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Development and Characterization of Catalytic Systems for Biomass-Derived Chemical Feedstocks


Orazov, Marat (2017) Development and Characterization of Catalytic Systems for Biomass-Derived Chemical Feedstocks. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/Z9X63JZZ.


Heterogeneous catalysis by Brønsted and/or Lewis acid sites isolated within microporous environments is a topic that is perpetually growing in scope and importance. While Brønsted acid sites in zeolites have been studied and applied extensively in the petrochemical industry, new opportunities for green processes based on renewable chemical feedstocks call for applications of new microporous materials that possess Lewis acid sites (e.g., zeotypes with framework Sn, Ti, Zr, or Hf). Characterization of such materials and the specific structures of the Lewis acid sites provides insights for rational catalyst design and application.

This work provides experimental evidence for the identities of the active sites in Sn-Beta zeotype for the 1,2-intramolecular hydride shift (1,2-HS) reaction that results in D-glucose isomerization to D-fructose, and for the 1,2-intramolecular carbon shift (1,2-CS) reaction that results in D-glucose isomerization to D-mannose. Specifically, by selective poisoning experiments, the partially-hydrolyzed, "open" Sn site is shown to be the active site for the 1,2-HS reaction. The participation of the proximal silanol of such an open Sn site in the 1,2-HS reaction is demonstrated thorough alkali-exchange experiments. Such experiments also reveal that the active site for the 1,2-CS reaction is an open Sn site with a cation-exchanged proximal silanol.

1,2-CS catalysts, in general, are shown to also catalyze retro-aldol reactions of hexoses at moderate temperatures (ca. 100 °C), and to be compatible with microporous 1,2-HS catalysts in tandem catalytic schemes that enable production of alkyl lactates.

Finally, the Lewis acidity of framework Zn in zincosilicate microporous materials is demonstrated through probe-molecule infrared spectroscopy. One such material is then shown to catalyze Diels-Alder cycloaddition-dehydration reactions of oxygenated furans and ethylene. To the best of our knowledge, these materials are the first heterogeneous catalysts reported to catalyze the direct formation of terephthalate esters from ethylene and dimethyl 2,5-furandicarboxylate with appreciable selectivity.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:heterogeneous catalysis, microporous materials, zeolites, Sn-Beta, glucose isomerization, fructose, mannose, 1,2-intramolecular hydride shift, 1,2-intramolecular carbon shift, retro-aldol reactions, lactic acid, alkyl lactates, zincosilicates, Lewis acids, Diels-Alder reactions, furans, terephthalic acid, renewable monomers
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemical Engineering
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Davis, Mark E.
Thesis Committee:
  • Davis, Mark E. (chair)
  • Flagan, Richard C.
  • Agapie, Theodor
  • Labinger, Jay A.
Defense Date:15 July 2016
Funding AgencyGrant Number
US Department of Energy, Office of Science, Office of Basic Energy Sciences DE-SC0001004
National Science Foundation Graduate Research Fellowship Program DGE-1144469
Record Number:CaltechTHESIS:07202016-150438490
Persistent URL:
Related URLs:
URLURL TypeDescription adapted for Chapter 2 adapted for Chapter 3 adapted for Chapter 4
Orazov, Marat0000-0003-1621-1331
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:9894
Deposited By: Marat Orazov
Deposited On:09 Mar 2017 22:47
Last Modified:04 Oct 2019 00:14

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