Oxygen-induced doping on reduced PEDOT

The conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) has shown promise as air electrode in renewable energy technologies like metal-air batteries and fuel cells. PEDOT is based on atomic elements of high abundance and is synthesized at low temperature from solution. The mechanism of oxygen reduction reaction (ORR) over chemically polymerized PEDOT: Cl still remains controversial with eventual role of transition metal impurities. However, regardless of the mechanistic route, we here demonstrate yet another key active role of PEDOT in the ORR mechanism. Our study demonstrates the decoupling of conductivity (intrinsic property) from electrocatalysis (as an extrinsic phenomenon) yielding the evidence of doping of the polymer by oxygen during ORR. Hence, the PEDOT electrode is electrochemically reduced (undoped) in the voltage range of ORR regime, but O-2 keeps it conducting; ensuring PEDOT to act as an electrode for the ORR. The interaction of oxygen with the polymer electrode is investigated with a battery of spectroscopic techniques.
Funding Agencies|European Research Council (ERC) [307596]; Knut and Alice Wallenberg foundation; Wenner-Gren Foundations; Swedish Research Council; Swedish Foundation for Strategic Research [0-3D]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]