Visualisation and quantification of flooding phenomena in gas diffusion electrodes (GDEs) used for electrochemical CO2 reduction: A combined EDX/ICP–MS approach

The most promising strategy to up-scale the electrochemical CO2 reduction reaction (ec-CO2RR) is based on the use of gas diffusion electrodes (GDEs) that allow current densities close to the range of 1 A/cm2 to be reached. At such high current densities, however, the flooding of the GDE cathode is often observed in CO2 electrolysers. Flooding hinders the access of CO2 to the catalyst, and by thus leaving space for (unwanted) hydrogen evolution, it usually leads to a decrease of the observable Faradaic efficiency of CO2 reduction products. To avoid flooding as much as possible has thus become one of the most important aims of to-date ec-CO2RR engineering, and robust analytical methods that can quantitatively assess flooding are now in demand. As flooding is very closely related to the formation of carbonate salts within the GDE structure, in this paper we use alkali (in particular, potassium) carbonates as a tracer of flooding. We present a novel analytical approach —based on the combination of cross-sectional energy-dispersive X-ray (EDX) mapping and inductively coupled plasma mass spectrometry (ICP--MS) analysis— that can not only visualise, but can also quantitatively describe the electrolysis time dependent flooding in GDEs, leading to a better understanding of electrolyser malfunctions.

Molecular Inhibition for Selective CO2 Conversion

Electrochemical CO2 reduction presents a sustainable route to the production of chemicals and fuels. Achieving a narrow product distribution with copper catalysts is challenging and conventional material modifications offer limited control over selectivity. Here, we show that the mild cathodic potentials required to reach high currents in an alkaline gas-fed flow cell permits retention of a surface-bound thiol (4-mercaptopyridine), enabling molecule-directed selective formate generation at high reaction rates. Combined experimental and computational results showed that formate production is favoured due to the inhibition of a CO producing pathway caused by destabilising interactions with the anchored molecule. The immobilisation of molecules to inhibit specific carbon-based products therefore offers a novel approach to rationally tune the selectivity of heterogeneous catalysts.

Scale Effect on Producing Gaseous and Liquid Chemical Fuels via CO2 Reduction

Producing chemical fuels from sunlight is a sustainable way to utilize solar energy and reduce carbon emissions. Within the current photovoltaic-electrolysis or photoelectrochemical-based solar fuel generation system, electrochemical CO2 reduction is the key step. Although there has been important progress in developing new materials and devices, scaling up electrochemical CO2 reduction is essential to promote the industrial application of this technology. In this work, we use Ag and In as the representative electrocatalyst for producing gas and liquid products in both small and big electrochemical cells. We find that gas production is blocked more easily than liquid products when scaling up the electrochemical cell. Simulation results show that the generated gas product, CO, forms bubbles on the surface of the electrocatalyst, thus blocking the transport of CO2, while there is no such trouble for producing the liquid product such as formate. This work provides methods for studying the mass transfer of CO, and it is also an important reference for scaling up solar fuel generation devices that are constructed based on electrochemical CO2 reduction.