Please use this identifier to cite or link to this item: http://arks.princeton.edu/ark:/88435/dsp01n870zr02t
 Title: ELECTROCHEMISTRY OF LUTIDINIUM ON A PLATINUM SURFACE: INSIGHTS FOR CATALYSIS AND CARBON DIOXIDE REDUCTION Authors: Li, Yifan Advisors: Bocarsly, Andrew Bruce Department: Chemistry Class Year: 2014 Abstract: Increasing levels of greenhouse gases in the atmosphere necessitate mitigative measures for carbon dioxide (CO$$_{2}$$) emissions. One recent but promising development is the renewables-powered electrocatalytic reduction of CO$$_{2}$$ to value-added products. Although pyridinium has been previously observed to catalyze CO$$_{2}$$ reduction using solar energy at high e ciency and low overpotential, the mechanism of this reaction on both semiconductor and metal surfaces is poorly understood. In this study,I investigate the dimethylpyridinium species 3,5- and 2,6-lutidinium, for both their e ectiveness at catalyzing CO$$_{2}$$ reduction and their electrochemisty on the platinum electrode. Bulk electrolysis at reductive potentials, proton NMR, and headspace GC analysis reveal that both lutidinium species fail to produce CO$$_{2}$$ reduction products to observable amounts. However, the observation of an unexpected extraneous anodic wave in cyclic voltammetry under CO$$_{2}$$ atmosphere suggests an interaction between lutidinium and CO2 that has heretofore never been investigated. Step-sweep voltammetry reveals that the peak most likely results from the oxidation of a new product, possibly through a lutidinium-CO$$_{2}$$ reaction. A mechanism involving the formation of a lutidinyl carbamate is proposed to explain these observations. The existence of such a compound could lend considerable insight to the mechanism of pyridinium-catalyzed CO$$_{2}$$ reduction on a Pt surface. Extent: 80 pages URI: http://arks.princeton.edu/ark:/88435/dsp01n870zr02t Type of Material: Princeton University Senior Theses Language: en_US Appears in Collections: Chemistry, 1926-2016