Product-to-intermediate relay achieving complete oxygen reduction reaction (cORR) with Prussian blue integrated nanoporous polymer cathode in fuel cells

The oxygen reduction reaction (ORR) is an essential process in electrocatalysis limiting the commercialization of sustainable energy conversion technologies, such as fuel cells. The use of conducting polymers as molecular porous and conducting catalysts obtained from the high abundance elements enables the route towards low cost and high-throughput fabrication of disposable plastic electrodes of fuel cells. Poly(3,4-ethylenedioxythiophene) (PEDOT) is a 2-electron ORR electrocatalyst yielding specifically hydrogen peroxide that limits the full utilization of chemical energy of oxygen. Here, we demonstrated an innovative product-to-intermediate relay approach achieving complete oxygen reduction reaction (cORR) with Prussian blue (PB) integrated microporous PEDOT cathode in fuel cells. The microporous structured PEDOT electrode prepared via a simple cryosynthesis allows the bulk integration and stabilization of the poor conducting PB co-catalyst into the PEDOT ion-electron conductor, while the microporous PEDOT allows effective oxygen diffusion into the matrix. We evaluated systematically the effect of sequential PEDOT 2-electron ORR followed by PB co-catalysis launching hydrogen peroxide reduction reaction (HPRR) into H2O. This resulted in the establishment of electronic and ionic transport between PEDOT and PB catalyst enabling the combination of enhanced ORR electrocatalysis by means of the ORR course extension from 2- to 4-electron reduction to achieve cORR. The cORR performance delivered by the product-to-intermediate relay between microporous PEDOT and PB co-catalysis led to a four times increase in power density of model proton-exchange membrane fuel cell (PEMFC) assembled from the polymer-based air-breathing cathode. [Display omitted] •The inorganic redox material was integrated into the bulk of conducting polymer.•The conducting polymer enables both electronic and ionic transports to immobilized inorganic semiconductor.•The conducting polymer contributes with intrinsic 2-electron oxygen reduction reaction yielding convertible product.•We achieved the multistep electrochemical conversion of oxygen to water on conducting polymer.•We developed one of the first polymer-based air cathode for proton-exchange membrane fuel cell.