• • Air-calcined Cu/SiO2 (Cu/SiO2-A) achieved 92.37% DMS conversion and 64.15% BDO yield at 210 °C, 5.0 MPa, WHSV 0.6 h−1, H2/DMS molar ratio 100, demonstrating superior performance for industrial BDO production.
• • Air calcination induced the strongest metal-support interaction, leading to highest copper dispersion and largest population of stabilized Cu+ species, which are critical for hydrogen activation and carbonyl adsorption.
• • The catalyst exhibited abundant surface acidity, promoting C=O polarization and synergistic metal-acid cooperation, essential for selective hydrogenation to BDO.
• • Calcination atmosphere engineering is a potent, cost-effective strategy to tune Cu/SiO2 catalysts, offering a scalable approach to optimize metal-support interactions for efficient hydrogenation processes.
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