Renewable energy is becoming an increasingly important component of the world’s energy supply as the threat of global warming continues to rise. There is a need to reduce the cost of this renewable energy and a future challenge to deal with the strain intermittent power sources like renewables place on the power grid. In this dissertation, electrochemistry is harnessed to address possible solutions to both of these issues. First, it is used to develop a low cost alternative photovoltaic material. Then, it is used to investigate the production of chemical fuel stocks which can be used for energy storage.
In chapter 2, advances are made in the electrochemical deposition of indium (In) on molybdenum foil which enables the deposition of electronic-grade purity, continuous films with thicknesses in the micron range. As an example application, the electrodeposited In films are phosphorized via the thin-film vapor-liquid-solid growth method. The resulting poly-crystalline InP films display excellent optoelectronic quality, comparable to films grown from more standard vacuum deposition techniques. This demonstrates the versatility of the developed electrochemical deposition procedure.
In the remaining chapters, renewable fuel production is investigated. First in chapter 3, molybdenum disulfide (MoS2) is examined as a catalyst for the hydrogen evolution reaction(HER). Typically, high-cost synthesized MoS2 is used as the catalyst because the pristine MoS2mineral is known to be a poor catalyst. The fundamental challenge with pristine MoS2 is the inert HER activity of the predominant (0001) basal surface plane. Here, we report a general thermal process in which the basal plane is texturized to increase the density of HER-active edge sites. The process generates high HER catalytic performance in pristine MoS2 across various morphologies such as the bulk mineral, films composed of micron-scale flakes, and even films of a commercially-available spray of nanoflake MoS2
In chapters 4-6, the electrochemical reduction of carbon dioxide (CO2R) is investigated as this reaction can produce hydrocarbons and alcohols as opposed to just hydrogen. First in chapter 4, the electrochemical cell, which is used to test the activity of CO2R catalysts, is scrutinized. The electrochemical cell is a mini-chemical reactor and it is important to monitor the reaction conditions within the reactor to ensure that they are constant throughout the study. I show that operating cells with high catalyst surface area to electrolyte volume ratios (S/V) at high current densities can have subtle consequences during CO2R, particularly as they relate to the bulk electrolyte CO2 concentration. By using the pH in the cell to measure the CO2 concentration, significant undersaturation of CO2 is observed in the bulk electrolyte, even at modest current densities of 10 mA cm^-2. Undersaturation of CO2 produces large changes in the faradaic efficiency observed on copper electrodes, with hydrogen production becoming increasingly favored. I show that the size of the CO2 bubbles being introduced into the cell is critical for maintaining the equilibrium CO2 concentration in the electrolyte and I design an electrochemical cell that is able to maintain near-equilibrium CO2 concentrations for catalyst testing.
Then in chapter 5, the use of selected-ion flow-tube mass spectrometry (SIFT-MS) as an analytical tool to detect the products of CO2R is investigated. The real-time analysis of the products of CO2R is especially of interest to enable the study of how and when the liquid products of the reaction are generated. This is currently only possible in some limited situations and an analytical tool that can do quantitative analysis of all the products of the CO2R reaction in real-time does not exist. I show that SIFT-MS is a promising technique which can uniquely detect the hydrocarbon, alcohols, and aldehydes produced during CO2R on copper. Furthermore, SIFT-MS should be able to provide quantitative results; however, further study is needed to rigorously prove this.
Finally in chapter 6, a CO2R catalyst platform is developed based on templated electrochemically deposited nanowires. This platform is used to investigate the role of high surface area in catalyst activity and selectivity. It is found that high surface area Cu nanowires can be made that still produce hydrocarbons, in contrast to several other reports in the literature. This platform is also used to investigate the sequential reduction of CO2. Here silver nanowires are deposited on top of a planar Cu substrate. The Ag can convert the CO2 to CO in close proximity to the Cu catalyst which can further upgrade the CO to hydrocarbons and alcohols. It is found that the sequential catalysis approach successfully selects for the production of hydrocarbons through the 2 electron CO intermediate and shuts down the production of the competing 2 electron product formic acid which is a dead-end reaction pathway.
December 31, 2016
Lobaccaro, P. (2016). Electrochemical Approaches to Renewable Energy. United States: University of California, Berkeley.