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dc.contributor.advisorYuriy Román-Leshkov and Heather J. Kulik.en_US
dc.contributor.authorGani, Terry Zhi Hao.en_US
dc.contributor.otherMassachusetts Institute of Technology. Department of Chemical Engineering.en_US
dc.date.accessioned2021-05-14T16:28:45Z
dc.date.available2021-05-14T16:28:45Z
dc.date.issued2020en_US
dc.identifier.urihttps://hdl.handle.net/1721.1/130605
dc.descriptionThesis: Ph. D., Massachusetts Institute of Technology, Department of Chemical Engineering, September, 2020en_US
dc.descriptionCataloged from the official PDF of thesis. "July 2020."en_US
dc.descriptionIncludes bibliographical references (pages 170-200).en_US
dc.description.abstractSupported transition metal (TM) complexes are an emerging class of materials with many potential applications in the chemical industry ranging from separations to catalysis. They offer increased tunability and often also improved performance over their bulk heterogeneous counterparts. Their study and rational design is, however, accompanied by several unique considerations and challenges that we address in this thesis. The first part of the thesis broadly develops and applies computational screening strategies for supported TM complexes. First, we detail how weak C-H[superscript ...]O hydrogen bonds can be exploited to increase selectivity of ferrocenium (Fc⁺)-based polymer electrode materials for formate adsorption over perchlorate adsorption while maintaining reasonable desorption rates in the reduced (ferrocene, Fc) state. Through a systematic characterization of formate and perchlorate interactions with a small (ca.en_US
dc.description.abstract40) but diverse set of functionalized Fc⁺ complexes, we identify and rationalize design rules for functionalizations that simultaneously increase selectivity for formate in aqueous environments while permitting rapid release from Fc. Next, we screen a larger (ca. 500) set of model Fe(II) complexes for methane hydroxylation in order to assess if linear free energy relationships (LFERs), extensively developed to reduce the computational cost of computationally screening bulk heterogeneous catalysts, can also be applied to supported single-site TM catalysts. We demonstrate that structural distortions achievable in porous frameworks and chelating ligands break these LFERs by altering relative d-orbital splittings, thereby revealing a potential strategy for improving the activity of these catalysts.en_US
dc.description.abstractFinally, to address a particularly pervasive issue in density functional theory (DFT) studies of first-row open-shell TM complexes, we investigate how the fraction of exact exchange parameterized in the functional affects computed reaction and spin-splitting energies. We rationalize this sensitivity in terms of differences in metal-ligand electron delocalization and introduce the metal-ligand bond valence as a simple, yet robust, descriptor that unifies understanding of exchange sensitivity for catalytic properties and spin-state ordering in TM complexes.en_US
dc.description.statementofresponsibilityby Terry Zhi Hao Gani.en_US
dc.format.extent200 pagesen_US
dc.language.isoengen_US
dc.publisherMassachusetts Institute of Technologyen_US
dc.rightsMIT theses may be protected by copyright. Please reuse MIT thesis content according to the MIT Libraries Permissions Policy, which is available through the URL provided.en_US
dc.rights.urihttp://dspace.mit.edu/handle/1721.1/7582en_US
dc.subjectChemical Engineering.en_US
dc.titleMechanistic studies and design of supported transition metal complexesen_US
dc.typeThesisen_US
dc.description.degreePh. D.en_US
dc.contributor.departmentMassachusetts Institute of Technology. Department of Chemical Engineeringen_US
dc.identifier.oclc1249555719en_US
dc.description.collectionPh.D. Massachusetts Institute of Technology, Department of Chemical Engineeringen_US
dspace.imported2021-05-14T16:28:44Zen_US
mit.thesis.degreeDoctoralen_US
mit.thesis.departmentChemEngen_US


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