Enantiomerically enriched, polycrystalline molecular sieves

Brand, Stephen K.; Schmidt, Joel E.; Deem, Michael W.; Daeyaert, Frits; Ma, Yanhang; Terasaki, Osamu; Orazov, Marat; Davis, Mark E.

doi:10.1073/pnas.1704638114

Enantiomerically enriched, polycrystalline molecular sieves

Journal Article · Mon May 01 00:00:00 EDT 2017 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1704638114· OSTI ID:1429468

Brand, Stephen K. ^[1]; Schmidt, Joel E. ^[2]; Deem, Michael W. ^[3]; Daeyaert, Frits ^[3]; Ma, Yanhang ^[4]; Terasaki, Osamu ^[5]; Orazov, Marat ^[6]; Davis, Mark E. ^[7]

California Inst. of Technology (CalTech), Pasadena, CA (United States). Dept. of Chemical Engineering; California Institute of Technology
California Inst. of Technology (CalTech), Pasadena, CA (United States). Dept. of Chemical Engineering; Univ. of Utrecht (Netherlands). Debye Inst. for Nanomaterials Science
Rice Univ., Houston, TX (United States). Dept. of Bioengineering and Dept. of Physics and Astronomy
ShanghaiTech Univ. (China). School of Physical Science and Technology
ShanghaiTech Univ. (China). School of Physical Science and Technology; Stockholm Univ. (Sweden). Dept. of Materials and Environmental Chemistry
California Inst. of Technology (CalTech), Pasadena, CA (United States). Dept. of Chemical Engineering; Stanford Univ., CA (United States). Dept. of Chemical Engineering
California Inst. of Technology (CalTech), Pasadena, CA (United States). Dept. of Chemical Engineering

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).

View Accepted Manuscript (DOE)

Research Organization:: Rice Univ., Houston, TX (United States)

Sponsoring Organization:: California Inst. of Technology (CalTech), Pasadena, CA (United States); Chevron Corporation, San Ramon, CA (United States); ShanghaiTech Univ. (China); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: FG02-03ER15456

OSTI ID:: 1429468

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 20 Vol. 114; ISSN 0027-8424

Publisher:: National Academy of Sciences, Washington, DC (United States)Copyright Statement

Country of Publication:: United States

Language:: English

References (39)

Asymmetric Catalysis: Science and Opportunities (Nobel Lecture) Copyright© The Nobel Foundation 2002. We thank the Nobel Foundation, Stockholm, for permission to print this lecture. Noyori, Ryoji Angewandte Chemie International Edition, Vol. 41, Issue 12 https://doi.org/10.1002/1521-3773(20020617)41:12<2008::AID-ANIE2008>3.0.CO;2-4	journal	June 2002
Zeolites and Catalysis Čejka, Jiři; Corma, Avelino; Zones, Stacey https://doi.org/10.1002/9783527630295	book	April 2010
A Pure Silica Chiral Polymorph with Helical Pores Rojas, Alex; Camblor, Miguel A. Angewandte Chemie International Edition, Vol. 51, Issue 16 https://doi.org/10.1002/anie.201108753	journal	March 2012
Towards the Rational Design of Efficient Organic Structure-Directing Agents for Zeolite Synthesis Moliner, Manuel; Rey, Fernando; Corma, Avelino Angewandte Chemie International Edition, Vol. 52, Issue 52 https://doi.org/10.1002/anie.201304713	journal	October 2013
Synthesis of a Specified, Silica Molecular Sieve by Using Computationally Predicted Organic Structure-Directing Agents Schmidt, Joel E.; Deem, Michael W.; Davis, Mark E. Angewandte Chemie International Edition, Vol. 53, Issue 32 https://doi.org/10.1002/anie.201404076	journal	June 2014
Facile Synthesis, Characterization, and Catalytic Behavior of a Large-Pore Zeolite with the IWV Framework Schmidt, Joel E.; Chen, Cong-Yan; Brand, Stephen K. Chemistry - A European Journal, Vol. 22, Issue 12 https://doi.org/10.1002/chem.201504717	journal	February 2016
Ring-opening of 1,2-epoxyalkane with alcohols over H-ZSM-5 in liquid phase Ogawa, Haruo; Miyamoto, Yasuhiro; Fujigaki, Tamiki Catalysis Letters, Vol. 40, Issue 3-4 https://doi.org/10.1007/BF00815291	journal	January 1996
Synthesis and characterisation of chiral Cu(I) complexes of substituted pyrrolidine ligands. Efficient catalysts for cyclopropanation reactions Carmona, A.; Corma, A.; Iglesias, M. Inorganica Chimica Acta, Vol. 244, Issue 2 https://doi.org/10.1016/0020-1693(95)04773-5	journal	March 1996
Separation of enantiomers: needs, challenges, perspectives Maier, Norbert M.; Franco, Pilar; Lindner, Wolfgang Journal of Chromatography A, Vol. 906, Issue 1-2 https://doi.org/10.1016/S0021-9673(00)00532-X	journal	January 2001
Asymmetric induction in carbenoid reaction by means of a dissymmetric copper chelate Nozaki, H.; Moriuti, S.; Takaya, H. Tetrahedron Letters, Vol. 7, Issue 43 https://doi.org/10.1016/S0040-4039(01)89263-7	journal	January 1966
Present and future synthesis challenges for zeolites Coronas, Joaquín Chemical Engineering Journal, Vol. 156, Issue 2 https://doi.org/10.1016/j.cej.2009.11.006	journal	January 2010
Enantioselective adsorption and diffusion of S-/R-glycidol in homochiral zeolites: A molecular simulation study Zhang, Liling; Jiang, Jianwen Journal of Membrane Science, Vol. 367, Issue 1-2 https://doi.org/10.1016/j.memsci.2010.10.038	journal	February 2011
An attempt to predict and rationalize relative stabilities and preferential germanium location in Si/Ge zeolites Sastre, German; Pulido, Angeles; Corma, Avelino Microporous and Mesoporous Materials, Vol. 82, Issue 1-2 https://doi.org/10.1016/j.micromeso.2005.01.021	journal	July 2005
Crystallization of zeolite beta in the presence of chiral amine or rhodium complex Takagi, Yukio; Komatsu, Takayuki; Kitabata, Yasuyoshi Microporous and Mesoporous Materials, Vol. 109, Issue 1-3 https://doi.org/10.1016/j.micromeso.2007.06.005	journal	March 2008
Synthesis and characterization of pure silica zeolite beta obtained by an aging–drying method Taborda, Farlán; Willhammar, Tom; Wang, Zhengyang Microporous and Mesoporous Materials, Vol. 143, Issue 1 https://doi.org/10.1016/j.micromeso.2011.02.030	journal	August 2011
Translating new materials discoveries in zeolite research to commercial manufacture Zones, S. I. Microporous and Mesoporous Materials, Vol. 144, Issue 1-3 https://doi.org/10.1016/j.micromeso.2011.03.039	journal	October 2011
Structure projection reconstruction from through-focus series of high-resolution transmission electron microscopy images Wan, Wei; Hovmöller, Sven; Zou, Xiaodong Ultramicroscopy, Vol. 115 https://doi.org/10.1016/j.ultramic.2012.01.013	journal	April 2012
Facile Synthesis and Catalysis of Pure-Silica and Heteroatom LTA Boal, Ben W.; Schmidt, Joel E.; Deimund, Mark A. Chemistry of Materials, Vol. 27, Issue 22 https://doi.org/10.1021/acs.chemmater.5b03579	journal	November 2015
Synthesis of Germanosilicate Molecular Sieves from Mono- and Di-Quaternary Ammonium OSDAs Constructed from Benzyl Imidazolium Derivatives: Stabilization of Large Micropore Volumes Including New Molecular Sieve CIT-13 Boal, Ben W.; Deem, Michael W.; Xie, Dan Chemistry of Materials, Vol. 28, Issue 7 https://doi.org/10.1021/acs.chemmater.6b00031	journal	March 2016
Design of Heterogeneous Catalysts for Fuels and Chemicals Processing: An Overview Bravo-Suárez, Juan J.; Chaudhari, Raghunath V.; Subramaniam, Bala ACS Symposium Series https://doi.org/10.1021/bk-2013-1132.ch001	book	January 2013
Zeolite and molecular sieve synthesis Davis, Mark E.; Lobo, Raul F. Chemistry of Materials, Vol. 4, Issue 4 https://doi.org/10.1021/cm00022a005	journal	July 1992
Facile Preparation of Aluminosilicate RTH across a Wide Composition Range Using a New Organic Structure-Directing Agent Schmidt, Joel E.; Deimund, Mark A.; Davis, Mark E. Chemistry of Materials, Vol. 26, Issue 24 https://doi.org/10.1021/cm503625u	journal	December 2014
Improved Postsynthesis Strategy to Sn-Beta Zeolites as Lewis Acid Catalysts for the Ring-Opening Hydration of Epoxides Tang, Bo; Dai, Weili; Wu, Guangjun ACS Catalysis, Vol. 4, Issue 8 https://doi.org/10.1021/cs500891s	journal	July 2014
Synthesis, Structure, and Optical Activity of HPM-1, a Pure Silica Chiral Zeolite Rojas, Alex; Arteaga, Oriol; Kahr, Bart Journal of the American Chemical Society, Vol. 135, Issue 32 https://doi.org/10.1021/ja405088c	journal	July 2013
Asymmetric Catalysis with Chiral Porous Metal–Organic Frameworks: Critical Issues Wang, Cheng; Zheng, Min; Lin, Wenbin The Journal of Physical Chemistry Letters, Vol. 2, Issue 14 https://doi.org/10.1021/jz200492d	journal	June 2011
A zeolite family with chiral and achiral structures built from the same building layer Tang, Liqiu; Shi, Lei; Bonneau, Charlotte Nature Materials, Vol. 7, Issue 5 https://doi.org/10.1038/nmat2169	journal	April 2008
Electron crystallography for determining the handedness of a chiral zeolite nanocrystal Ma, Yanhang; Oleynikov, Peter; Terasaki, Osamu Nature Materials, Vol. 16, Issue 7 https://doi.org/10.1038/nmat4890	journal	May 2017
Synthesis of chiral polymorph A-enriched zeolite Beta with an extremely concentrated fluoride route Tong, Mingquan; Zhang, Daliang; Fan, Weibin Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep11521	journal	June 2015
Needs and trends in rational synthesis of zeolitic materials Wang, Zhuopeng; Yu, Jihong; Xu, Ruren Chem. Soc. Rev., Vol. 41, Issue 5 https://doi.org/10.1039/C1CS15150A	journal	January 2012
CIT-7, a crystalline, molecular sieve with pores bounded by 8 and 10-membered rings Schmidt, Joel E.; Xie, Dan; Rea, Thomas Chemical Science, Vol. 6, Issue 3 https://doi.org/10.1039/C4SC03935A	journal	January 2015
Enantiopure anion templated synthesis of a zeolitic metal–organic framework Xu, Zhong-Xuan; Ma, Yu-Lu; Zhang, Jian Chemical Communications, Vol. 52, Issue 9 https://doi.org/10.1039/C5CC09308B	journal	January 2016
Synthesis of new zeolite structures Li, Jiyang; Corma, Avelino; Yu, Jihong Chemical Society Reviews, Vol. 44, Issue 20 https://doi.org/10.1039/C5CS00023H	journal	January 2015
Synthesis of polymorph A-enriched beta zeolites in a HF-concentrated system Zhang, Guanqun; Wang, Bingchun; Zhang, Weiping Dalton Transactions, Vol. 45, Issue 15 https://doi.org/10.1039/C6DT00424E	journal	January 2016
Chiral zeolitic materials: structural insights and synthetic challenges Yu, Jihong; Xu, Ruren Journal of Materials Chemistry, Vol. 18, Issue 34 https://doi.org/10.1039/b804136a	journal	January 2008
Chiral silicate zeolites Dryzun, Chaim; Mastai, Yitzhak; Shvalb, Ayelet Journal of Materials Chemistry, Vol. 19, Issue 14 https://doi.org/10.1039/b817497k	journal	January 2009
Computational prediction of chemically synthesizable organic structure directing agents for zeolites Pophale, Ramdas; Daeyaert, Frits; Deem, Michael W. Journal of Materials Chemistry A, Vol. 1, Issue 23 https://doi.org/10.1039/c3ta10626h	journal	January 2013
Spontaneous nucleation and growth of pure silica zeolite-? free of connectivity defects Camblor, Miguel A.; Corma, Avelino; Valencia, Susana Chemical Communications, Issue 20 https://doi.org/10.1039/cc9960002365	journal	January 1996
Chiral Symmetry Breaking in Sodium Chlorate Crystallizaton Kondepudi, D. K.; Kaufman, R. J.; Singh, N. Science, Vol. 250, Issue 4983 https://doi.org/10.1126/science.250.4983.975	journal	November 1990
Zeolite-Catalyzed Ring-Opening of Epoxides with Amines Onaka, Makoto; Kawai, Motomitsu; Izumi, Yusuke Chemistry Letters, Vol. 14, Issue 6 https://doi.org/10.1246/cl.1985.779	journal	June 1985

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