Dengfeng Dai,Chao Feng,Minmin Wang,Qingzhou Du,Dandan Liu,Yuan Pan,Yunqi Liu
Biomass-based chemicals as a renewable alternative to petroleum-based chemicals are of great significance. The conversion of biomass-based furfuryl alcohol to pentanediol, including 1,5-pentanediol and 1,2-pentanediol, is explored over a series of bifunctional Cu/MFI catalysts in a continuous-flow reactor. These catalysts are synthesized by supporting copper nanoparticles on MFI zeolites with varying molar ratios of SiO2/Al2O3. Among them, the Z60-10Cu catalyst containing balanced Cu0–Cu+ and Brønsted acid sites exhibits excellent performance, and a high furfuryl alcohol conversion of 99.5% and selectivity of 85.2% for 1,5-pentanediol (69.2%) and 1,2-pentanediol (16.0%) could be achieved (hydrogen pressure: 2.5 MPa) at 160 °C. The experimental results and the results obtained using the DFT technique revealed that the high catalytic activity realized during the processes of ring-opening and hydrogenation could be attributed to the synergistic effect between the Cu species and Brønsted acid sites. The Brønsted acid sites on the Si(OH)Al groups significantly affect the ring-opening process of furfuryl alcohol. The methoxy group on furfuryl alcohol adsorbs on the Cu+ sites, and the hydrogenation saturation of the ring-opening intermediate is realized under the influence of the activated hydrogen units on the Cu0 sites. The results reported herein could help promote the continuous production of high value-added pentanediol from biomass-based raw materials in the presence of non-noble metal catalysts. An economical and feasible path for the transformation of biomass resources into high value-added fine chemicals could also be developed.
Cu/ZnO/Al2O3 (CZA) catalyst remains the benchmark for methanol synthesis but suffers from active-site sintering and insufficient CO2 activation. In this study, we proposed a dual strategy to enhance and regulate the active sites of CZA: hydrothermal treatment induces Cu–Zn coordination to create high-density Cu–ZnO1–x interfaces that promote CO2 conversion, while subsequent La doping regulates Cu0/Cu+ species to favor methanol selectivity. As a result, the maximum space-time yield (STY) of methanol over the designed CZA&5%La-LRCP (prepared by the ligand-regulated coprecipitation method) catalyst improved significantly from 283.0 gMeOH·kgcat–1·h–1 for the conventional coprecipitation-prepared CZA to 400.4 gMeOH·kgcat–1·h–1 under the tested conditions, surpassing most literature reports on La-doped Cu-based catalysts. Comprehensive characterizations and kinetic studies revealed that high-density Cu–ZnO1–x interfaces enhance CO2 adsorption and activation, while uniformly distributed electron-enriched Cu0/Cu+ species promote H2 dissociation and facilitate formate formation and transformation, together establishing an efficient pathway for CO2 activation and hydrogenation. This study demonstrates a promising strategy for the rational design of CO2hydrogenation catalysts through the synergistic modulation of interfacial structure and electronic properties.
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