Spatially PatternedArchitectures to Modulate CO₂ Reduction Cascade CatalysisKinetics

Electrochemical CO₂ reduction using renewable sources of electrical energy holds promise for converting CO₂ into fuels and chemicals. The complex interactions among chemical/electrochemical reactions and mass transport make it difficult to analyze the effect of an individual process on electrode performance based only on experimental methods. Here, we developed a generalized steady-state simulation to describe an electrode surface in which sequential cascade catalysts are patterned in a periodic trench design. If appropriately constructed, this trench geometry is hypothesized to be able to yield a higher net current density for a CO₂ reduction (CO₂R) cascade reaction. We have used realistic experimental reaction kinetics to investigate the role of trench geometry in mass transport, local microenvironments, and selectivity for a model CO₂R cascade reaction. The model considers local concentration gradients of bicarbonate species at quasi-equilibrium and catalytic surface reactions based on concentration-dependent Butler–Volmer kinetics. Our results suggest that varying the spatial distribution of active sites plays a significant role in facilitating effective mass transport between active sites, modulating selectivity for the cascade reaction, and enhancing the yield of desirable cascade products. Moreover, we observe that this trench geometry significantly alters the cascade reaction rate by affecting the local pH, which can cause inadvertent depletion of available aqueous CO₂ to limit the CO₂R cascade kinetics and modest suppression of the hydrogen evolution reaction (HER). The results highlight the trade-offs between mass transport, pH, and reaction kinetics that become apparent only when considering the coupled physics of all processes at the electrode surface. This model can thus serve as a primary tool to build more selective and efficient patterned architectures for the CO₂R cascade catalysis.