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The Electrochemical Behavior Of Molybdenum And Tungsten Tri-Nuclear Metal Clusters With Ethanoate Ligands

Kennedy, Edward Nelson

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2017, Doctor of Philosophy (PhD), Wright State University, Environmental Sciences PhD.
The goal of this research was to study the electrochemical behavior of tri-nuclear clusters of molybdenum and tungsten. In addition, the feasibility of using these clusters as catalysts for the purpose of oxidizing ethanol was investigated. Four tri-nuclear cluster compounds were studied: hexa-µ2-acetatotriaquadi-µ3-oxotrimolybdenum (IV, IV, IV) trifluoromethanesulfonate [Mo3O2(O2CCH3)6(H2O)3](CF3SO3)2, hexa-µ2-acetatotriaquadi-µ3-oxodimolybdenum (IV, IV) tungsten (IV) trifluoromethanesulfonate [Mo2W2O2(O2CCH3)6(H2O)3](CF3SO3)2, hexa-µ2-acetatotriaquadi-µ3-oxomolybdenum (IV) ditungsten (IV, IV) trifluoromethanesulfonate [MoW2O2(O2CCH3)6(H2O)3](CF3SO3)2, and hexa-µ2-acetatotriaquadi-µ3-oxotritungsten (IV, IV, IV) trifluoromethanesulfonate [W3O2(O2CCH3)6(H2O)3](CF3SO3)2. Data was gathered from experimental results with cyclic voltammetry for the four tri-nuclear clusters. Initially, an ionic liquid, EMIBF4 (1-ethyl-3-methylimidazolium tetrafluoroborate), was used as the solvent. Subsequent solvents for use with these clusters were investigated, including ACN (acetonitrile) and NMF (N-methylformamide). The secondary solvent system settled on was the DMSO-TBAHFP solvent system. Each tri-nuclear cluster displayed a reversible redox reaction and one or more irreversible reduction reactions. The redox peak potentials were found to be Ep,a: -0.44V and Ep,c: -0.42V for Mo3, Ep,a: -0.32V and Ep,c: -0.43V for Mo2W, Ep,a: -0.31 V and Ep,c: -0.44 V for MoW2, and Ep,a: -0.42 and Ep,c: -0.46 for the W3 tri-nuclear cluster. The irreversible reduction reactions for each tri-nuclear cluster were observed at Ep,c(2): -0.74 for Mo3, Ep,c(2): -1.15 for Mo2W, Ep,c(2): -1.14 for MoW2, and Ep,c(2): -0.84 for the W3 tri-nuclear cluster. The diffusion coefficients in DMSO were determined to be DMo3 = 9.105E-06 cm2s-1, DMo2W = 1.743E-05 cm2s-1, DMoW2 = 1.764E-05 cm2s-1, and DW3 = 1.991E-05 cm2s-1. Exploring the electrocatalytic capability of these compounds was another effort made, by attempting to electroplate the compounds on platinum electrodes. Although some types of deposition events did appear to occur, it is unlikely they were of the intact tri-nuclear clusters. Thus far, the ethanol molecule has been partially oxidized, but breaking the carbon-carbon bond in the molecule proved to be a challenge that was not achieved.
Vladimir Katovic, Ph.D. (Advisor)
Jay Johnson, Ph.D. (Advisor)
Suzanne Lunsford, Ph.D. (Committee Member)
William Heineman, Ph.D. (Committee Member)
Christopher Barton, Ph.D. (Committee Member)
Doyle Watts, Ph.D. (Committee Member)
202 p.

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Citations

  • Kennedy, E. N. (2017). The Electrochemical Behavior Of Molybdenum And Tungsten Tri-Nuclear Metal Clusters With Ethanoate Ligands [Doctoral dissertation, Wright State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=wright1500558409183996

    APA Style (7th edition)

  • Kennedy, Edward. The Electrochemical Behavior Of Molybdenum And Tungsten Tri-Nuclear Metal Clusters With Ethanoate Ligands. 2017. Wright State University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=wright1500558409183996.

    MLA Style (8th edition)

  • Kennedy, Edward. "The Electrochemical Behavior Of Molybdenum And Tungsten Tri-Nuclear Metal Clusters With Ethanoate Ligands." Doctoral dissertation, Wright State University, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=wright1500558409183996

    Chicago Manual of Style (17th edition)