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The role of adsorbed species in various electrocatalytic processes: Electrochemical and in situ infrared spectroscopic studies

Huang, Haitao
http://rave.ohiolink.edu/etdc/view?acc_num=case1056050643

Abstract Details

1992, Doctor of Philosophy, Case Western Reserve University, Chemistry.
The objective of this thesis research is to understand the role of adsorbed species in various electrocatalytic processes using electrochemical techniques and in situ Fourier transform infrared reflection absorption spectroscopy (FTIRRAS). The work focuses on three types of electrode processes, all of which involve adsorbed species as reactants, intermediates or products, or function even as catalysts. They are (1) CO2 electroreduction to CO on Pt, (2) O2 reduction catalyzed by adsorbed transition metal tetra-sulfonated phthalocyanines (MeTsPc, Me = Co and Fe) and (3) the reduction of self-assembled layers of N-ethyl-N′-octadecyl-4,4′-bipyridinium (EOB) on metal surfaces. The electroreduction of CO2 was studied on both polycrystalline and single crystalline platinum electrodes in acid solutions using electrochemical and FTIRRAS techniques. The catalytic activity of Pt and the product distribution were found to be dependent on the surface plane. Various effects on the CO2 reduction reaction were examined including the variation of pH and electrode rotation rate, deuteration of the acid solution and the presence of impurities. Mechanistic pathways and reaction kinetics are discussed. The determination of the diffus ion coefficient of CO2 in acid solutions using the FTIRRAS technique was demonstrated. FeTsPc was investigated on silver surfaces in an N2-saturated 0.1 M HClO4 solution using FTIRRAS. The orientation of FeTsPc on the electrode surface was discussed as a function of potential and oxidation state. The catalytic activity and stability for O2 reduction of CoTsPc adsorbed on ordinary pyrolytic graphite (OPG) electrodes in acid solutions were found to be greatly improved in the presence of a coating of poly(4-vinylpyridine) (PVP). This may be explained in terms of the interactions between the PVP and CoTsPc. The structure and orientation of self-assembled layers of EOB on metal electrode surfaces (Pt, Au and Ag) were monitored as a function of potential with in situ FTIRRAS in aqueous solutions. The results obtained indicate that upon reduction of the EOB either undergoes dimerization or otherwise interacts electronically with the electrode surface or other ions in the solution, giving rise to vibronically coupled allowed modes which are ordinarily IR forbidden. Effects of the anion of the supporting electrolyte on the electrochemical behavior of the EOB layer were examined.
Ernest Yeager (Advisor)
274 p.
Chemistry, Physical
adsorbed species electrocatalytic processes Electrochemical situ infrared spectroscopic studies

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Citations

  • Huang, H. (1992). The role of adsorbed species in various electrocatalytic processes: Electrochemical and in situ infrared spectroscopic studies [Doctoral dissertation, Case Western Reserve University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=case1056050643

    APA Style (7th edition)

  • Huang, Haitao. The role of adsorbed species in various electrocatalytic processes: Electrochemical and in situ infrared spectroscopic studies. 1992. Case Western Reserve University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=case1056050643.

    MLA Style (8th edition)

  • Huang, Haitao. "The role of adsorbed species in various electrocatalytic processes: Electrochemical and in situ infrared spectroscopic studies." Doctoral dissertation, Case Western Reserve University, 1992. http://rave.ohiolink.edu/etdc/view?acc_num=case1056050643

    Chicago Manual of Style (17th edition)

case1056050643
453
© 1992, all rights reserved.
This open access ETD is published by Case Western Reserve University School of Graduate Studies and OhioLINK.