Chemical Research in Chinese Universities ›› 2024, Vol. 40 ›› Issue (1): 55-63.doi: 10.1007/s40242-024-3243-1

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Predication of Selective Ring-opening Hydrogenolysis for Furfuryl Alcohol to Produce Pentanediol over Dual-atom Catalysts

WANG Tingting1,2, WANG Jia1, XI Yongjie1, HU Bin1, LI Fuwei1,2   

  1. 1. State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, P. R. China 2. University of Chinese Academy of Sciences, Beijing 100049, P. R. China
  • Received:2023-10-31 Online:2024-02-01 Published:2024-01-24
  • Contact: XI Yongjie, HU Bin, LI Fuwei;;
  • Supported by:
    This work was supported by the National Key R&D Program of China (No. 2022YFA1504601), a Startup Program of the State Key Laboratory for Oxo Synthesis and Selective Oxidation of LICP, China (No. E0SX0184), the National Natural Science Foundation of China (Nos. 22102193, 21972151), and the Key Research Program of Frontier Science of CAS (No. QYZDJSSW-SLH051).

Abstract: Selective activation of C-O bond is of fundamental importance in the precise conversion of oxygenates into value-added compounds in an atom-economic and sustainable manner, and meanwhile, the structurally well-defined dual-atoms catalysts (DACs) have been scarcely investigated in this field. In this study, a series of transition metal DACs anchored on nitrogen-doped graphene (TM2/NC, TM=Pt, Ir, Rh, Pd, Ru, Co, Ni and Cu) was constructed to make a comprehensive investigation of their selectivity in the hydrogenative transformation of furfuryl alcohol (FAL), an important biomass platform molecule, to 1,2-pentanediol (1,2-PeD) via selective cleavage of furanic C5-O bond, by density functional theory (DFT) calculations and microkinetic modeling. We found that Ir2/NC demonstrated a high selectivity for the cleavage of furanic C5-O bond to produce 1,2-PeD, while the production of THFAL or 1,5-pentanediol (1,5-PeD) on other TM2/NC catalysts are more favorable. Furthermore, we found that the selective C-O bond cleavage of FAL furan ring is affected by the orbital overlap between the d-orbitals of the anchored metal atoms and the p-orbitals of the adsorbed C atom in FAL, suggesting that the selectivity of the C-O bond cleavage is inextricably related with the electronic property of the anchored metals.

Key words: Furfuryl alcohol, Hydrogenation, Dual-atom catalyst, Density functional theory (DFT) calculation