A major contribution to global warming is CO2 emitted from the combustion of fossil fuels. Electrochemical processes can help to mitigate the elevated CO2 emissions through either the conversion of CO2 into value-added chemicals or the replacement of fossil fuels with clean fuels such as hydrogen produced from water oxidation. The present dissertation focuses on the mechanistic aspects of electrochemical processes. Electrochemical water oxidation is hindered by the low efficiency of oxygen evolution reaction (OER) at the anode whereas electrochemical reduction of CO2 (ERCO2) is hampered by high overpotentials and poor product selectivity. In this dissertation, we studied the catalytic activity of transition metal-based catalysts, including FeNi spinels, metal-oxide/copper, and d metal cyclam complexes, for both OER and ERCO2 using the density functional theory (DFT) computational approach.We report a combined effort of fabricating FeNi oxide catalysts and identifying the active component of the catalyst for OER. Our collaborators at the University of California, Santa Cruze fabricated a series of FeNi spinels-based materials including Ni(OH)Fe2O4(Cl), Ni(OH)Fe2O4, Fe(OH)Fe2O4(Cl), Fe(OH)Fe2O4, Ni(OH)O(Cl), Ni(OH)O and some show exceptional activity for OER. Combined experimental characterization and computational mechanistic study based on the computational hydrogen electrode (CHE) model revealed that Ni(OH)Fe2O4(Cl) is the active ensemble for exceptional OER performance. We also investigated CO2 reduction to C1 products at the metal-oxide/copper interfaces ((MO)4/Cu(100), M = Fe, Co and Ni) based on the CHE model. The effect of tuning metal-oxide/copper interfaces on product selectivity and limiting potential was clearly demonstrated. This study showed that the catalyst/electrode interface and solvent can be regulated to optimize product selectivity and lower the limiting potential for ERCO2. Applied potential affects the stability of species on the surface of the electrode. The proton-coupled electron transfer (PCET) equilibrium assumed in the CHE model does not capture the change in free energy under the influence of the applied potential. In contrast, the constant electrode potential (CEP) model captures changes in free energy due to applied potential, we applied the CEP model to ERCO2 and OER on (MO)4/Cu(100) and compared the results with those from the CHE model. The results demonstrate that the CHE and the CEP models predict different limiting potentials and product selectivity for ERCO2, but they predict similar limiting potentials for OER. The results demonstrate the importance of accounting for the applied potential effect in the study of more complex multi-step electrochemical processes. We also studied transition metal-based homogeneous catalysts for ERCO2. We examined the performance of transition metal(M) - cyclam(L) complexes as molecular catalysts for the reduction of CO2 to HCOO- and CO, focusing on the effect of changing the metal ions in cyclam on product selectivity (either HCOO- or CO), limiting potential and competitive hydrogen evolution reaction. Our results show that among the complexes, [LNi]2+ and [LPd]2+ can catalyze CO2 reduction to CO, and [LMo]2+ and [LW]3+ can reduce CO2 to HCOO-. Notably, [LMo]2+, [LW]3+, [LW]2+ and [LCo]2+ have a limiting potential less negative than -1.6 V and are based on earth-abundant elements, making them attractive for practical application. In summary, the dissertation demonstrates high-performance catalysts can be designed from earth-abundant transition metals for electrochemical processes that would alleviate the high CO2 level in the environment. On the other hand, completely reversing the increasing trend of CO2 level in the atmosphere requires a collective human effort.

For more than a decade, since 2009, biodiesel production has led to excessive production of its by-product, glycerol, consequently decreasing its market value and creating waste issues for the biodiesel industry. Valorization of glycerol is a promising strategy to enhance the sustainability of the biodiesel industry. Electrochemical oxidation of glycerol stands out among the other methods (i.e., hydrogenolysis, dehydration, and catalytic oxidation) due to its simplicity, eco-friendliness, and cost-effectiveness. Glycerol electrooxidation reaction has a wide range of products including C3 (i.e., glyceric acid), C2 (i.e., glycolic acid) and C1 (i.e., formic acid) products, and a complex reaction pathway. Moreover, some of the products spontaneously convert to each other or form decomposition products in the strong alkaline medium, making the product analysis challenging. Therefore, this thesis started by establishing a foundation for the quantitative technical analysis method of glycerol electrooxidation products. Proton Nuclear Magnetic Resonance (H-NMR) was developed as an alternative to High-Performance Liquid Chromatography (HPLC) by providing the capability to assess the products in their medium and detect the chemical conversions in alkaline medium. Additionally, H-NMR is a highly sensitive technique with a low detection limit of 0.01mM for the GOR product, and its accuracy was confirmed with less than 8% error by using a sample product mixture with known concentrations. Most importantly, the proposed chemical pathways were determined by using H-NMR, assisting in a deeper understanding of the glycerol electrooxidation mechanism in an alkaline medium. Subsequently, this thesis explores an efficient catalyst for the glycerol electrooxidation reaction since the state-of-the-art catalysts developed for the glycerol electrooxidation reaction mostly include noble metals hindering their commercialization due to their high price and low stability resulting from susceptibility to CO poisoning. Specifically, catalysts that can hinder the C-C cleavage provide more economic advantages since C3 products have higher market prices than the C2 and C1 products. Thus, the primary aim of this thesis is to develop a cost-effective catalyst with high selectivity towards C3 products, by demonstrating high activity, and stability to make the glycerol electrooxidation reaction economically feasible. This thesis uses the catalyst development strategy of alloying the noble metal with the transition metal, where Pt and Cu were chosen, respectively. PtxCu100-x/C bimetallic alloy catalysts were prepared using the chemical reduction method. The effect of Pt:Cu ratio on the electrochemical performance was studied by using a three-electrode cell in an alkaline medium, revealing the Pt31Cu69/C as the best-performing catalyst with the highest Pt-mass normalized current density (5.9 mA μgPt-1), highest geometrical current density (75.3 mA cm-2), and low onset potential (~0.38V vs RHE) among Pt/C and other PtxCu100-x/C catalysts. Conducting parametric studies on the electrolyte concentrations and applied potential, the C3 selectivity of Pt31Cu69/C catalyst demonstrated the highest selectivity to GLY (75 %) and C3 (86 %) after 10 h chronoamperometry at optimal conditions. Subsequently, the impact of the metal oxide effect on the Pt-based catalyst, PtCu/C-CeO2, and Pt/C-CeO2 were prepared using the ball milling method. The CeO2 impact on the selectivity towards C3 products was investigated. PtCu/C-CeO2 showed the highest selectivity and concentration for C3 products compared to Pt/C-CeO2, Pt/C and PtCu/C. Additionally, temperature impact on the performance towards glycerol electrooxidation reaction was studied, revealing temperature increase further increases the selectivity and concentration for C3 products (90%, and 18.4 mM). All the catalysts prepared in this thesis were characterized physically using analytical techniques of transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), and inductively coupled plasma optical emission spectroscopy (ICP-OES). / Thesis / Doctor of Philosophy (PhD) / Fossil fuels need to be replaced by clean alternatives due to sustainability concerns. Consequently, as a renewable energy source, biodiesel production has been booming since 2009, producing large amounts of glycerol as a side-product. This overproduction devalorizes glycerol, creating a disposal problem for the biodiesel industry. Electrochemical valorization is a sustainable approach to upgrade glycerol into useful compounds such as glyceric acid and tartronic acid that have medical, food and cosmetic applications. However, glycerol electrooxidation reaction (GOR) has a complex reaction pathway with a wide range of products that can be converted to each other spontaneously in an alkaline medium, making it challenging to fully understand the GOR mechanism, thereby negatively impacts GOR catalyst development. This thesis develops the proton nuclear magnetic resonance method for quantitative analysis of GOR products, highlights the chemical reaction pathways in alkaline electrolyte, and develops PtCu/C and PtCu/C-CeO2 catalysts as selective GOR catalysts towards the valuable C3 products.

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