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 00:00:00 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]

---

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), Vol. 141:3; ISSN 0013-4651
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION
54 ENVIRONMENTAL SCIENCES
BISMUTH
CATALYTIC EFFECTS
ELECTRODEPOSITION
DMSO
OXIDATION
LEAD OXIDES
TOXIC MATERIALS
WASTE PROCESSING
ELECTROLYTIC CELLS
CHALCOGENIDES
CHEMICAL REACTIONS
DEPOSITION
ELECTROLYSIS
ELEMENTS
HAZARDOUS MATERIALS
LEAD COMPOUNDS
LYSIS
MANAGEMENT
MATERIALS
METALS
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PROCESSING
SULFOXIDES
SURFACE COATING
WASTE MANAGEMENT
400400* - Electrochemistry
320305 - Energy Conservation
Consumption
& Utilization- Industrial & Agricultural Processes- Industrial Waste Management
540320 - Environment
Aquatic- Chemicals Monitoring & Transport- (1990-)
540220 - Environment
Terrestrial- Chemicals Monitoring & Transport- (1990-)