caa a22 4500 605513740 CHVBK 20210128100701.0 cr unu---uuuuu 210128e20151101xx s 000 0 eng 10.1007/s00894-015-2843-6 doi (NATIONALLICENCE)springer-10.1007/s00894-015-2843-6 Theoretical insight into the conversion of xylose to furfural in the gas phase and water [Elektronische Daten] [Meng Wang, Chao Liu, Qibin Li, Xiaoxiao Xu] Furfural (FF) is a valuable ring-containing organic compound in the decomposition of xylose and can be produced massively in hydrothermal condition. In this study, density functional theory (DFT) methods are employed to investigate the formation mechanism of FF from xylose and the solvent effects on FF formation. Kinetic and thermodynamic analyses indicate that xylulose could be the intermediate that leads to the formation of FF in the gas phase and water. The formation of xylulose is initiated by a six-membered transition state with energy barriers of 163.6 and 150.8 kJ mol−1 in the gas phase and water, respectively. It is found that the strong stabilization of the reactants and transition states and the overall energy barriers of formation pathways of FF are reduced in water. The formation of FF is more thermodynamically favored in water compared with that in the gas phase. In addition, the inclusion of an explicit water molecule transforms four-membered transition states of ring-opening reaction, hydrogenation-cyclization, and dehydrations into less distorted six-membered transition states, which leads to the significant reduction of reaction barriers of FF formation. Springer-Verlag Berlin Heidelberg, 2015 Density functional theory nationallicence Furfural nationallicence Solvent effects nationallicence Xylose nationallicence Wang Meng Key laboratory of low-grade Energy Utilization Technologies and Systems, Ministry of Education, College of Power Engineering, Chongqing University, 400044, Chongqing, China aut Liu Chao Key laboratory of low-grade Energy Utilization Technologies and Systems, Ministry of Education, College of Power Engineering, Chongqing University, 400044, Chongqing, China aut Li Qibin College of Aerospace Engineering, Chongqing University, 400044, Chongqing, China aut Xu Xiaoxiao Key laboratory of low-grade Energy Utilization Technologies and Systems, Ministry of Education, College of Power Engineering, Chongqing University, 400044, Chongqing, China aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/11(2015-11-01), 1-10 1610-2940 21:11<1 2015 21 894 https://doi.org/10.1007/s00894-015-2843-6 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2843-6 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Wang Meng Key laboratory of low-grade Energy Utilization Technologies and Systems, Ministry of Education, College of Power Engineering, Chongqing University, 400044, Chongqing, China aut NATIONALLICENCE 700 1- Liu Chao Key laboratory of low-grade Energy Utilization Technologies and Systems, Ministry of Education, College of Power Engineering, Chongqing University, 400044, Chongqing, China aut NATIONALLICENCE 700 1- Li Qibin College of Aerospace Engineering, Chongqing University, 400044, Chongqing, China aut NATIONALLICENCE 700 1- Xu Xiaoxiao Key laboratory of low-grade Energy Utilization Technologies and Systems, Ministry of Education, College of Power Engineering, Chongqing University, 400044, Chongqing, China aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/11(2015-11-01), 1-10 1610-2940 21:11<1 2015 21 894