Ruud Kortlever

Catalysts and Reaction Pathways for the Electrochemical Reduction of Carbon Dioxide

The electrochemical reduction of CO2 has gained significant interest recently as it has the potential to trigger a sustainable solar-fuel-based economy. In this Perspective, we highlight several heterogeneous and molecular electrocatalysts for the reduction of CO2 and discuss the reaction pathways through which they form various products. Among those, copper is a unique catalyst as it yields hydrocarbon products, mostly methane, ethylene, and ethanol, with acceptable efficiencies. As a result, substantial effort has been invested to determine the special catalytic properties of copper and to elucidate the mechanism through which hydrocarbons are formed. These mechanistic insights, together with mechanistic insights of CO2 reduction on other metals and molecular complexes, can provide crucial guidelines for the design of future catalyst materials able to efficiently and selectively reduce CO2 to useful products.

Electrochemical CO2 reduction on Cu2O-derived copper nanoparticles: controlling the catalytic selectivity of hydrocarbons

The catalytic activity and hydrocarbon selectivity in electrochemical carbon dioxide (CO2) reduction on cuprous oxide (Cu2O) derived copper nanoparticles is discussed. Cuprous oxide films with [100], [110] and [111] orientation and variable thickness were electrodeposited by reduction of copper(ii) lactate on commercially available copper plates. After initiation of the electrochemical CO2 reduction by these oxide structures, the selectivity of the process was found to largely depend on the parent Cu2O film thickness, rather than on the initial crystal orientation. Starting with thin Cu2O films, besides CO and hydrogen, selective formation of ethylene is observed with very high ethylene-to-methane ratios (∼8 to 12). In addition to these products, thicker Cu2O films yield a remarkably large amount of ethane. Long term Faradaic efficiency analysis of hydrocarbons shows no sign of deactivation of the electrodes after 5 hours of continuous experiment. Online mass spectroscopy studies combined with X-ray diffraction data suggest the reduction of the Cu2O films in the presence of CO2, generating a nanoparticulate Cu morphology, prior to the production of hydrogen, CO, and hydrocarbons. Optimizing coverage, number density and size of the copper nanoparticles, as well as local surface pH, may allow highly selective formation of the industrially important product ethylene.

Electrocatalytic reduction of carbon dioxide to carbon monoxide and methane at an immobilized cobalt protoporphyrin

The electrochemical conversion of carbon dioxide and water into useful products is a major challenge in facilitating a closed carbon cycle. Here we report a cobalt protoporphyrin immobilized on a pyrolytic graphite electrode that reduces carbon dioxide in an aqueous acidic solution at relatively low overpotential (0.5 V), with an efficiency and selectivity comparable to the best porphyrin-based electrocatalyst in the literature. While carbon monoxide is the main reduction product, we also observe methane as by-product. The results of our detailed pH-dependent studies are explained consistently by a mechanism in which carbon dioxide is activated by the cobalt protoporphyrin through the stabilization of a radical intermediate, which acts as Brønsted base. The basic character of this intermediate explains how the carbon dioxide reduction circumvents a concerted proton–electron transfer mechanism, in contrast to hydrogen evolution. Our results and their mechanistic interpretations suggest strategies for designing improved catalysts.

Three-dimensional porous hollow fibre copper electrodes for efficient and high-rate electrochemical carbon dioxide reduction

Aqueous-phase electrochemical reduction of carbon dioxide requires an active, earth-abundant electrocatalyst, as well as highly efficient mass transport. Here we report the design of a porous hollow fibre copper electrode with a compact three-dimensional geometry, which provides a large area, three-phase boundary for gas–liquid reactions. The performance of the copper electrode is significantly enhanced; at overpotentials between 200 and 400 mV, faradaic efficiencies for carbon dioxide reduction up to 85% are obtained. Moreover, the carbon monoxide formation rate is at least one order of magnitude larger when compared with state-of-the-art nanocrystalline copper electrodes. Copper hollow fibre electrodes can be prepared via a facile method that is compatible with existing large-scale production processes. The results of this study may inspire the development of new types of microtubular electrodes for electrochemical processes in which at least one gas-phase reactant is involved, such as in fuel cell technology.

Electrochemical carbon dioxide and bicarbonate reduction on copper in weakly alkaline media

The electrochemical reduction of CO2 on copper is an intensively studied reaction. However, there has not been much attention for CO2 reduction on copper in alkaline electrolytes, because this creates a carbonate buffer in which CO2 is converted in HCO3− and the pH of the electrolyte decreases. Here, we show that electrolytes with phosphate buffers, which start off in the alkaline region and, after saturation with CO2, end up in the neutral region, behave differently compared to CO2 reduction in phosphate buffers which starts off in the neutral region. In initially alkaline buffers, a reduction peak is observed, which is not seen in neutral buffer solutions. In contrast with earlier literature reports, we show that this peak is not due to the formation of a CO adlayer on the electrode surface but due to the production of formate via direct bicarbonate reduction. The intensity of the reduction peak is influenced by electrode morphology and the identity of the cations and anions in solution. It is found that a copper nanoparticle-covered electrode gives a rise in intensity in comparison with mechanically polished and electropolished electrodes. The peak is observed in the SO42−-, ClO4−-, and Cl−- containing electrolytes, but the formate-forming peak is not seen with Br− and I−.

Iridium-based double perovskites for efficient water oxidation in acid media

The development of active, cost-effective and stable oxygen-evolving catalysts is one of the major challenges for solar-to-fuel conversion towards sustainable energy generation. Iridium oxide exhibits the best available compromise between catalytic activity and stability in acid media, but it is prohibitively expensive for large-scale applications. Therefore, preparing oxygen-evolving catalysts with lower amounts of the scarce but active and stable iridium is an attractive avenue to overcome this economical constraint. Here we report on a class of oxygen-evolving catalysts based on iridium double perovskites which contain 32 wt% less iridium than IrO2 and yet exhibit a more than threefold higher activity in acid media. According to recently suggested benchmarking criteria, the iridium double perovskites are the most active catalysts for oxygen evolution in acid media reported until now, to the best of our knowledge, and exhibit similar stability to IrO2.

Enhanced electrocatalytic activity of Au@Cu core@shell nanoparticles towards CO2 reduction

The development of technologies for the recycling of carbon dioxide into carbon-containing fuels is one of the major challenges in sustainable energy research. Two of the main current limitations are the poor efficiency and fast deactivation of catalysts. Core–shell nanoparticles are promising candidates for enhancing challenging reactions. In this work, Au@Cu core–shell nanoparticles with well-defined surface structures were synthesized and evaluated as catalysts for the electrochemical reduction of carbon dioxide in neutral medium. The activation potential, the product distribution and the long term durability of this catalyst were assessed by electrochemical methods, on-line electrochemical mass spectrometry (OLEMS) and on-line high performance liquid chromatography. Our results show that the catalytic activity and the selectivity can be tweaked as a function of the thickness of Cu shells. We have observed that the Au cubic nanoparticles with 7–8 layers of copper present higher selectivity towards the formation of hydrogen and ethylene; on the other hand, we observed that Au cubic nanoparticles with more than 14 layers of Cu are more selective towards the formation of hydrogen and methane. A trend in the formation of the gaseous products can be also drawn. The H2 and CH4 formation increases with the number of Cu layers, while the formation of ethylene decreases. Formic acid was the only liquid species detected during CO2 reduction. Similar to the gaseous species, the formation of formic acid is strongly dependent on the number of Cu layers on the core@shell nanoparticles. The Au cubic nanoparticles with 7–8 layers of Cu showed the largest conversion of CO2 to formic acid at potentials higher than 0.8 V vs. RHE. The observed trends in reactivity and selectivity are linked to the catalyst composition, surface structure and strain/electronic effects.