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Jeffrey F. Van Humbeck. Palmer, Ryan D. (Ryan Dee) Massachusetts Institute of Technology. Department of Chemistry. Massachusetts Institute of Technology. Department of Chemistry 2016-07-01T18:46:38Z 2016-07-01T18:46:38Z 2016 2016 http://hdl.handle.net/1721.1/103507 952590430 Thesis: S.M., Massachusetts Institute of Technology, Department of Chemistry, 2016. Cataloged from PDF version of thesis. Includes bibliographical references. Metal organic frameworks (MOFs) are a relatively new class of crystalline, porous materials at the interface of organic and inorganic chemistry that have been applied in gas absorption and storage systems, thin-film devices, and heterogeneous catalysts. While numerous examples of size-exclusive catalysis have been reported, to our knowledge no reports of size-selective oligomerization catalysis have been reported to date. Herein, chemically stable Zr based MOFs, namely UiO-67 and PCN-777, are investigated as possible candidates to promote size-selective oligomerization catalysis. Using acylated propylene-glycol methyl ethers as model substrates, the mass transport properties of these materials was investigated. Unfortunately, slow mass transport of solvated substrates through pores assumed to be sufficiently large for facile diffusion may prevent MOFs from serving as suitable scaffolds. Indeed, pore apertures large enough for quick diffusion rates may require pore volumes too large to allow reasonable size-selectivity. by Ryan D. Palmer. S.M. 58 pages eng Massachusetts Institute of Technology M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission. http://dspace.mit.edu/handle/1721.1/7582 Chemistry. Mass transport in metal-organic frameworks as a limiting step in size-selective oligomerization Mass transport in MOFs as a limiting step in size-selective oligomerization Thesis application/pdf false Publication unknown unknown <Publication xmlns="https://www.openaire.eu/cerif-profile/1.1/" id="be17904b-ea29-459c-aa05-afe5cc327879"> <Type xmlns="https://www.openaire.eu/cerif-profile/vocab/COAR_Publication_Types">http://purl.org/coar/resource_type/c_1843</Type> <Language>eng</Language> <Title>Mass transport in metal-organic frameworks as a limiting step in size-selective oligomerization</Title> <Subtitle>Mass transport in MOFs as a limiting step in size-selective oligomerization</Subtitle> <PublishedIn> <Publication> </Publication> </PublishedIn> <PublicationDate>2016</PublicationDate> <Authors> <Author> <DisplayName>Palmer, Ryan D. (Ryan Dee)</DisplayName> <Affiliation> <OrgUnit> </OrgUnit> </Affiliation> </Author> </Authors> <Editors> </Editors> <Publishers> <Publisher> <DisplayName>Massachusetts Institute of Technology</DisplayName> <OrgUnit /> </Publisher> </Publishers> <License>http://dspace.mit.edu/handle/1721.1/7582</License> <Keyword>Chemistry.</Keyword> <Abstract>Metal organic frameworks (MOFs) are a relatively new class of crystalline, porous materials at the interface of organic and inorganic chemistry that have been applied in gas absorption and storage systems, thin-film devices, and heterogeneous catalysts. While numerous examples of size-exclusive catalysis have been reported, to our knowledge no reports of size-selective oligomerization catalysis have been reported to date. Herein, chemically stable Zr based MOFs, namely UiO-67 and PCN-777, are investigated as possible candidates to promote size-selective oligomerization catalysis. Using acylated propylene-glycol methyl ethers as model substrates, the mass transport properties of these materials was investigated. Unfortunately, slow mass transport of solvated substrates through pores assumed to be sufficiently large for facile diffusion may prevent MOFs from serving as suitable scaffolds. Indeed, pore apertures large enough for quick diffusion rates may require pore volumes too large to allow reasonable size-selectivity.</Abstract> <Access xmlns="http://purl.org/coar/access_right" > </Access> </Publication>