Journal
ACS CATALYSIS
Volume 7, Issue 11, Pages 7822-7829Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.7b01582
Keywords
Dehydration; Elimination reactions; Zeolite; Heterogeneous catalysis; Homogeneous catalysis
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Funding
- U.S. Department of Energy (DOE), Energy Efficiency and Renewable Energy Office, Bioenergy Technologies Office [PNNL-TUM/CN 212303]
- U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences
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Hydronium ions in the pores of zeolite H-ZSM5 show high catalytic activity in the elimination of water from cyclohexanol in aqueous phase. Substitution induces subtle changes in rates and reaction pathways, which are concluded to be related to steric effects. Exploring the reaction pathways of 2-, 3-, and 4-methylcyclohexanol (2-McyOH, 3-McyOH, and 4McyOH), 2- and 4-ethylcyclohexanol (2-EcyOH and 4-EcyOH), 2-n-propylcyclohexanol (2-PcyOH), and cyclohexanol (CyOH) it is shown that the E2 character increases with closer positioning of the alkyl and hydroxyl groups. Thus, 4-McyOH dehydration proceeds via an El-type elimination, while cis-2-McyOH preferentially reacts via an E2 pathway. The entropy of activation decreased with increasing alkyl chain length (ca. 20 J mol(-1) KT-1 per CH2 unit) for 2-substituted alcohols, which is concluded to result from constraints influencing the configurational entropy of the transition states.
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