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 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, replicating natural carbon fixation.
Research developed in this field encompasses design and assembly of devices (and their components) for the direct production of solar fuels, photoelectrochemistry and its application in fuel cells, and engineering of enzymes and photoautotrophic microorganisms for microbial biofuel and biohydrogen production from sunlight. Many, if not most, of the artificial approaches are bio-inspired, i.e., they rely on biomimetics.
Overview
The photosynthetic reaction can be divided into two half-reactions (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. Researchers of artificial photosynthesis are developing photocatalysts to perform both of these reactions separately. 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 solar photons.[1]
Whereas photovoltaics can provide direct electrical current from sunlight, the inefficiency of fuel production from photovoltaic electricity (indirect process) and the fact sunshine is not constant throughout time sets a limit to its use.[2][3] A way of using natural photosynthesis is via the production of biofuel through biomass, also an indirect process that suffers from low energy conversion efficiency (due to photosynthesis' own low efficiency in converting sunlight to biomass), and clashes with the increasing need of land mass for human food production.[4] Artificial photosynthesis aims then to produce a fuel from sunlight that can be 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 of the future.[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 method.[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 further gas purification. 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 with 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
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.[13]
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 Ångström Laboratories in Uppsala.[14] The consortium was built with a multidisciplinary approach to focus on learning from natural photosynthesis and applying this knowledge in biomimetic systems.[15] Research in artificial photosynthesis is undergoing a boom at the beginning of the 21st century.[2] In 2000, Commonwealth Scientific and Industrial Research Organisation (CSIRO) researchers publicize their intent to focus on carbon dioxide capture and conversion to hydrocarbons.[16][17] 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 catalyst designing.[18][19]
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] With the funding of the United States Air Force Office of Scientific Research,[20] in 2008, 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.[21][22] The catalyst was able to split water into oxygen and protons using sunlight, and could potentially be coupled to a hydrogen-producing catalyst such as platinum. Furthermore, while the catalyst broke down during catalysis, it could self-repair.[23] This experimental catalyst design was considered a major breakthrough in the field by many researchers.[24][25]
Whereas CO is the prime reduction product of CO2, more complex carbon compounds are usually desired. In 2008, Princeton chemistry professor Andrew B. Bocarsly reported the direct conversion of carbon dioxide and water to methanol using solar energy in a highly efficient photochemical cell.[26]
While Nocera and coworkers had accomplished water splitting to oxygen and protons, a light-driven process to produce hydrogen from protons still needed to be developed. In 2009, the Leibniz Institute for Catalysis reported inexpensive iron carbonyl complexes able to do just this.[27][28] 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.[29] Both 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.[30] 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 off the back metal substrate which also eliminated the problem 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.[31] 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.[32]
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."[33] 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.[34][35]
In 2010, the DOE established, as one of its Energy Innovation Hubs, the Joint Center for Artificial Photosynthesis.[36] 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[37]
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 frog foam.[38]
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.[39] 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.[40] 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.[41]
Research developed in this field encompasses design and assembly of devices (and their components) for the direct production of solar fuels, photoelectrochemistry and its application in fuel cells, and engineering of enzymes and photoautotrophic microorganisms for microbial biofuel and biohydrogen production from sunlight. Many, if not most, of the artificial approaches are bio-inspired, i.e., they rely on biomimetics.
Overview
The photosynthetic reaction can be divided into two half-reactions (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. Researchers of artificial photosynthesis are developing photocatalysts to perform both of these reactions separately. 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 solar photons.[1]
Whereas photovoltaics can provide direct electrical current from sunlight, the inefficiency of fuel production from photovoltaic electricity (indirect process) and the fact sunshine is not constant throughout time sets a limit to its use.[2][3] A way of using natural photosynthesis is via the production of biofuel through biomass, also an indirect process that suffers from low energy conversion efficiency (due to photosynthesis' own low efficiency in converting sunlight to biomass), and clashes with the increasing need of land mass for human food production.[4] Artificial photosynthesis aims then to produce a fuel from sunlight that can be 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 of the future.[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 method.[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 further gas purification. 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 with 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
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.[13]
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 Ångström Laboratories in Uppsala.[14] The consortium was built with a multidisciplinary approach to focus on learning from natural photosynthesis and applying this knowledge in biomimetic systems.[15] Research in artificial photosynthesis is undergoing a boom at the beginning of the 21st century.[2] In 2000, Commonwealth Scientific and Industrial Research Organisation (CSIRO) researchers publicize their intent to focus on carbon dioxide capture and conversion to hydrocarbons.[16][17] 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 catalyst designing.[18][19]
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] With the funding of the United States Air Force Office of Scientific Research,[20] in 2008, 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.[21][22] The catalyst was able to split water into oxygen and protons using sunlight, and could potentially be coupled to a hydrogen-producing catalyst such as platinum. Furthermore, while the catalyst broke down during catalysis, it could self-repair.[23] This experimental catalyst design was considered a major breakthrough in the field by many researchers.[24][25]
Whereas CO is the prime reduction product of CO2, more complex carbon compounds are usually desired. In 2008, Princeton chemistry professor Andrew B. Bocarsly reported the direct conversion of carbon dioxide and water to methanol using solar energy in a highly efficient photochemical cell.[26]
While Nocera and coworkers had accomplished water splitting to oxygen and protons, a light-driven process to produce hydrogen from protons still needed to be developed. In 2009, the Leibniz Institute for Catalysis reported inexpensive iron carbonyl complexes able to do just this.[27][28] 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.[29] Both 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.[30] 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 off the back metal substrate which also eliminated the problem 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.[31] 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.[32]
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."[33] 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.[34][35]
In 2010, the DOE established, as one of its Energy Innovation Hubs, the Joint Center for Artificial Photosynthesis.[36] 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[37]
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 frog foam.[38]
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.[39] 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.[40] 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.[41]
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