[FeFe]-Hydrogenase-Catalyzed H₂ Production in a Photoelectrochemical Biofuel Cell

Abstract

The Clostridium acetobutylicum [FeFe]-hydrogenase HydA has been investigated as a hydrogen production catalyst in a photoelectrochemical biofuel cell. Hydrogenase was adsorbed to pyrolytic graphite edge and carbon felt electrodes. Cyclic voltammograms of the immobilized hydrogenase films reveal cathodic proton reduction and anodic hydrogen oxidation, with a catalytic bias toward hydrogen evolution. When corrected for the electrochemically active surface area, the cathodic current densities are similar for both carbon electrodes, and approximately 40% of those obtained with a platinum electrode. The high surface area carbon felt/hydrogenase electrode was subsequently used as the cathode in a photoelectrochemical biofuel cell. Under illumination, this device is able to oxidize a biofuel substrate and reduce protons to hydrogen. Similar photocurrents and hydrogen production rates were observed in the photoelectrochemical biofuel cell using either hydrogenase or platinum cathodes.

Solar Water Splitting with a Hydrogenase Integrated in Photoelectrochemical Tandem Cells

“…Previously, the H 2 evolving Clostridium acetobutylicum [FeFe] hydrogenase HydA, adsorbed on a pyrolytic graphite edge electrode, had been connected to a porphyrin‐sensitized TiO 2 photoanode. This PEC cell relied on the consumption of sacrificial NADH (nicotinamide adenine dinucleotide),1d whereas we demonstrate overall water splitting in this work. BiVO 4 is a well‐established photoanode for water oxidation,9 which was synthesized on FTO‐coated glass according to previous reports 10.…”

Hydrogen production at high Faradaic efficiency by a bio-electrode based on TiO2 adsorption of a new [FeFe]-hydrogenase from Clostridium perfringens

“…5 To this end both [NiFe]-and [FeFe]-hydrogenases (H2ases) have been used on a wide variety of solid electrodes, such as pyrolytic graphite edge (PGE), glassy carbon and carbon felt electrodes, gold electrodes, TiO2 electrodes but also carbon nanotubes and nanowires, CdTe nanocrystals and CdS nanorods. Electrochemical, photoluminescence and Raman spectroscopy studies demonstrate that the hydrogenases remain catalytically active and therefore can be exploited as efficient catalysts [5][6][7][8][9][10]. Several electrochemical setups have been proposed exploiting the catalytic properties of both 10 [NiFe]-and [FeFe]-hydrogenases from various bacterial and some algal species [6,[11][12].…”

“…Moreover, carbon materials are less expensive compared to platinum electrodes and they have high electroactive surface area on which hydrogenases can be adsorbed, especially the carbon felt electrode [6]. 15 In previous years, semiconductor-based electrodes have attracted a great deal of interest both for hydrogenase-coupling in the perspective for the possible photoactivation by direct UV/Vis illumination or by mean of antenna systems coupled to the semiconductors.…”

Integrated photosystem II-based photo-bioelectrochemical cells

“…Recently, extensive research efforts were directed towards the development of photoelectrochemical or solar cells mimicking photosynthesis [8][9][10][11][12][13] , or to the application of the native photosystems to power photoelectrochemical cells. For example, dye-sensitized solar cells that include synthetic photosensitizers and enzymes were reported, and the resulting hybrid systems were implemented to generate the hydrogen fuel 14 , or photocurrents 15 . Nonetheless, in these systems the cathodic reactions were not directly coupled to the product generated at the photoanodes, resulting in a waste product.…”