RESUMEN
The electrochemical reduction of CO2 is widely studied as a sustainable alternative for the production of fuels and chemicals. The electrolyte's bulk pH and composition play an important role in the reaction activity and selectivity and can affect the extent of the buildup of pH gradients between the electrode surface and the bulk of the electrolyte. Quantifying the local pH and how it is affected by the solution species is desirable to gain a better understanding of the CO2 reduction reaction. Local pH measurements can be realized using Scanning Electrochemical Microscopy (SECM); however, finding a pH probe that is stable and selective under CO2 reduction reaction conditions is challenging. Here, we have used our recently developed voltammetric pH sensor to perform pH measurements in the diffusion layer during CO2 reduction using SECM, with high time resolution. Using a 4-hydroxylaminothiophenol (4-HATP)/4-nitrosothiophenol (4-NSTP) functionalized gold ultramicroelectrode, we compare the local pH developed above a gold substrate in an argon atmosphere, when only hydrogen evolution is taking place, to the pH developed in a CO2 atmosphere. The pH is monitored at a fixed distance from the surface, and the sample potential is varied in time. In argon, we observe a gradual increase of pH, while a plateau region is present in CO2 atmosphere due to the formation of HCO3 - buffering the reaction interface. By analyzing the diffusion layer dynamics once the sample reaction is turned "off", we gain insightful information on the time scale of the homogeneous reactions happening in solution and on the time required for the diffusion layer to fully recover to the initial bulk concentration of species. In order to account for the effect of the presence of the SECM tip on the measured pH, we performed finite element method simulations of the fluid and reaction dynamics. The results show the significant localized diffusion hindrance caused by the tip, so that in its absence, the pH values are more acidic than when the tip is present. Nonetheless, through the simulation, we can account for this effect and estimate the real local pH values across the diffusion layer.
RESUMEN
Mass-transport-limited catalysis and membrane transport can be characterized by concentration profiles surrounding active surfaces. Scanning electrochemical microscopy (SECM) is a tool that has been used to measure concentration profiles; however, the presence and geometry of the tip can distort these profiles due to hindered diffusion, which in turn alters chemical behavior at the catalytic surface. To fully characterize the behavior of surface features such as catalytic sites, it is essential to account for and analytically remove the effect of tip presence. In this work, atomic force microscopy-based SECM (AFM-SECM) measurements over poly(tetrafluoroethylene) (PTFE) and gold electrode surfaces are used to measure negative and positive-feedback approach curves, respectively. By inversely fitting these approach curves with a finite element method (FEM) model, we derive kinetic and geometric tip parameters that characterize the effect of tip presence. Tip effects may be removed in the model to estimate concentration profiles and reaction properties for the case where no tip is present. A maximum 120% increase in the concentration at one tip radii above the surface is observed due to the presence of the tip, where the concentration field is compressed vertically, in proportion to surface feature size and tip separation. Conical AFM-SECM tips, with a higher ratio of tip height to the base size, introduce less concentration distortion than disk-shaped AFM-SECM tips.
RESUMEN
Catalytic activity toward the oxygen reduction reaction (ORR) of platinum group metal-free (PGM-free) electrocatalysts integrated with an enzyme (bilirubin oxidase, BOx) in neutral media was studied. The effects of chemical and morphological characteristics of PGM-free materials on the enzyme enhancement of the overall ORR kinetics was investigated. The surface chemistry of the PGM-free catalyst was studied using X-ray Photoelectron Spectroscopy. Catalyst surface morphology was characterized using two independent methods: length-scale specific image analysis and nitrogen adsorption. Good agreement of macroscopic and microscopic morphological properties was found. Enhancement of ORR activity by the enzyme is influenced by chemistry and surface morphology of the catalyst itself. Catalysts with a higher nitrogen content, specifically pyridinic moieties, showed the greatest enhancement. Furthermore, catalysts with a higher fraction of surface roughness in the range of 3-5â nm exhibited greater performance enhancement than catalysts lacking features of this size.
