Origins of hydrogen peroxide selectivity during oxygen reduction on organic mixed ionic-electronic conducting polymers
Artikel i vetenskaplig tidskrift, 2023

Electrochemical reduction of atmospheric oxygen provides carbon emission-free pathways for the generation of electricity from chemical fuels and for the distributed production of green chemical oxidants like hydrogen peroxide. Recently, organic mixed ionic-electronic conducting polymers (OMIECs) have been reported as a new class of active electrode materials for the oxygen reduction reaction. This work sets out to identify the operative oxygen reduction mechanism of OMIECs through a multi-faceted experimental and theoretical approach. Using a combination of pH-dependent electrochemical characterization, operando UV-Vis and Raman spectroscopy, and ab initio calculations, we find that the n-type OMIEC, p(NDI-T2 P75), displays pH-dependent activity for the selective reduction of oxygen to the 2-electron hydrogen peroxide product. We use microkinetic simulations of the electrochemical behavior to rationalize our experimental observations through a polaron-mediated, non-adsorptive pathway involving chemical reduction of oxygen to the 1-electron superoxide intermediate followed by pH-dependent catalytic disproportionation to hydrogen peroxide. Finally, this pathway is applied to understand the experimental oxygen reduction reactivity across several n- and p-type OMIECs.

Författare

Ana De La Fuente Durán

Stanford University

Allen Yu Lun Liang

Stanford University

Ilaria Denti

Stanford University

Hang Yu

Imperial College London

Drew Pearce

Imperial College London

Adam Marks

Stanford University

Emily Penn

Stanford University

Jeremy Treiber

Stanford University

Karrie Weaver

Stanford University

Lily Turaski

Stanford University

Iuliana P. Maria

Imperial College London

University of Oxford

Sophie Griggs

University of Oxford

Xingxing Chen

Anhui University

Alberto Salleo

Stanford University

William C. Chueh

Stanford University

J. Nelson

Imperial College London

Alexander Giovannitti

Stanford University

Chalmers, Kemi och kemiteknik, Tillämpad kemi

J. Tyler Mefford

Stanford University

Energy and Environmental Sciences

1754-5692 (ISSN) 17545706 (eISSN)

Vol. 16 11 5409-5422

Ämneskategorier

Oorganisk kemi

Materialkemi

DOI

10.1039/d3ee02102e

Mer information

Senast uppdaterat

2024-03-07