Time-Resolved Local pH Measurements during CO 2 Reduction Using Scanning Electrochemical Microscopy: Buffering and Tip Effects

JACS Au, vol. 1, pp. 1915–1924

Abstract

High Resolution Image Download MS PowerPoint Slide The electrochemical reduction of CO 2 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 CO 2 reduction reaction. Local pH measurements can be realized using Scanning Electrochemical Microscopy (SECM); however, finding a pH probe that is stable and selective under CO 2 reduction reaction conditions is challenging. Here, we have used our recently developed voltammetric pH sensor to perform pH measurements in the diffusion layer during CO 2 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 CO 2 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 CO 2 atmosphere due to the formation of HCO 3 – 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.

Authors 6

1. Mariana C. O. Monteiro Aachen

   Leiden University

   Affiliation as printed

   Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands

2. Alex Mirabal

   Michigan State University

   Affiliation as printed

   Department of Chemical & Materials Engineering, Michigan State University, East Lansing, Michigan 48824, United States

3. Leon Jacobse

   Deutsches Elektronen-Synchrotron DESY

   Affiliation as printed

   Centre for X-ray and Nano Science CXNS, Deutsches Elektronen-Synchrotron DESY, Notkestrasse 85, D-22607 Hamburg, Germany

4. Katharina Doblhoff-Dier Aachen

   Leiden University

   Affiliation as printed

   Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands

5. Scott Calabrese Barton

   Michigan State University

   Affiliation as printed

   Department of Chemical & Materials Engineering, Michigan State University, East Lansing, Michigan 48824, United States

6. Marc T. M. Koper corresponding Aachen

   Leiden University

   Affiliation as printed

   Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands