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dc.contributor.advisorBocarsly, Andrew Ben_US
dc.contributor.advisorBernasek, Steven Len_US
dc.contributor.authorDetweiler, Zachary Millleren_US
dc.contributor.otherChemistry Departmenten_US
dc.description.abstractTwo systems were studied using in situ measurement techniques, demonstrating the importance of creative experimental design. The electroreduction of CO2 at heterogeneous indium electrodes in aqueous solution was analyzed by cyclic voltammetry. Bulk electrolyses showed that increased indium oxide presence prior to electrolysis improved the Faradaic efficiency of CO2 reduction to formate in 0.5 M K2SO2 aqueous solutions at a pH of 4.4. In order to more accurately assign speciation at the electrode surface ex situ O2 and H2O dosing of metallic indium under UHV was studied with XPS, HREELS and TPD. Ambient pressure XPS showed that the ratio of oxide to hydroxide at the indium interface is strongly dependent on the partial pressure of water; decreasing as P(H2O) increases. Using this information, a qualitative picture of the indium interface could be generated. In situ ATR-FTIR with an indium thin film as the working electrode showed that bulk oxide quickly reduces with applied potential, but an interfacial oxide is still present at high reductive overpotential. Additionally, an adsorbed carbonate at the thin film interface was observed upon introducing CO2 to the cell. The implication of a surface bound carbonate as the CO2 reduction intermediate draws on a mechanism that has not previously been discussed in the electrochemical reduction of CO2. The previous study of this mechanism from Ficscher-Tropsch literature helps to predict the further reduced products found at more electropositive metals, such as copper or magnesium, the latter of which is described here. Additionaly described here is a series of ILs that were employed as electrolyte for reversible silver deposition. BMIM N(TfO)2 was found to be the most promising of those studied, intrinsically giving a more uniform deposit that was bright and reversible. Deposit formation was studied using SEM and EDX as a function of deposition potential and deposition time. In situ reflectometry was employed to get a direct measure of deposit reflectivity on ITO coated glass as a function of time. A promising device system has been elucidated as a result and future considerations have been identified from coincident electrochemical and spectroscopic measurements.en_US
dc.publisherPrinceton, NJ : Princeton Universityen_US
dc.relation.isformatofThe Mudd Manuscript Library retains one bound copy of each dissertation. Search for these copies in the <a href=> library's main catalog </a>en_US
dc.subjectcarbon dioxide conversionen_US
dc.subjectsilver electrodepositionen_US
dc.subjectsurface scienceen_US
dc.subject.classificationMaterials Scienceen_US
dc.titleA view of aqueous electrochemical carbon dioxide reduction to formate at indium electrodes, and the reversible electrodeposition of silver in ionic liquids through the lens of fundamental surface scienceen_US
dc.typeAcademic dissertations (Ph.D.)en_US
Appears in Collections:Chemistry

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