Infoscience

Thesis

Electrochemical Reduction of CO2 Catalyzed by Metal Oxides

A rapidly growing population and industrialization have caused the exploitation of natural resources in keeping with fossil fuels shortage. Due to the combustion of fossil fuels, the concentration of CO2 in the earth's atmosphere, which is a potent greenhouse gas, has been increasing dramatically and contributes to the current climate change. Meanwhile, CO2 can be considered as an abundant and inexpensive carbon feedstock, especially if carbon sequestration is required for future fossil fuel-based power stations. Electrochemical reduction of CO2 to form useful chemicals or fuels is a potentially efficient method of CO2 utilization and recycling. The advantage of the electrochemical CO2 reduction is that natural renewable sources, like solar power, wind power, hydropower or nuclear power can supply electric power for CO2 conversion. Various products, such as carbon monoxide, oxalic acid, formic acid, alcohols and hydrocarbons have been reduced from CO2 First in chapter 1, the general remarks about electrochemical reduction of CO2, especially on metal electrodes are introduced. It also includes the introduction of photoelectochemical CO2 reduction and literature review study about electrocatalytic CO2 reduction with organic molecules as mediators and catalysts. In chapter 2, our interest in Mo-based electrocatalysts led us to study the activity of MoO2 for CO2 reduction. MoO2 microparticles indeed act as an active catalyst for the electrochemical reduction of CO2 in organic solvents such as acetonitrile (MeCN) and dimethylformamide (DMF). In the context of this study, it was found that the CO2 reduction activity is much higher at -20 oC than at RT, and it can be promoted by a small amount of water. The selectivity of CO2 reduction depends on the temperature, overpotential and water concentration. Chapter 3 describes the electrochemical reduction of CO2, improved and modified by using imidazolium ionic liquids (ILs) as an electrolyte in organic solvent with MoO2/Pb electrode. The important role of ILs in changing the pathway of the reduction was observed. Particularly, the use of imidazolium ILs instead of tetraalkylammonium salt as an electrolyte altered the product from oxalate to CO. Besides, the overpotential of the CO2 reduction was shifted to the less negative potentials compared to previous work, and the current density as well increased. At a low water concentration, the catalytic activity was promoted and the total Faradaic efficiency (FE) was up to 100% with more than 60% of CO formation. Furthermore, imidazolium ILs together with our MoO2/Pb electrode lowered the overpotential of CO2 reduction by about 40 mV. In addition to the high selectivity for CO formation, the imidazolium ILs can perform a role as co-catalyst for lowering the CO2 reduction potential. Finally, chapter 4 shows the possibility of photoelectrochemical CO2 reduction to extend our research with various catalysts. In this work, we could derive a photoelectrochemical method to deposit Sn/SnOx catalyst on the surface protected cuprous oxide (Cu2O) photocathodes. The deposition of Sn/SnOx catalyst was optimized on the photocathode and it exhibited reliable CO2 reduction activity in a mild aqueous condition. Sn/SnOx-Cu2O photocathode showed the onset potential of the photocurrent at +0.1 V vs. RHE, which is very promising result. At a constant potential electrolysis of -0.1 V vs. RHE, a FE of 50% for formate formation was obtained and the total FE was around 86%.

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