Insights into the spontaneous formation of hybrid PdOx/PEDOT films: electroless deposition and oxygen reduction activity. Issue 43 (6th July 2018)

• Record Type: Journal Article
• Authors: Vigil, Julian A.; Brumbach, Michael T.; Duay, Jonathon; Lambert, Timothy N.
• Is Part Of: RSC advances. Volume 8:Issue 43(2018)
• Page Start: 24428
• Page End: 24433
• Publication Date: 2018-07-06
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c8ra03505a
• Languages: English
• ISSNs: 2046-2069

Abstract

Abstract : Hybrid PdO x /PEDOT films efficiently catalyse the direct 4e − oxygen reduction reaction in alkaline electrolyte. Abstract : Hybrid palladium oxide/poly(3, 4-ethylenedioxythiophene) (PdO x /PEDOT) films were prepared through a spontaneous reaction between aqueous PdCl4 2− ions and a nanostructured film of electropolymerized PEDOT. Spectroscopic and electrochemical characterization indicate the presence of mixed-valence Pd species as-deposited (19 ± 7 at% Pd 0, 64 ± 3 at% Pd 2+, and 18 ± 4 at% Pd 4+ by X-ray photoelectron spectroscopy) and the formation of stable, electrochemically reversible Pd 0 /α-PdO x active species in alkaline electrolyte and furthermore in the presence of oxygen. The elucidation of the Pd speciation as-deposited and in solution provides insight into the mechanism of electroless deposition in neutral aqueous conditions and the electrocatalytically active species during oxygen reduction in alkaline electrolyte. The PdO x /PEDOT film catalyses 4e − oxygen reduction ( n = 3.97) in alkaline electrolyte at low overpotential (0.98 V vs. RHE, onset potential), with mass- and surface area-based specific activities competitive with, or superior to, commercial 20% Pt/C and state-of-the-art Pd- and PEDOT-based nanostructured catalysts. The high activity of the nanostructured hybrid PdO x /PEDOT film is attributed to effective dispersion of accessible, stable Pd active sites in the PEDOT matrix.