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Published May 16, 2017 | Published + Supplemental Material
Journal Article Open

Enantiomerically enriched, polycrystalline molecular sieves

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).

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.

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Published - PNAS-2017-Brand-5101-6.pdf

Supplemental Material - pnas.1704638114.sapp.pdf

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August 21, 2023
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