The Electrostatic Stimulation of Adsorbed Carbon Monoxide Oxidation on Pt in Aqueous Acidic Electrolytes

Abstract

The oxidation of adsorbed carbon monoxide on Pt electrodes, CO(ads)|Pt, in aqueous electrolytes ranks among the most studied reactions in electrocatalysis both from theoretical[1]and experimental viewpoints.[2][3] Much of the interest in this electron transfer process stems from the role CO(ads) plays as an impurity that affects adversely the operation of H2|O2 fuel cells. Consensus appears to have been reached regarding the role of adsorbed hydroxyl, OH.(ads) in controlling the activation and ultimate oxidation of CO(ads). The present contribution illustrates the use of electrochemical stimulation techniques developed in our laboratory[4] to explore new aspects of this process not as yet unveiled by the use of more conventional methods. As described in our earlier publications,[4,5] electrode stimulation refers to changes in the rates of heterogeneous electron transfer processes involving adsorbed species induced by modifications in the electrostatic potential in the solution immediately adjacent to the electrode generated by the passage of current between an electrode placed very close to the working electrode, WE, polarized at constant potential, and a second electrode far away from it. The electrochemical cell used for these experiments consisted of a glass tube covered at each end with custom-made Teflon caps and, thus, similar in design to that described by Qi et al.[4] Experiments were performed in Ar-purged 0.1 M H2SO4 involving CO adsorbed at saturation coverages on polycrystalline Pt, polarized at EWE = 0.8 V, a potential very close to the onset of CO(ads) oxidation with a Au disk electrode placed directly above it working as a stimulating electrode, SE, i.e. face to face configuration. Shown in Fig. 1 are plots of the current flowing through the SE (red), iSE and iWE (black) (see Left Panel) and their expanded views during stimulation (Middle Panel) and CO full oxidation (Right Panel), respectively. As shown in the middle panel in this figure. the passage of a negative iSE, elicits a positive iWE ascribed to CO oxidation, which persists even when iSE turns positive, until the end of the stimulation process (see Right Panel), which takes several seconds. In brief, a single stimulation lasting 140 ms can trigger the full oxidation of the entire adsorbed CO layer in CO|Pt over a subsequent period of ca. 4 s. The most likely explanation for this unique effect may be found in the formation of adsorbed OH. on sites previously covered with CO, as the CV of bare Pt would strongly suggest, which will promote the subsequent oxidation of CO(ads), a process that will propagate through the entire Pt surface. Further support for this mechanism was provided by an experiment in which the WE potential was stepped down to 0.4 V immediately after the stimulation was applied, which stopped virtually instantaneously the further oxidation of CO(ads). Experiments are now in progress to image the surface of the CO|Pt electrode during and after the stimulation to monitor in real time the rates of propagation and to provide a more details theoretical model to account for this phenomenon. References 1 Gao, W.; Mueller, J.E.; Jiang, Q.; Jacob, T. Angew. Chem. Int. Ed. 2012, 51, 9448 –94522 Scott, S.B.; Kibsgaarda, J.; Vesborga, P.C.K.; Chorkendorff, I. Electrochim. Acta 2021, 374, 1378423 Scott, S.B.; Kibsgaarda, J.; Vesborga, P.C.K.; Chorkendorff, I. Electrochim. Acta 2021, 374, 1378444 Han, Q.; Georgescu, N. S.; Gibbons, J.; Scherson, D. Electrochim. Acta 2019, 325, 1349575 Heer, A.S.; Mantelli, H; Han, Q.; Georgescu, N. S.; Scherson, D. in preparation. Acknowledgement Support for this work provided by NSF, CHE-1808592.Fig. 1. Plots of iWE and iSE recorded for EWE = 0.8 V prior, during and following WE stimulation (see text for details) (Left Panel). The middle and right panels show expanded views of the data in the left panel during stimulation and CO full oxidation, respectively. Figure 1