Devens Gust

Solar Fuels via Artificial Photosynthesis

Because sunlight is diffuse and intermittent, substantial use of solar energy to meet humanitys needs will probably require energy storage in dense, transportable media via chemical bonds. Practical, cost effective technologies for conversion of sunlight directly into useful fuels do not currently exist, and will require new basic science. Photosynthesis provides a blueprint for solar energy storage in fuels. Indeed, all of the fossil-fuel-based energy consumed today derives from sunlight harvested by photosynthetic organisms. Artificial photosynthesis research applies the fundamental scientific principles of the natural process to the design of solar energy conversion systems. These constructs use different materials, and researchers tune them to produce energy efficiently and in forms useful to humans. Fuel production via natural or artificial photosynthesis requires three main components. First, antenna/reaction center complexes absorb sunlight and convert the excitation energy to electrochemical energy (redox equivalents). Then, a water oxidation complex uses this redox potential to catalyze conversion of water to hydrogen ions, electrons stored as reducing equivalents, and oxygen. A second catalytic system uses the reducing equivalents to make fuels such as carbohydrates, lipids, or hydrogen gas. In this Account, we review a few general approaches to artificial photosynthetic fuel production that may be useful for eventually overcoming the energy problem. A variety of research groups have prepared artificial reaction center molecules. These systems contain a chromophore, such as a porphyrin, covalently linked to one or more electron acceptors, such as fullerenes or quinones, and secondary electron donors. Following the excitation of the chromophore, photoinduced electron transfer generates a primary charge-separated state. Electron transfer chains spatially separate the redox equivalents and reduce electronic coupling, slowing recombination of the charge-separated state to the point that catalysts can use the stored energy for fuel production. Antenna systems, employing a variety of chromophores that absorb light throughout the visible spectrum, have been coupled to artificial reaction centers and have incorporated control and photoprotective processes borrowed from photosynthesis. Thus far, researchers have not discovered practical solar-driven catalysts for water oxidation and fuel production that are robust and use earth-abundant elements, but they have developed artificial systems that use sunlight to produce fuel in the laboratory. For example, artificial reaction centers, where electrons are injected from a dye molecule into the conduction band of nanoparticulate titanium dioxide on a transparent electrode, coupled to catalysts, such as platinum or hydrogenase enzymes, can produce hydrogen gas. Oxidizing equivalents from such reaction centers can be coupled to iridium oxide nanoparticles, which can oxidize water. This system uses sunlight to split water to oxygen and hydrogen fuel, but efficiencies are low and an external electrical potential is required. Although attempts at artificial photosynthesis fall short of the efficiencies necessary for practical application, they illustrate that solar fuel production inspired by natural photosynthesis is achievable in the laboratory. More research will be needed to identify the most promising artificial photosynthetic systems and realize their potential.

Photoassisted Overall Water Splitting in a Visible Light-Absorbing Dye-Sensitized Photoelectrochemical Cell

Iridium oxide nanoparticles stabilized by a heteroleptic ruthenium tris(bipyridyl) dye were used as sensitizers in photoelectrochemical cells consisting of a nanocrystalline anatase anode and a Pt cathode. The dye coordinated the IrO(2) x nH(2)O nanoparticles through a malonate group and the porous TiO(2) electrode through phosphonate groups. Under visible illumination (lambda > 410 nm) in pH 5.75 aqueous buffer, oxygen was generated at anode potentials positive of -325 mV vs Ag/AgCl and hydrogen was generated at the cathode. The internal quantum yield for photocurrent generation was ca. 0.9%. Steady-state luminescence and time-resolved flash photolysis/transient absorbance experiments were done to measure the rates of forward and back electron transfer. The low quantum yield for overall water splitting in this system can be attributed to slow electron transfer (approximately 2.2 ms) from IrO(2) x nH(2)O to the oxidized dye. Forward electron transfer does not compete effectively with the back electron transfer reaction from TiO(2) to the oxidized dye, which occurred on a time scale of 0.37 ms.

Light-driven production of ATP catalysed by F0F1-ATP synthase in an artificial photosynthetic membrane

Energy-transducing membranes of living organisms couple spontaneous to non-spontaneous processes through the intermediacy of protonmotive force (p.m.f.) — an imbalance in electrochemical potential of protons across the membrane. In most organisms, p.m.f. is generated by redox reactions that are either photochemically driven, such as those in photosynthetic reaction centres, or intrinsically spontaneous, such as those of oxidative phosphorylation in mitochondria. Transmembrane proteins (such as the cytochromes and complexes I, III and IV in the electron-transport chain in the inner mitochondrial membrane) couple the redox reactions to proton translocation, thereby conserving a fraction of the redox chemical potential as p.m.f. Many transducer proteins couple p.m.f. to the performance of biochemical work, such as biochemical synthesis and mechanical and transport processes. Recently, an artificial photosynthetic membrane was reported in which a photocyclic process was used to transport protons across a liposomal membrane, resulting in acidification of the liposomes internal volume. If significant p.m.f. is generated in this system, then incorporating an appropriate transducer into the liposomal bilayer should make it possible to drive a non-spontaneous chemical process. Here we report the incorporation of FOF1-ATP synthase into liposomes containing the components of the proton-pumping photocycle. Irradiation of this artificial membrane with visible light results in the uncoupler- and inhibitor-sensitive synthesis of adenosine triphosphate (ATP) against an ATP chemical potential of ∼12 kcal mol−1, with a quantum yield of more than 7%. This system mimics the process by which photosynthetic bacteria convert light energy into ATP chemical potential.

Chemical compass model of avian magnetoreception

Approximately 50 species, including birds, mammals, reptiles, amphibians, fish, crustaceans and insects, are known to use the Earth’s magnetic field for orientation and navigation. Birds in particular have been intensively studied, but the biophysical mechanisms that underlie the avian magnetic compass are still poorly understood. One proposal, based on magnetically sensitive free radical reactions, is gaining support despite the fact that no chemical reaction in vitro has been shown to respond to magnetic fields as weak as the Earth’s (∼50 μT) or to be sensitive to the direction of such a field. Here we use spectroscopic observation of a carotenoid–porphyrin–fullerene model system to demonstrate that the lifetime of a photochemically formed radical pair is changed by application of ≤50 μT magnetic fields, and to measure the anisotropic chemical response that is essential for its operation as a chemical compass sensor. These experiments establish the feasibility of chemical magnetoreception and give insight into the structural and dynamic design features required for optimal detection of the direction of the Earth’s magnetic field.

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

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.

Improving the efficiency of water splitting in dye-sensitized solar cells by using a biomimetic electron transfer mediator

Photoelectrochemical water splitting directly converts solar energy to chemical energy stored in hydrogen, a high energy density fuel. Although water splitting using semiconductor photoelectrodes has been studied for more than 40 years, it has only recently been demonstrated using dye-sensitized electrodes. The quantum yield for water splitting in these dye-based systems has, so far, been very low because the charge recombination reaction is faster than the catalytic four-electron oxidation of water to oxygen. We show here that the quantum yield is more than doubled by incorporating an electron transfer mediator that is mimetic of the tyrosine-histidine mediator in Photosystem II. The mediator molecule is covalently bound to the water oxidation catalyst, a colloidal iridium oxide particle, and is coadsorbed onto a porous titanium dioxide electrode with a Ruthenium polypyridyl sensitizer. As in the natural photosynthetic system, this molecule mediates electron transfer between a relatively slow metal oxide catalyst that oxidizes water on the millisecond timescale and a dye molecule that is oxidized in a fast light-induced electron transfer reaction. The presence of the mediator molecule in the system results in photoelectrochemical water splitting with an internal quantum efficiency of approximately 2.3% using blue light.

Making electrical contacts to molecular monolayers

Electrical contacts between a metal probe and molecular monolayers have been characterized using conducting atomic force microscopy in an inert environment and in a voltage range that yields reversible current-voltage data. The current through alkanethiol monolayers depends on the contact force in a way that is accounted for by the change of chain-to-chain tunnelling with film thickness. The electronic decay constant, βN, was obtained from measurements as a function of chain length at constant force and bias, yielding βN = 0.8±0.2 per methylene over a ±3 V range. Current-voltage curves are difficult to reconcile with this almost constant value. Very different results are obtained when a gold tip contacts a 1,8-octanedithiol film. Notably, the current-voltage curves are often independent of contact force. Thus the contact may play a critical role both in the nature of charge transport and the shape of the current-voltage curve.

All-Photonic Multifunctional Molecular Logic Device

Photochromes are photoswitchable, bistable chromophores which, like transistors, can implement binary logic operations. When several photochromes are combined in one molecule, interactions between them such as energy and electron transfer allow design of simple Boolean logic gates and more complex logic devices with all-photonic inputs and outputs. Selective isomerization of individual photochromes can be achieved using light of different wavelengths, and logic outputs can employ absorption and emission properties at different wavelengths, thus allowing a single molecular species to perform several different functions, even simultaneously. Here, we report a molecule consisting of three linked photochromes that can be configured as AND, XOR, INH, half-adder, half-subtractor, multiplexer, demultiplexer, encoder, decoder, keypad lock, and logically reversible transfer gate logic devices, all with a common initial state. The system demonstrates the advantages of light-responsive molecules as multifunctional, reconfigurable nanoscale logic devices that represent an approach to true molecular information processing units.

Molecular switches controlled by light

The photochemical processes of singlet-singlet energy transfer and photoinduced electron transfer are important not only in natural and artificial photosynthetic energy conversion, but also in a variety of other scientific and technological applications. Controlling these functions at the molecular level using outside stimuli is an interesting scientific challenge. Photochromes, organic molecules that are isomerized by light between two stable forms, can be covalently linked to other chromophores, and changes in their properties resulting from photoisomerization used to switch electron and energy transfer on or off. Simple single- and double-throw molecular switches have been constructed, as well as Boolean logic gates. Such molecules are potentially useful in light-controlled molecular data processing and storage applications.

Biology and technology for photochemical fuel production

Sunlight is the ultimate energy source for the vast majority of life on Earth, and organisms have evolved elegant machinery for energy capture and utilization. Solar energy, whether converted to wind, rain, biomass or fossil fuels, is also the primary energy source for human-engineered energy transduction systems. This tutorial review draws parallels between biological and technological energy systems. Aspects of biology that might be advantageously incorporated into emerging technologies are highlighted, as well as ways in which technology might improve upon the principles found in biological systems. Emphasis is placed upon artificial photosynthesis, as well as the use of protonmotive force in biology.