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Enantiomerically enriched, polycrystalline molecular sieves

Brand, Stephen K. and Schmidt, Joel E. and Deem, Michael W. and Daeyaert, Frits and Ma, Yanhang and Terasaki, Osamu and Orazov, Marat and Davis, Mark E. (2017) Enantiomerically enriched, polycrystalline molecular sieves. Proceedings of the National Academy of Sciences of the United States of America, 114 (20). pp. 5101-5106. ISSN 0027-8424. PMCID PMC5441830. http://resolver.caltech.edu/CaltechAUTHORS:20170502-074819722

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Abstract

Zeolite and zeolite-like molecular sieves are being used in a large number of applications such as adsorption and catalysis. Achievement of the long-standing goal of creating a chiral, polycrystalline molecular sieve with bulk enantioenrichment would enable these materials to perform enantioselective functions. Here, we report the synthesis of enantiomerically enriched samples of a molecular sieve. Enantiopure organic structure directing agents are designed with the assistance of computational methods and used to synthesize enantioenriched, polycrystalline molecular sieve samples of either enantiomer. Computational results correctly predicted which enantiomer is obtained, and enantiomeric enrichment is proven by high-resolution transmission electron microscopy. The enantioenriched and racemic samples of the molecular sieves are tested as adsorbents and heterogeneous catalysts. The enantioenriched molecular sieves show enantioselectivity for the ring opening reaction of epoxides and enantioselective adsorption of 2-butanol (the R enantiomer of the molecular sieve shows opposite and approximately equal enantioselectivity compared with the S enantiomer of the molecular sieve, whereas the racemic sample of the molecular sieve shows no enantioselectivity).


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1073/pnas.1704638114DOIArticle
http://www.pnas.org/content/114/20/5101PublisherArticle
http://www.pnas.org/lookup/suppl/doi:10.1073/pnas.1704638114/-/DCSupplementalPublisherSupporting Information
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5441830/PubMed CentralArticle
Additional Information:© 2017 National Academy of Sciences. Freely available online through the PNAS open access option. Contributed by Mark E. Davis, April 3, 2017 (sent for review March 21, 2017; reviewed by Avelino Corma and Alexander Katz). Published online before print May 1, 2017. S.K.B. thanks Dr. Sonjong Hwang (Caltech) for his assistance with solid-state NMR data collection, Dr. Jay Winkler (Caltech) for assistance with the solid-state circular dichroism experiments, and Dr. Stacey I. Zones (Chevron). Y.M. thanks Peter Oleynikov (ShanghaiTech) for many useful discussions, and ShanghaiTech University for startup funding to support this work. We thank the Chevron Energy and Technology Company for proving funding for the work that was performed at Caltech. This work was also supported by Department of Energy Basic Sciences Grant DE-FG02-03ER15456 (to M.W.D. and F.D.). Author contributions: S.K.B., J.E.S., M.W.D., F.D., Y.M., O.T., M.O., and M.E.D. designed research; S.K.B., J.E.S., Y.M., and M.O. performed research; S.K.B., J.E.S., M.W.D., Y.M., O.T., M.O., and M.E.D. analyzed data; S.K.B., J.E.S., and M.E.D. wrote the paper; and M.W.D. and F.D. performed computational work. Reviewers: A.C., Instituto de Tecnología Química (UPV-CSIC); and A.K., University of California, Berkeley. The authors declare no conflict of interest. This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.1073/pnas.1704638114/-/DCSupplemental.
Funders:
Funding AgencyGrant Number
Chevron Energy and Technology Co.UNSPECIFIED
Department of Energy (DOE)DE-FG02-03ER15456
Subject Keywords:chirality; zeolite; asymmetric catalysis; chiral adsorption
PubMed Central ID:PMC5441830
Record Number:CaltechAUTHORS:20170502-074819722
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20170502-074819722
Official Citation:Stephen K. Brand, Joel E. Schmidt, Michael W. Deem, Frits Daeyaert, Yanhang Ma, Osamu Terasaki, Marat Orazov, and Mark E. Davis Enantiomerically enriched, polycrystalline molecular sieves PNAS 2017 114 (20) 5101-5106; published ahead of print May 1, 2017, doi:10.1073/pnas.1704638114
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:77115
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:02 May 2017 16:03
Last Modified:17 Jul 2017 22:00

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