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A rational approach for a photosystem II-based electrode assembly is described, integrating redox polymers with high surface area hierarchically structured electrodes.

Hydrogen is one of the most promising alternatives for fossil fuels. However, the power output of hydrogen/oxygen fuel cells is often restricted by mass transport limitations of the substrate. Here, we present a dual-gas breathing H2/air biofuel cell that overcomes these limitations. The cell is equipped with a hydrogen-oxidizing redox polymer/hydrogenase gas-breathing bioanode and an oxygen-reducing bilirubin oxidase gas-breathing biocathode (operated in a direct electron transfer regime). The bioanode consists of a two layer system with a redox polymer-based adhesion layer and an active, redox polymer/hydrogenase top layer. The redox polymers protect the biocatalyst from high potentials and oxygen damage. The bioanodes show remarkable current densities of up to 8 mA cm-2. A maximum power density of 3.6 mW cm-2 at 0.7 V and an open circuit voltage of up to 1.13 V were achieved in biofuel cell tests, representing outstanding values for a device that is based on a redox polymer-based hydrogenase bioanode.

This manuscript provides the first systematic characterization of the electrochemical properties of the high mobility n-type polymer poly{[N,N′-bis(2octyldodecyl)-naphthalene-1,4,5,8-bis (dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)} (P(NDI2OD-T2)) and its corresponding monomer 2,6-bis(2-bromothien-5-yl)naphthalene-1,4,5,8-tetracarboxylic-N,N′-bis(2-octyldodecyl) diimide (Br-NDI2OD-T2-Br) by cyclic voltammetry and in situ spectroelectrochemistry. Both monomer and polymer reveal a 2-fold reduction to the dianion via a radical anion species. The comparison between monomeric and polymeric species allows the explanation of the electrochemical behavior of P(NDI2OD-T2) according to redox polymers with localization of charges on the naphthalene bisimide unit. Measurements with electrolyte gated transistors suggest electron hopping transport according to mixed valence conductivity. In the last section of this paper we discuss a significant first cycle effect upon electrochemical reduction which had not been reported for ntype polymers before. The effect is even more pronounced for samples with controlled morphology, that is, high amounts of aggregation in the films. In agreement with solution experiments we attribute the appearance of the signal at −1.04 V (E 1/2 = −1.00 V) to the radical anion form of the solvated species.