Insights into the spontaneous formation of hybrid PdOx/PEDOT films: electroless deposition and oxygen reduction activity

Vigil, Julian A.; Brumbach, Michael T.; Duay, Jonathon; Lambert, Timothy N.

doi:10.1039/c8ra03505a

Insights into the spontaneous formation of hybrid PdO_x/PEDOT films: electroless deposition and oxygen reduction activity

Journal Article · Fri Jul 06 00:00:00 EDT 2018 · RSC Advances

DOI:https://doi.org/10.1039/c8ra03505a· OSTI ID:2469880

^[1]; Brumbach, Michael T. ^[1]; Duay, Jonathon ^[1]; ^[1]

Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

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% Pd⁰, 64 ± 3 at% Pd²⁺, and 18 ± 4 at% Pd⁴⁺ by X-ray photoelectron spectroscopy) and the formation of stable, electrochemically reversible Pd⁰/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.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: NA0003525

OSTI ID:: 2469880

Journal Information:: RSC Advances, Journal Name: RSC Advances Journal Issue: 43 Vol. 8; ISSN 2046-2069

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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