3 · 研究领域：Catalysts for Methane Reforming、Catalytic Processes in Materials Science、CO2 Reduction Techniques and Catalysts

In this work, we report a noble-metal-free CoO x /In 2 O 3 catalyst (0 < x < 1) with stable Co–O–In bonds synthesized via hydrothermal method, achieving a breakthrough methanol space-time yield of 0.67 g CH 3 OH .g cat –1 ·h –1 at 3 MPa (>300 h stability) and 0.91 g CH 3 OH .g cat –1 ·h –1 at 5 MPa─surpassing non-noble references (e.g., CoIn-BP-1:0.43 g CH 3 OH .g cat –1 ·h –1 ) and rivaling Pd/In 2 O 3 (0.89 g CH 3 OH .g cat –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 Co 0 sites ( x = 0.95, for H 2 dissociation) and oxygen vacancies (44%, for CO 2 adsorption) synergistically accelerate methanol formation via the HCOO* → H 3 CO* pathway, while Co 0 deficiency ( x > 0.95) causes incomplete H 2 dissociation and CO formation, and Co 0 excess ( x < 0.95) triggers CO 2 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·g cat –1 ·h –1 ), establishing a new paradigm for sustainable methanol synthesis.