Xing Gao,Suyang Tian,Yunyun Jin,Xiaoyue Wan,Chunmei Zhou,Rizhi Chen,Yihu Dai,Yanhui Yang
Highly selective liquid-phase hydrogenation of furfural was efficiently catalyzed by PtFe alloy nanoparticles supported on CeO2. An initial reaction rate at ∼1500 h–1, a near 100% selectivity toward furfuryl alcohol (FA), and a satisfactory recycling stability were achieved on Pt3Fe/CeO2 catalyst. Based on the well-established knowledge of the modification effects of Fe additives on the geometric and electronic properties of Pt sites, this work further demonstrated that the bimetallic PtFe sites could promote H2-activated dissociation for accelerating the hydrogenation reaction in comparison with the monometallic Pt/CeO2 catalyst. The results of isotopic and kinetic experiments to study the solvent effects elucidated that the reaction pathway of catalytic transfer hydrogenation with isopropanol as the hydrogen donor could be ruled out. The results also suggested that isopropanol-involved hydrogen exchange processes with hydrogen and FA could easily occur during the reactions. Furthermore, the furfural hydrogenation could be significantly affected by the solvent intermolecular hydrogen bonding interactions.
Xin Jin,Qi Xia,Jie Ding,Jian Shen,Chaohe Yang,Raghunath V. Chaudhari
Rational control of catalytic selectivity still remains a grand challenge in the field of biomass conversion to value-added chemicals. In this paper, we used PtFe catalyst as an example to understand fundamentals for lattice strain, electronic reconfiguration, reaction kinetics and catalytic selectivity for aqueous conversion biopolyols. Structurally strained face centered tetragonal (fct) PtFe crystals were synthesized and it was confirmed that such unique PtFe nanostructures display intriguing electronic coupling effect and partial charge distribution, as revealed by surface characterization using TEM, XRD and XPS, as well as DFT calculation. Bimetallic PtFe-fct catalysts exhibit a remarkable catalytic activity (TOF: 24 312 h–1 at 65 °C and 1 MPa O2), enhanced selectivity (tartronic acid: 54%) and improved stability for aqueous phase oxidation of biopolyols, in comparison with conventional fcc morphology. Kinetic modeling further indicates that relatively lower oxidation barrier and restrained decarboxylation reaction are key for improving selectivity on PtFe-fct catalysts.
危险品化学品经营许可证（带存储）