Application of an electrochemical quartz crystal microbalance to a study of the anodic deposition of PbO[sub 2] and Bi-PbO[sub 2] films on gold electrodes

Journal Article · Tue Mar 01 04:00:00 EST 1994 · Journal of the Electrochemical Society; (United States)

DOI:https://doi.org/10.1149/1.2054786· OSTI ID:7107315

Gordon, Jr, J S; Young, Jr, V G; Johnson, D C ^[1]

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1. Iowa State Univ., Ames, IA (United States). Dept. of Chemistry

The net rate of change in surface mass measure with respect to faradaic charge ([Delta]m/[Delta]q) is calculated for electrodeposited films from the slopes of plots of frequency vs. charge (df/dq). Abrupt changes in df/dq observed early in the deposition of PbO[sub 2] and some Bi-PbO[sub 2] films correspond to the transition from two-dimensional island growth to one-dimensional growth of the continuous films. Further, these changes in df/dq are a consequence of differences in the surface hydration of the deposited films in comparison with the AuO substrate. XPS data indicate that Bi/Pb ratios in Bi-PbO[sub 2] films correspond approximately to the [Bi[sup 3+]]/[Pb[sup 2+]] ratios in the deposition solutions. Further, voltammetric data for oxidation of dimethylsulfoxide indicate the catalytic activity of the Bi-PbO[sub 2] films increases with the increased Bi/Pb ratios in these films. Nevertheless, limiting values of [Delta]m/[Delta]q are virtually identical for the deposition of the Bi-PbO[sub 2] films containing variable Bi-Pb ratios. The precision of the EQCM data does not allow designation of exact compositions of these various Bi-PbO[sub 2] films. Nevertheless, the authors speculate that the EQCM data indicate the deposition of Bi[sup 3+] as Bi(5) with some Bi(4), and the incorporation of H[sub 2]O in the Bi-PbO[sub 2] films. Limiting values of [Delta]m/[Delta]q = ca. 1.22 mg/C for thick lead oxide films deposited in the absence of Bi[sup 3+] are within experimental error of the theoretical value of 1.24 mg/C for pure PbO[sub 2] and the authors conclude there is no evidence from the EQCM data for incorporation of H[sub 2]O and/or supporting electrolyte into these films.

• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 7107315
• Journal Information: Journal of the Electrochemical Society; (United States), Journal Name: Journal of the Electrochemical Society; (United States) Vol. 141:3; ISSN JESOAN; ISSN 0013-4651
• Country of Publication: United States
• Language: English

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