The bionic leaf is one step closer to reality.

Daniel Nocera, a professor of energy

science at Harvard who pioneered the use of artificial photosynthesis, says that he
and his colleague Pamela Silver have devised a system that completes the process
of making liquid fuel from sunlight, carbon dioxide, and water. And theyve done it
at an efficiency of 10 percent, using pure carbon dioxidein other words, one-tenth
of the energy in sunlight is captured and turned into fuel. That is much higher than
natural photosynthesis, which converts about 1 percent of solar energy into the
carbohydrates used by plants, and it could be a milestone in the shift away from
fossil fuels. In nature, plants use sunlight to make carbohydrates from carbon
dioxide and water. Artificial photosynthesis seeks to use the same inputssolar
energy, water, and carbon dioxideto produce energy-dense liquid fuels. Nocera
and Silvers system uses a pair of catalysts to split water into oxygen and hydrogen,
and feeds the hydrogen to bacteria along with carbon dioxide. The bacteria, a
microrganism that has been bioengineered to specific characteristics, converts the
carbon dioxide and hydrogen into liquid fuels.

Several companies, including Joule Unlimited and LanzaTech, are working to produce
biofuels from carbon dioxide and hydrogen, but they use bacteria that consume
carbon monoxide or carbon dioxide, rather than hydrogen. Noceras system, he
says, can operate at lower temperatures, higher efficiency, and lower costs. The
new system can use pure carbon dioxide in gas form, or carbon dioxide captured
from the airwhich means it could be carbon-neutral, introducing no additional
greenhouse gases into the atmosphere. The 10 percent number, thats using pure
CO2, says Nocera. Allowing the bacteria themselves to capture carbon dioxide from
the air, he adds, results in an efficiency of 3 to 4 percentstill significantly higher
than natural photosynthesis. Thats the power of biology: these biorganisms have
natural CO2 concentration mechanisms.

An artificial leaf a solution to part of our

energy problems?
Part of the solution to the worlds energy problems may be under development in a lab at Ume
University. At UmU a team of researchers is working on a leaf-like membrane that converts
sunlight and water into an environmentally friendly fuel. The scientists want to mimic
photosynthesis, but also make it much more efficient.
The greatest source of energy that exists is the sun. The sunlight that reaches the earth in one
hour contains more energy than we humans consume in a year. The question is merely how to
capture, convert, and store solar energy in order to exploit it optimally.

The primary aim is to develop a more efficient method for transforming solar energy into a
storable fuel, which can be used when needed to, for example, power vehicles or heat homes.
Our goal is to demonstrate that this concept works efficiently al lab scale; subsequently others
can work out the actual applications, says Johannes Messinger, professor of biological
chemistry at Ume University.

Simple idea with certain challenges

Johannes Messingers research team is developing a membrane that, when placed in water and
exposed to sunlight, can split water, producing hydrogen and oxygen. This work is possible due
to funding by the Knut and Alice Wallenberg Foundation.

Briefly, the method involves absorption of sunlight by pigments or semiconductors, which then
create positive and negative charges. These charges must then be separated so that the positive
ones are gathered on one side and the negative ones on the other side of the membrane. When the
positive and negative charges hit catalysts on the membrane surface, chemical reactions take
place that lead to water splitting, yielding molecular hydrogen and oxygen.

The idea is simple, but it entails a number of challenges that we need to solve, such as how we
can channel the negative and positive charges to each side of the membrane.
Another challenge is that a strong oxidizing power is needed to split the water, which means that
there is the risk that the membrane itself might become oxidized and damaged. Other processes
can also damage the membrane. Plants and cyanobacteria solve the problem by recreating the
parts that are destroyed once every half hour, in full sunlight, but an artificial leaf has to be stable
over a long period. Whats more, the technology needs to be inexpensive and efficient if its to be
useful.

The secret lies in photosystem II

Throughout his research career, Johannes Messinger has been involved in studying natural
photosynthesis and how water is split into oxygen and hydrogen-like products.

Splitting water is a process that takes place in green plants, algae, and cyanobacteria within a
large protein complex known as photosystem II. Here water is divided into molecular oxygen,
protons, and electrons. In artificial photosynthesis, the idea is to efficiently combine the protons
and electrons to produce molecular hydrogen.

The scientists are trying to mimic natural processes with various types of catalysts. In order to
split water, a metal-oxide complex is used, similar to what is found in photosystem II. And to
combine protons and electrons into hydrogen, an active iron complex is used, that is similar to
that found in enzymes hydrogenases - of various microorganisms.

The metal complex has to be stable, efficient, and inexpensive, and the metal must be available
in large quantities. Manganese, cobalt, and nickel are some of the metals we use in our
experiments.

The best thing about the process is that its entirely environmentally friendly. It starts with
water, which is split and then returns to water in a cycle when the hydrogen is combusted, and its
stored energy is used as heat or electricity.

Better than the original

The researchers goal is to be able to create artificial photosynthesis that is more efficient than
the original.

Plants use energy from photosynthesis also to grow and multiply. For photosynthesis to
function, the sunlight cant be too intense. We want to be able to expose the membrane to intense
sunlight. And of course the artificial system also lacks the growth phases, says Johannes
Messinger.

Ordinary plants reach barely one-percent efficiency in their conversion of sunlight into fuel.
Johannes and his team are aiming, in collaboration with several other groups at Ume University,
to attain up to 1015-percent efficiency.

A research group at MIT in Boston is working with a concept similar to ours, except theyre
using other materials. Theyve reached up to 2.5-percent efficiency, which shows that the idea
works. The drawback with their process is that its too expensive to be mass-produced.
Should be printable

To make the process more inexpensive to produce, Johannes and his associates are trying to
make the membrane printable.

The idea is to use roll-to-roll technology, similar to the way a newspaper is printed. That
technology is already in use today in the production of the next generation of lighting, for
example. But it will take several years for us to get that far.

He also believes that once the technology of a membrane works, which powered by sunlight
produces hydrogen from water, it will also be possible to transfer the method to construct devices
producing methanol or ethanol from sunlight, water and CO2.

Johannes Messinger came to Ume University in 2008 from the Max Planck Institute in
Mhlheim an der Ruhr, Germany, where he was a group leader. In Ume he is coordinating a
team of researchers consisting of chemists, physicists, and plant biologists that have joined
forces to contribute an environmentally friendly solution to the worlds energy needs.

Theres truly an excellent scientific environment here at the Chemical Biological Center in
Ume. Its just the place to advance this work on artificial photosynthesis.
---------------------------------------------------------------------------------------------------------------------
---------------------

Artificial photosynthesis is a chemical process that replicates the natural process of

photosynthesis, a process that converts sunlight, water, and carbon dioxide into carbohydrates
and oxygen. The term, artificial photosynthesis, is commonly used to refer to any scheme for
capturing and storing the energy from sunlight in the chemical bonds of a fuel (a solar fuel).
Photocatalytic water splitting converts water into hydrogen ions and oxygen, and is a main
research area in artificial photosynthesis. Light-driven carbon dioxide reduction is another
studied process, that replicates natural carbon fixation.

Research developed in this field encompasses the design and assembly of devices for the direct
production of solar fuels, photoelectrochemistry and its application in fuel cells, and the
engineering of enzymes and photoautotrophic microorganisms for microbial biofuel and
biohydrogen production from sunlight. Many, if not most, of the artificial approaches to artificial
photosynthesis are bio-inspired, i.e., they rely on biomimetics.

Contents

1 Overview

2 History

3 Current research

o 3.1 Hydrogen catalysts

o 3.2 Water-oxidizing catalysts

o 3.3 Photosensitizers

o 3.4 Carbon dioxide reduction catalysts

o 3.5 Other materials and components

4 Light-driven methodologies under development

o 4.1 Photoelectrochemical cells

o 4.2 Photocatalytic water splitting in homogeneous systems

o 4.3 Hydrogen-producing artificial systems

o 4.4 NADP+/NADPH coenzyme-inspired catalyst

 o 4.5 Photobiological production of fuels

5 Employed research techniques

6 Advantages, disadvantages, and efficiency

7 See also

8 References

9 External links

Overview
The photosynthetic reaction can be divided into two half-reactions of oxidation and reduction,
both of which are essential to producing fuel. In plant photosynthesis, water molecules are photo-
oxidized to release oxygen and protons. The second stage of plant photosynthesis (also known as
the Calvin-Benson cycle) is a light-independent reaction that converts carbon dioxide into
glucose (fuel). Researchers of artificial photosynthesis are developing photocatalysts that are
able to perform both of these reactions. Furthermore, the protons resulting from water splitting
can be used for hydrogen production. These catalysts must be able to react quickly and absorb a
large percentage of the incident solar photons.[1]

Natural (left) versus artificial photosynthesis (right)

Whereas photovoltaics can provide energy directly from sunlight, the inefficiency of fuel
production from photovoltaic electricity (indirect process) and the fact that sunshine is not
constant throughout the day sets a limit to its use.[2][3] One way of using natural photosynthesis is
via the production of a biofuel, which is an indirect process that suffers from low energy
conversion efficiency (due to photosynthesis' own low efficiency in converting sunlight to
biomass), the cost of harvesting and transporting the fuel, and clashes with the increasing need of
land mass for food production.[4] Artificial photosynthesis aims then to produce a fuel from
sunlight that can be conveniently stored and used when sunlight is not available, by using direct
processes, that is, to produce a solar fuel. With the development of catalysts able to reproduce the
key steps of photosynthesis, water and sunlight would ultimately be the only needed sources for
clean energy production. The only by-product would be oxygen, and production of a solar fuel
has the potential to be cheaper than gasoline.[5]

One process for the creation of a clean and affordable energy supply is the development of
photocatalytic water splitting under solar light. This method of sustainable hydrogen production
is a key objective in the development of alternative energy systems.[6] It is also predicted to be
one of the more, if not the most, efficient ways of obtaining hydrogen from water.[7] The
conversion of solar energy into hydrogen via a water-splitting process assisted by
photosemiconductor catalysts is one of the most promising technologies in development.[citation
needed]
This process has the potential for large quantities of hydrogen to be generated in an
ecologically sound manner.[citation needed] The conversion of solar energy into a clean fuel (H2) under
ambient conditions is one of the greatest challenges facing scientists in the twenty-first century.[8]

Two approaches are generally recognized in the construction of solar fuel cells for hydrogen
production:[9]

A homogeneous system is one where catalysts are not compartmentalized,

that is, components are present in the same compartment. This means that
hydrogen and oxygen are produced in the same location. This can be a
drawback, since they compose an explosive mixture, demanding gas product
separation. Also, all components must be active in approximately the same
conditions (e.g., pH).

A heterogeneous system has two separate electrodes, an anode and a

cathode, making possible the separation of oxygen and hydrogen production.
Furthermore, different components do not necessarily need to work in the
same conditions. However, the increased complexity of these systems makes
them harder to develop and more expensive.

Another area of research within artificial photosynthesis is the selection and manipulation of
photosynthetic microorganisms, namely green microalgae and cyanobacteria, for the production
of solar fuels. Many strains are able to produce hydrogen naturally, and scientists are working to
improve them.[10] Algae biofuels such as butanol and methanol are produced both at laboratory
and commercial scales. This approach has benefited from the development of synthetic biology,
[10]
which is also being explored by the J. Craig Venter Institute to produce a synthetic organism
capable of biofuel production.[11][12]

History
The artificial photosynthesis was first anticipated by the Italian chemist Giacomo Ciamician in
1912.[13] In a lecture that was later published in Science[14] he proposed a switch from the use of
fossil fuels to radiant energy provided by the sun and captured by technical photochemistry
devices. In this switch he saw a possibility to close the gap between the rich north and poor south
and ventured a guess that this switch from coal to solar energy would "not be harmful to the
progress and to human happiness."[15]

In the late 60s, Akira Fujishima discovered the photocatalytic properties of titanium dioxide, the
so-called Honda-Fujishima effect, which could be used for hydrolysis.[16]

The Swedish Consortium for Artificial Photosynthesis, the first of its kind, was established in
1994 as a collaboration between groups of three different universities, Lund, Uppsala and
Stockholm, being presently active around Lund and the ngstrm Laboratories in Uppsala.[17]
The consortium was built with a multidisciplinary approach to focus on learning from natural
photosynthesis and applying this knowledge in biomimetic systems.[18]

Research into artificial photosynthesis is undergoing a boom at the beginning of the 21st century.
[2]
In 2000, Commonwealth Scientific and Industrial Research Organisation (CSIRO) researchers
publicized their intent to focus on carbon dioxide capture and its conversion to hydrocarbons.[19]
[20]
In 2003, the Brookhaven National Laboratory announced the discovery of an important
intermediate step in the reduction of CO2 to CO (the simplest possible carbon dioxide reduction
reaction), which could lead to better catalysts.[21][22]

One of the drawbacks of artificial systems for water-splitting catalysts is their general reliance on
scarce, expensive elements, such as ruthenium or rhenium.[2] In 2008, with the funding of the
United States Air Force Office of Scientific Research,[23] MIT chemist and head of the Solar
Revolution Project Daniel G. Nocera and postdoctoral fellow Matthew Kanan attempted to
circumvent this issue by using a catalyst containing the cheaper and more abundant elements
cobalt and phosphate.[24][25] The catalyst was able to split water into oxygen and protons using
sunlight, and could potentially be coupled to a hydrogen gas producing catalyst such as platinum.
Furthermore, while the catalyst broke down during catalysis, it could self-repair.[26] This
experimental catalyst design was considered a major breakthrough in the field by many
researchers.[27][28]

Whereas CO is the prime reduction product of CO2, more complex carbon compounds are
usually desired. In 2008, Andrew B. Bocarsly reported the direct conversion of carbon dioxide
and water to methanol using solar energy in a highly efficient photochemical cell.[29]

While Nocera and coworkers had accomplished water splitting to oxygen and protons, a light-
driven process to produce hydrogen is desirable. In 2009, the Leibniz Institute for Catalysis
reported inexpensive iron carbonyl complexes able to do just that.[30][31] In the same year,
researchers at the University of East Anglia also used iron carbonyl compounds to achieve
photoelectrochemical hydrogen production with 60% efficiency, this time using a gold electrode
covered with layers of indium phosphide to which the iron complexes were linked.[32] Both of
these processes used a molecular approach, where discrete nanoparticles are responsible for
catalysis.

Visible light water splitting with a one piece multijunction cell was first demonstrated and
patented by William Ayers at Energy Conversion Devices in 1983.[33] This group demonstrated
water photolysis into hydrogen and oxygen, now referred to as an "artificial leaf" or "wireless
solar water splitting" with a low cost, thin film amorphous silicon multijunction cell directly
immersed in water. Hydrogen evolved on the front amorphous silicon surface decorated with
various catalysts while oxygen evolved from the back metal substrate which also eliminated the
hazard of mixed hydrogen/oxygen gas evolution. A Nafion membrane above the immersed cell
provided a path for proton transport. The higher photovoltage available from the multijuction
thin film cell with visible light was a major advance over previous photolysis attempts with UV
sensitive single junction cells. The group's patent also lists several other semiconductor
multijunction compositions in addition to amorphous silicon.

In 2009, F. del Valle and K. Domen showed the impact of the thermal treatment in a closed
atmosphere using Cd1-xZnxS photocatalysts. Cd1-xZnxS solid solution reports high activity in
hydrogen production from water splitting under sunlight irradiation.[34] A mixed
heterogeneous/molecular approach by researchers at the University of California, Santa Cruz, in
2010, using both nitrogen-doped and cadmium selenide quantum dots-sensitized titanium
dioxide nanoparticles and nanowires, also yielded photoproduced hydrogen.[35]

Artificial photosynthesis remained an academic field for many years. However, in the beginning
of 2009, Mitsubishi Chemical Holdings was reported to be developing its own artificial
photosynthesis research by using sunlight, water and carbon dioxide to "create the carbon
building blocks from which resins, plastics and fibers can be synthesized."[36] This was confirmed
with the establishment of the KAITEKI Institute later that year, with carbon dioxide reduction
through artificial photosynthesis as one of the main goals.[37][38]

In 2010, the DOE established, as one of its Energy Innovation Hubs, the Joint Center for
Artificial Photosynthesis.[39] The mission of JCAP is to find a cost-effective method to produce
fuels using only sunlight, water, and carbon-dioxide as inputs. JCAP is led by a team from
Caltech, led by Professor Nathan Lewis and brings together more than 120 scientists and
engineers from Caltech and its lead partner, Lawrence Berkeley National Laboratory. JCAP also
draws on the expertise and capabilities of key partners from Stanford University, the University
of California at Berkeley, UCSB, UCI, and UCSD, and the Stanford Linear Accelerator. In
addition, JCAP serves as a central hub for other solar fuels research teams across the United
States, including 20 DOE Energy Frontier Research Center. The program has a budget of $122M
over five years, subject to Congressional appropriation[40]

Also in 2010, a team led by professor David Wendell at the University of Cincinnati successfully
demonstrated photosynthesis in an artificial construct consisting of enzymes suspended in a foam
housing.[41]

In 2011, Daniel Nocera and his research team announced the creation of the first practical
artificial leaf. In a speech at the 241st National Meeting of the American Chemical Society,
Nocera described an advanced solar cell the size of a poker card capable of splitting water into
oxygen and hydrogen, approximately ten times more efficient than natural photosynthesis.[42] The
cell is mostly made of inexpensive materials that are widely available, works under simple
conditions, and shows increased stability over previous catalysts: in laboratory studies, the
authors demonstrated that an artificial leaf prototype could operate continuously for at least
forty-five hours without a drop in activity.[43] In May 2012, Sun Catalytix, the startup based on
Nocera's research, stated that it will not be scaling up the prototype as the device offers few
savings over other ways to make hydrogen from sunlight.[44] Leading experts in the field have
supported a proposal for a Global Project on Artificial Photosynthesis as a combined energy
security and climate change solution.[45] Conferences on this theme have been held at Lord Howe
Island in 2011,[46] at Chicheley Hall in the UK in 2014[47] and at Canberra and Lord Howe island
in 2016.[48]

Current research
In energy terms, natural photosynthesis can be divided in three steps:[9][18]

Light-harvesting complexes in bacteria and plants capture photons and

transduce them into electrons, injecting them into the photosynthetic chain.

Proton-coupled electron transfer along several cofactors of the photosynthetic

chain, causing local, spatial charge separation.

Redox catalysis, which uses the aforementioned transferred electrons to

oxidize water to dioxygen and protons; these protons can in some species be
utilized for dihydrogen production.

A triad assembly, with a photosensitizer (P) linked in tandem to a water oxidation

catalyst (D) and a hydrogen evolving catalyst (A). Electrons flow from D to A when
catalysis occurs.

Using biomimetic approaches, artificial photosynthesis tries to construct systems doing the same
type of processes. Ideally, a triad assembly could oxidize water with one catalyst, reduce protons
with another and have a photosensitizer molecule to power the whole system. One of the
simplest designs is where the photosensitizer is linked in tandem between a water oxidation
catalyst and a hydrogen evolving catalyst:

The photosensitizer transfers electrons to the hydrogen catalyst when hit by

light, becoming oxidized in the process.

This drives the water splitting catalyst to donate electrons to the

photosensitizer. In a triad assembly, such a catalyst is often referred to as a
donor. The oxidized donor is able to perform water oxidation.

The state of the triad with one catalyst oxidized on one end and the second one reduced on the
other end of the triad is referred to as a charge separation, and is a driving force for further
electron transfer, and consequently catalysis, to occur. The different components may be
assembled in diverse ways, such as supramolecular complexes, compartmentalized cells, or
linearly, covalently linked molecules.[9]

Research into finding catalysts that can convert water, carbon dioxide, and sunlight to
carbohydrates or hydrogen is a current, active field. By studying the natural oxygen-evolving
complex (OEC), researchers have developed catalysts such as the "blue dimer" to mimic its
function or inorganic-based materials such as Birnessite with the similar building block as the
OEC.[49] Photoelectrochemical cells that reduce carbon dioxide into carbon monoxide (CO),
formic acid (HCOOH) and methanol (CH3OH) are under development.[50] However, these
catalysts are still very inefficient.[5]

Hydrogen catalysts

Hydrogen is the simplest solar fuel to synthesize, since it involves only the transference of two
electrons to two protons. It must, however, be done stepwise, with formation of an intermediate
hydride anion:

2 e + 2 H + H + + H H 2

The proton-to-hydrogen converting catalysts present in nature are hydrogenases. These are
enzymes that can either reduce protons to molecular hydrogen or oxidize hydrogen to protons
and electrons. Spectroscopic and crystallographic studies spanning several decades have resulted
in a good understanding of both the structure and mechanism of hydrogenase catalysis.[51][52]
Using this information, several molecules mimicking the structure of the active site of both
nickel-iron and iron-iron hydrogenases have been synthesized.[9][53] Other catalysts are not
structural mimics of hydrogenase but rather functional ones. Synthesized catalysts include
structural H-cluster models,[9][54] a dirhodium photocatalyst,[55] and cobalt catalysts.[9][56]

Water-oxidizing catalysts

Water oxidation is a more complex chemical reaction than proton reduction. In nature, the
oxygen-evolving complex performs this reaction by accumulating reducing equivalents
(electrons) in a manganese-calcium cluster within photosystem II (PS II), then delivering them to
water molecules, with the resulting production of molecular oxygen and protons:

2 H2O O2 + 4 H+ + 4e

Without a catalyst (natural or artificial), this reaction is very endothermic, requiring high
temperatures (at least 2500 K).[7]

The exact structure of the oxygen-evolving complex has been hard to determine experimentally.
[57]
As of 2011, the most detailed model was from a 1.9 resolution crystal structure of
photosystem II.[58] The complex is a cluster containing four manganese and one calcium ions, but
the exact location and mechanism of water oxidation within the cluster is unknown.
Nevertheless, bio-inspired manganese and manganese-calcium complexes have been
synthesized, such as [Mn4O4] cubane-type clusters, some with catalytic activity.[59]

Some ruthenium complexes, such as the dinuclear -oxo-bridged "blue dimer" (the first of its
kind to be synthesized), are capable of light-driven water oxidation, thanks to being able to form
high valence states.[9] In this case, the ruthenium complex acts as both photosensitizer and
catalyst.

Many metal oxides have been found to have water oxidation catalytic activity, including
ruthenium(IV) oxide (RuO2), iridium(IV) oxide (IrO2), cobalt oxides (including nickel-doped
Co3O4), manganese oxide (including layered MnO2 (birnessite),[49] Mn2O3), and a mix of Mn2O3
with CaMn2O4. Oxides are easier to obtain than molecular catalysts, especially those from
relatively abundant transition metals (cobalt and manganese), but suffer from low turnover
frequency and slow electron transfer properties, and their mechanism of action is hard to
decipher and, therefore, to adjust.[6]

Recently Metal-Organic Framework (MOF)-based materials have been shown to be a highly

promising candidate for water oxidation with first row transition metals.[60][61] The stability and
tunability of this system is projected to be highly beneficial for future development.[62]

Photosensitizers

Structure of [Ru(bipy)3]2+, a broadly used photosensitizer.

Nature uses pigments, mainly chlorophylls, to absorb a broad part of the visible spectrum.
Artificial systems can use either one type of pigment with a broad absorption range or combine
several pigments for the same purpose.
Ruthenium polypyridine complexes, in particular tris(bipyridine)ruthenium(II) and its
derivatives, have been extensively used in hydrogen photoproduction due to their efficient visible
light absorption and long-lived consequent metal-to-ligand charge transfer excited state, which
makes the complexes strong reducing agents.[9] Other noble metal-containing complexes used
include ones with platinum, rhodium and iridium.[9]

Metal-free organic complexes have also been successfully employed as photosensitizers.

Examples include eosin Y and rose bengal.[9] Pyrrole rings such as porphyrins have also been
used in coating nanomaterials or semiconductors for both homogeneous and heterogeneous
catalysis.[6][50]

As part of current research efforts artificial photonic antenna systems are being studied to
determine efficient and sustainable ways to collect light for artificial photosynthesis. Gion
Calzaferri (2009) describes one such antenna that uses zeolite L as a host for organic dyes, to
mimic plant's light collecting systems.[63] The antenna is fabricated by inserting dye molecules
into the channels of zeolite L. The insertion process, which takes place under vacuum and at high
temperature conditions, is made possible by the cooperative vibrational motion of the zeolite
framework and of the dye molecules.[64] The resulting material may be interfaced to an external
device via a stopcock intermediate.[65][66]

Carbon dioxide reduction catalysts

In nature, carbon fixation is done by green plants using the enzyme RuBisCO as a part of the
Calvin cycle. RuBisCO is a rather slow catalyst compared to the vast majority of other enzymes,
incorporating only a few molecules of carbon dioxide into ribulose-1,5-bisphosphate per minute,
but does so at atmospheric pressure and in mild, biological conditions.[67] The resulting product is
further reduced and eventually used in the synthesis of glucose, which in turn is a precursor to
more complex carbohydrates, such as cellulose and starch. The process consumes energy in the
form of ATP and NADPH.

Artificial CO2 reduction for fuel production aims mostly at producing reduced carbon
compounds from atmospheric CO2. Some transition metal polyphosphine complexes have been
developed for this end; however, they usually require previous concentration of CO2 before use,
and carriers (molecules that would fixate CO2) that are both stable in aerobic conditions and able
to concentrate CO2 at atmospheric concentrations haven't been yet developed.[68] The simplest
product from CO2 reduction is carbon monoxide (CO), but for fuel development, further
reduction is needed, and a key step also needing further development is the transfer of hydride
anions to CO.[68]

Other materials and components

Charge separation is a key property of dyad and triad assemblies. Some nanomaterials employed
are fullerenes (such as carbon nanotubes), a strategy that explores the pi-bonding properties of
these materials.[6] Diverse modifications (covalent and non-covalent) of carbon nanotubes have
been attempted to increase the efficiency of charge separation, including the addition of
ferrocene and pyrrole-like molecules such as porphyrins and phthalocyanines.[6]

Since photodamage is usually a consequence in many of the tested systems after a period of
exposure to light, bio-inspired photoprotectants have been tested, such as carotenoids (which are
used in photosynthesis as natural protectants).[69]

Light-driven methodologies under development

Photoelectrochemical cells

Main article: Photoelectrochemical cell

Photoelectrochemical cells are a heterogeneous system that use light to produce either electricity
or hydrogen. The vast majority of photoelectrochemical cells use semiconductors as catalysts.[50]
There have been attempts to use synthetic manganese complex-impregnated Nafion as a working
electrode, but it has been since shown that the catalytically active species is actually the broken-
down complex.[70]

A promising, emerging type of solar cell is the dye-sensitized solar cell. This type of cell still
depends on a semiconductor (such as TiO2) for current conduction on one electrode, but with a
coating of an organic or inorganic dye that acts as a photosensitizer; the counter electrode is a
platinum catalyst for H2 production.[50] These cells have a self-repair mechanism and solar-to-
electricity conversion efficiencies rivaling those of solid-state semiconductor ones.[50]

Photocatalytic water splitting in homogeneous systems

Main article: Photocatalytic water splitting

Direct water oxidation by photocatalysts is a more efficient usage of solar energy than
photoelectrochemical water splitting because it avoids an intermediate thermal or electrical
energy conversion step.[71]

Bio-inspired manganese clusters have been shown to possess water oxidation activity when
adsorbed on clays together with ruthenium photosensitizers, although with low turnover
numbers.[9]

As mentioned above, some ruthenium complexes are able to oxidize water under solar light
irradiation.[9] Although their photostability is still an issue, many can be reactivated by a simple
adjustment of the conditions they work in.[9] Improvement of catalyst stability has been tried
resorting to polyoxometalates, in particular ruthenium-based ones.[6][9]
Whereas a fully functional artificial system is usually envisioned when constructing a water
splitting device, some mixed approaches have been tried. One of these involve the use of a gold
electrode to which photosystem II is linked; an electric current is detected upon illumination.[72]

Hydrogen-producing artificial systems

A H-cluster FeFe hydrogenase model compound covalently linked to a ruthenium

photosensitizer. The ruthenium complex absorbs light and transduces its energy to
the iron compound, which can then reduce protons to H 2.

The simplest photocatalytic hydrogen production unit consists of a hydrogen-evolving catalyst

linked to a photosensitizer.[73] In this dyad assembly, a so-called sacrificial donor for the
photosensitizer is needed, that is, one that is externally supplied and replenished; the
photosensitizer donates the necessary reducing equivalents to the hydrogen-evolving catalyst,
which uses protons from a solution where it is immersed or dissolved in. Cobalt compounds such
as cobaloximes are some of the best hydrogen catalysts, having been coupled to both metal-
containing and metal-free photosensitizers.[9][74] The first H-cluster models linked to
photosensitizers (mostly ruthenium photosensitizers, but also porphyrin-derived ones) were
prepared in the early 2000s.[9] Both types of assembly are under development to improve their
stability and increase their turnover numbers, both necessary for constructing a sturdy, long-lived
solar fuel cell.

As with water oxidation catalysis, not only fully artificial systems have been idealized:
hydrogenase enzymes themselves have been engineered for photoproduction of hydrogen, by
coupling the enzyme to an artificial photosensitizer, such as [Ru(bipy)3]2+ or even photosystem I.
[9][73]

NADP+/NADPH coenzyme-inspired catalyst

In natural photosynthesis, the NADP+ coenzyme is reducible to NADPH through binding of a

proton and two electrons. This reduced form can then deliver the proton and electrons,
potentially as a hydride, to reactions that culminate in the production of carbohydrates (the
Calvin cycle). The coenzyme is recyclable in a natural photosynthetic cycle, but this process is
yet to be artificially replicated.
A current goal is to obtain an NADPH-inspired catalyst capable of recreating the natural cyclic
process. Utilizing light, hydride donors would be regenerated and produced where the molecules
are continuously used in a closed cycle. Brookhaven chemists are now using a ruthenium-based
complex to serve as the acting model. The complex is proven to perform correspondingly with
NADP+/NADPH, behaving as the foundation for the proton and two electrons needed to convert
acetone to isopropanol.

Currently, Brookhaven researchers are aiming to find ways for light to generate the hydride
donors. The general idea is to use this process to produce fuels from carbon dioxide.[75]

Photobiological production of fuels

Some photoautotrophic microorganisms can, under certain conditions, produce hydrogen.

Nitrogen-fixing microorganisms, such as filamentous cyanobacteria, possess the enzyme
nitrogenase, responsible for conversion of atmospheric N2 into ammonia; molecular hydrogen is
a byproduct of this reaction, and is many times not released by the microorganism, but rather
taken up by a hydrogen-oxidizing (uptake) hydrogenase. One way of forcing these organisms to
produce hydrogen is then to annihilate uptake hydrogenase activity. This has been done on a
strain of Nostoc punctiforme: one of the structural genes of the NiFe uptake hydrogenase was
inactivated by insertional mutagenesis, and the mutant strain showed hydrogen evolution under
illumination.[76]

Many of these photoautotrophs also have bidirectional hydrogenases, which can produce
hydrogen under certain conditions. However, other energy-demanding metabolic pathways can
compete with the necessary electrons for proton reduction, decreasing the efficiency of the
overall process; also, these hydrogenases are very sensitive to oxygen.[10]

Several carbon-based biofuels have also been produced using cyanobacteria, such as 1-butanol.
[77]

Synthetic biology techniques are predicted to be useful in this field. Microbiological and
enzymatic engineering have the potential of improving enzyme efficiency and robustness, as well
as constructing new biofuel-producing metabolic pathways in photoautotrophs that previously
lack them, or improving on the existing ones.[10][77] Another field under development is the
optimization of photobioreactors for commercial application.[78]

Employed research techniques

Research in artificial photosynthesis is necessarily a multidisciplinary field, requiring a multitude
of different expertise.[10] Some techniques employed in making and investigating catalysts and
solar cells include:

Organic and inorganic chemical synthesis.

 Electrochemistry methods, such as photoelectrochemistry, cyclic
voltammetry, electrochemical impedance spectroscopy Dielectric
spectroscopy, and bulk electrolysis.

Spectroscopic methods:

o fast techniques, such as time-resolved spectroscopy and ultrafast laser

spectroscopy;

o magnetic resonance spectroscopies, such as nuclear magnetic

resonance, electron paramagnetic resonance;

o X-ray spectroscopy methods, including x-ray absorption such as XANES

and EXAFS, but also x-ray emission.

Crystallography.

Molecular biology, microbiology and synthetic biology methodologies.

Advantages, disadvantages, and efficiency

Advantages of solar fuel production through artificial photosynthesis include:

The solar energy can be immediately converted and stored. In photovoltaic

cells, sunlight is converted into electricity and then converted again into
chemical energy for storage, with some necessary loss of energy associated
with the second conversion.

The byproducts of these reactions are environmentally friendly. Artificially

photosynthesized fuel would be a carbon-neutral source of energy, which
could be used for transportation or homes.

Disadvantages include:

Materials used for artificial photosynthesis often corrode in water, so they

may be less stable than photovoltaics over long periods of time. Most
hydrogen catalysts are very sensitive to oxygen, being inactivated or
degraded in its presence; also, photodamage may occur over time. [9][73]

The overall cost is not yet advantageous enough to compete with fossil fuels
as a commercially viable source of energy.[3]

A concern usually addressed in catalyst design is efficiency, in particular how much of the
incident light can be used in a system in practice. This is comparable with photosynthetic
efficiency, where light-to-chemical-energy conversion is measured. Photosynthetic organisms are
able to collect about 50% of incident solar radiation, however the theoretical limit of
photosynthetic efficiency is 4.6 and 6.0% for C3 and C4 plants respectively.[79] In reality, the
efficiency of photosynthesis is much lower and is usually below 1%, with some exceptions such
as sugarcane in tropical climate.[80] In contrast, the highest reported efficiency for artificial
photosynthesis lab prototypes is 22.4%.[81] However, plants are efficient in using CO2 at
atmospheric concentrations, something that artificial catalysts still cannot perform.[82]

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