Nonidealities in CO₂ Electroreduction Mechanisms Revealed by Automation-Assisted Kinetic Analysis

In electrocatalysis, mechanistic analysis of reaction rate data often relies on the linearization of relatively simple rate equations; this is the basis for typical Tafel and reactant order dependence analyses. However, for more complex reaction phenomena, such as surface coverage effects or mixed control, these common linearization strategies will yield incomplete or uninterpretable results. Cohesive kinetic analysis, which is often used in thermocatalysis and involves quantitative model fitting for data collected over a wide range of reaction conditions, requires more data but also provides a more robust strategy for interrogating reaction mechanisms. In this work, we report a robotic system that improves the experimental workflow for collecting electrochemical rate data by automating sequential testing of up to 10 electrochemical cells, where each cell can have a different electrode, electrolyte, gas-phase reactant composition, and applied voltage. We used this system to investigate the mechanism of carbon dioxide electroreduction to carbon monoxide at several immobilized metal tetrapyrroles. Specifically, at cobalt phthalocyanine (CoPc), cobalt tetraphenylporphyrin (CoTPP), and iron phthalocyanine (FePc), we see signatures of complex reaction mechanisms, where observed bicarbonate and CO₂ order dependences change with applied potential. We illustrate how phenomena such as electrolyte poisoning and potential-dependent degrees of rate control can explain the observed kinetic behaviors. Our mechanistic analysis suggests that CoPc and CoTPP share a similar reaction mechanism, akin to one previously proposed, whereas the mechanism for FePc likely involves a species later in the catalytic cycle as the most abundant reactive intermediate. Our study illustrates that complex reaction mechanisms that are not amenable to common Tafel and order dependence analyses may be quite prevalent across this class of immobilized metal tetrapyrrole electrocatalysts.