气候变化领域集成服务门户(CCPortal): Universal kinetic solvent effects in acid-catalyzed reactions of biomass-derived oxygenates

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DOI	10.1039/c7ee03432f
	Universal kinetic solvent effects in acid-catalyzed reactions of biomass-derived oxygenates
	Walker T.W.; Chew A.K.; Li H.; Demir B.; Zhang Z.C.; Huber G.W.; Van Lehn R.C.; Dumesic J.A.
发表日期	2018
ISSN	17545692
起始页码	617
结束页码	628
卷号	11 期号:3
英文摘要	The rates of Brønsted-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: γ-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. © The Royal Society of Chemistry 2018.
英文关键词	Catalysis; Dehydration; Hydrogen bonds; Molecular dynamics; Molecules; Organic solvents; Rate constants; Reaction kinetics; Sugar substitutes; Accessible surface areas; Acid-catalyzed reactions; Classical molecular dynamics; Dehydration reactions; Ethyl tert-butyl ether; Linear combinations; Solvent composition; Solvent environments; Solvents; biomass; catalysis; catalyst; chemical compound; chemical reaction; dehydration; experimental study; hydrogen; hydrolysis; molecular analysis; reaction kinetics; solvent
语种	英语
来源期刊	Energy & Environmental Science
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/190292
作者单位	Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, WI 53706, United States; Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian Liaoning, 116023, China; University of Chinese Academy of Sciences, Beijing, 100049, China; DOE Great Lakes Bioenergy Research Center, University of Wisconsin-Madison, Madison, WI 53706, United States
推荐引用方式 GB/T 7714	Walker T.W.,Chew A.K.,Li H.,et al. Universal kinetic solvent effects in acid-catalyzed reactions of biomass-derived oxygenates[J],2018,11(3).
APA	Walker T.W..,Chew A.K..,Li H..,Demir B..,Zhang Z.C..,...&Dumesic J.A..(2018).Universal kinetic solvent effects in acid-catalyzed reactions of biomass-derived oxygenates.Energy & Environmental Science,11(3).
MLA	Walker T.W.,et al."Universal kinetic solvent effects in acid-catalyzed reactions of biomass-derived oxygenates".Energy & Environmental Science 11.3(2018).