Calcination Atmosphere-Engineered Cu/SiO2 Catalysts for Efficient Hydrogenation of Dimethyl Succinate to 1,4-Butanediol
The catalytic hydrogenation of biomass-derived dimethyl succinate (DMS) to 1,4-butanediol (BDO) is a pivotal route for producing high-value C4 chemicals in green chemistry. Cu/SiO2 catalysts are known for high selectivity in hydrogenating ester groups, with performance correlated to copper species microstructure. Although calcination critically defines this active structure, systematic influence of calcination atmosphere remains underexplored. Here, Cu/SiO2 catalysts were prepared via urea-assisted hydrothermal method and calcined under different atmospheres to elucidate effects on physicochemical properties and hydrogenation performance. Comprehensive characterization (N2 physisorption, FT-IR, H2-TPR, XRD, TEM, N2O pulse chemisorption, XPS, NH3-TPD) revealed that calcination atmosphere profoundly alters metal-support interaction, regulating dispersion and chemical state of copper species. Specifically, air calcination promoted stronger metal-support interaction, enhancing copper dispersion and increasing proportion of key active Cu+ species. Consequently, air-calcined catalyst achieved 92.37% DMS conversion and 64.15% BDO yield under optimized conditions (210 °C, 5.0 MPa, WHSV 0.6 h−1, H2/DMS molar ratio 100). This work underscores calcination atmosphere engineering as potent strategy for optimizing metal-support interactions in heterogeneous catalysts for efficient hydrogenation.