Spatially Patterned Architectures to Modulate CO2 Reduction Cascade Catalysis Kinetics

• Published in: ACS catalysis Vol. 15; no. 7; pp. 5894 - 5905
• Main Authors: García-Batlle, Marisé, Fernandez, Pablo, Sheehan, Colton J., He, Shi, Mallouk, Thomas E., Parsons, Gregory N., Cahoon, James F., Lopez, Rene
• Format: Journal Article
• Language: English
• Published: American Chemical Society 04.04.2025
• Subjects: spatial rearrangement; cascade catalysis; modeling; CO2 reduction; COMSOL; geometrical parametrization
• ISSN: 2155-5435; 2155-5435
• DOI: 10.1021/acscatal.5c01176

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.