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Nanoscale Organization of Thiol and Arylsulfonic Acid on Silica Leads to a Highly Active and Selective Bifunctional, Heterogeneous Catalyst

Margelefsky, Eric L. and Bendjériou, Anissa and Zeidan, Ryan K. and Dufaud, Véronique and Davis, Mark E. (2008) Nanoscale Organization of Thiol and Arylsulfonic Acid on Silica Leads to a Highly Active and Selective Bifunctional, Heterogeneous Catalyst. Journal of the American Chemical Society, 130 (40). pp. 13442-13449. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:MARjacs08

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Abstract

Ordered mesoporous silicas functionalized with alkylsulfonic acid and thiol group pairs have been shown to catalyze the synthesis of bisphenols from the condensation of phenol and various ketones, with activity and selectivity highly dependent on the distance between the acid and thiol. Here, a new route to thiol/sulfonic acid paired catalysts is reported. A bis-silane precursor molecule containing both a disulfide and a sulfonate ester bond is grafted onto the surface of ordered mesoporous silica, SBA-15, followed by simultaneous disulfide reduction and sulfonate ester hydrolysis. The resulting catalyst, containing organized pairs of arylsulfonic acid and thiol groups, is significantly more active than the alkylsulfonic acid/thiol paired catalyst in the synthesis of bisphenol A and Z, and this increase in activity does not lead to a loss of regioselectivity. The paired catalyst has activity similar to that of a randomly bifunctionalized arylsulfonic acid/thiol catalyst in the bisphenol A reaction but exhibits greater activity and selectivity than the randomly bifunctionalized catalyst in the bisphenol Z reaction.


Item Type:Article
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http://dx.doi.org/10.1021/ja804082mDOIUNSPECIFIED
Additional Information:Copyright © 2008 American Chemical Society. Received May 30, 2008. Web Release Date: September 13, 2008. This work was supported in part by the National Science Foundation under Grant No. OISE-0436985 and the Department of Energy (M.E.D.). E.L.M. also acknowledges support from a National Science Foundation Graduate Research Fellowship, and A.B. would like to thank the CNRS for a postdoctoral grant. The International Relation Department of the CNRS is also acknowledged by V.D. for specific funding for this project (PICS 4016). Supporting Information Available: 13C{1H} CP/MAS NMR spectra of SBA-g4, SBA-A, SBA-g2,4, SBA-AT-r, and SBA-T; N2 adsorption/desorption isotherms of SBA-15, SBA-g3, and SBA-AT-p; X-ray diffraction data of SBA-15, SBA-g3, and SBA-AT-p; TGA data of SBA-g3 and SBA-AT-p. This material is available free of charge via the Internet at http://pubs.acs.org.
Funders:
Funding AgencyGrant Number
National Science FoundationOISE-0436985
Department of EnergyUNSPECIFIED
Centre National de la Recherche Scientifique (CNRS)PICS 4016
Issue or Number:40
Record Number:CaltechAUTHORS:MARjacs08
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:MARjacs08
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:12137
Collection:CaltechAUTHORS
Deposited By: Archive Administrator
Deposited On:24 Oct 2008 22:46
Last Modified:03 Oct 2019 00:25

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