Developing Catalysts Integrated in Gas-Diffusion Electrodes for CO2 Electrolyzers.

ConspectusAs the demand for a carbon-neutral society grows rapidly, research on CO2 electrolysis has become very active. Many catalysts are reported for converting CO2 into value-added products by electrochemical reactions, which have to perform at high Faradaic and energy efficiency to become commercially viable. Various types of CO2 electrolyzers have been used in this effort, such as the H-cell, flow cell, and zero-gap membrane-electrode assembly (MEA) cell. H-cell studies are conducted with electrodes immersed in CO2-saturated electrolyte and have been used to elucidate reaction pathways and kinetic parameters of electrochemical CO2 reduction on many types of catalytic surfaces. From a transport phenomenological perspective, the low solubility and diffusion of CO2 to the electrode surface severely limit the maximum attainable current density, and this metric has been shown to have significant influence on the product spectrum. Flow and MEA cells provide a solution in the form of gas-diffusion electrodes (GDEs) that enable gaseous CO2 to closely reach the catalyst layer and yield record-high current densities. Because GDEs involve a complicated interface consisting of the catalyst surface, gaseous CO2, polymer overlayers, and liquid electrolyte, catalysts with high intrinsic activity might not show high performance in these GDE-based electrolyzers. Catalysts showing low overpotentials at low current densities may suffer from poor electron conductivity and mass transfer limitations at high current densities. Furthermore, the stability of the GDE-based catalysts is often compromised as CO2 electrolysis is pursued with high activity, most notoriously by electrolyte flooding.In this Account, we introduce recent examples where the electrocatalysts were integrated in GDEs, achieving high production rates. The performance of such systems is contingent on both GDE and cell design, and various parameters that affect the cell performance are discussed. Gaseous products, such as carbon monoxide, methane, and ethylene, and liquid products, such as formate and ethanol, have been mainly reported with high partial current density using the flow or MEA cells. Different strategies to this end are described, such as controlling microenvironments by the use of polymers mixed within the catalyst layer or the functionalization of catalyst surfaces with ligands to increase local concentrations of intermediates. Unique CO2 electrolyzer designs are also treated, including the incorporation of light-responsive plasmonic catalysts in the GDE, and combining the electrolyzer with a fermenter utilizing a microbial biocatalyst to synthesize complex multicarbon products. Basic conditions which the catalyst should satisfy to be adapted in the GDEs are listed, and our perspective is provided.

Highly Durable Heterogeneous Atomic Catalysts.

ConspectusSingle-atom catalysts (SACs), in which surface metal atoms are isolated on the surface of a support, have received a tremendous amount of attention recently because this structure would utilize precious metals fully, without occluding atoms inside nanoparticles, and enable unique surface reactions which typical nanoparticle catalysts cannot induce. Various synthesis methods and characterization techniques have been reported that yield enhanced activity and selectivity. The single-atom structures were realized on various supports such as metal oxide/carbide/nitride, porous materials derived from zeolite or metal-organic frameworks, and carbon-based materials. Additionally, when the metal atoms are isolated on other metal nanoparticles, this material is denoted as a single-atom alloy (SAA). The single-atom structure, however, cannot catalyze the surface reaction that necessitates ensemble sites, where several metal atoms are located nearby. Very recently, ensemble catalysts, in which all of the metal atoms are exposed at the surface with neighboring metal atoms, have been reported, overcoming the limitation of single-atom catalysts. We call all of these materials (SACs, SAAs, and ensemble catalyst) heterogeneous atomic catalysts, indicating that the surface metal atomic structure is intentionally controlled. To use these atomic catalysts for practical applications, high durability should be guaranteed, which has received relatively less attention.In this Account, we discuss recent examples of heterogeneous atomic catalysts with high durability. Structural stability, indicating whether the surface atomic structure is thermodynamically stable, should be carefully considered. Typically, metal atoms are immobilized on a highly defective support, stabilizing both the metal atom and the support. The surface metal atoms might become destabilized upon the adsorption of chemical intermediates. This transient behavior should be carefully monitored; density functional theory (DFT) calculations are particularly useful in estimating this stability. Aside from structural stability, the catalyst performance can be degraded significantly by poisoning with impurities. If the single-atom sites are susceptible to impurities with stronger adsorption, the surface reaction would not occur efficiently, leading to a decrease in activity without structure degradation. A long-term durability test should be performed for target reactions. Heterogeneous atomic catalysts have been used for various electrochemical, photocatalytic, and thermal reactions. Although electricity, light, and heat are just different forms of energy, the specific conditions which the catalyst should satisfy are different. Whereas precious metal atoms are mostly used as surface-active sites, the properties of the support are different depending on the type of reaction. For example, the support should have high conductivity for electrochemical reactions, it should be able to absorb light for photocatalytic reactions, and it should be durable at high temperature in the presence of steam for thermal reactions. Highly durable heterogeneous atomic catalysts are certainly possible with a great potential for practical applications. These new catalysts can accelerate the current paradigm shift toward more sustainable chemical production.

Nonconductive Metal Oxide Gas Diffusion Layer for Mitigating Electrowetting during CO2 Electrolysis.

Gas diffusion electrodes (GDEs) are extensively used for high current density electrochemical CO2 electrolysis (ECO2R), enabled by significantly reducing mass transfer resistance of CO2 to the catalyst layer. Conventionally, these GDEs are based upon hydrophobic carbon-based gas-diffusion layers (GDLs) that facilitate the gas transport; however, these supports are prone to flood with electrolyte during electrolysis. This potential-induced flooding, known as electrowetting, is related to the inherent conductivity of carbon and limits the activity of ECO2R. To investigate the effect of electrical conductivity more carefully, a GDE is constructed based on a Cu mesh with a nonconductive microporous GDL applied to this substrate, the latter composed of a mixture of metal oxide and polytetrafluoroethylene. With alumina as the metal oxide, a stable operation is obtained at -200 mA cm-2 with 70% selectivity for ECO2R (with over half toward C2+ products) without flooding as observed by in situ microscopy. On the contrary, with a Vulcan carbon-based GDL, the initial activity is rapidly lost as severe flooding ensues. It is reasoned that electrowetting is averted by virtue of the nonconductive nature of alumina, providing a new perspective on alternative GDL compositions and their influence on ECO2R performance.

Photo-assisted electrochemical CO2 reduction using a translucent thin film electrode.

Herein, we introduce a new concept of photo-assisted electrochemical CO2 reduction through a translucent thin film electrode. The light-compatible thin film electrode directly exposes Au nanoparticle-loaded Ag nanowires to gaseous CO2, obtaining a CO production rate of 0.7 mmol cm-2 h-1 with a photocurrent density of 6.05 mA cm-2 at -1.1 VRHE.