Artificial Photosynthesis: Energy From Sunlight and Water 2008
Artificial Photosynthesis: Energy From Sunlight and Water 2008
Artificial photosynthesis
O N O N O O N N N N O N N
Ru
HN Et O2C
N N N
Mn Mn
O O O O
1
N N
2007:53. 2000
COPIES , DECEMBER
2007
DESIGN AND REPRODUCTION : EDITA COMMUNICATION PRINTER : EDITA VSTRA AROS TEXT: THE SWEDISH ENERGY AGENCY AND ASSOCIATE PROFESSOR ANN MAGNUSON ILLUSTRATIONS : THE CONSORTIUM FOR ARTIFICIAL PHOTOSYNTHESIS IMAGES : PER WESTERGRD, EYEQNET, SCANPIX
Introduction
Climate issues are creating a growing demand for sustainable energy systems based on renewable energy sources with minimal environmental impact. Guaranteed supply is another important demand. A vast amount of energy reaches the Earths surface every year, even as far north in Scandinavia. The total energy received in Sweden as sunlight is approximately 400,000 TWh (terawatt-hours) per year. In comparison, annual energy consumption in Sweden is about 400 TWh. The question is, how can this solar energy be transformed simply and cost-effectively into useful forms of energy such as heat, electricity and fuel. Solar energy is unfortunately at a minimum during the winter, when the dark and cold mean our energy needs are greatest. It is therefore necessary to store the solar energy in a suitable energy carrier. Hydrogen gas is one of several possible energy carriers. One of its advantages is that the use of hydrogen gas does not lead to the emission of any carbon dioxide. But the current methods for producing hydrogen are based on fossil fuels. An energy-efficient and emission-free way of producing hydrogen would make it one of several interesting energy carriers for a sustainable energy system. That is why there is research into potential future technologies for hydrogen gas production, using artificial photosynthesis to mimic the way plants make energy from sunlight and water.
Hydrogen gas is a versatile energy carrier. It can be used for transportation as well as for heating and power production. In the EU projects CUTE and ECTOS, buses driven by hydrogen gas have been tested with good results in ten different European cities, among them Stockholm.
few percent. But the hydrogen-producing capability can be improved by modifying the genetic makeup (DNA) of these microorganisms. There is a great deal of research into improving this efficiency being carried out all around the world, and especially in Sweden. Artificial photosynthesis As the name suggests, artificial photosynthesis is a way to mimic the photosynthesis of plants artificially, circumventing the expense in time and material (and space) that growing a plant takes. The energy derived from artificial photosynthesis will be used directly to create a fuel (hydrogen gas). The hydrogen gas will be made by sunlight and water, using photochemistry.
life in the plant, reproduction and build-up of biomass. The secondary reactions have not evolved for energy efficiency; on the contrary, it is in these secondary reactions that energy is consumed (lost for human use) in the plants. The light reactions, on the other hand, are highly efficient, converting as much as 40-50 percent of the captured solar energy into energy carriers. Artificial photosynthesis for hydrogen production mimics the chemical and physical principles governing the light reactions, so it will be highly efficient.
energy
can
artificial
photosynthesis
The theoretical maximum efficiency of artificial photosynthesis the proportion of absorbed energy that can be stored is estimated to be about 40-50 percent, based on comparisons with natural photosynthesis. In practice, about 15 percent efficiency is considered realistic. How much useful energy is that? Let us look at an example. Each year, Sweden receives about 1000 kWh of influx of sunlight energy per square metre, in both the south and the north of the country. The energy usage in a standard single-storey house is about 150 kWh per year and square metre. A device that covers the roof of that house, converting solar energy into fuel with 15 percent efficiency, would produce enough fuel to supply the energy requirements of the house throughout the year, including the large amount of heating that the Swedish climate demands. To provide energy for our transport systems, our hypothetical device would need to cover an area of about 70 square metres per person. In other words, less than one fifth of 1 percent of the total area of Sweden would suffice to supply the countrys transport systems with fuel. These examples show that the development of solar energy does not mean that vast areas have to be covered by solar panels.
Scientific teamwork
Research on artificial photosynthesis is being done on a relatively small scale around the world, including in the USA, Japan, France, Germany and Australia. Each case involves mainly basic research activities; nobody has yet come up with a functioning prototype for a fuel-producing system
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by mimicking photosynthesis. Most of the international research groups focus on mimicking particular aspects of photosynthesis, and in many cases energy production is not a goal at all. The most common goal is to create molecular systems that look and behave similarly to parts of the natural photosynthetic apparatus. The Swedish vision is of a complete chemical system that can produce fuel directly from sunlight and water. The inspiration for this and thoughts about how it can be accomplished comes from frontline research into natural photosynthesis. These are complicated issues and no scientist can succeed on his or her own
An education in chemistry or molecular biology is the basis for research on artificial photosynthesis.
Can I study artificial photosynthesis at the university? A new masters programme in chemistry, called Chemistry for Renewable Energy, will start at Uppsala University in the autumn of 2008. It will be open to students with Bachelor of Science degrees, with an emphasis on chemistry. The courses include photochemistry and photobiology, artificial photosynthesis, solar cells, batteries and fuel cells. More information can be found at: www.chemistry.uu.se/master.
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Photosystem II
and hydrogen ions, which are important for the creation of energy-rich products, are also released as the water is split. An artificial system will use both electrons and hydrogen ions to make hydrogen gas. The key to it all is to split the water molecules in the first place. That is difficult.
LIGHT
Mn Link P
e-
Link
e-
CO2 Carbohydrates
Photosystem II
An artificial photosystem mimics the natural Photosystem II in several ways. Both have a light-absorbing component: P in Photosystem II and Ru in the artificial system. When light is absorbed, an electron is moved to electron-acceptor compounds. In nature they are quinones; similar acceptors (highlighted in blue) are used in the artificial system. Electrons are taken from a manganese complex (Mn) in both the natural and artificial system. Water is split in Photosystem II, and more electrons are liberated. The artificial system also extracts electrons from water, but not yet as efficiently.
O N
Acceptor
O O N N O N O N N N N O O
Acceptors
P 680
Tyr Mn
N N
Ru Ru
HN Et O2C
Mn
O
O
O
Mn Mn
O
N N N
Mn
Mn Mn Mn
O O O O N
LIGHT
Link
e-
Ru Link A
e-
2H2 (hydrogen)
Artificial photosynthesis
the arrangement in Photosystem II. The aim is to mimic the series of events that takes place when plants convert the energy in sunlight to a chemical form. This is how the artificial system is supposed to work: When the ruthenium (Ru) is struck by light, an electron is sent to the acceptor part (A) of the supermolecule. The electron hole in the ruthenium complex is filled by an electron, which is transported from the manganese complex (Mn) to the ruthenium. The manganese complex then takes electrons from water molecules (H2O). The result of these events is the release of electrons, which can be utilized for producing a fuel. In addition, hydrogen ions (H+) and oxygen (O2) are also liberated. Thus far, the artificial system mimics the natural. The important part is what the electrons are used for how the energy is secured and stored. In this case, the consortium has a different solution to the one plants have. We humans would like fuel production that is as efficient as possible, so the electrons and hydrogen ions will be used to make hydrogen using a chemical catalyst.
The supermolecule
O N O N N O N N N N Ru Ru N N O O
eO
O N O
HN
A coupled ruthenium-manganese compound, supermolecule. 1. When light strikes the ruthenium complex (Ru), it sends an electron to the acceptor (highlighted in blue). 2. The electron hole in the ruthenium complex is filled by an electron from the manganese complex (Mn). 3. The manganese attracts water molecules and extracts electrons from them. This course of events can then be repeated two or three times.
e-
Et O2C
N N N
Mn Mn Mn
O O O O O
N
H2O
H2O
is a long-held view in the scientific community that four manganese ions are necessary for water oxidation: one manganese ion for each electron that is extracted. Chemically, it is difficult to combine four manganese ions, so in early attempts the scientists settled for two. This ended up working beyond expectations. The supermolecule in the picture has two manganese ions connected to one side of the ruthenium complex, and two acceptor molecules on the other. When the ruthenium absorbs light energy, an electron is sent to the acceptor, and one electron is transported from the manganese to the ruthenium. Thus far, the molecule worked as expected. What the scientists in the consortium did not expect was that three or four electrons can be transported from the manganese, although there are only two manganese ions in the molecule.
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The next surprise was that the manganese ions actually extract electrons from water. Although the water-splitting is nowhere near as efficient as in Photosystem II, it has taken the scientists closer to a solution to the water-oxidation puzzle. The final dilemma that the consortium has to resolve is to make the mechanism come full circle: to make the system reset itself so that more water molecules can be split in a sustainable process.
A sensational discovery
So far, the consortium has produced close to 50 different manganese and ruthenium compounds. The molecule in the figure is the most advanced, and has produced a sensational result, at least on the research level: it is the only artificial molecule in the world that combines several essential building blocks for an artificial photosystem with unique photochemical properties. First, it can move more than one electron from the donor side to the acceptor side. When positive and negative charges exist on separate locations in a molecule, one speaks of a charge-separated state. The second unique property is that the charge separation in this molecule is unusually long-lived. Long-lived charge separation is well known in nature. Water-splitting in Photosystem II is a very slow process (a thousandth of a second is a long time on a chemical time scale). The electron that gets transported must be tied up long enough for water-splitting to take place, so that the energy can be used to make fuel. For research on artificial photosynthesis, solving the problem of short-lived charge separation has always been an important priority.
Lasting results
This is where the research stands today. A supermolecule has been designed that absorbs light and moves electrons to an electron acceptor. Several electrons can be moved from a manganese complex on the donor side of the molecule, and the manganese takes electrons from water. To this end the scientists have managed to mimic key events taking place in Photosystem II. These are lasting results that make the consortium optimistic about the future. The remaining challenge is to make a manganese complex that can split water catalytically, so that the system can take electrons from water over and over again in a useful and sustainable way. The Swedish consor17
2H+
NC OC S Cys O C
H2
CO
2H+
OC OC
CN
H2
CO
Fe Fe
S S
Fe Fe
X NH
Fe
S S
OC
Fe
CO CO
eN N N N
Light
Ru
N
A natural hydrogenase
A natural hydrogenase (left) that produces hydrogen. The biomimetic catalyst (right) has an iron-iron complex resembling the natural enzyme, and which can produce large amounts of hydrogen under controlled conditions. In the near future, this is how it will work: when the ruthenium complex absorbs light, it sends an electron to the iron complex. When the iron has received two electrons, the complex reacts with two hydrogen ions (H+), and hydrogen (H2 ) is formed
tium is also working hard to develop the part of the supermolecules that will produce hydrogen.
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Cyanobacteria are photosynthetic microorganisms that can produce hydrogen from sunlight and water. This picture shows a particular kind of bacterial cell, called a heterocyst, which can take atmospheric nitrogen and convert it into valuable nutrients. When that happens, energy-rich hydrogen is formed as a waste product, and then consumed by the mechanism of the cell. Scientists are developing ways to domesticate the cyanobacteria, so that it liberates the hydrogen rather than consuming it.
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exchange of ideas between colleagues are important parts of the day-today work. New and fruitful ideas are being born in the interplay between biology and chemistry, so it is important that research into biological hydrogen production is done in parallel with artificial photosynthesis.
Major progress
Summing up, research into artificial photosynthesis has made major progress over the past four or five years. The consortium has designed a supermolecule consisting of a lightabsorbing component, a donor component and an acceptor component. It mimics key aspects of Photosystem II in plants, and has the most stable charge separation of all artificial molecules of its kind. Other newly created molecules, designed to mimic natural hydrogenases, are producing hydrogen catalytically. The new catalysts are the most efficient hydrogen-generating molecules to have been made synthetically. A big issue in chemical science how catalytic water oxidation can be accomplished is close to being resolved, thanks to investigations of synthetic manganese complexes. The compounds that the Consortium for Artificial Photosynthesis has been working with for years have been shown to react with water in a fruitful way.
H2
H2O H2O H2O H2O H2O H2O H2O H2O H2O
H2O
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O2
O2
H2
O2 + 4H
H+
H+
eMn2---Ru
eRu---Fe2
H2
2 H2O
2H+
In theory, a solar-fuel apparatus might work like this: a ruthenium-manganese complex absorbs light and ejects electrons. The complex splits water to extract electrons and oxygen, and hydrogen ions are formed. The hydrogen ions pass through the membrane to the other side, where a ruthenium-iron complex absorbs light and uses the hydrogen ions and electrons to make hydrogen gas.
There is still work left to be done before the dream of artificial photosynthesis can become a reality. Water-splitting has to be catalytic it must be continuous over time and hydrogen production using synthetic catalysts has to be driven by light. Given more time, the consortium is optimistic about solving these issues as well. And when these goals are achieved, the development of an apparatus for solar-fuel production can begin.
The future
What will a future solar-fuel system look like? There are several alternatives. One big supermolecule might do all the work, and many such molecules together inside a solar panel would split water and emit hydrogen. Another possibility is to divide the two processes, so that water-splitting molecules are in one place, while hydrogen-producing molecules are in another. The apparatus would then consist of two compartments, or tanks, separated from each other. The compartments should be filled with water, and separated by a membrane. On one side of the membrane, water is split, releasing electrons, hydrogen ions and oxygen. On the other side of the membrane, the hydrogen ions and electrons are used to make hydrogen. Both processes are driven by sunlight. All these ideas are plausible solutions to the practical problem of designing a solar-fuel apparatus, but it is still too early to say what the winning concept will be. So far, the consortium is working on a basic research level, meaning that the primary goal is to resolve issues around the fundamental principles of artificial photosynthesis. There is no working prototype yet, but one can speculate about what it might ultimately look like.
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One possibility is a kind of solar panel that could be placed on unexploited surfaces such as rooftops. When the solar-fuel apparatus is working, it will produce life-giving oxygen at one end and powerful hydrogen fuel at the other. The hydrogen can be used immediately, or stored in hydrogen-absorbing materials such as metal hydrides. It is anticipated that the system will be nearly self-sufficient: all that will be required is to fill the tank with more water now and then. The apparatus could be built in modules, so it could easily be taken apart for maintenance.
Great expectations
How close to reality is the dream of a truly sustainable energy source? It is not clear today how the complete conversion all the way from sunlight to fuel will be achieved. But we know how to convert sunlight into chemical reactions, and we know how to make fuels chemically. Connecting these two is one of the great challenges in research, and it is hard to tell how long it will take. New discoveries and innovations often happen in steps, both large and small. A realistic scenario is that a working prototype of a supermolecular system is ready within 5-10 years, and that the first solarfuel apparatus will see the light of day in 10-15 years. Our ambition is to replace environmentally damaging forms of energy with clean, renewable and readily available energy sources. Artificial photosynthesis for fuel production from sunlight and water has the potential to meet this ambition. There is still a long way to go and major efforts from creative scientists are needed before the goal can be reached. Otherwise it will remain a dream.
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The Swedish Consortium for Artificial Photosynthesis works at the Department of Photochemistry and Molecular Science, Uppsala University, and at the Department of Chemical Physics, Lund University
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