Engineering Cells, Membranes and Light Harvesting/Photosystem II Super-Complexes in Bio-Photoelectrochemical Cells

Abstract

Photosynthetic organisms, membranes and complexes are attractive starting materials for solar energy conversion (SEC). Our overall goal is to develop methods to perform SEC using these materials in simple, inexpensive and a fashion that will be non-polluting and will not compete with the growth of food materials. I will describe here how the remarkable photocatalytic activity of the photosynthetic apparatus can provide overall water splitting with oxygen and hydrogen production in Bio-Photo-Electro-Chemical (BPEC) cells via the simplest and cleanest of processes wither in the absence or presence of added electron transport molecules. With plant thylakoids, electrons are shuttled by FeCN to a transparent FTO electrode, yielding a photocurrent density of 0.5 mA·cm-2. Hydrogen evolution occurs at the cathode at a bias as low as 0.8 V. A tandem cell comprising the BPEC cell with the thylakoid membranes and a Si photovoltaic module achieves overall water splitting with solar to hydrogen conversion efficiency of 0.3% (Pinhassi et al. Nature Communications 2016). With cyanobacterial cells, electrons from the respiratory system are energized by the photosynthetic system and transferred directly to a graphite electrode, utilizing endogenous electron carriers, especially NADPH (Saper et al. Nature Communications 2018 and Shlosberg et al. iScience 2020). The current produced can be used for hydrogen production at low additional bias for significantly longer durations than the plant thylakoids.Another route is to use isolated photosynthetic complexes and chemically connect them to the electrochemical cell. One of the issues with this strategy is the small number of light absorbing chromophores connected to the complex, lowering the photochemical efficiency. Connection of isolated light harvesting (LH) complexes can help to overcome this deficiency. Photosystem II (PSII) is the only enzyme that catalyzes light-induced water oxidation being the basis for its application as a biophotoanode in various bio-photovoltaics and photo-bioelectrochemical cells. However, the absorption spectrum of PSII limits the quantum efficiency in the range of visible light, due to a gap in the green absorption region of chlorophylls (500 - 600 nm). To overcome this limitation, we have used two strategies: stabilizing the interaction between PSII and Phycobilisomes (PBSs) –LH complex or direct connection to modified gold-nanoparticles (Au-NPs) that serve both as LH and electron conduit. Integration of the PBS-PSII super-complexes within an Os-complex-modified hydrogel on macro-porous indium tin oxide electrodes (MP-ITO) resulted in notably improved, wavelength dependent, incident photon-to-electron conversion efficiencies (Hartmann et al. J. Mat. Chem. A. 2020). With the Au-NPs, record currents were obtained, with strong improvement in the SPR range of wavelengths that are not absorbed by chlorophylls.