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Solar chemical refers to a number of possible processes that harness
solar energy Solar energy is radiant light and heat from the Sun that is harnessed using a range of technologies such as solar power to generate electricity, solar thermal energy (including solar water heating), and solar architecture. It is an essenti ...
by absorbing sunlight in a
chemical reaction A chemical reaction is a process that leads to the IUPAC nomenclature for organic transformations, chemical transformation of one set of chemical substances to another. Classically, chemical reactions encompass changes that only involve the pos ...
. The idea is conceptually similar to
photosynthesis Photosynthesis is a process used by plants and other organisms to convert light energy into chemical energy that, through cellular respiration, can later be released to fuel the organism's activities. Some of this chemical energy is stored i ...
in plants, which converts solar energy into the chemical bonds of glucose molecules, but without using living organisms, which is why it is also called
artificial photosynthesis Artificial photosynthesis is a chemical process that biomimics the natural process of photosynthesis to convert sunlight, water, and carbon dioxide into carbohydrates and oxygen. The term artificial photosynthesis is commonly used to refer to ...
. A promising approach is to use focused sunlight to provide the energy needed to split water into its constituent
hydrogen Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic, an ...
and
oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as wel ...
in the presence of a metallic catalyst such as
zinc Zinc is a chemical element with the symbol Zn and atomic number 30. Zinc is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodi ...
. This is normally done in a two-step process so that hydrogen and oxygen are not produced in the same chamber, which creates an explosion hazard. Another approach involves taking the hydrogen created in this process and combining it with carbon dioxide to create methane. The benefit of this approach is that there is an established infrastructure for transporting and burning methane for power generation, which is not true for hydrogen. One main drawback to both of these approaches is common to most methods of energy storage: adding an extra step between energy collection and electricity production drastically decreases the efficiency of the overall process.


Background

As early as 1909, the dimerization of
anthracene Anthracene is a solid polycyclic aromatic hydrocarbon (PAH) of formula C14H10, consisting of three fused benzene rings. It is a component of coal tar. Anthracene is used in the Economic production, production of the red dye alizarin and other dyes ...
into dianthracene was investigated as a means of storing solar energy, as well as the photodimerization of the naphthalene series. In the 70’s and 80’s a fuel had been made from another reversible chemical, the norbornadiene to quadricyclane transformation cycle, but this failed because the reversal process had a low potential. Ruthenium-based molecules were also attempted, but this was dismissed because ruthenium is both rare and too heavy of a material. In the past decade, a new hybrid nanostructure was theorized as a new approach to this previously known concept of solar energy storage.


Chemical storage

Photodimerization is the light induced formation of dimers and
photoisomerization In chemistry, photoisomerization is a form of isomerization induced by photoexcitation. Both reversible and irreversible photoisomerizations are known for photoswitchable compounds. The term "photoisomerization" usually, however, refers to a re ...
is the light induced formation of
isomers In chemistry, isomers are molecules or polyatomic ions with identical molecular formulae – that is, same number of atoms of each element – but distinct arrangements of atoms in space. Isomerism is existence or possibility of isomers. ...
. While photodimerization stores the energy from sunlight in new chemical bonds, photoisomerization stores solar energy by reorienting existing chemical bonds into a higher energy configuration. In order for an isomer to store energy then, it must be metastable as shown above. This results in a trade-off between the stability of the fuel isomer and how much energy must be put in to reverse the reaction when it is time to use the fuel. The isomer stores energy as strain energy in its bonds. The more strained the bonds are the more energy they can store, but the less stable the molecule is. The
activation energy In chemistry and physics, activation energy is the minimum amount of energy that must be provided for compounds to result in a chemical reaction. The activation energy (''E''a) of a reaction is measured in joules per mole (J/mol), kilojoules pe ...
, Ea, is used to characterize how easy or hard it is for the reaction to proceed. If the activation energy is too small the fuel will tend to spontaneously move to the more stable state, providing limited usefulness as a storage medium. However, if the activation energy is very large, the energy expended to extract the energy from the fuel will effectively reduce the amount of energy that the fuel can store. Finding a useful molecule for a
solar fuel A solar fuel is a synthetic chemical fuel produced from solar energy. Solar fuels can be produced through photochemical (i.e. activation of certain chemical reactions by photons), photobiological (i.e., artificial photosynthesis), thermochemical ( ...
requires finding the proper balance between the yield, the light absorption of the molecule, the stability of the molecule in the metastable state, and how many times the molecule can be cycled without degrading. Various ketones, azepines and
norbornadiene Norbornadiene is an organic compound and a bicyclic hydrocarbon. Norbornadiene is of interest as a metal-binding ligand, whose complexes are useful for homogeneous catalysis. It has been intensively studied owing to its high reactivity and distin ...
s among other compounds, such as
azobenzene Azobenzene is a photoswitchable chemical compound composed of two phenyl rings linked by a N=N double bond. It is the simplest example of an aryl azo compound. The term 'azobenzene' or simply 'azo' is often used to refer to a wide class of simi ...
and its derivatives, have been investigated as potential energy storing isomers. The
norbornadiene Norbornadiene is an organic compound and a bicyclic hydrocarbon. Norbornadiene is of interest as a metal-binding ligand, whose complexes are useful for homogeneous catalysis. It has been intensively studied owing to its high reactivity and distin ...
-
quadricyclane Quadricyclane is a strained, multi-cyclic hydrocarbon with the formula CH2(CH)6. A white volatile colorless liquid, it is highly strained molecule (78.7 kcal/mol). Isomerization of quadricyclane proceeds slowly at low temperatures.Petrov, V. A; ...
couple and its derivatives have been extensively investigated for solar energy storage processes. Norbornadiene is converted to quadricyclane using energy extracted from sunlight, and the controlled release of the strain energy stored in quadricyclane (about 110 kJ/mole) as it relaxes back to norbornadiene allows the energy to be extracted again for use later. Research into both the azobenzene and norbonadiene-quadricyclane systems was abandoned in the 1980s as unpractical due to problems with degradation, instability, low energy density, and cost. With recent advances in computing power though, there has been renewed interest in finding materials for solar thermal fuels. In 2011, researchers at MIT used time-dependent density functional theory, which models systems at an atomic level, to design a system composed of azobenzene molecules bonded to
carbon nanotube A scanning tunneling microscopy image of a single-walled carbon nanotube Rotating single-walled zigzag carbon nanotube A carbon nanotube (CNT) is a tube made of carbon with diameters typically measured in nanometers. ''Single-wall carbon na ...
(CNT) templates. The CNT substrates will allow customizable interactions between neighboring molecules which greatly helps in fine tuning the properties of the fuel, for example an increase in the amount of energy stored. Through experimental procedures, researchers were able to get the first proof of principle that the hybrid nanostructure works as a functional thermal fuel. Azobenzenes have the advantage of absorbing wavelengths that are very abundant in sunlight, when this happens the molecule transforms from a trans-isomer to a cis-isomer which has a higher energy state of about 0.6 eV. To bring the molecule back down to its original state, i.e. release the energy it had collected, there are a few options. The first is to apply heat but that is associated with a cost which, relative to the amount of heat that will be produced from the release, is not cost efficient. The second, more effective option is to use a catalyst that lowers the thermal barrier and allows the heat to be released, almost like a switch. The transition back from cis to trans can also be triggered by blue visible light. This system provides an
energy density In physics, energy density is the amount of energy stored in a given system or region of space per unit volume. It is sometimes confused with energy per unit mass which is properly called specific energy or . Often only the ''useful'' or extract ...
comparable to lithium-ion batteries, while simultaneously increasing the stability of the activated fuel from several minutes to more than a year and allowing for large numbers of cycles without significant degradation. Further research is being done in search of even more improvement by examining different possible combinations of substrates and photoactive molecules.


Applications

There are a wide variety of both potential and current applications for solar chemical fuels. One of the major pros of this technology is its scalability. Since the energy can be stored and then later converted to heat when needed, it is ideal for smaller on the go units. These range from portable stoves or small personal heaters that can be charged in the sun to providing medical sanitation in off-grid areas, and plans are even in the works to use the system developed at MIT as a window de-icing system in automobiles. It also has the ability to be scaled up and heat larger homes or buildings or even heat bodies of water. A solar thermal fuel would ideally be able to cycle indefinitely without degradation, making it ideal for larger scale implementations that generally would need more replacements of other forms of storage.


References


External links


ANU Thermochemical energy storage system
- Australian National University, Canberra.
Laboratory for Solar Technology
- Paul Scherrer Institute, Villigen, Switzerland.

March 2004 article on Paul Scherrer Institute work

Plataforma Solar de Almería, Spain,

- Israel,

UK. {{DEFAULTSORT:Solar Chemical Photovoltaics Fuel production