Local environment plays an important role in steering the reaction pathways in electrochemical CO 2 reduction reaction. Here, we present three approaches to modulate local CO 2 concentration in gas-diffusion electrode flow electrolyzers. Employing monodisperse Cu 2 O nanoparticles as the model catalysts, we demonstrate that providing a moderate local CO 2 concentration is effective in promoting C-C coupling. Ultimately, this study serves as a rational guide to tune CO 2 mass transport in gas-diffusion electrode electrolyzers for the optimal production of valuable multi-carbon molecules.

Development of efficient and selective electrocatalysts is a key challenge to achieve an industry-relevant electrochemical CO 2 reduction reaction (CO 2 RR) to produce commodity chemicals. Here, we report that Au 25 clusters with Authiolate staple motifs can initiate electrocatalytic reduction of CO 2 to CO with nearly zero energy loss and achieve a high CO 2 RR current density of 540 mA cm −2 in a gas-phase reactor. Electrochemical kinetic investigations revealed that the high CO 2 RR activity of the Au 25 originates from the strong CO 2 binding affinity, leading to high CO 2 electrolysis performance in both concentrated and dilute CO 2 streams. Finally, we demonstrated an 18.0% solar-to-CO conversion efficiency using a Au 25 electrolyzer powered by a Ga 0.5 In 0.5 P/GaAs photovoltaic cell. The electrolyzer also showed 15.9% efficiency and a 5.2% solar-driven single-path CO 2 conversion rate in a 10% CO 2 gas stream, the CO 2 concentration in a typical flue gas.

Electrochemical CO2 conversion offers a promising route for value-added products such as formate, carbon monoxide, and hydrocarbons. As a result of the highly required overpotential for CO2 reduction, researchers have extensively studied the development of catalyst materials in a typical H-type cell, utilizing a dissolved CO2 reactant in the liquid phase. However, the low CO2 solubility in an aqueous solution has critically limited productivity, thereby hindering its practical application. In efforts to realize commercially available CO2 conversion, gas-phase reactor systems have recently attracted considerable attention. Although the achieved performance to date reflects a high feasibility, further development is still required in order for a well-established technology. Accordingly, this review aims to promote the further study of gas-phase systems for CO2 reduction, by generally examining some previous approaches from liquid-phase to gas-phase systems. Finally, we outline major challenges, with significant lessons for practical CO2 conversion systems.

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Photoelectrochemical (PEC) cells have attracted much attention as a viable route for storing solar energy and producing value-added chemicals and fuels. However, the competition between light absorption and electrocatalysis at a restrained cocatalyst area on conventional planar-type photoelectrodes could limit their conversion efficiency. Here, we demonstrate a new monolithic photoelectrode architecture that eliminate the optical-electrochemical coupling by forming locally nanostructured cocatalysts on a photoelectrode. As a model study, Ni inverse opal (IO), an ordered three-dimensional porous nanostructure, was used as a surface-area-controlled electrocatalyst locally formed on Si photoanodes. The optical-electrochemical decoupling of our monolithic photoanodes significantly enhances the PEC performance for the oxygen evolution reaction (OER) by increasing light absorption and by providing more electrochemically active sites. Our Si photoanode with local Ni IOs maintains an identical photolimiting current density but reduces the overpotential by about 120 mV compared to a Si photoanode with planar Ni cocatalysts with the same footprint under 1 sun illumination. Finally, a highly efficient Si photoanode with an onset potential of 0.94 V vs reversible hydrogen electrode (RHE) and a photocurrent density of 31.2 mA/cm at 1.23 V vs RHE in 1 M KOH under 1 sun illumination is achieved with local NiFe alloy IOs.