Artificial

photosynthesis
Deriving energy
from sunlight
and water

THE SWEDISH ENERGY AGENCY. ET 18:2003. 2000 COPIES

DESIGN AND REPRODUCTION : ETC PRODUKTION
PRINTER: ELANDERS SKOGS GRAFISKA AB , MALM
TEXT: THE SWEDISH ENERGY AFGENCY
EDITORIAL SERVICES: JOURNALISTGRUPPEN
ILLUSTRATIONS: THE CONSORTIUM FOR ARTIFICIAL PHOTOSYNTHESIS,
THE PROTEIN DATA BANK
IMAGES: ETC BILD, PRESSENS BILD, EYEQNET, BILDHUSET

Artificial photosynthesis:
Producing energy
from sunlight and water
Hydrogen gas is an efficient energy carrier. It can be used within the entire
energy sector as a fuel, for heating and for electricity generation. If hydrogen
gas could be produced cost-efficiently in a sustainable manner, the worlds
energy needs could be met for a long time to come.
The aim of artificial photosynthesis is to produce hydrogen gas using sunlight and water in a photochemical process. The method mimics parts of
natural photosynthesis. The key reaction in natural photosynthesis is the
ability to split water. This key reaction has also been at the centre of attention for research into artificial photosynthesis. In Sweden, the Consortium
for Artificial Photosynthesis is carrying out this research
An international research evaluation of the consortiums activities was carried out in February 2003. The main conclusions were that the consortium
has made excellent progress so far and that the possibility of using sunlight
to create hydrogen gas from water has increased during the past few years.
Based partly on this successful evaluation, the consortium was recently
granted renewed funding for a further three-and-a-half-year period.
The Swedish Energy Agency manages most of the funding for Swedish
energy research, development and demonstration activities. This Research
Overview is one in a series describing the cutting edge of research in various branches of Swedish energy research. The aim is to present energy research in a broader perspective, and to make easily accessible information
available to the general public. Dr Ann Magnuson of the University of Lund
was chief editor for this overview. The project leaders were Dr Jrgen Held
and Mrs Christina Bergstrm of the Swedish Energy Agency.
The Swedish Energy Agency is working towards achieving a sustainable
energy system. The artificial photosynthesis research field is a promising
step in this direction.
Thomas Korsfeldt
Director General

Birgitta Palmberger
Head of the Energy
Technology Department

Introduction
The basis for all research on solar energy and artificial photosynthesis is
the fact that the need for abundant and accessible energy is a major driving force in our society. Without an adequate energy supply, industrial
society falters. The demands on our energy system are growing continuously, and the goal is a system relying on renewable energy sources that
are sustainable and environmentally friendly. Guaranteed supply is another important demand.
A vast amount of energy from the sun reaches the earths surface every year, even way up north in Scandinavia. The total energy received in
Sweden as sunlight is approximately 400 000 TWh per year. In comparison, the yearly energy consumption in Sweden is about 400 TWh. The
question is, how can all this available solar energy be transformed into
useful energy forms such as heat, electricity and fuel, in a simple and
cost-efficient way? Solar energy is unfortunately at a minimum in the
winter, when it is dark and cold, and when our energy needs are greatest.
It is therefore necessary to find a way to store the solar energy in a suitable energy carrier, such as hydrogen.

Hydrogen: the energy carrier for the future?

Hydrogen is a combustible element that liberates a lot of energy when
used as a fuel. It is well suited as a fuel for vehicles, for heating and for
electricity production. In addition, hydrogen is environmentally clean
when produced from solar energy. Water is the only waste product that
forms when hydrogen is burnt or consumed in a fuel cell. Technical innovations for the transport, storage and use of hydrogen are already advanced all over Europe. The technological stage is set for a future hydrogen economy. The question of where the hydrogen should come from
remains to be answered.

Techniques for converting sunlight into hydrogen

Blue-green algae of the

strain Nostoc. Research on
hydrogen-producing algae
is focused on the hydrogen
metabolism and the realisation of a sustainable biological hydrogen production

Biological hydrogen production

Cyanobacteria (commonly known as blue-green algae) and green algae
are both capable of converting solar energy to hydrogen gas. The process
is catalysed by hydrogenases: proteins that can consume or produce hydrogen, or both. The efficiency of this process is still very low, only a few
percent. But the hydrogen-producing capability can be improved by modifying the genetic makeup (DNA) of these micro-organisms. This research is also being carried out in Sweden.
Solar cells and electrolysis
Quite efficient solar cells are already producing electricity. Silicon-based
solar cells, thin film cells and a new type, Grtzel or wet solar cells, are
all under development and have reached an advanced level of refinement
already. So there is plenty of research and development into solar electricity technologies going on, and it is expected to reach a breakthrough
during the next few years. The efficiency for using solar energy to produce electricity is expected to be about 15-20%. However, the use of
electricity to produce hydrogen via electrolysis is associated with large
energy losses. Almost half the electrical energy from the solar cell is lost
as heat during electrolysis of water to produce oxygen and hydrogen gas.
Photoelectrochemical solar cell
In some systems, the light-harvesting material and the electrode are one
and the same. In this case, the hydrogen production takes place directly in

Hydrogen gas is a versatile

energy carrier. It is just as efficient as an automotive fuel
as it is for warming and
electricity production. In a
future hydrogen-gas-based
system, a solar apparatus on
the roof can meet a home's
annual energy needs

the solar cell and, theoretically, you can expect higher efficiency. An efficiency of slightly more than 10% has been proven, but only by using costly materials with limited life spans.
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.

How efficient is natural photosynthesis?

When we estimate the efficiency of natural photo-synthesis in plants, we
often count only what we can actually harvest as biomass or food. We
then find that less than one percent of the captured light energy is actually converted into biomass (fuel). This seems very little, prompting the
argument that natural photosynthesis, and any attempt to mimic it, is inefficient. This is misleading. Two processes in natural photosynthesis are
interconnected in the path from the capture of solar energy to the formation of energy-rich compounds. The most fundamental of these are
the light reactions where solar energy is captured and converted into early energy carriers. In secondary reactions (dark reactions), these energy carriers are used to promote life in the plant, reproduction and build8

up of biomass. The light reactions are highly efficient, converting as

much as 40-50 percent of the captured solar energy into energy carriers.
The dark reactions are not developed for energy efficiency and it is here the energy is used (lost for energy production) to produce complex
materials. In artificial photo-synthesis for hydrogen production, it is the
light reactions that will be mimicked, so artificial photosynthesis will be
highly efficient.

How efficient can artificial photosynthesis be?

The southernmost part of Sweden lies at the 55th latitude. From there the
country extends almost 2000km northwards, far into the polar region.
The annual influx of sunlight energy that reaches Sweden is about
1000kWh per square metre, in both the south or the north of the country.
The theoretical value for the maximum efficiency of hydrogen production by artificial photosynthesis is 4050%. In practice, an efficiency of
about 15% is considered realistic.
Imagine a device that covers the roof of a single-storey house, converting solar energy into fuel with an efficiency of 15%. It 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 cover an area of about 70 square metres per
person. In other words, less than one fifth of one percent of the total
area of Sweden would suffice to supply the country's 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. Note also that
the efficiency of the process depends on several para-meters. The final
yield is also influenced by progress in finding efficient technical solutions for storage and transport of the collected energy.

International research
Research on artificial photosynthesis is being done on a relatively small
scale around the world, for example in the USA, Japan, Germany, France, Italy and Ireland. Most of these research groups focus on partial
aspects of artificial photosynthesis. The most common goal is not energy-related, but rather to create molecular systems that look and behave
9

similarly to parts of the natural photosynthetic apparatus. This type of

research focuses on particular details of photosynthesis. The systems
that these groups work on often consist of closed electrochemical circuits.
The Swedish researchers aim to develop supramolecular chemistry
to produce a fuel from sunlight and water. The inspiration behind this,
and new ideas about how it could be accomplished, comes from frontline research within the field of natural photosynthesis. These are
complicated issues, and no scientist is capable of doing it on his or her
own.

The Consortium for Artificial Photosynthesis

The Consortium for Artificial Photosynthesis was founded in 1994
and consists of five research groups at three different universities:
the biochemical photosynthesis group led by Stenbjrn Styring at
Lund University; the organic synthesis group led by Bjrn kermark
and Licheng Sun at Stockholm University; the physical chemistry
group led by Leif Hammarstrm at Uppsala University; the group
for femtosecond chemistry led by Villy Sundstrm at Lund University; and the recently added biotechnological group at Uppsala University, led by Peter Lindblad. The Styring group is investigating both
natural photosynthesis and artificial systems. The two groups in
Lund also provide their knowledge of natural photosynthetic processes, which gives a platform of ideas to their colleagues in the consortium.
The consortium comprises about 40 people working in close collaboration, where frequent visits and in-depth communication between
members give it unique strength.
The specific goal is to produce a chemical catalyst for splitting water,
a task that has been considered extraordinarily difficult by the research
community. The consortium has a genuine chance to succeed, however, by
recognising that extensive multidisciplinary collaboration is necessary to
achieve rapid and effective progress.
The success of the consortium, with experts from different subject areas, has made Sweden a world-leading country in research on artificial photosynthesis for energy production.
10

THE GREEN LINE

WHERE IS CHLOROPHYLL?

Chlorophyll is the green

pigment that absorbs light.
It is found in the membranes of chloroplasts in leaves. The green, chlorophyllrich proteins inside these
membranes, are like little
solar energy plants. Photosystem II is one of them. It
produces energy-rich compounds, using sunlight and
water as starting materials

PHOTOSYSTEM II

The Swedish model for solar energy

The aim is to make hydrogen from solar energy using pure water as a
raw material, through what has become known as biomimetic chemistry. With knowledge of the energy-producing processes in nature, a
system for artificial photosynthesis can now be developed. An important part of the research work is therefore to study key reactions in the
natural photosynthesis process. In photosynthesis, plants harvest energy from the sun; that energy is used to split water in order to extract
chemically useful energy, which finally is refined into the form of
11

When light hits the chlorophyll (P), the electrons (e-)

move from water (H20) to
the acceptor (Q). The
electrons end their journey
in the creation of carbohydrates, with carbon dioxide
as a building block.
Electrons are extracted
from water, with manganese (Mn) as a catalyst. When
water (H20) is split, oxygen
(O2) and hydrogen ions are
released.

LIGHT

Mn Link P
e-

Link

e-

CO2
Carbohydrates

energy-rich materials such as wood. The products from the water-splitting process are hydrogen ions and oxygen gas, the very oxygen that
we breathe. The hydrogen ions can in principle be used to make hydrogen gas in an artificial photosystem.

From natural to artificial photosynthesis

Plants contain two types of photosynthetic reaction centres: Photosystem I and Photosystem II. Photosystem II is the inspiration behind
the work on artificial photosynthesis. It is a membrane-bound enzyme
that exists in all plants and algae, and which can be pictured as a small
solar-powered generator. In a complex set of light-driven reactions,
electrons are transported from water to an electron acceptor. This process generates a potential, an energy-rich state, across the membrane in
which Photosystem II is confined. The result of these electron-transporting reactions is that water is split into oxygen gas and hydrogen
ions.

Water oxidation in Photosystem II

Photosystem II is the key to almost all life on earth as we know it,
because it can use plain water as its only raw material. The most difficult step, chemically speaking, is taking the electrons out of the water
molecules. This is also the step you wish to mimic with artificial photosynthesis.
The point is that water is an unlimited electron source. If an apparatus for solar energy based on artificial photosynthesis is to be able to
produce energy that can be stored, it must have a sacrificial electron
12

e- e-

Qa

Qb

Electrones to
carbohydrates

P
Tyr
HO

eeee-

Mn

H
H

Mn

O
O

Mn

Photosystem II: The mecanism for water splitting is

complicated. When P absorbs light, an electron (e)
is moved to the acceptor
(Q). P replenishes its
electron deficiency by taking electrons from manganese (Mn), which take
electrons from water. Tyrosine (Tyr), plays a central
role as mediator between P
and the manganese complex.

Mn
O

source, and there will always be enough water. The ability of Photosystem II to extract electrons from water is the reason plants are the dominating life form on earth. Where there is light and water, there is
always life. When hydrogen gas is burnt, water is the waste product, so
the chemical circuit can be closed by an artificial system.
Oxidation of water in Photosystem II is done by four atoms of
manganese. The manganese is a catalyst that collaborates closely with an
amino acid called tyrosine. The manganese has the ability to bind water,
and to break apart the water molecules so that they can deliver one
electron after another to the chlorophyll P. When four electrons have been extracted from two water molecules, oxygen and hydrogen ions are
released. The four electrons are delivered one at a time to P, via tyrosine
(TyrZ).
This all seems very complicated, and it is, but Photosystem II is the
only known chemical catalyst for splitting water, and it is therefore important to understand its components down to the last atom. Late in the
autumn of 2000, a research group in Berlin succeeded in solving a problem that many had tried to solve for almost 20 years: they could show
13

FROM

natural
photosynthesis

TO

artificial
photosynthesis
Acceptor

Acceptors
N

P680
Tyr

Ru

N
N

HO

N
N

Me

NH

EtO2C
O

Mn

H
H

Mn

O
O

Mn

Mn

Mn

Mn

O O

Me Me

Ruthenium: chemical
symbol Ru. Atomic weight
101. Nobel metal that belongs to the group of platinum metals, and is found in
deposits of, among other
ores, platinum and iridium
in South Africa, North
America and Russia.

in atomic detail how the core of Photosystem II is constructed. This was

a major breakthrough for research into nat-ural photosynthesis and was
of crucial importance for future work. The three basic parts of photosynthetic water-splitting are:
1. A light-harvesting molecule. In nature this is chlorophyll.
2. A tyrosine that mediates electron transport and catalyses the reaction.
3. A manganese complex that sends electrons to the chlorophyll, forming
an active surface for water-splitting.

Biomimetic chemistry
The consortium is using principles from nature, but is developing
systems that have no counterpart in nature. Instead of chlorophyll, artificial photosynthesis uses chemical compounds containing the noble
metal ruthenium. Its properties are like those of chlorophyll, in that
ruthenium complexes absorb light of similar wavelengths as chlorophyll, and have similarly oxidizing potential, strong enough to drive the
oxidation of water.
14

The advantage of ruthenium complexes over chlorophyll is that the

ruthenium complexes are robust, while chlorophyll is remarkably sensitive to light. Plants live with their light sensitivity and compensate for it
through a complicated system for healing and recovery.
Artificial photosynthesis, however, has to be constructed so that it is as
fail-safe and low-maintenance as possible.
The idea, which is unique to the Swedish consortium, is to create a
supermolecular system. In this system, a ruthenium complex is connected to a manganese complex, which should be similar to the manganese complex in Photosystem II. The goal is for the manganese complex to extract electrons from water and then give the electrons one by
one to the ruthenium, just as the electron extraction occurs in Photosystem II.
Eight years ago, when this project started, the scientists realized that
it was difficult to connect ruthenium and manganese in one complex,
and it took quite a while before the first compound took form. It was a
simple molecule with one ruthenium centre loosely connected to one
manganese ion. The basic idea proved to be correct: the two metals
could be connected and light-induced chemistry could be accomplished.

Coupled supercomplexes
In 1995-1996 another major breakthrough came to the field of photosynthesis. It was discovered that tyrosine, which links the manganese
complex and the chlorophyll P, had a central and very important role in
the water-splitting reaction. It had for a long time been considered an
innocent bystander. Armed with this new knowledge, the consortium
built a new compound where a ruthenium complex was linked to a tyrosine. This ruthenium-tyrosine complex has since provided invaluable new knowledge about light-driven electron transfer from manganese to tyrosine. Surprisingly enough, it has also contributed to new research about natural photosynthesis through feedback, which would
have been impossible to conduct via the traditional biological research
methods.
The scientists in the Consortium for Artificial Photosynthesis have
now produced some 50 different manganese-ruthenium complexes. As
15

A linked ruthenium-manganese complex. 1) When

light hits ruthenium (Ru), it
expels an electron. 2) The
manganese (Mn) quickly
sends an electron to Ru.
After that, the procedure
can be repeated two or
three times.

ee- e-

1
LJUS

Ru

N
N
O

N
N

2
Me

NH

EtO2C

Mn
N

Mn
O O

Me Me

the enterprise advances, the know-how and skills for building these
complicated systems is accumulating. In nature, four manganese ions are
connected together, and the next step therefore was to connect more than
one manganese ions with the ruthenium complex. The insight that tyrosine plays a central role for water oxidation gave rise to the idea that a
similar system with manganese and tyrosine in conjunction is also essential for an artificial system.
16

LIGHT

Link

e-

Ru Link A
e-

2H2 (hydrogen)

In a future solar energy

system, the light will be
captured by ruthenium (Ru).
Electrons will move from
the donor (D) to the acceptor (A). The electrons will
be taken from water, just as
in nature, and will be used
to make hydrogen.

The new complex can give away several electrons when it is hit by
light. This can be repeated three to four times, and in this respect the artificial system mimics the natural system well. In natures Photosystem
II, the four manganese ions and the tyrosine together can provide four
electrons before water is split into its components. Yet so far the artificial system can not split water.
It is now clear how close the association to the natural system is:
1. There is a light-harvesting molecule, the ruthenium complex.
2. A tyrosine is mediating the electron transfer.
3. A manganese complex sends three to four electrons to the ruthenium, and is capable of binding water molecules.
The consortium is now working intensively on improving this supermolecule by making changes to its chemical structure. After all, the goal is
to extract electrons from water, not only from the manganese.

The goal? A real supermolecule

The consortium has so far directed all its resources towards the key reaction, where electrons are extracted from water using energy from the
sun. If this is achieved, the possibility of using water as an electron source for energy production will be real. How is it possible to make a fuel
from this? The consortium has just reached this point, and is about to
begin solving this question.
There are easier ways to produce hydrogen gas than water splitting,
and similar systems for making hydrogen have been described in the scientific literature, not, however, driven by light. For this purpose, the
17

Improved H2 production

LI G H T
H2 evoluction

Hydrogen evolution in the

blue-green algae Nostoc.
There is only little net H2
production from the natural
Nostoc (green), while the
algae that have been genetically modified, evolve
much H2 (red).

Natural H2 production

10
Ti

20

30

( i )

ruthenium complexes will be connected to a catalyst that should produce hydrogen gas, combining the electrons and the hydrogen ions extracted from the water-splitting reaction.
The working hypothesis today is that the link, which keeps the ruthenium complex and the new catalyst together, should be able to transfer
electrons efficiently. Again, nature is the source of inspiration. Consortium researchers are now working on coupling a quinone to the ruthenium centre. The first trial with a quinone bound to the ruthenium was a
success, with an electron being transferred from the ruthenium to the
quinone.

The hydrogen connection

Unicellular algae, which can produce hydrogen, create biological catalysts (enzymes) that make hydrogen gas from hydrogen ions and
electrons. Many of the chemical principles of interest for an artificial
system are therefore already present in these organisms. Peter Lindblad
leads research on these algae at Uppsala University, in an effort to improve the yield of their natural hydrogen production.
18

O
C

NC
CO

Fe
S

Cys

CN

Fe
S

2H+

CO

H2

OC
OC
OC

NH

CO

Fe

Fe
S

CO

S
O

CO

eHN

e-

N
N
N Ru
N N

LI GH T

A natural, hydrogen evolving enzyme, a hydrogenase (left). The catalytic center contains iron (Fe) and
sulfur (S). To the right is a
synthetic, biomimicking
ruthenium-iron complex, similar in structure to the
hydrogenase. When the
ruthenium absorbs light, it
sends electrons to the ironsulfer center, and reduces
hydrogen ions to hydrogen
gas.

The particular enzymes that these algae make, called hydrogenases,

contain iron and sulphur as their active components.
Similar iron-sulphur complexes can be made artificially, and the consortium has started work on linking ruthenium and manganese to such
iron-sulphur complexes. This is where the collaboration between the
consortium and researchers into biological hydrogen production begins.
Hopefully the progress on hydrogen-producing systems will be as rich
and successful as the development of ruthenium-manganese chemistry
has been.
Eventually, all these components will be connected together into one
supermolecule. In the centre it will contain ruthenium; on one side the
ruthenium will be connected to a manganese complex, and on the other
to an iron-sulphur complex via a quinone.
When the ruthenium absorbs light, it ejects an electron, which is
transported via the quinone to the iron and ends up in hydrogen. A new
electron is fed in to the ruthenium from the manganese complex via the
tyrosine. After two such light-driven electron transfers, hydrogen gas is
formed. After four such reactions the manganese takes four electrons
19

An imaginary solar panel

with two separate compartments. Water is split in
the A-compartment and
oxygen is evolved. Hydrogen is evolved in the Bcompartment.

H2

H 2O
H2O

H2O

B
A

H2O

H2O

H 2O

H 2O

B
A

H2 O

H2O

O2

from water. This sequence of reactions can then be repeated. If this scenario succeeds, then the great challenge in this research will be overcome and the technical development of a solar energy apparatus may
begin.

The future
What will a future solar energy system look like? One possibility is a
kind of solar panel that could be placed on unexploited surfaces such as
rooftops. The apparatus should contain two compartments, or tanks, separated from each other. The idea so far is that the compartments are filled with water. A membrane not unlike the membrane in the natural
system could separate the two tanks.
On one side of the membrane, water is split by a manganese complex
and oxygen is evolved. On the other side, a catalyst made of platinum or
an iron-sulphur complex evolves hydrogen gas.
20

O2

H2

O2 + 4H+

e-

H2

e-

M n- - Ru

Ru- - Fe

2H+

2H2O
= Ruthenium - manganese

Anode

= Ruthenium - iron

Catode

Membrane

In theory, a solar energy

apparatus might work like
this: A ruthenium manganese complex absorbs light
and ejects electrons. The
ruthenium manganese then
takes back four electrons
from two water molecules,
which are split into oxygen
gas and hydrogen ions. The
electrons that were given to
the electrode, is then used
to reduce the hydrogen
ions to hydrogen gas.

When the solar energy apparatus is working, it will be producing life-giving oxygen at one end and powerful hydrogen fuel in 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, and all that will need to be done is
to fill up the tank with more water now and then. The apparatus could
possibly be built in modules so that it could easily be taken apart during
maintenance. The artificial supermolecules, with manganese, iron and
ruthenium, will last a long time; when they need to be replenished, it
will be possible to recycle the waste materials in order to minimize environmental strain.

Great expectations
How close is the dream of a truly sustainable energy source to coming
true? It is not clear today how the complete conversion all the way from
sunlight to fuel will be done. But we know how to convert sunlight into chemical reactions, and we know how to make fuels chemically. How
long it will take to connect these two is hard to tell: new discoveries and
21

innovations often happen in steps, both large and small. A realistic scenario is that a working prototype of a supermolecular system is ready
within five to seven years, and that the first solar energy apparatus will
see the light of day within 15 to 20 years.
It is our ambition that environmentally damaging forms of energy
will be replaced by clean, renewable, abundant and readily available
energy sources. Artificial photosynthesis for fuel production from sunlight and water has the potential to fulfil 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.

22

23

An effective and sustainable energy supply

The Swedish Energy Agency is working to help develop
safe, environmentally friendly and efficient energy
systems in Sweden and abroad. The agency supports
more than 700 research and development projects,
including a major project on artificial photosynthesis.
Hydrogen gas is an efficient energy carrier. If it could
be produced costefficiently and sustainably, the
worlds energy needs could be met for a long time to
come. The aim of artificial photosynthesis is to
produce hydrogen gas using sunlight and water in a
photochemical process. The method mimics parts of
natural photosynthesis. The key reaction being studied
is natural photosynthesis's ability to split water.
This scientific summary describes in accessible
language where research is leading in this exciting field.

The Swedish Energy Agency

P.O. Box 310
SE- 631 04 Eskilstuna
Phone: +46 16- 544 20 00
Fax: +46 16- 544 20 29
www.stem.se