Universal kinetic solvent effects in acid-catalyzed reactions of biomass-derived oxygenates

doi:10.1039/c7ee03432f

	Universal kinetic solvent effects in acid-catalyzed reactions of biomass-derived oxygenates
	Van Lehn, Reid C.2; Walker, Theodore W.2; Chew, Alex K.2; Li, Huixiang 1,3; Demir, Benginur 2,4; Zhang, Z. Conrad 3; Huber, George W.2; Dumesic, James A.2,4
刊名	ENERGY & ENVIRONMENTAL SCIENCE
	2018-03-01
卷号	11 期号:3 页码:617-628
ISSN号	1754-5692
DOI	10.1039/c7ee03432f
文献子类	Article
英文摘要	The rates of BrOnsted-acid-catalyzed reactions of ethyl tert-butyl ether, tert-butanol, levoglucosan, 1,2-propanediol, fructose, cellobiose, and xylitol were measured in solvent mixtures of water with three polar aprotic cosolvents: -valerolactone; 1,4-dioxane; and tetrahydrofuran. As the water content of the solvent environment decreases, reactants with more hydroxyl groups have higher catalytic turnover rates for both hydrolysis and dehydration reactions. We present classical molecular dynamics simulations to explain these solvent effects in terms of three simulation-derived observables: (1) the extent of water enrichment in the local solvent domain of the reactant; (2) the average hydrogen bonding lifetime between water molecules and the reactant; and (3) the fraction of the reactant accessible surface area occupied by hydroxyl groups, all as a function of solvent composition. We develop a model, constituted by linear combinations of these three observables, that predicts experimentally determined rate constants as a function of solvent composition for the entire set of acid-catalyzed reactions.
WOS关键词	INITIO MOLECULAR-DYNAMICS ; GENERAL FORCE-FIELD ; LIGNOCELLULOSIC BIOMASS ; LIQUID FUELS ; DIMETHYL-SULFOXIDE ; FRUCTOSE DEHYDRATION ; CONVERSION REACTIONS ; COMPUTER-SIMULATION ; PLATFORM CHEMICALS ; TRANSITION-STATES
WOS研究方向	Chemistry ; Energy & Fuels ; Engineering ; Environmental Sciences & Ecology
语种	英语
出版者	ROYAL SOC CHEMISTRY
WOS记录号	WOS:000428184700012
内容类型	期刊论文
源URL	[http://cas-ir.dicp.ac.cn/handle/321008/169066]
专题	大连化学物理研究所_中国科学院大连化学物理研究所
通讯作者	Van Lehn, Reid C.; Dumesic, James A.
作者单位	1.Univ Chinese Acad Sci, Beijing 100049, Peoples R China 2.Univ Wisconsin, Dept Chem & Biol Engn, Madison, WI 53706 USA 3.Chinese Acad Sci, Dalian Inst Chem Phys, Dalian Natl Lab Clean Energy, 457 Zhongshan Rd, Dalian 116023, Peoples R China 4.Univ Wisconsin, DOE Great Lakes Bioenergy Res Ctr, Madison, WI 53706 USA
推荐引用方式 GB/T 7714	Van Lehn, Reid C.,Walker, Theodore W.,Chew, Alex K.,et al. Universal kinetic solvent effects in acid-catalyzed reactions of biomass-derived oxygenates[J]. ENERGY & ENVIRONMENTAL SCIENCE,2018,11(3):617-628.
APA	Van Lehn, Reid C..,Walker, Theodore W..,Chew, Alex K..,Li, Huixiang.,Demir, Benginur.,...&Dumesic, James A..(2018).Universal kinetic solvent effects in acid-catalyzed reactions of biomass-derived oxygenates.ENERGY & ENVIRONMENTAL SCIENCE,11(3),617-628.
MLA	Van Lehn, Reid C.,et al."Universal kinetic solvent effects in acid-catalyzed reactions of biomass-derived oxygenates".ENERGY & ENVIRONMENTAL SCIENCE 11.3(2018):617-628.