Probe effects during concentration determination in scanning electrochemical microscopy

Efficient, sustainable chemical reactions will play a large role in addressing many growing issues, including alternative energy production, greenhouse gas conversion, and pharmaceuticals. Electrochemical reactions are attractive due to their relatively mild reaction conditions and direct use of electricity. The understanding and design of the local liquid-solid interface will guide future progress in electrocatalytic reactions.Over time, nature has evolved many highly efficient reactions through enzymatic reactions. These long-studied catalysts provide complex reaction environments that: 1) enhance interaction with reactants, 2) protect intermediates from side reactions, 3) increase the rates of reactions, and 4) selectively react to a specific product. The overarching lesson to be learned is that the local reaction environment plays a large role in the catalyst's reactivity, selectivity, and efficiency. One way to characterize the local environment is through scanning electrochemical microscopy (SECM), in which a small electrochemical probe is rastered over an interface. A quantitative correlation of the probe response to concentration provides a direct measurement of the local environment.The presence of the SECM probe itself can induce changes in the local environment. Comparing the changed local environment (in situ) to what it would be without the probe present (operando), shows large differences of up to 120% under specific operating conditions. A few physical parameters such as the surface site geometry are shown to have an impact on how significant the probe effects are. Additional parameters such as the tip geometry and tip-surface separation are also to have an impact.A finite element method (FEM) simulation informed by experiments is used to examine the above-mentioned tip effects. It is found that fitting responses to other frequently used electrochemical measurements, such as approach curves and CVs, to parameterize the model appropriately describes experimental SECM results. We first apply this method to study platinum nanoparticles, where a ̃50 nm resolution is the highest resolution to our knowledge for AFM-SECM. Through statistical analysis of the surface, an isolated nanoparticle SECM response is correlated with a concentration profile. It is found that the concentration profile has minimal probe effects due to the use of a conical electrode.Applying a similar approach, we also study the probe effects in pH detection during hydrogen evolution and CO2 reduction. Where we match experimental results to parameterize the system. It shown that there is a pH difference of up to ̃7 pH units underneath the probe due to hindered diffusion. However, even with these large differences, the probes are still able to reflect the trends seen without the probe present. Moreover, it is shown that the physical parameters have correlated responses, indicating that hindered diffusion is controlled by the insulation radius and tip-surface separation.Finally, the importance of the analyte is discussed with regard to its interaction with the tip. In addition to the concentration impact on the response signal, the compatibility with the tip need be considered. Degradation of the tip and/or the redox couple of choice will detrimentally affect the ability to examine the local interface. We show that, of the redox couples examined, ferrocene-based compounds appear to best satisfy the most crucial factors of stability and mild redox potentials.Overall, this work studies and removes the impact of the probe for local concentration detection using SECM. This work acts as a guide to quantitatively study the local environment of electrocatalyzed reactions. This is realized through a combined experimental-FEM approach in which the simulation is informed by experiments such that it's representative of the experimental environment.