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We raise here a series of critical issues regarding artificial photosynthesis with the intention of increasing awareness about what needs to be done to bring about a working prototype. Factors under consideration include energy and electron transfers, coupled redox reactions, repair mechanisms, and integrated photosystems.
Andrew C. Benniston and Anthony Harriman* Molecular Photonics Laboratory, School of Chemistry, Bedson Building, Newcastle University, Newcastle upon Tyne NE1 7RU, UK *E-mail: email@example.com
Natural photosynthesis, the process whereby CO2 is converted into carbohydrate and water is oxidized to molecular oxygen, has supplied the overwhelming majority of stored energy available on our planet1. This stored energy, which is mostly in the form of fossil fuels, had sufficed for billions of years and it is only very recently that the stocks of fuel have started to deplete at a rate faster than Nature can replenish2,3. Indeed, our insatiable appetite for instant energy is set to expand at an unprecedented pace and our capability to generate CO2 knows no bounds. The need to provide additional energy and to deal with the ensuing ecological problems associated with current lifestyles in the developed world pose tremendous challenges for the scientific community4. The urgency, and therefore the funding, devoted to solving these problems is set exclusively by the price of oil and, as a consequence, the attention given to meeting these challenges is driven by market forces. Once again we are entering a period of wildly fluctuating oil prices and this time, unlike the 1970s, it is unlikely that the cost per barrel will fall steeply after an uncomfortable ride. The search for renewable energy supplies is now a major issue for all stable governments but it must be accompanied by new initiatives to reduce CO2 levels and, in as much as it is possible, sequester CO2 from the atmosphere. This is
precisely how photosynthesis works and although many intriguing alternatives merit consideration at a local level, it is crucial that scientists are given the opportunity to produce a viable form of artificial photosynthesis. The overall challenge is massive and needs to be addressed by a multinational force dedicated to the task – it is far beyond the capability of a single investigator. Most of the chemistry associated with natural photosynthesis is understood at a reasonably precise level5. The reagents, chemical reactions, rates, and mechanisms have been known for decades6,7 and although refinements continue to be made, the basic understanding is in place8. Likewise, the structure and level of organization of the essential features of photosynthesis have been elucidated by biophysicists and further defined by protein crystallography (a full compendium of X-ray-determined structures of membrane proteins can be found at http://www.mpibp-frankfurt.mpg.de/michel/public/ memprotstruct.html) and advanced theory9. How can we utilize this information to engineer an artificial leaf? This is the key question and the answer is that no one knows. We can, however, set out the state of current knowledge and thereby expose the main challenges that remain. In so doing, we emphasize the underlying chemistry. Our rationale for this approach is that we need first to devise suitable chemical processes before attempting to build working prototypes. The
DECEMBER 2008 | VOLUME 11 | NUMBER 12
ISSN:1369 7021 © Elsevier Ltd 2008
Other reports have focussed on energy transfer in polymeric media. Electronic energy is transferred around the ring. but artificial systems tend to supplement this route with electron exchange interactions occurring within more strongly coupled chromophoric arrays14. need to be developed once the chemistry is in place. The arrows show the pathways for energy migration depending on which chromophore is illuminated. The color code attempts to show the internal energy gradient in that the fluorene molecule (blue) absorbs high-energy photons and the bodipy (red) is the terminus.Artificial photosynthesis REVIEW engineering principles. porphyrin-based ribbons have been reported17 and attempts have been made to develop porphyrin-based wheels and rings18. daunting in themselves. this cascade effect is readily achievable but does require careful design and choice of chromophores. A fine example of this is the molecular array shown in Fig. which involves through-space interactions. (Reproduced by permission of McDermott et al. This latter metastable reagent is responsible for rapid aging and ultimate destruction of the photon (a) (b) Fig.11. which comprises four different. in an incoherent manner until it migrates to a different ring. Nature has opted to transfer excitation energy between weakly coupled chromophores via the so-called Förster mechanism13. Many such arrays act cooperatively both to shuttle photons to the right place and to avoid the problems of overload at high light intensity. arrays. There is. The natural system is highly ordered but this is not true for most artificial prototypes. A crucial feature of all such systems is the need to avoid involvement of triplet states. The first attempts to create ordered networks for electronic energy transfer were described by Mobius and Kuhn21 and involved monomolecular layers of cyanine dyes coated onto transparent slides. (a) Ring of 18 B850 bacteriochlorophyll-a molecules and (b) ring of nine B800 bacteriochlorophyll-a molecules with a different ring between the helices of the apoproteins.) DECEMBER 2008 | VOLUME 11 | NUMBER 12 27 . despite their synthetic attractiveness. Nature accomplishes this essential task by using light-harvesting complexes to collect incident photons. it must be concentrated at some stage in the overall storage process. The α-apoproteins are colored yellow and the β-apoproteins green. electronic energy transfer is fast and highly efficient. More recently. By ensuring that an energy gradient is set up within a molecular system. oxygen15. leading to the development of solar concentrators of the type illustrated in Fig. These were followed by detailed studies of clusters. Capturing the photons Sunshine is diffuse and although sufficient sunlight reaches the surface of the Earth to satisfy all our energy needs. between cofacial pigments. dendrimers. since these will inevitably transfer energy to oxygen and form the highly destructive species known as singlet molecular collector. The light-harvesting complex is a highly organized array of chlorophyll molecules as illustrated in Fig. the photon reaches a light-harvesting complex with a reaction center complex embedded in its center. Eventually. 322. organic chromophores. however. an additional requirement in that energy produced following excitation must percolate through the system to terminate preferably on a single chromophore19. The structural elegance and chemical efficacy of the natural system have stimulated great interest in artificial analogs. move them over large distances and direct them to a site where the chemistry takes place10. 1 Representation of the X-ray structure of bacterial light-harvesting complexes. It is worth noting that essentially all absorbed photons terminate at the bodipy unit. mostly involving porphyrin-based chromophores12. and polymers. The first artificial photon collectors comprised covalently linked porphyrin dimers that displayed highly efficient excitation energy transfer over short distances16. yet complementary. 111. 220. In all cases. extremely long.
unlike in the natural system. attention has turned to the possibility of energy transfer occurring in crystalline media.25 using dye-loaded zeolites. it operates as a photon collector in the crystalline state by Charge separation The light-harvesting complex directs photons to a Reaction Center Complex (RCC) where the absorbed photon is used to drive an electron-transfer reaction that leads to charge separation across a 28 DECEMBER 2008 | VOLUME 11 | NUMBER 12 . since thiophene groups are easily polymerized. Energy transfer can then be directed along the channel. Considerable work has gone into the optimization of the photon-collecting properties of the sensitizers27–31 Fig. pyrene (purple). Quite separately. In this case. Thus. these results are encouraging for creating models using the bodipy chromophore. Each unit is selected for its complimentary absorption profile. rationally designed dyes are either incorporated into channels inside the zeolite or used to block the pore. Furthermore. 2 A tailor-made artificial light-harvesting array based on fluorene (blue). Finally. 4 is not as elaborate as the multichromophore systems outlined above. The upper panel was taken without illumination while the lower panel shows fluorescence from the thin film. Here. Note that a wide spectral range is harvested in this way. 3 Example of an organic solar concentrator in the form of a very low concentration of dye dispersed in a polymeric film and coated onto a glass surface. More recently. research has progressed into the design of light-harvesting units for dye-injection solar cells of the type pioneered by Grätzel26. and into engineering the cells for stable performance32–35. Arrows depict the pathways for energy migration to the terminal unit. energy occurs by way of both through-space and through-bond processes. and bodipy (red) units. as indicated in the insert. transferring energy from the p-quaterthiophene residue (yellow) to the bodipy core. Considering that artificial systems will be required to operate in the solid state. the manufacture of polymeric materials looks entirely feasible. Here. although the dyad23 shown in Fig. a dye sensitizer is used to inject charge into nanostructured surfaces such as fractal TiO2 in contact with a suitable redox-active electrolyte. The energy-transfer rate increases six-fold when the dyad is dispersed in a soft glass.REVIEW Artificial photosynthesis Fig. perylene (green). with essentially every absorbed photon being directed to the bodipy core. Note how the fluorescence is localized at the edge. we note the novel experiments reported by Calzaferri and coworkers24. Further attention has been paid to photon collectors for low band-gap organicbased solar cells36–40 and many of the basic concepts are common to all types of light harvesters.
aided by elegant theoretical models42.) biological. and facilitated by tremendous advances made in our understanding of simple electron-transfer processes by pioneers such as Mataga46. which fluoresces strongly.Artificial photosynthesis REVIEW Fig.) The insert shows how the RCC fits inside one of the light-harvesting rings. The essential breakthrough was made by Gust et al. Energy transfer becomes more efficient as the orthogonality is relaxed. Spatial arrangement of the cofactors in the photosynthetic reaction center complex of the purple bacteria Rhodobacter sphaeroides.43. Electron transfer then occurs.50. based on the realization that the rate of electron transfer decreases exponentially Fig. and the crystal packing diagram of the molecules as determined by X-ray crystallography. lipid bilayer membrane (Fig. By way of such a cascade of electron-transfer steps. Early work on artificial versions of the RCC used porphyrin–quinone dyads but these suffered from fast charge recombination49. but it should be realized that electron transfer occurs exclusively along the right-hand branch. B = orange. transmembrane electron transfer is achieved. (Reproduced by permission of Dr R. Note the symmetry of the tetrapyrrole-based cofactors. despite the orthogonal connection. as determined by X-ray crystallography. 4. by way of the light-harvesting complex. (Reproduced in part by permission of Benniston et al. stimulated by studies of the crystal structure of the bacterial RCC44. 5)41. F = green. QB) and finally to the second quinone (purple. Wheeler. QA). Closs47. Photons arrive at a special pair of bacteriochlorophyll molecules (green). Illustration of a bodipy-based molecular dyad used for studying intramolecular electronic energy transfer. then to the first quinone (yellow. DECEMBER 2008 | VOLUME 11 | NUMBER 12 29 . Color code: S = yellow. UV photons absorbed by the oligothiophene unit are transferred efficiently to the bodipy dye. who reported the first molecular triad. Research into artificial analogs of the natural RCC has advanced rapidly. N = blue. C = gray.23.45. and Wasielewski48. 5. Nature has evolved this cascade-type effect in which the electron and positive hole move further apart through a series of short-range jumps as a means to circumvent rapid charge recombination between the electron and hole. There is an iron center associated with the quinone residues. first to the monomeric bacteriochlorophyll (blue) and subsequently to the free-base bacteriopheophytin (red).
Provided the thermodynamics can be satisfied. etc. forming the highly dangerous species. which is also the primary electron donor. 6 Simplified energy-level diagram showing the principle of charge separation via sequential electron-transfer steps. All such attempts have failed. often having the quinone replaced with a fullerene derivative.54. It is evident that the final design of a molecular system for artificial photosynthesis will require the coupling of the light-harvesting Fig. 30 DECEMBER 2008 | VOLUME 11 | NUMBER 12 .. singlet molecular oxygen. this ‘special ingredient’ has defied identification and there are many who doubt its existence! The situation is illustrated in Fig. this latter species can decay via charge recombination or undergo intersystem crossing to form a triplet-excited state localized on either donor or acceptor. Note that a certain fraction of the initial excitation energy is lost at each stage. 7 Simplified energy diagram showing processes that take place following illumination of a molecular dyad. tetrads52. In competition with fluorescence. forming a charge-separated state. especially when dealing with high-energy states able to form triplet species57. such as the hydrogenbonded systems reported primarily by Sessler et al. as well as covalent analogs.REVIEW Artificial photosynthesis Fig. A persistent line of enquiry has been to pursue unusually long-lived charge-separated states without the need for extended synthesis. A great variety of molecular dyads have been synthesized in order to critically examine various aspects of electron-transfer theory. The triplet is liable to transfer energy to oxygen. Excitation results in formation of the singlet-excited state localized on the chromophore. Excitation leads to formation of the singletexcited state localized on the chromophore. Charge recombination is now very slow because of the large distance separating the charges. 7. pentads53. In turn. the wrong design could be disastrous. It is important to realize that simply making long molecules is not the answer to the charge-recombination problem and careful choice of the individual units is essential (Fig. These have included weakly associated conjugates. charge-separated state56. The basic idea is to move electrons from one side of the supermolecule to the other side as quickly and as efficiently as possible. Even so. that are loosely modeled on the architecture of the RCC but allow for the fact that there is no need to accurately duplicate all the structural facets. some superb molecular structures have been described that closely resemble the natural RCC. This species can fluoresce but can also transfer an electron to an appended acceptor. which is also the primary donor (D1). so that the positive and negative charges become spatially remote. hole transfer can occur to move the oxidizing equivalent to the secondary donor (D2). The advantages of such simple dyads are obvious but something rather special is needed to circumvent the inherently fast rates of charge recombination. Considering the time and effort required to synthesize elaborate multicomponent molecules. Unfortunately. with increasing separation between the reactants. Secondary electron transfer to form the extended radical ion pair can compete with charge recombination to reform the ground state. although there have been several erroneous reports to the contrary55. This has necessitated the formulation of a set of ‘rules’ that must be fulfilled in order to claim a long-lived. This has led to the introduction of countless triads51. 6). charge separation occurs to form the radical ion pair in which an electron has been transferred to the primary acceptor (A1).
to avoid back-reactions between the Fig. and in particular Gust et al. and often four or more. The resultant charge-separated state is susceptible to fast charge recombination. is how to extend such work to engineer photoactive films with oriented arrays of multicomponent supermolecules that can be printed on large surface areas and that retain the activity of isolated molecules in a polar solvent. with his Langmuir–Blodgett films. however. the lifetime of the charge-separated state is 25 μs. but these lack the true element of directionality needed to drive photochemical water cleavage. 8 Illustration of a molecular array that acts as both a photon collector and an artificial reaction center. from where electron transfer to the attached C60 residue takes place. artificial photosynthesis lags far behind photoelectrochemical systems. Secondly. Arrows show pathways for energy migration to the terminal free-base porphyrin. Again. As with electronic energy transfer. At this time. Such experiments have led to a deeper understanding of how electrons tunnel through protein matrices60. the question must be posed as to how it is possible to impose directionality on the electron-transfer event. Some success has been achieved with self-assembled π-stacks. There are two inherent problems to overcome. and it is clear that new initiatives are urgently needed. For the example shown. This is sufficient time to allow useful catalytic processes to compete with long-range charge recombination. Selective illumination of the peripheral zinc porphyrin causes energy migration first to the central group and then to the free-base porphyrin shown in green. the species generated by photolysis are the result of oneelectron transfers but formation of stable chemicals requires at least two. In this way. Modified enzymes have been prepared by several groups and employed to direct an electron from a donor on the surface to a specific site within the protein. the charges become spatially isolated and the rate of charge recombination decreases. during which the excitation energy is converted into heat. As such. Photocatalytic cycle Photochemistry provides direct access to potent oxidizing or reducing species that can be used to drive redox reactions. Others have assembled molecular dyads around DNA duplexes and thereby set up one-dimensional electron-transfer pathways61.62 have been highly successful in this field. electrons. such as organic photovoltaics63. The key puzzle. Firstly. 858 utilizes a unique combination of zinc and free-base porphyrins and an electron-affinic C60 terminal. but hole transfer (ht) occurs from the free-base porphyrin π-radical cation to one of the appended zinc porphyrins. some kind of charge accumulation is needed to couple the photochemical steps to product formation.64 or dye-injection solar cells65. the first rationale attempts to study electron transfer in organized media were made by Kuhn59.Artificial photosynthesis REVIEW portion to the artificial reaction center. The positive hole formed initially on the free-base porphyrin migrates to the zinc porphyrin under thermodynamic control to create a charge-separated state in high yield that survives for 25 μs. The example shown in Fig. More elaborate systems have been used to pump electrons across liposomes and membranes. Building ever more intricate molecular systems that closely resemble the structural features of the RCC is an interesting academic challenge but gets us no nearer to a successful artificial photosynthetic system. The resultant excited state transfers an electron to C60 in about 25 ps. leading to useful chemical feedstocks. DECEMBER 2008 | VOLUME 11 | NUMBER 12 31 .
the example shown in Fig. This latter reaction would be an ideal way to generate cheap supplies of fertilizer for developing countries but there are no viable systems known at the present time. Suitable substrates might be waste materials or glycerol left over from biofuel production. Here. Self-repair is an essential feature of natural photosynthesis. The net reaction is the conversion of ethanol to acetaldehyde and H2 gas. In fact. Molecular self-repair Perhaps the most intriguing aspect of biological systems is their ability to induce self-repair. The system is shown as a two-electron cycle. virtually no man-made materials that have a dynamic function possess the ability to sense and repair the inevitable damage that occurs during operation. and used for fuel production as required. the photooxidation of persulfate to O2 has been perfected using a range of chromophores and with colloidal RuO2 or IrO2 as catalyst70. Prolonged attempts to replace the colloidal redox catalyst with simpler molecules able to undergo several changes in oxidation state. The photoactive ingredient is a tin(IV) porphyrin and the primary donor is NADH. 32 DECEMBER 2008 | VOLUME 11 | NUMBER 12 . 10. many individual photocycles have been optimized for the generation of certain small molecules. Ideally. The absence of any genuinely effective catalyst for CO2 reduction remains a massive stumbling block. Using water as the electron source. most notably manganese porphyrins. The reduced porphyrin is used to chemically reduce methyl viologen (MV2+). especially using seawater as the substrate. 9 is the most advanced photosystem of this type69. it is necessary to design and subsequently link two separate cycles – one forming a fuel and the other providing the all-important oxidizing agent. This latter species is recovered in a separate catalytic process in which colloidal Pt reduces water to H2. On the contrary. now that the structure of the natural O2-evolving catalyst is available72–74. but a genuinely effective catalyst for CO2 reduction remains elusive86–93. stored. We emphasize that such coupled systems represent the only viable approach to storing sunlight as chemical potential. individual photosystems would be engineered to produce H2 and O2 but they would need to be connected via a common relay. The idea that an artificial analog built from organic molecules and maintained under Fig. Indeed. The overall scheme is shown as Fig. Even less is known about how to selectively reduce CO2 to formic acid84. It is much more difficult to identify suitable catalysts for CO2 reduction and even more so for NH3 formation. 9 Advanced photosystem for the photochemical dehydrogenation of ethanol. for example. Photochemical generation of H2 from organic substrates in the presence of a suitable electron-storage catalyst is trivial66.REVIEW Artificial photosynthesis photochemical products. an oxygenevolving catalyst is known that can regenerate each 30 minutes under solar irradiation94 while highly reactive singlet oxygen formed during side-reactions is consumed by carotenoids95. although its subsequent dissociation into CO2 and H2 is well known85. The catalyst can be a precious metal colloid67 or an enzyme68 and the system can be made to work extremely well. Quinones are often considered as potential relays but there has been little genuine progress in effecting this type of coupled system. while the need to invoke CO2 reduction has become almost as important as seeking new energy supplies. In contrast. many different approaches have been tried. Turnover numbers tend to be modest and the harsh experimental conditions destroy the chromophore. The search for improved oxidation catalysts continues75–80. it is clear that there are no artificial analogs. The only realistic option is to couple O2 generation with the two-electron reduction of a relay (Q) and to use the resultant QH2 as a raw material in a separate photocycle under conditions where the H2-evolving catalyst is localized at the collection point82. the second cycle would reduce CO2 to formic acid83. for example. This product could be concentrated and used either as a feedstock or as a source of H2. water is the source of the O2 and the reduced relay can be isolated. Producing a mixture of gaseous H2 and O2 is clearly undesirable81 and there are major problems involved in collecting H2 evolved over a wide area. That is not to imply that strenuous efforts to identify suitable catalysts have not been made. Milder conditions can be used for halide oxidation and this is a viable alternative to O2 production. This latter species is regenerated using alcohol dehydrogenase (ADH) as selective catalyst. It stops only when the chromophore has been fully hydrogenated or when the substrate runs out. have not been successful71. Likewise.
Suitable catalysts are mandatory. Complacency (a) (b) (c) Fig. One such strategy is exemplified in Fig. whose purpose is to absorb photons and initiate the necessary redox chemistry. illumination of the donor results in through-bond electron transfer to the acceptor but occurs only if the linkage is intact. to be utilized to create organic molecules as substitutes for fossil fuels. are becoming commonplace. Providing a repair mechanism could be put in place. In each case.Artificial photosynthesis REVIEW Fig. excision and replacement. the array would eventually re-establish its full working capacity. This aspect of artificial photosynthesis is still in its infancy but four possible mechanisms can be identified: redundancy. Closing remarks Solar panels on the roof. The ability to create intelligent artificial repair enzymes is of course a major challenge. is now a necessity. illumination in aerobic conditions can operate without self-protection is foolhardy. 11 Illustration of artificial self-repair processes. We have to develop new catalysts to drive these reactions under mild conditions and to integrate fundamental principles of light-induced electron transfer into ordered arrays where individual molecules act cooperatively on a large scale. charging a battery in the basement. or even two arms. The challenge is immense but so too is the reward. once an esoteric research dream. S refers to a sensitizer. DECEMBER 2008 | VOLUME 11 | NUMBER 12 33 . 10 Simplified representation of a two-color photosystem for solar energy conversion using a relay. No amount of engineering will overcome this problem and it is crucial that practical photosystems are equipped with some kind of built-in protection against photochemical damage. Cars powered by the electrolysis of water no longer reside solely in the world of fiction. What price power stations harnessing sunlight and turning out designer fuels for the chemical industry using water as the sole source of electrons? The photofixation of CO2. which might differ for each reaction. became damaged over time the system will not necessarily shut down. If one. and on-site repair. where two of the blue porphyrin arms are redundant during a complete photon cycle96. reservoir effects. 11. including (a) redundancy. and (c) inclusion of a bridge that could be cut out and replaced by selective chemistry at the connections. (b) the reservoir effect.
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