Role of water in cyclopentanone self-condensation reaction catalyzed by MCM-41 functionalized with sulfonic acid groups

Li, Gengnan; Wang, Bin; Chen, Banghao; Resasco, Daniel E.

doi:10.1016/j.jcat.2019.07.032

Role of water in cyclopentanone self-condensation reaction catalyzed by MCM-41 functionalized with sulfonic acid groups

Journal Article · Mon Aug 05 00:00:00 EDT 2019 · Journal of Catalysis

DOI:https://doi.org/10.1016/j.jcat.2019.07.032· OSTI ID:1824939

^[1]; ^[2]; Chen, Banghao ^[3]; ^[2]

Univ. of Oklahoma, Norman, OK (United States); University of Oklahoma Norman OK (United States)
Univ. of Oklahoma, Norman, OK (United States)
Florida State Univ., Tallahassee, FL (United States)

Water is ubiquitous in many catalytic reactions used in the upgrading of biomass. Therefore, quantifying and controlling the influence of water in activity, selectivity, and catalyst deactivation is essential for advancing this technology. In this work, we report a kinetic study of the cyclopentanone self-condensation over functionalized MCM-41 catalysts with varying acid densities and in the presence of controlled amounts of water. It is observed that small amounts of water enhance the activity of these catalysts. A detailed analysis of the experimental data indicates that the rate limiting step is the enol formed via protonation and tautomerization of a cyclopentanone molecule attacks the electrophilic carbon of a second carbonyl. On catalyst with high density of sulfonic acid groups, the best fitting of the experimental data is obtained with a kinetic model in which the Csingle bondC bond forming step mostly occurs with the second carbonyl molecule adsorbed (and polarized) by an adjacent acid site (Langmuir-Hinshelwood, L-H). By contrast, at a lower density of sulfonic acid groups, the number of active sites with enough proximity greatly decreases and the Csingle bondC bond forming occurs with the second carbonyl in the liquid phase (Eley-Rideal, E-R). In this case, it is observed that when water is added to the reaction mixture, the best description of the kinetics switches from E-R to L-H. Evidently, the water can help bridging active sites remotely located on the surface, extending the polarizing effect of the second acid site.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Oklahoma, Norman, OK (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0018284

OSTI ID:: 1824939

Alternate ID(s):: OSTI ID: 1546810

Journal Information:: Journal of Catalysis, Journal Name: Journal of Catalysis Vol. 377; ISSN 0021-9517

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Role of water in cyclopentanone self-condensation reaction catalyzed by MCM-41 functionalized with sulfonic acid groups

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