3D electrode materials for enhanced performance of photobioelectrodes based on photosystem I and II
Fred Listad a, M. Riedel a, D. Ciornii a, A. Zouni b
a Biosystems Technology, Institute of Life Sciences and Biomedical Technologies Technical University of Applied Sciences Wildau Hochschulring 1, 15745 Wildau, Germany
b Biophysics of Photosynthesis, Institute for Biology Humboldt University of Berlin, Germany
nanoGe Fall Meeting
Proceedings of nanoGe Fall Meeting19 (NGFM19)
#SolFuel19. Solar Fuel Synthesis: From Bio-inspired Catalysis to Devices
Berlin, Germany, 2019 November 3rd - 8th
Organizers: Roel van de Krol and Erwin Reisner
Invited Speaker, Fred Listad, presentation 322
DOI: https://doi.org/10.29363/nanoge.ngfm.2019.322
Publication date: 16th July 2019

The coupling of photoactive proteins with electrodes has developed to a recent research trend based on the progress in understanding and handling of these complex bioentities and the developments in materials sciences. The focus is mainly on the application of these systems for light-to-current and light-to-chemicals conversions [1,2]

3D electrodes have been demonstrated to be a powerful tool in enhancing the performance parameters of photobioelectrodes. We have demonstrated that photosystem I (from T. elongatus) can be integrated into inverse-opal ITO electrodes which are prepared by a template-based approach [3]. Here advantageously spin coating could be used to increase the thickness of the electrode structures. Limitations can however, occur when light penetration becomes limiting. Thus, we have developed a new procedure for preparing 3D ITO electrodes by starting from liquid precursors. Here higher transparency can be achieved compared to the previous method based on ITO nanoparticles. In these systems PSI is wired via a redox protein (cytochrome c) to the electrode surface. Cathodic photocurrent densities up to 270µA/cm2 could be achieved.

The electrode material can however, not only be used to harbor a large amount of photoactive protein, but it can also be exploited in order to improve the potential dependent photocurrent behavior. This is based on the light sensitivity of the electrode material in combination with the light reaction at the biomolecule. For this purpose, 3D TiO2 electrodes have been prepared and PbS quantum dots deposited in order to obtain a light-sensitive electrode [4]. This electrode has been combined with photosystem II (PSII). In order to connect PSII efficiently with the TiO2/PbS electrode an osmium-based redox polymer has been applied (poly(1-vinylimidazole-co-allylamine)-Os(bipy)2Cl). Also in this case a template-based preparation approach is used employing simple spin coating steps to adjust the thickness of the 3D structure [5].

Investigations of the electrode architectures show that the photocurrent magnitude can be well correlated to the amount of PSII integrated within the 3D structure. Interestingly the electrons from water oxidation can be collected at very low potential starting from -550mV vs Ag/AgCl. This is about 200mV below the redox potential of the acceptor site in PSII and illustrates one beneficial feature of the new developed system.

This photobioanode has been coupled to a bilirubin oxidase (BOD) based cathode to create a photobioelectrochemical cell. Here, a transparent electrode has been developed which allows also the illumination of the whole cell through the cathode. For this purpose, 3D electrodes based on the same template procedure have been prepared with antimony tin oxide as material (ATO). The ATO surface has been modified with pyrenecarboxylic acid in order to provide a suitable surface for the direct electron transfer of the enzyme. Here current densities of about 135 µA/cm2 have been obtained in air-saturated solution for the oxygen reduction process.  By combing both electrodes, a photobioelectrochemical cell can be fabricated, which does not need any fuel to be supplied. The PBC gives a rather high open cell voltage of about 1V under illumination and a maximum power density of about 50µW/cm2


[1] V. M. Friebe, R. N. Frese, Current Opinion in Electrochemistry, 2017, Vol. 5, 126-134.

[2] D. Ciornii, M. Riedel, K. R. Stieger, S. C. Feifel, M. Hejazi, H. Lokstein, A. Zouni, F. Lisdat, JACS, 2017, Vol. 139 (46), p. 16478-16481

[3] K. R. Stieger, S. C. Feifel, H. Lokstein, M. Hejazi, A. Zouni and F. Lisdat, J. Mater. Chem. A 2016, Vol. 4, p. 17009-17017

[4] M. Riedel, W. J. Parak, A. Ruff, W. Schuhmann, F. Lisdat, ACS Catalysis, 2018, Vol. 8, 5212-5220

[5] M. Riedel, J. Wersig, A. Ruff, W. Schuhmann, A. Zouni, F. Lisdat, Angew. Chem. 2019, Vol. 58,  801

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