Dr. Liu, doctoral candidate under the supervision of Profs. Julio Lloret-Fillol and Núria López, has successfully defended his PhD thesis. The dissertation, entitled Electrochemical Reduction of Carbon Dioxide (CO2) to Value-Added Carbon Products was publicly defended on Thursday, 4 December 2025.
Abstract
This dissertation develops electrocatalytic strategies for the selective transformation of CO2 into value-added chemicals and fuels. The first part focuses on controlling local environments in aqueous electrochemical CO2 reduction (ECO2R) using manganese-based covalent organic frameworks (COFbpyMn). Proton management is established as a central design principle. Hydrophobic polymers such as Teflon were incorporated into catalyst films to suppress the competing hydrogen evolution reaction, while amines with tailored pKa values were introduced as proton shuttles in the electrolyte. These additives promoted formation of the key [Mn–H] intermediate, thereby directing product selectivity towards HCO2⁻ or HCO2H at pH 2.4, while high-pKa-based additives favored CO formation.
The second part investigates the structural dynamics of COFbpyMn under electrochemical potential. Operando spectroscopies (EPR, SEIRA, ATR-IR, UV–Vis) revealed electric-field-induced restructuring at the electrode interface, including framework reorganization and the emergence of Mn–Mn dimer species. These results underscore the adaptive nature of reticular frameworks under working conditions.
The final part explores deeper CO2 reduction pathways using CoPc supported on engineered Toray carbon paper. Pyrolysis-generated porosity concentrated CO intermediates and enhanced CoPc dispersion, thereby boosting methanol selectivity.
Overall, this dissertation establishes design principles linking local environment control, intermediate management, and electrode architecture in molecular-based ECO2R systems.
The evaluation committee was composed of Dr. Marta Liras (IMDEA Energia, Spain), Dr. Sergio Fernández Martín (Universitat de Girona, Spain) and Dr. Federico Franco (Università degli Studi di Trieste, Italy).
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