Photoactive and conductive biohybrid films by polymerization of pyrrole through voids in photosystem I multilayer films.

The combination of conducting polymers with electro- and photoactive proteins into thin films holds promise for advanced energy conversion materials and devices. The emerging field of protein electronics requires conductive soft materials in a composite with electrically insulating proteins. The electropolymerization of pyrrole through voids in a drop-casted photosystem I (PSI) multilayer film enables the straightforward fabrication of photoactive and conductive biohybrid films. The rate of polypyrrole (PPy) growth is reduced by the presence of the PSI film but is insensitive to its thickness, suggesting that rapid diffusion of pyrrole through the voids within the PSI film enables initiation at vacant areas on the gold surface. The base thickness of the composite tends to increase with time, as PPy chains propagate through and beyond the PSI film, coalescing to exhibit a tubule-like morphology as observed by scanning electron microscopy. Increasing amounts of PPy greatly increase the capacitance of the composite films in a manner almost identical to that of pure PPy films grown from unmodified gold, consistent with a high polymer/aqueous interfacial area and a conductive composite film. While PPy is not photoactive here, all composite films, including those with large amounts of PPy, exhibit photocurrents when irradiated by white light in the presence of redox mediator species. Optimization of the Py electropolymerization time is necessary, as increasing amounts of PPy lead to decreased photocurrent density due to a combination of light absorbance by the polymer and reduced accessibility of redox species to active PSI sites.

Photosystem I Enhances the Efficiency of a Natural, Gel-Based Dye-Sensitized Solar Cell.

The photosystem I (PSI) protein complex is known to enhance bioelectrode performance for many liquid-based photoelectrochemical cells. A hydrogel as electrolyte media allows for simpler fabrication of more robust and practical solar cells in comparison to liquid-based devices. This paper reports a natural, gel-based dye-sensitized solar cell that integrates PSI to improve device efficiency. TiO2-coated FTO slides, dyed by blackberry anthocyanin, act as a photoanode, while a film of PSI deposited onto copper comprises the photocathode. Ascorbic acid (AscH) and 2,6-dichlorophenolindophenol (DCPIP) are the redox mediator couple inside an agarose hydrogel, enabling PSI to produce excess oxidized species near the cathode to improve device performance. A comparison of performance at low pH and neutral pH was performed to test the pH-dependent properties of the AscH/DCPIP couple. Devices at neutral pH performed better than those at lower pH. The PSI film enhanced photovoltage by 75 mV to a total photovoltage of 0.45 V per device and provided a mediator concentration-dependent photocurrent enhancement over non-PSI devices, reaching an instantaneous power conversion efficiency of 0.30% compared to 0.18% without PSI, a 1.67-fold increase. At steady state, power conversion efficiencies for devices with and without PSI were 0.042 and 0.028%, respectively.