Selective C-C Coupling in Carbon Dioxide Electroreduction via Efficient Spillover of Intermediates As Supported by Operando Raman Spectroscopy

Developing efficient systems for the conversion of carbon dioxide to valuable chemicals using solar power is critical for mitigating climate change and ascertaining the worlds future supply of clean fuels. Here, we introduce a mesoscopic cathode consisting of Cu nanowires decorated with Ag islands, by the reduction of Ag-covered Cu2O nanowires prepared via galvanic replacement reaction. This catalyst enables CO2 reduction to ethylene and other C2+ products with a faradaic efficiency of 76%. Operando Raman spectroscopy reveals intermediate formation of CO at Ag sites which undergo subsequent spillover and hydrogenation on the Cu nanowires. Our Cu-Ag bimetallic design enables a similar to 95% efficient spillover of intermediates from Ag to Cu, delivering an improved activity toward the formation of ethylene and other C2+ products. We also demonstrate a solar to ethylene conversion efficiency of 4.2% for the photoelectrochemical CO2 reduction using water as electron and proton donor, and solar power together with perovskite photovoltaics to drive the uphill reaction.

Electrochemical Reduction of CO2 Catalyzed by Metal Oxides

Yeonji Oh

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%.

EPFL2015

Photo‐Electrochemical Conversion of CO 2 Under Concentrated Sunlight Enables Combination of High Reaction Rate and Efficiency

Etienne Boutin, Sophia Haussener, Mahendra Patel, Silvan Suter

Photo-electrochemical production of solar fuels from carbon dioxide, water, and sunlight is an appealing approach. Nevertheless, it remains challenging to scale despite encouraging demonstrations at low power input. Higher current densities require notable voltage input as ohmic losses and activation overpotentials become more significant, resulting in lower solar-to-CO conversion efficiencies. A concentrated photovoltaic cell is integrated into a custom-made heat managed photo-electrochemical device. The heat is transferred from the photovoltaic module to the zero-gap electrolyzer cell by the stream of anodic reactant and produce synergetic effects on both sides. With solar concentrations up to 450 suns (i.e., 450 kW m−2) applied for the first time to photo-electrochemical reduction of CO2, a partial current for CO production of 4 A is achieved. At optimal conditions, the solar-to-CO conversion efficiency reaches 17% while maintaining a current density of 150 mA cm−2 in the electrolyzer and a CO selectivity above 90%, representing an overall 19% solar-to-fuel conversion efficiency. This study represents a first demonstration of photo-electrochemical CO2 reduction under highly concentrated light, paving the way for resource efficient solar fuel production at high power input.

Wiley2022

Assessment of Solar Thermal Power Technologies

James Spelling

In the present climate of growing awareness about the dangers of global climate change, the development of new renewable energy technologies is primordial in the efforts to reduce emissions of carbon dioxide and other greenhouse gases. Rapid increases in the price of oil and worries about the stability and security of the extraction of fossil fuels have lead to renewed interest in the development of local energy sources, thereby reducing dependence on foreign fuel sources. Amid the plethora of option available, one of the more promising solutions is the increased use of solar power. Two main contrasting technologies exist for the conversion of the Sun’s energy into useful work, namely photovoltaic cells and solar thermal systems. The development of photovoltaic power has shown massive growth in recent years despite high costs, due mainly to the modular nature of the cells which allow their installation by private citizens, coupled with a number of government incentives. Development of solar thermal power generation has however been reasonably limited until recently, with the only continually operated commercial plants being the Luz SEGS I-IX plants at Kramer Junction in the United Sates. Solar thermal power generation shows great potential for supplying the base electricity needs of numerous countries in the sun-belt regions, stretching from the tropics to the Mediterranean. This has lead to a recent renewal in the development of such systems, notably with the construction of the PS10 central receiver plant in Spain. The Spanish government plans to bring the total solar generation capacity to a total of 300 MW by 2013. In other countries around the world, interest is growing in solar thermal power, with increased government and private spending fuelling research and innovation. Most solar thermal conversion technologies are still at the experimental stage, and no single technology has yet to impose its dominance. Different countries and research groups hold different solutions dear, but if solar thermal power is to become a fully mature electricity generating technology, the best of these diverse solutions must be combined in order to achieve optimal performance of the power plants.