Conference Session # C13
Paper # 2201
ARTIFICIAL PHOTOSYNTHESIS: THE SOLUTION TO AN ENGERY
PROBLEM
Adedoyin Ojo (ado15@pitt.edu) and Katreena Thomas (kat73@pitt.edu)
Abstract - It is important to explore alternative, nonconventional energy sources that would not only be safe for
the environment, but also renewable, effective and cheap.
The process of artificial photosynthesis proves particularly
beneficial in this effect. Artificial photosynthesis is a process
which involves harnessing the powers of the sun and
mimicking a leaf’s process of photosynthesis to produce
energy. In our paper, we will explore and evaluate the
process of artificial photosynthesis, how it works, its
applications, and the different approaches to how artificial
photosynthesis is being achieved. We shall specifically focus
on the artificial leaf because it is the most effective
technique to approaching artificial photosynthesis. Finally,
we will explore the ethical aspects of artificial
photosynthesis with regards to its use in underdeveloped
countries.
Key
words—Artificial
leaf,
photosynthesis, water splitting
catalyst,
THE PROCESS OF PHOTOSYNTHESIS
Photosynthesis is when plants transform light energy into
chemical energy. Plants have been using this system to
create the energy they need to grow and sustain themselves.
The energy from light is captured and used to convert water,
carbon dioxide, and minerals into oxygen and organic
compounds. Photosynthesis is an oxidation-reduction
process where the light is used to cause the oxidation, or
removal of electrons, from water [4]. This process produces
oxygen gas, hydrogen ions, and electrons. The process is
accomplished using two steps. The first step is light reaction.
In this step, ATP (adenine triphosphate), a molecule that
provides energy, is created using the energy absorbed from
the chlorophyll. Water is then broken down into oxygen and
hydrogen ions. The electron from the splitting of the water
molecule is then transferred to another energy producing
molecule called NADPH. In the second step, called the dark
reaction, ATP and NADPH transfer electrons. Also the
carbon from carbon dioxide is broken apart from the
molecule. The carbon is then combined in process called the
Calvin cycle to create carbohydrates, like glucose, and other
products. Excess oxygen gas is released into the atmosphere
[5].
hydrolysis,
ENERGY AS AN ISSUE
Commercial solar panels and that are currently being used
are quite expensive when compared to gas, oil, and other
fossil fuels as an energy source. Also solar panels are limited
with the amount of electricity it can produce. It can only
produce electricity during the day when sunlight is available.
During the night, another energy source will be needed to
provide electricity. The emphasis on solar research is needed
to develop a sustainable system that requires little
preparation with minimal expenses [1]. “Sunlight has the
greatest potential of any power source to solve the world’s
energy problems, in one hour, enough sunlight strikes the
Earth to provide the entire planet’s energy needs for one
year [2],[3]” said Daniel Nocera, a chemist at the
Massachusetts Institute of Technology. With prices of
energy on the rise, people are looking for cheaper and
cleaner ways to get the energy they need. Solar energy
seems to be the best source of energy but methods of
capturing that energy tend to be costly. “A perfect solution
to the energy problem is to mimic the natural system which
has served us so well,” said James Barber, a biochemist at
Imperial College in London [3]. An application of artificial
photosynthesis is the artificial leaf, which has already proven
to be a useful product. Artificial photosynthesis can
definitely be that system.
GUIDANCE FROM NATURE
In order to truly see how artificial photosynthesis works, it is
important to understand the key elements and processes of
natural photosynthesis that need to be artificially replicated
in a simpler system. Photosynthesis involves two very
distinctive stages: the absorption of light by chlorophyll
which is followed by several electron transfer reactions. The
oxidation of water into molecular oxygen is one important
process of the electron transfer reactions [6]. Another key
component of these reactions is photosystem II which is
basically a system made up of proteins within which plants
perform the actual electron trasnsfer process [7]. In the
electron-transfer reactions, the electrons go through several
steps to generate intermediates rich in energy in a setup
known as ‘photosystem I.’ Afterwards, several dark (lightindependent) reactions take place and the products of the
electron transfer reactions, ATP and NADPH, form C-C
bonds of carbohydrates. The good thing about artificial
photosynthesis is that it is capable of stopping at any time;
so if wanted, it could stop with the formation of H2, or it
could stop after reducing CO2 to fuel [6]. This is the key to
the energy producing aspect of artificial photosynthesis. The
diagrammatic representation of the important components
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Adedoyin Ojo and Katreena Thomas
FIGURE 1
DIAGRAMMATIC REPRESENTATION OF IMPORTANT COMPONENTS AND PROCESSES OF NATURAL
PHOTOSYNTHESIS [6]
and processes of natural photosynthesis is shown in Figure
1. In order to make use of the visible light portion of solar
radiation (350 – 750 nm), plants use chlorophyll with other
pigments such as xanthophylls and carotenoids to absorb
light. To ensure that light can be captured effectively and
correctly transferred to the reaction center, chlorophyll
molecules must be structured in a specific arrangement
(antenna array) [8]. To simulate the natural process of
photosynthesis, artificial systems must somehow mimic the
two features described: using dye molecules to absorb the
visible portion of sunlight and mimicking the natural process
of energy transfer and electron transfer.
atmosphere. Thus, artificial photosynthesis can be described
as a biomimetic approach in which the vital reaction
processes of natural photosynthesis are reconstructed and
used in a much simpler system to essentially perform the
functions of photosynthesis [6]. Basically, for artificial
photosynthesis to be accomplished, there need to be
something to capture the sunlight and then something to split
the water molecules. The issue isn’t with the capture of
sunlight, but the splitting of water molecules. In order for
this to take place, the system needs a catalyst, or an inducer
of some sort. In the laboratory, many catalysts often degrade
quickly or they don’t produce the same output as a more
organic catalyst [1].
ARTIFICIAL PHOTOSYNTHESIS: IMITATING
The Artificial System
NATURE
A typical artificial photosynthesis system requires four
important components; an antenna, a reaction center, a fuel
production catalyst, and a water oxidation catalyst [1].
In natural photosynthesis, a majority of sunlight is
captured using antenna systems. These systems harvest and
transfer the energy from one system to another and
eventually to a reaction center. For artificial photosynthesis,
an antenna is needed to capture energy across the entire light
spectrum in order to produce the necessary fuels [1].
A reaction center uses the energy it received from the
antenna and transfers it to an electron acceptor. This transfer
creates a small amount of electricity. Reaction centers also
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By drawing energy from the sun, natural photosynthesis
proceeds through a series of important chemical reactions
such as the oxidation of water to molecular oxygen and the
decomposition of carbon dioxide into the form of sugar or
fuel. These processes take place as a result of light-induced
multi-electron transfer reactions which involve chlorophyll
and other enzymes. Artificial photosynthesis essentially tries
to recreate or reconstruct these natural processes in a
relatively simpler system so that solar energy can be
effectively used to create high energy fuels as well as
eliminate the amount of carbon dioxide already in the
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separate the oxidizing and reducing agents of the molecule
to opposite side of the membrane it is in. In an artificial
system, the reaction centers have to be designed so that the
electrical charge lasts longs enough so that the oxidizing and
reducing agents can be transferred to catalysts in order to
produce fuel [1].
The water oxidizing catalyst is used to split water into
oxygen and hydrogen, while also replenishing itself. Some
of the catalysts that have been used are iridium oxide and
platinum. These catalysts work well, but are very expensive,
and couldn’t be produced on a mass scale. An abundant
inexpensive natural catalyst is needed for artificial
photosynthesis to be effective. Cobalt oxide and manganese
are metal oxides that seem to fit the description of a perfect
water oxidizing catalyst [1].
The fuel production catalyst is needed to produce fuel in
the form of hydrogen, hydrocarbons, or other fuels. Platinum
has also been used for this component, but it is too
expensive. A possible alternative to platinum is a
hydrogenase enzyme. However hydrogenase is relatively
large and is sensitive to deactivation by oxygen. Although,
using hydrogenase has worked, it doesn’t work in all cases.
The ideal fuel catalyst uses inexpensive materials and is
stable [1].
This same provision applies for the reduction of water to H 2;
a strong reductant and redox catalyst must be present to
reduce the water protons to H2.
2H (aq) +2e  H2 (g) (Ered = 0.00V)
(3) [6]
Electrolysis of water to hydrogen
There are two key aspects involved in the total
decomposition of water in artificial systems: the first aspect
involves a photochemical component in which the oxidizing
or reducing equivalents are generated and the second aspect
entails finding a good enough redox catalyst to assist in the
formation of the molecular gases.
Metals such as platinum are recognized as good catalysts
for hydrogen production. To generate hydrogen, through the
electrolysis of water, a platinum electrode must serve as the
cathode and a metal oxide such as rubidium oxide or iridium
oxide must serve as the anode.
Another way to generate hydrogen is through a widely
recognized (in the science world) procedure which involves
the use of a one-electron redox agent such as Methyl
viologen because it is soluble in water and has a more
negative redox potential than hydrogen. Therefore, when
methyl viologen is in the presence of an appropriate catalyst,
it quickly produces H2 from water [6].
METHODS OF ARTIFICIAL PHOTOSYNTHESIS
Evolving oxygen from water
Several biomimetic approaches to the capture and storage of
solar energy include: i) devising an appropriate structure that
can take over the function of chlorophyll; ii) producing a
good catalyst that would allow the formation of molecular
hydrogen (H2) and oxygen (O2); iii) using sunlight to
decompose water to H2 and O2; iv) converting sunlight to
electricity directly and v) reducing CI2 to simpler
compounds that can be converted to fuel. In this paper, we
will focus on the second and third approaches.
Scientists have been more successful in this area. Oxygen
can be extracted from water through the use of bulk
electrodes or homogeneous redox catalysts. Metal oxides
such as RuO2 have been used to test the evolution of oxygen
by using chemical oxidants such as Ce(IV). An experiment
by Pennsylvania State University professor Tom Mallauk
showed that nanocrystals of metal oxides such as iridium
oxide and Niobium oxide are effective as catalysts for water
oxidations. More recently, the U.S Department of Energy’s
Lawrence Berkeley National Laboratory, headed by Heinz
Frei and Feng Jiao, was able to demostrate that nano-sized
crystals of cobalt oxide grown in mesoporous silica can
effectively be used as oxygen producing catalysts.
Decomposition of water to H2 and O2 molecules (‘water
splitting’)
One challenge that scientists have faced is the
decomposition of water into its molecular form of H2 and O2
according to
2H2O  2H2 + O2
E = 1.23V vs. NHE
Qualifying to be an effective catalyst – Frei and Jiao’s
use of nano-sized crystals of cobalt oxide in mesoporous
silica as water molecule splitting catalysts.
(1) [6]
For a substance to qualify as a practical and effective
catalyst for photooxidation, it must exhibit turnover
frequency (TOF) and density (size) that correspond to the
solar flux at ground level in order to avoid wasting of solar
photons (sunlight). For instance, a catalyst that has a
turnover frequency of 100 s-1 would require a density of one
catalytic site per square nanometer. Catalysts that have lower
rates or take up larger space would need a high surface area
support that would provide at least hundreds of catalytic
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The oxidation of O2 requires the presence of a strong oxidant
(with E ≥ 1.23 V at pH 0) and a redox catalyst that would
allow the formation of O2 and by-pass the one-electron
intermediates as shown below.
2H2O (l)  O2 (g) + 4H (aq) + 4e (Eox = 1.23 V)
(2) [6]
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sites per square nanometer. In addition, catalysts would need
to function at a thermodynamic potential that is relatively
close to that of the redox reaction so that the maximum solar
energy is converted to chemical energy (fuel). In this
respect, inorganic oxide materials are suitable substances to
be used as catalysts. Past scientific research has shown that
iridium oxide perfectly fulfills the requirements. However,
Frei and Jiao found that although it is efficient and fast,
iridium is not an abundant metal on earth and is thus,
unsuitable to be used on a large scale. Therefore, an
alternative metal oxide which is equally effective but more
readily available was needed. For guidance, they turned to
the actual natural process of photosynthesis for guidance [7].
Plants perform the actual photooxidation process within
Photosystem II; enzymes which contain manganese serve as
the catalyst in this case. However, organometallic complexes
based on manganese and modeled off the Photosystem II
have turned out to be water insoluble and were not looking
too practical [6],[8]. Thus, Frei and Jiao turned to cobalt
oxide which is not only highly abundant and important as an
industrial catalyst, but also capable of dissolving in water.
When micron-sized particles of cobalt oxide were tested,
Frei and Jiao found that they were both inefficient and too
slow to operate as photocatalysts. However, when the
particles were cut down to nano size, their yield was about
1600 times higher than the micron-sized particles and their
turnover frequency was at 1140 oxygen molecules per
second per cluster. They worked excellently! Thus, Feng and
Jiao had found their catalyst; what was needed was a solid
body or structure in which to place the catalyst to facilitate
its growth. For this process, mesoporous silica was used and
the cobalt nanocrystals were put in place to grow within the
parallel nanoscale channels of the silica through a technique
known as “wet impregnation.” The elements of cobalt oxide
that performed best were rod-shaped crystals that measured
were 8 nanometers wide and 50 nanometers long which had
interconnected to form a bundle of clusters shaped like a
sphere. This shape, according to Frei, was a major reason for
the high turnover frequency [7]. The rod-shaped crystals
formed bundled clusters interconnected by short bridge. This
structure is a main factor in the increased efficiency of the
system.
FIGURE 2
LOGO, INSTITUTE FOR ELECTRICAL AND REPRESENTATION OF ROD SHAPED
NANO-CRYSTALS OF COBALT AND A GRAPH OF ITS EFFECT ON OXYGEN
EVOLUTION [7]
THE ARTIFICIAL LEAF
Splitting water with sunlight is not a new idea. However the
devices that were being used expensive catalysts like
platinum or it used harsh acids and bases or it had to be
protected with expensive forms of glass [9]. The artificial
leaf is the most practical method of achieving artificial
photosynthesis. The artificial leaf is the product of Daniel
Nocera’s, a professor at the Massachusetts Institute of
Technology, goal of achieving a practical energy source.
The artificial leaf is about the size of a credit card. The
inside of the leaf contains silicon solar cells that are covered
with a layer of indium tin oxide. The cells contain Nocera’s
special catalyst compounds that help with the production of
hydrogen and oxygen gas. As sunlight hits the leaf, which is
placed in water, hydrogen and oxygen bubble out of both
sides of the leaf. “This is really what I started out to do in
Gray's lab—to make an unsupported device that could split
water with nothing else but sunlight,” said Nocera [9].
Nocera was able to show that the leaf worked continuously
for three days. The leaf is able to work at room temperature.
"It's doing exactly the same thing as a leaf," he says. "It's
sunlight in; hydrogen and oxygen out. And you can use the
hydrogen and oxygen at some later time,” said Nocera [9].
The Chemical Reaction of the Leaf
The effectiveness, speed and overall size of the cobalt
oxide nanocrystal clusters can be comparable to
Photosystem II. With the abundance of cobalt oxide and the
relative stability of the nanoclusters, this new catalytic
component effectively achieves the aim of photooxidation
and the overall goal of artificial photosynthesis [7].
The silicon solar cells of the leaf provide an electric current
to the system. The catalyst in the cells consists of cobalt
phosphate. The current from the solar cells cause the cobalt
phosphate to cause a catalytic reaction in the water.
Basically the energy from the cobalt phosphate is strong
enough to attract the hydrogen ions and capture them as a
gas [9].
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Finding the Perfect Catalyst
Sun catalytix
In order for the reaction to be effective, a strong catalyst is
needed to transport and assemble atoms. One of the more
recent catalysts to be used is nickel borate. Nickel borate is
similar to cobalt phosphate but it requires a higher pH.
However if it can be react with pH of water, seven, then
researchers can control the thickness of the artificial leaves
and electric potential at which it operates [9].
However the key aspect of the cobalt phosphate catalyst
is that it doesn’t oxidize. It will heal and replenish itself as it
is working. A lot of low-cost materials will eventually
corrode whereas the cobalt phosphate will not [9].
In 2009, Nocera co-founded Sun Catalytix, a Massachusetts
based technology firm, in order to put his research to work
for people. The company’s goal is the personalize energy
and get people to stop relying on traditional methods of
getting energy, like using a centralized power grids. “Your
home becomes its own solar power station,” Nocera explains
Sun Catalytic recently received a $4 million grant from the
Advanced Research Projects Agency-Energy (ARPA-E) that
they are using to work on a second-generation product. Sun
Catalytix estimates that it would take about three to five
years to create a commercial product [11],[9].
The Use of Fuel Cells
A fuel cell is a device that converts chemical energy into
electricity. Basically the chemical reactions in the cell allow
electrons to be released. The electrons then flow through an
external circuit from one electrode to another electrode
producing electricity. As long as the fuel cell has a
continuous supply of fuel and an oxidant like oxygen, the
fuel cell won’t run down or require charging [10]. "I needed
to overcome the corrosion problem and my discovery was
the first self-healing catalyst," Nocera explains. "There are
masses of interesting science problems to be solved if you
work backwards that way,” said Nocera [9].
How the Leaf Can Be Used
The idea is similar to solar panels. Instead of panels, the roof
of a home would be covered with silicon shingles that have
small amounts of water flowing around them. Then as
sunlight hits the shingles, it would stimulate the reaction and
create hydrogen and oxygen. At night, the gases can be
stored in a fuel cell in order to generate electricity. Also the
hydrogen gas can be burned in a turbine to be used for heat
energy. "I get up in the morning saying, 'what science can I
do to make this as cheaply as possible, and then I'll work on
efficiency'," Nocera explains [9]
FIGURE 3
THE ARTIFICIAL LEAF IN ACTION [12]
REVOLUTIONIZING ENERGY USE IN
UNDERDEVELOPED COUNTRIES
Downfalls
A plant leaf converts approximately 1% of the energy it gets
from sunlight. Nocera says that he can get about 2.5%
efficiency from the artificial leaf. However, this inefficiency
doesn’t come from the chemical reaction, but from the semiconduction of the silicon cells. Also the quality of fuel cells
presents an issue. Better fuel cells tend to be more costly.
However, with more research on semi-conducting materials,
and possible use for military purposes, money may not be a
factor [9].
“A practical artificial leaf has been one of the Holy Grails of
science for decades. We believe we have done it. The
artificial leaf shows particular promise as an inexpensive
source of electricity for homes of the poor in developing
countries. Our goal is to make each home its own power
station. One can envision villages in India and Africa not
long from now purchasing an affordable basic power system
based on this technology” [13]. This statement was
confidently declared by Daniel Norcera at the 241 st National
Meeting of the American Chemical Society. For years,
Norcera has possessed a vision of seeing his work with
artificial photosynthesis effectively used in developing areas
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of the world. Basically, because his work is still in its early
stages, Norcera needs a small scale area (such as
underdeveloped nations) to test out his product and to see
how well it works. However, in doing this, Norcera is not
only testing his research but also providing to developing
areas an energy source that is convenient, safe and cheap
[13]. Norcera is already in the stage of bring turning his
vision into reality. In late 2010, he signed a funding
agreement with Ratan Tata, the CEO of a successful Indian
firm in which the Tata group is allowed to commercialize
Nocera's invention which produces power from water. It is
the hope of the Tata group that, in a few years, Norcera’s
work would be well-developed and available for use in the
country [14]. A similar kind of deal could be used in other
developing areas of the world.
past years suggest that encouraging progress is being made
in the field. Artificial photosynthesis is being relentlessly
pursued because it boasts certain advantages compared to
current solar energy technology. For instance, the molecular
nanoparticles are cheaper and less heavy, and better for the
environment. More importantly, unlike current solar energy
technology, artificial photosynthesis has the potential to
reverse global warming (because its processes involve taking
in carbon dioxide and releasing oxygen) if manipulated for
use on a large industrial scale [17]. With the amazing
possibilities of such a technology within the energy industry
and on the environment, intensified and continual research to
improving the technology should be a top priority. Thomas
Edison said, “I’d put my money on the sun and solar energy,
what a source of power! I hope we don’t have to wait until
oil and coal run out, before we tackle that” [18]. The fact
that scientists and engineers are working hard towards
validating that statement speaks volumes about human
capacity for growth, inventive use of resources and pursuit
of knowledge. “They’re developing a way to turn sunlight
and water into fuel for our cars,” says President Obama in
his most recent State of the Union Address in reference to a
$122 million research program on artificial photosynthesis
[19]. As of now, solar energy provides about 1.5% of the
world’s energy needs. Solar panels only produce about 0.1%
of that energy. Also since the sun only shines during the day,
there isn’t a way to store the energy for use at night [19].
The use of artificial photosynthesis, not only provides
energy but it can be stored as a hydrogen liquid that can be
used later. The most recent discoveries within
photosynthesis use cheap materials and resources that are
easily found and abundant on earth. The artificial
photosynthesis method that Dan Nocera has discovered can
be applied to many situations, such as powering a third
world country and steering away from nonrenewable energy
sources. With more research and funding, artificial
photosynthesis could definitely be a solution to utilizing the
sun’s immense energy. "It's a step," says Dan Nocera. "It's
heading in the right direction [20]."
Artificial photosynthesis is also an ethical way of solving
the solar energy issue. It promotes sustainability and with
the application of the artificial leaf, it supports technological
advancement. Artificial photosynthesis is an important topic
from many viewpoints. It will prove to be beneficial to many
people in the future.
From An Engineering Perspective
In the National Society of Professional Engineers code of
ethics, section III, 3, d: “Engineers are encouraged to adhere
to the principles of sustainable development in order to
protect the environment for future generations.” Also stated
as a footnote in the NSPE code of ethics is: “Sustainable
development is the challenge of meeting human needs for
natural resources, industrial products, energy, food,
transportation, shelter, and effective waste management
while conserving and protecting environmental quality and
the natural resource base essential for future development
[15].” Research on artificial photosynthesis definitely
achieves this aspect of the code of ethics. With enough
research and time, artificial photosynthesis can be a tool to
solving energy issues for the future, making life easier in the
year to come. The artificial leaf uses materials that are
abundant in nature and doesn’t have any byproducts that are
harmful to humans.
In the Institute of Electrical and Electronics Engineers
code of ethics section A, 5 it states that its members agree to
improve the understanding of technology; its appropriate
application, and potential consequences [16].” With more
research, the artificial leaf can prove to be an outstanding
piece of technology that can be applied to numerous energy
related crises throughout the world. The basic design of the
artificial leaf that is being developed now can be changed
and manipulated to better suit the energy needs of the future.
Improvisation is an important aspect of engineering and with
the development of the artificial leaf; the technology can
only be improved.
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2011,
from
www.economist.com/blogs/babbage/2011/02/artificial_photosynthesis
[20] Roach, J. (n.d.). Future of Technology - 'Artificial leaf' makes real fuel
. Future of Technology. Retrieved October 3, 2011, from
http://futureoftech.msnbc.msn.com/_news/2011/09/30/8064321-artificialleaf-makes-real-fuel
ACKNOWLEDGMENTS
We would like to thank our writing instructor, Diane Kerr
for offering insightful comments and advice on how to
proceed with our rough draft. We also thank Benjamin
Hunter, our session chair, and Ming Le, our session co-chair
for their part in helping us to develop a game plan for the
paper. Finally, we thank our good friends, Harry Hawkins
and Ashley McCray for proofing reading our paper and
pointing out the little mistakes made.
Additional Resources Section
Calzaferri, G. (2009, December 4). Artificial Photosynthesis. Springerlink.
Retrieved
March
1,
2012,
from
www.springerlink.com/content/x9836781r784l793/fulltext.pdf
University of Pittsburgh
Eleventh Annual Freshman Conference
Swanson School of Engineering
April 9, 2011
7