Mechanism studies of 5-HMF pyrolysis by quantum chemistry

【摘要】 The pyrolysis of 5-HMF was investigated using density functional theory methods at B3LYP/6-31 G++（d, p） level. Two possible pyrolytic pathways were proposed and full optimization of the energy gradient for the structures of reactants, products, intermediates and transition states of various reactions was implemented. The standard kinetic parameters in each reaction pathway were calculated and the formation and evolution mechanism of main pyrolysis products were analyzed. Bond dissociation energies calculation results show that the bond dissociation energy of CH₃—OH of 5-HMF is the lowest and the order of all kinds of bond dissociation energy is CH₃—OH<C—H<CH₃ OH—C_aromatic<CHO—C_aromatic<C_aromatic—H. In pathway（1）, the energy barrier of furfural is 322.8 kJ/mol, the energy barrier of 2-furfuryl alcohol is 375.4 kJ/mol; the energy barrier of furan-2,5-dicarbaldehyde is 496.1 kJ/mol; the energy barrier of 5-methyl furfural is 375.8 kJ/mol, and the energy barrier of 2-methyl furan is 375.8 kJ/mol. In pathway（2）, the activation energy required for open-loop with H₂O is higher.更多还原

【Abstract】 The pyrolysis of 5-HMF was investigated using density functional theory methods at B3LYP/6-31 G++（d, p） level. Two possible pyrolytic pathways were proposed and full optimization of the energy gradient for the structures of reactants, products, intermediates and transition states of various reactions was implemented. The standard kinetic parameters in each reaction pathway were calculated and the formation and evolution mechanism of main pyrolysis products were analyzed. Bond dissociation energies calculation results show that the bond dissociation energy of CH₃—OH of 5-HMF is the lowest and the order of all kinds of bond dissociation energy is CH₃—OH<C—H<CH₃ OH—C_aromatic<CHO—C_aromatic<C_aromatic—H. In pathway（1）, the energy barrier of furfural is 322.8 kJ/mol, the energy barrier of 2-furfuryl alcohol is 375.4 kJ/mol; the energy barrier of furan-2,5-dicarbaldehyde is 496.1 kJ/mol; the energy barrier of 5-methyl furfural is 375.8 kJ/mol, and the energy barrier of 2-methyl furan is 375.8 kJ/mol. In pathway（2）, the activation energy required for open-loop with H₂O is higher.更多还原