Origins of hydrogen peroxide selectivity during oxygen reduction on organic mixed ionic-electronic conducting polymers

09 December 2022, Version 1


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 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, ab initio calculations, and steady-state microkinetic simulations, we find that the n-type OMIEC, p(NDI-T2 P75), reduces oxygen selectively to hydrogen peroxide through a non-catalytic, outer-sphere pathway. This pathway serves as a general guide to understand the reactivity of an expanded set of n- and p-type OMIECs investigated in this work and provides a framework to rationalize when (or if) organic compounds function as heterogeneous catalysts for oxygen reduction.


oxygen reduction reaction
hydrogen peroxide
microkinetic modeling
operando spectroscopy
density functional theory

Supplementary materials

Supplementary Information
Methods, Tables S1-S2, Figures S1-S15, Supplementary Discussion, and Supplementary References


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