SUMMARYThe U.S. Department of Energy and the National Renewable Energy Laboratory are developing technologies to produce hydrogen from renewable, sustainable sources. A cost goal of $2.00-$3:00 kg À1 of hydrogen has been identified as the range at which delivered hydrogen becomes cost competitive with gasoline for passenger vehicles. Electrolysis of water is a standard commercial technology for producing hydrogen. Using wind and solar resources to produce the electricity for the process creates a renewable system. Biomass-to-hydrogen processes, including gasification, pyrolysis, and fermentation, are less well-developed technologies. These processes offer the possibility of producing hydrogen from energy crops and from biomass materials such as forest residue and municipal sewage. Solar energy can be used to produce hydrogen from water and biomass by several conversion pathways. Concentrated solar energy can generate high temperatures at which thermochemical reactions can be used to split water. Photoelectrochemical water splitting and photobiology are long-term options for producing hydrogen from water using solar energy. All these technologies are in the development stage.

When titanium dioxide (TiO2) is irradiated with near-UV light, this semiconductor exhibits strong bactericidal activity. In this paper, we present the first evidence that the lipid peroxidation reaction is the underlying mechanism of death of Escherichia coli K-12 cells that are irradiated in the presence of the TiO2 photocatalyst. Using production of malondialdehyde (MDA) as an index to assess cell membrane damage by lipid peroxidation, we observed that there was an exponential increase in the production of MDA, whose concentration reached 1.1 to 2.4 nmol · mg (dry weight) of cells−1 after 30 min of illumination, and that the kinetics of this process paralleled cell death. Under these conditions, concomitant losses of 77 to 93% of the cell respiratory activity were also detected, as measured by both oxygen uptake and reduction of 2,3,5-triphenyltetrazolium chloride from succinate as the electron donor. The occurrence of lipid peroxidation and the simultaneous losses of both membrane-dependent respiratory activity and cell viability depended strictly on the presence of both light and TiO2. We concluded that TiO2 photocatalysis promoted peroxidation of the polyunsaturated phospholipid component of the lipid membrane initially and induced major disorder in the E. coli cell membrane. Subsequently, essential functions that rely on intact cell membrane architecture, such as respiratory activity, were lost, and cell death was inevitable.

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The photobiological production of H2 gas, using water as the only electron donor, is a property of two types of photosynthetic microorganisms: green algae and cyanobacteria. In these organisms, photosynthetic water splitting is functionally linked to H(2) production by the activity of hydrogenase enzymes. Interestingly, each of these organisms contains only one of two major types of hydrogenases, [FeFe] or [NiFe] enzymes, which are phylogenetically distinct but perform the same catalytic reaction, suggesting convergent evolution. This idea is supported by the observation that each of the two classes of hydrogenases has a different metallo-cluster, is encoded by entirely different sets of genes (apparently under the control of different promoter elements), and exhibits different maturation pathways. The genetics, biosynthesis, structure, function, and O2 sensitivity of these enzymes have been the focus of extensive research in recent years. Some of this effort is clearly driven by the potential for using these enzymes in future biological or biohybrid systems to produce renewable fuel or in fuel cell applications.

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Hydrogen photoproduction by micro-organisms combines the photosynthetic properties of oxygenic and non-oxygenic microbes with the activity of H2-producing enzymes in nature: hydrogenases and nitrogenases. The overall efficiency of the process depends on the separate efficiencies of photosynthesis and enzymatic catalysis. This tutorial review discusses the biochemical pathways for H2 production in different organisms, barriers to be overcome, and possible suggestions for integrating photobiological H2 production with fermentative, anaerobic systems for a potentially more efficient process.

We report carbon mass balance and kinetic data for the total oxidation of cells, spores, and biomolecules deposited on illuminated titanium dioxide surfaces in contact with air. Carbon dioxide formation by photocatalytic oxidation of methanol, glucose, Escherichia coli, Micrococcus luteus, Bacillus subtilis (cells and spores), Aspergillus niger spores, phosphatidylethanolamine, bovine serum albumin, and gum xanthan was determined as a function of time. The quantitative data provide mass balance and rate information for removal of these materials from a photocatalytic surface. This kind of information is importantfor applications of photocatalytic chemistry in air and water purification and disinfection, self-cleaning surfaces, and the development of self-cleaning air filters.