Date of Award
Doctor of Philosophy
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.
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