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Reduction of Carbon Dioxide with Cobalt and Iron Porphyrins

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The free-base tetra-tolyl-porphyrin and the corresponding cobalt and iron porphyrin complexes were synthesized and characterized to show that this class of compound can be promising, tunable catalysts for carbon dioxide reduction. During cyclic voltammetry experiments, the iron porphyrin showed an on-set of ‘catalytic current’ at an earlier potential than the…

The free-base tetra-tolyl-porphyrin and the corresponding cobalt and iron porphyrin complexes were synthesized and characterized to show that this class of compound can be promising, tunable catalysts for carbon dioxide reduction. During cyclic voltammetry experiments, the iron porphyrin showed an on-set of ‘catalytic current’ at an earlier potential than the cobalt porphyrin’s in organic solutions gassed with carbon dioxide. The cobalt porphyrin yielded larger catalytic currents, but at the same potential as the electrode. This difference, along with the significant changes in the porphyrin’s electronic, optical and redox properties, showed that its capabilities for carbon dioxide reduction can be controlled by metal ions, allotting it unique opportunities for applications in solar fuels catalysis and photochemical reactions.

ContributorsSkibo, Edward Kim (Author) / Moore, Gary (Thesis director) / Woodbury, Neal (Committee member) / School of Molecular Sciences (Contributor) / School of Sustainability (Contributor) / Barrett, The Honors College (Contributor)

Created2016-05

Synthesis and Characterization of Molecular Catalysts with Applications in Solar Fuels

Description

Metalloporphyrins serve important roles in biological processes and in emerging technologies with applications to energy conversion. When electrochemically activated in solution, metalloporphyrins have the ability to catalyze the conversion of protons into hydrogen fuels. In this report, the synthesis and characterization of zinc, nickel, cobalt and copper analogs of 5,10,15,20-tetrakis(pentafluorophenyl)…

Metalloporphyrins serve important roles in biological processes and in emerging technologies with applications to energy conversion. When electrochemically activated in solution, metalloporphyrins have the ability to catalyze the conversion of protons into hydrogen fuels. In this report, the synthesis and characterization of zinc, nickel, cobalt and copper analogs of 5,10,15,20-tetrakis(pentafluorophenyl) porphyrin (PF20) and 5,10,15,20-tetra-p-tolyporphyrin (TTP) are described. All target compounds are characterized with UV-Vis spectroscopy and MALDI-TOF mass spectrometry. The freebase porphyrins and non-paramagnetic metalloporphyrins are further characterized by proton nuclear magnetic resonance spectroscopy and all proton resonances are assigned. Electrochemical measurements show the reduction potential of the fluorinated phenyl substituted porphyrins is shifted to less negative values as compared to the reduction potential measured using non-fluorinated analogs. These results illustrate the ability to use fluorine as a synthetic tool for altering the electronic properties of metalloporphyrins. Further, these findings serve a critical role in choosing metalloporphyrin electrocatalysts with the appropriate energetic and optical properties for integration to semiconductors with applications to solar-to- fuels technologies.

ContributorsNanyangwe, Sylvia Kapya (Author) / Moore, Gary (Thesis director) / Van Horn, Wade (Committee member) / School of Criminology and Criminal Justice (Contributor) / School of Molecular Sciences (Contributor) / Barrett, The Honors College (Contributor)

Created2018-05

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Reduction of Carbon Dioxide with Cobalt and Iron Porphyrins

Synthesis and Characterization of Molecular Catalysts with Applications in Solar Fuels

Le tombeau de couperin. IV. Regaudon

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