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

作　　者：WANG Tingting WANG Jia XI Yongjie HU Bin LI Fuwei 

机构地区：[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

出　　处：《Chemical Research in Chinese Universities》2024年第1期55-63,共9页高等学校化学研究（英文版）

基　　金：the National Key R&D Program of China(No.2022YFA1504601);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);the Key Research Program of Frontier Science of CAS(No.QYZDJSSW-SLH051).

摘　　要：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.

关 键 词：Furfuryl alcohol Hydrogenation Dual-atom catalyst Density functional theory(DFT)calculation 

分 类 号：O64[理学—物理化学]