Solar fuel

A solar fuel is a synthetic chemical fuel produced from solar energy. Solar fuels can be produced through photochemical, photobiological (i.e., artificial photosynthesis), thermochemical (i.e., through the use of solar heat supplied by concentrated solar thermal energy to drive a chemical reaction), and electrochemical reactions.[1][2][3][4] Light is used as an energy source, with solar energy being transduced to chemical energy, typically by reducing protons to hydrogen, or carbon dioxide to organic compounds.

A solar fuel can be produced and stored for later use, when sunlight is not available, making it an alternative to fossil fuels. Diverse photocatalysts are being developed to carry these reactions in a sustainable, environmentally friendly way.[5]

Overview

The world's dependence on the declining reserves of fossil fuels poses not only environmental problems but also geopolitical ones.[6] Solar fuels, in particular hydrogen, are viewed as an alternative source of energy for replacing fossil fuels especially where storage is essential. Electricity can be produced directly from sunlight through photovoltaics, but this form of energy is rather inefficient to store compared to hydrogen.[5] A solar fuel can be produced when and where sunlight is available, and stored and transported for later usage.

The most widely researched solar fuels are hydrogen and products of photochemical carbon dioxide reduction.

Solar fuels can be produced via direct or indirect processes. Direct processes harness the energy in sunlight to produce a fuel without intermediary energy conversions. In contrast, indirect processes have solar energy converted to another form of energy first (such as biomass or electricity) that can then be used to produce a fuel. Indirect processes have been easier to implement but have the disadvantage of being less efficient than, e.g., water splitting for the production of hydrogen, since energy is wasted in the intermediary conversion.[5]

Hydrogen production
See also: Hydrogen production

Photochemical
A sample of a photoelectric cell in a lab environment. Catalysts are added to the cell, which is submerged in water and illuminated by simulated sunlight. The bubbles seen are oxygen (forming on the front of the cell) and hydrogen (forming on the back of the cell).

In a solar photochemical process, hydrogen can be produced by electrolysis. To use sunlight in this process, a photoelectrochemical cell can be used, where one photosensitized electrode converts light into an electric current that is then used for water splitting. One such type of cell is the dye-sensitized solar cell.[7] This is an indirect process, since it produces electricity that then is used to form hydrogen. The other major indirect process using sunlight is conversion of biomass to biofuel using photosynthetic organisms; however, most of the energy harvested by photosynthesis is used in life-sustaining processes and therefore lost for energy use.[5]

A direct process can use a catalyst that reduces protons to molecular hydrogen upon electrons from an excited photosensitizer. Several such catalysts have been developed as proof of concept, but not yet scaled up for commercial use; nevertheless, their relative simplicity gives the advantage of potential lower cost and increased energy conversion efficiency.[5][8] One such proof of concept is the "artificial leaf" developed by Nocera and coworkers: a combination of metal oxide-based catalysts and a semiconductor solar cell produces hydrogen upon illumination, with oxygen as the only byproduct.[9]

Hydrogen can also be produced from some photosynthetic microorganisms (microalgae and cyanobacteria) using photobioreactors. Some of these organisms produce hydrogen upon switching culture conditions; for example, Chlamydomonas reinhardtii produces hydrogen anaerobically under sulfur deprivation, that is, when cells are moved from one growth medium to another that does not contain sulfur, and are grown without access to atmospheric oxygen.[10] Another approach was to abolish activity of the hydrogen-oxidizing (uptake) hydrogenase enzyme in the diazotrophic cyanobacterium Nostoc punctiforme, so that it would not consume hydrogen that is naturally produced by the nitrogenase enzyme in nitrogen-fixing conditions.[11] This N. punctiforme mutant could then produce hydrogen when illuminated with visible light.

Thermochemical

In the solar thermochemical[12] process, water is split into hydrogen and oxygen using direct solar heat, rather than electricity, inside a high temperature solar reactor[13] which receives highly concentrated solar flux from a solar field of heliostats that focus the highly concentrated sunlight into the reactor. In a process that typically uses cerium oxide[14] as the reactant, the first step is to strip the CeO2 into CeO at more than 1400 °C. After the thermal reduction step to reduce the metal oxide, hydrogen is then produced through hydrolysis at around 800 °C. Because hydrogen manufacture requires continuous performance, the solar thermochemical process includes thermal energy storage.[15] Another thermochemical method uses solar reforming of methane, a process that replicates traditional fossil fuel reforming process but substitutes solar heat.[16]

Carbon dioxide reduction
See also: Electrochemical reduction of carbon dioxide, Photoelectrochemical reduction of carbon dioxide, Photochemical reduction of carbon dioxide, and Biofuel

Carbon dioxide (CO2) can be reduced to carbon monoxide (CO) and other more reduced compounds, such as methane, using the appropriate photocatalysts. One early example was the use of Tris(bipyridine)ruthenium(II) chloride (Ru(bipy)3Cl2) and cobalt chloride (CoCl2) for CO2 reduction to CO.[17] Many compounds that do similar reactions have since been developed, but they generally perform poorly with atmospheric concentrations of CO2, requiring further concentration.[18] 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.[18]

Also in this case, the use of microorganisms has been explored. Using genetic engineering and synthetic biology techniques, parts of or whole biofuel-producing metabolic pathways can be introduced in photosynthetic organisms. One example is the production of 1-butanol in Synechococcus elongatus using enzymes from Clostridium acetobutylicum, Escherichia coli and Treponema denticola.[19] One example of a large-scale research facility exploring this type of biofuel production is the AlgaePARC in the Wageningen University and Research Centre, Netherlands.

Other applications
  • Electrolysis of water for hydrogen production combined with solar photovoltaics using alkaline, PEM, and SOEC electrolyzers;[20]
  • Electro-catalytic CO2 conversion using electrochemical reduction of CO2, UV light photolysis, metal oxide based photocatalytic reduction of CO2, and thermochemical reduction at high temperature
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See also

References
  1. "Sunshine to Petrol" (PDF). Sandia National Laboratories. Retrieved 11 April 2013.
  2. "Integrated Solar Thermochemical Reaction System". U.S. Department of Energy. Retrieved 11 April 2013.
  3. Matthew L. Wald (10 April 2013). "New Solar Process Gets More Out of Natural Gas". The New York Times. Retrieved 11 April 2013.
  4. Solar Fuels and Artificial Photosynthesis, Nobel Laureate Professor Alan Heeger, RSC 2012
  5. Styring, Stenbjörn (21 December 2011). "Artificial photosynthesis for solar fuels". Faraday Discussions. 155 (Advance Article): 357–376. Bibcode:2012FaDi..155..357S. doi:10.1039/C1FD00113B. PMID 22470985.
  6. Hammarström, Leif; Hammes-Schiffer, Sharon (21 December 2009). "Artificial Photosynthesis and Solar Fuels". Accounts of Chemical Research. 42 (12): 1859–1860. doi:10.1021/ar900267k. PMID 20020780. Retrieved 26 January 2012.
  7. Kalyanasundaram, K.; Grätzel, M. (June 2010). "Artificial photosynthesis: biomimetic approaches to solar energy conversion and storage". Current Opinion in Biotechnology. 21 (3): 298–310. doi:10.1016/j.copbio.2010.03.021. PMID 20439158.
  8. Andreiadis, Eugen S.; Chavarot-Kerlidou, Murielle; Fontecave, Marc; Artero, Vincent (September–October 2011). "Artificial Photosynthesis: From Molecular Catalysts for Light-driven Water Splitting to Photoelectrochemical Cells". Photochemistry and Photobiology. 87 (5): 946–964. doi:10.1111/j.1751-1097.2011.00966.x. PMID 21740444.
  9. Reece, Steven Y.; Hamel, Jonathan A.; Sung, Kimberly; Jarvi, Thomas D.; Esswein, Arthur J.; Pijpers, Joep J. H.; Nocera, Daniel G. (4 November 2011). "Wireless Solar Water Splitting Using Silicon-Based Semiconductors and Earth-Abundant Catalysts". Science. 334 (6056): 645–648. Bibcode:2011Sci...334..645R. doi:10.1126/science.1209816. PMID 21960528.
  10. Kosourov, Sergey; Tsygankov, Anatoly; Seibert, Michael; Ghirardi, Maria L. (30 June 2002). "Sustained hydrogen photoproduction by Chlamydomonas reinhardtii: Effects of culture parameters". Biotechnology and Bioengineering. 78 (7): 731–740. doi:10.1002/bit.10254. PMID 12001165.
  11. Lindberg, Pia; Schûtz, Kathrin; Happe, Thomas; Lindblad, Peter (November–December 2002). "A hydrogen-producing, hydrogenase-free mutant strain of Nostoc punctiforme ATCC 29133". International Journal of Hydrogen Energy. 27 (11–12): 1291–1296. doi:10.1016/S0360-3199(02)00121-0.
  12. Steinfeld, Aldo (2005). "Solar Thermochemical Production of Hydrogen". Solar thermochemical production of hydrogen—A review. pp. 421–443. CiteSeerX 10.1.1.703.9035.
  13. "Fabrication and testing of CONTISOL: A new receiver-reactor for day and night solar thermochemistry" (PDF). SolarPACES.
  14. Abanades, Stéphane; Flamant, Gilles (2006). "Thermochemical hydrogen production from a two-step solar-driven water-splitting cycle based on cerium oxides". Solar Energy. 80 (12): 1611–1623. Bibcode:2006SoEn...80.1611A. doi:10.1016/j.solener.2005.12.005.
  15. "How CSP's Thermal Energy Storage Works". SolarPACES. 10 November 2017.
  16. "Solar Reforming of Natural Gas". University of Adelaide.
  17. Lehn, Jean-Marie; Ziessel, Raymond (January 1982). "Photochemical generation of carbon monoxide and hydrogen by reduction of carbon dioxide and water under visible light irradiation". Proceedings of the National Academy of Sciences. 79 (2): 701–704. Bibcode:1982PNAS...79..701L. doi:10.1073/pnas.79.2.701. PMC 345815. PMID 16593151.
  18. Dubois, M. Rakowski; Dubois, Daniel L. (2009). "Development of molecular electrocatalysts for CO2 reduction and H2 production/oxidation". Accounts of Chemical Research. 42 (12): 1974–1982. doi:10.1021/ar900110c. PMID 19645445.
  19. Lan, Ethan I.; Liao, James C. (July 2011). "Metabolic engineering of cyanobacteria for 1-butanol production from carbon dioxide". Metabolic Engineering. 13 (4): 353–363. doi:10.1016/j.ymben.2011.04.004. PMID 21569861.
  20. Herron, Jeffrey A.; Kim, Jiyong; Upadhye, Aniruddha A.; Huber, George W.; Maravelias, Christos T. (2015). "A general framework for the assessment of solar fuel technologies". Energy & Environmental Science. 8: 126–157. doi:10.1039/C4EE01958J.
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