Nanoscience and Microsystems ETDs

Publication Date

Fall 11-1-2017

Abstract

This dissertation investigates the novel incorporation of inorganic and enzymatic catalysts. There is little literature on inorganic catalysts operating at biologically relevant pHs and as such a significant amount of this dissertation focuses on determination of catalyst activity. Mn amino-anitpyrene (MnAAPyr), Pt, Pt alloys, Mn-N-C and Pd catalysts on 3D graphene supports(3D-GNS), were explored for activity towards glycerol intermediates: oxalic acid, mesoxalic acid, glyoxalic acid, and formic acid. MnAAPyr was designed to mimic the reaction center of oxalate decarboxylase and oxalate oxidaze, the natural catalyst towards oxalic acid. It showed high activity towards oxalic acid, with onset potentials of 0.714±0.002V vs. SHE at pH = 4. Pt, PtSn (1:1), PtSn (19:1), PtRu (1:4), PtRuSn (5:4:1), and PtRhSn (3:1:4) were also tested towards the oxidation of oxalic acid. PtSn (1:1) and PtRu (1:4) showed higher mass activity than Pt and the other alloys. The hybrid catalyst, Pd/Mn-N-3D-GNS, also showed increased maximum currents from the oxidation of oxalic acid when compared to Pd and Mn-N-C. Tests determined that the mechanisms of formic acid oxidation on Pd/3D-GNS went through the preferred route of dehydrogenation and was selected for cascade incorporation. Within the 2-step cascade, OxDC converts oxalic acid to formic acid, which is then oxidized to carbon dioxide by Pd. A novel catalysts incorporation was utilized in which OxDC/3D-GNS was deposited onto Pd/3D-GNS in 2:1 ratios. Both steps in the cascade were demonstrated by the utilization of UV-VIS and electrochemical measurements which showed an increase in absorbance and current for OxDC and Pd, respectively.

Keywords

electro catalysis, catalytic cascade, hybrid catalysts

Document Type

Dissertation

Language

English

Degree Name

Nanoscience and Microsystems

Level of Degree

Doctoral

Department Name

Nanoscience and Microsystems

First Committee Member (Chair)

Plamen Atanassov

Second Committee Member

Fernando Garzon

Third Committee Member

Gautam Gupta

Fourth Committee Member

Sofia Babanova

Fifth Committee Member

Ivana Gonzales

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