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Title: Enantiomerically enriched, polycrystalline molecular sieves

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. For this study, 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).
Authors:
 [1] ;  [2] ;  [3] ;  [3] ;  [4] ;  [5] ;  [6] ;  [1]
  1. California Inst. of Technology (CalTech), Pasadena, CA (United States). Dept. of Chemical Engineering
  2. California Inst. of Technology (CalTech), Pasadena, CA (United States). Dept. of Chemical Engineering; Univ. of Utrecht (Netherlands). Debye Inst. for Nanomaterials Science
  3. Rice Univ., Houston, TX (United States). Dept. of Bioengineering and Dept. of Physics and Astronomy
  4. ShanghaiTech Univ. (China). School of Physical Science and Technology
  5. ShanghaiTech Univ. (China). School of Physical Science and Technology; Stockholm Univ. (Sweden). Dept. of Materials and Environmental Chemistry
  6. California Inst. of Technology (CalTech), Pasadena, CA (United States). Dept. of Chemical Engineering; Stanford Univ., CA (United States). Dept. of Chemical Engineering
Publication Date:
Grant/Contract Number:
FG02-03ER15456
Type:
Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 114; Journal Issue: 20; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Research Org:
Rice Univ., Houston, TX (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); California Inst. of Technology (CalTech), Pasadena, CA (United States); Chevron Corporation, San Ramon, CA (United States); ShanghaiTech Univ. (China)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; chirality; zeolite; asymmetric catalysis; chiral adsorption
OSTI Identifier:
1429468

Brand, Stephen K., Schmidt, Joel E., Deem, Michael W., Daeyaert, Frits, Ma, Yanhang, Terasaki, Osamu, Orazov, Marat, and Davis, Mark E.. Enantiomerically enriched, polycrystalline molecular sieves. United States: N. p., Web. doi:10.1073/pnas.1704638114.
Brand, Stephen K., Schmidt, Joel E., Deem, Michael W., Daeyaert, Frits, Ma, Yanhang, Terasaki, Osamu, Orazov, Marat, & Davis, Mark E.. Enantiomerically enriched, polycrystalline molecular sieves. United States. doi:10.1073/pnas.1704638114.
Brand, Stephen K., Schmidt, Joel E., Deem, Michael W., Daeyaert, Frits, Ma, Yanhang, Terasaki, Osamu, Orazov, Marat, and Davis, Mark E.. 2017. "Enantiomerically enriched, polycrystalline molecular sieves". United States. doi:10.1073/pnas.1704638114. https://www.osti.gov/servlets/purl/1429468.
@article{osti_1429468,
title = {Enantiomerically enriched, polycrystalline molecular sieves},
author = {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.},
abstractNote = {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. For this study, 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).},
doi = {10.1073/pnas.1704638114},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 20,
volume = 114,
place = {United States},
year = {2017},
month = {5}
}