Water splitting 1

Water splitting
Water splitting is the general term for a chemical reaction in which water is separated into oxygen and hydrogen.
Efficient and economical water splitting would be a key technology component of a hydrogen economy. Various
techniques for water splitting have been issued in water splitting patents [1] in the United States. In photosynthesis,
water splitting donates electrons to power the electron transport chain in Photosystem II.

Electrolysis
Electrolysis of water is the decomposition of water (H2O) into oxygen
(O2) and hydrogen gas (H2) due to an electric current being passed
through the water. In chemistry and manufacturing, electrolysis is a
method of separating chemically bonded elements and compounds by
passing an electric current through them. One important use of
electrolysis of water or artificial photosynthesis (photoelectrolysis in a
photoelectrochemical cell) is to produce hydrogen.

Electrolyser front with electrical panel in

foreground

Production of hydrogen from water requires large amounts of energy

and is uncompetitive with production from coal or natural gas.
Potential electrical energy supplies include hydropower, wind turbines,
or photovoltaic cells. Usually, the electricity consumed is more
valuable than the hydrogen produced so this method has not been
widely used. Other potential energy supplies include heat from nuclear
Electrolysis of water ship Hydrogen Challenger
reactors and light from the sun. Hydrogen can also be used to store
renewable electricity when it is not needed (like the wind blowing at
night) and then the hydrogen can be used to meet power needs during the day or fuel vehicles. This aspect helps
make hydrogen an enabler of the wider use of renewables, [2] .and internal combustion engines. (See hydrogen
economy.)

High pressure electrolysis

When the electrolysis is conducted at high pressures, the produced hydrogen gas is compressed at around 120–200
Bar (1740–2900 psi).[3] By pressurising the hydrogen in the electrolyser the need for an external hydrogen
compressor is eliminated, the average energy consumption for internal compression is around 3%.[4]

High-temperature electrolysis
When the energy supply is in the form of heat (solar thermal, or nuclear), the best path to hydrogen is through
high-temperature electrolysis (HTE). In contrast with low-temperature electrolysis, HTE of water converts more of
the initial heat energy into chemical energy (hydrogen), potentially doubling efficiency to about 50%. Because some
of the energy in HTE is supplied in the form of heat, less of the energy must be converted twice (from heat to
electricity, and then to chemical form), and so less energy is lost.
HTE processes are generally only considered in combination with a nuclear heat source, because the other
non-chemical form of high-temperature heat (concentrating solar thermal) is not consistent enough to bring down the
Water splitting 2

capital costs of the HTE equipment. Research into HTE and high-temperature nuclear reactors may eventually lead
to a hydrogen supply that is cost-competitive with natural gas steam reforming. HTE has been demonstrated in a
laboratory, but not at a commercial scale.

Photoelectrochemical water splitting

Using electricity produced by photovoltaic systems potentially offers the cleanest way to produce hydrogen. Again,
water is broken down into hydrogen and oxygen by electrolysis, but the electrical energy is obtained by a
photoelectrochemical cell (PEC) process. The system is also named artificial photosynthesis.[5] [6] [7] .

Photobiological water splitting

Biological hydrogen can be produced in an algae bioreactor. In the late 1990s
it was discovered that if the algae are deprived of sulfur it will switch from
the production of oxygen, i.e. normal photosynthesis, to the production of
hydrogen. It seems that the production is now economically feasible by
trespassing the 7–10 percent energy efficiency (the conversion of sunlight
into hydrogen) barrier[8] .

Thermal decomposition of water

Thermal decomposition, also called thermolysis, is defined as a chemical
reaction whereby a chemical substance breaks up into at least two chemical
substances when heated. At elevated temperatures water molecules split into
their atomic components hydrogen and oxygen. For example at 2200 °C
about three percent of all H2O molecules are dissociated into various An algae bioreactor for hydrogen
production.
combinations of hydrogen and oxygen atoms, mostly H, H2, O, O2, and OH.
Other reaction products like H2O2 or HO2 remain minor. At the very high
temperature of 3000 °C more than half of the water molecules are decomposed, but at ambient temperatures only one
molecule in 100 trillion dissociates by the effect of heat. However, catalysts can accelerate the dissociation of the
water molecules at lower temperatures.

Thermal water splitting has been investigated for hydrogen production since the 1960s [9] . The high temperatures
needed to obtain substantial amounts of hydrogen impose severe requirements on the materials used in any thermal
water splitting device. For industrial or commercial application, the material constraints have limited the success of
applications for hydrogen production from direct thermal water splitting and with few exceptions most recent
developments are in the area of catalytic and two step processes.

Nuclear-thermal
Some prototype Generation IV reactors operate at 850 to 1000 degrees Celsius, considerably hotter than existing
commercial nuclear power plants. General Atomics predicts that hydrogen produced in a High Temperature Gas
Cooled Reactor (HTGR) would cost $1.53/kg. In 2003, steam reforming of natural gas yielded hydrogen at $1.40/kg.
At 2005 gas prices, hydrogen cost $2.70/kg. Hence, just within the United States, a savings of tens of billions of
dollars per year is possible with a nuclear-powered supply. Much of this savings would translate into reduced oil and
natural gas imports.
One side benefit of a nuclear reactor that produces both electricity and hydrogen is that it can shift production
between the two. For instance, the plant might produce electricity during the day and hydrogen at night, matching its
electrical generation profile to the daily variation in demand. If the hydrogen can be produced economically, this
Water splitting 3

scheme would compete favorably with existing grid energy storage schemes. What is more, there is sufficient
hydrogen demand in the United States that all daily peak generation could be handled by such plants.[10] However,
Generation IV reactors are not expected until 2030 and it is uncertain if they can compete by then in safety and
supply with the distributed generation concept.

Solar-thermal
The high temperatures necessary to split water can be achieved through the use of concentrating solar power.
Hydrosol-2 is a 100-kilowatt pilot plant at the Plataforma Solar de Almería in Spain which uses sunlight to obtain the
required 800 to 1,200 °C to split water. Hydrosol II has been in operation since 2008. The design of this 100-kilowatt
pilot plant is based on a modular concept. As a result, it may be possible that this technology could be readily scaled
up to the megawatt range by multiplying the available reactor units and by connecting the plant to heliostat fields
(fields of sun-tracking mirrors) of a suitable size.[11]
An interesting approach to solar thermal hydrogen production is proposed by H2 Power Systems [12] . Material
constraints due to the required high temperatures above 2200°C are reduced by the design of a membrane reactor
with simultaneous extraction of hydrogen and oxygen that exploits a defined thermal gradient and the fast diffusion
of hydrogen. With concentrated sunlight as heat source and only water in the reaction chamber, the produced gases
are very clean with the only possible contaminant being water. A "Solar Water Cracker" with a concentrator of about
100 m² can produce almost one kilogram of hydrogen per sunshine hour.

Chemical production
A variety of materials react with water or acids to release hydrogen. Such methods are non-sustainable. In terms of
stoichiometry, these methods resemble the steam reforming process. The great difference between such chemical
methods and steam reforming (which is also a "chemical method"), is that the necessary reduced metals do not exist
naturally and require considerable energy for their production. For example, in the laboratory strong acids react with
zinc metal in Kipp's apparatus.
In the presence of sodium hydroxide, aluminium and its alloys react with water to generate hydrogen gas.[13] [14]
Unfortunately, due to its energetic inefficiency, aluminium is expensive and usable only for low volume hydrogen
generation. Also high amounts of waste heats must be disposed.
Although other metals can perform the same reaction, aluminium is among the most promising materials for future
development[15] because it is safer, cheaper and easier to transport than some other hydrogen storage materials like
sodium borohydride.
The initial reaction (1) consumes sodium hydroxide and produces both hydrogen gas and an aluminate byproduct.
Upon reaching its saturation limit, the aluminate compound decomposes (2) into sodium hydroxide and a crystalline
precipitate of aluminum hydroxide. This process is similar to the reactions inside an aluminium battery.
(1) Al + 3 H2O + NaOH → NaAl(OH)4 + 1.5 H2
(2) NaAl(OH)4 → NaOH + Al(OH)3
Overall:
Al + 3 H2O → Al(OH)3 + 1.5 H2
In this process, aluminium functions as a compact hydrogen storage material because 1 kg of aluminum can produce
up to 0.111 kg of hydrogen (or 11.1%) from water. When employed in a fuel cell, that hydrogen can also produce
electricity, recovering half of the water previously consumed.[16] The U.S. Department of Energy has outlined its
goals for a compact hydrogen storage device[17] and researchers are trying many approaches, such as by using a
combination of aluminum and NaBH4, to achieve these goals.[18]
Since the oxidation of aluminum is exothermic, these reactions can operate under mild temperatures and pressures,
providing a stable and compact source of hydrogen. This chemical reduction process is specially suitable for
Water splitting 4

back-up, remote or marine applications. While the passivation of aluminum would normally slow this reaction
considerably,[19] its negative effects can be minimized by changing several experimental parameters such as
temperature, alkali concentration, physical form of the aluminum, and solution composition.

Research
Research is being conducted over photocatalysis,[20] the acceleration of a photoreaction in the presence of a catalyst.
Its comprehension has been made possible ever since the discovery of water electrolysis by means of the titanium
dioxide. Artificial photosynthesis is a research field that attempts to replicate the natural process of photosynthesis,
converting sunlight, water and carbon dioxide into carbohydrates and oxygen. Recently, this has been successful in
splitting water into hydrogen and oxygen using an artificial compound called Nafion.[21]
High-temperature electrolysis (also HTE or steam electrolysis) is a method currently being investigated for the
production of hydrogen from water with oxygen as a by-product. Other research includes thermolysis on defective
carbon substrates, thus making hydrogen production possible at temperatures just under 1000°C[22]
The iron oxide cycle is a series of thermochemical processes used to produce hydrogen. The iron oxide cycle
consists of two chemical reactions whose net reactant is water and whose net products are hydrogen and oxygen. All
other chemicals are recycled. The iron oxide process requires an efficient source of heat.
The sulfur-iodine cycle (S-I cycle) is a series of thermochemical processes used to produce hydrogen. The S-I cycle
consists of three chemical reactions whose net reactant is water and whose net products are hydrogen and oxygen.
All other chemicals are recycled. The S-I process requires an efficient source of heat.
More than 352 thermochemical cycles have been described for water splitting or thermolysis.[23] [24] , These cycles
promise to produce hydrogen and oxygen from water and heat without using electricity.[25] Since all the input energy
for such processes is heat, they can be more efficient than high-temperature electrolysis. This is because the
efficiency of electricity production is inherently limited. Thermochemical production of hydrogen using chemical
energy from coal or natural gas is generally not considered, because the direct chemical path is more efficient.
For all the thermochemical processes, the summary reaction is that of the decomposition of water:

All other reagents are recycled. None of the thermochemical hydrogen production processes have been demonstrated
at production levels, although several have been demonstrated in laboratories.
There is also research into the viability of nanoparticles and catalysts to lower the temperature at which water
splits.[26] [27]
Research is concentrated on the following cycles [28] :

Thermochemical cycle LHV Temperature

Efficiency (°C/F)

Cerium(IV) oxide-cerium(III) oxide cycle (CeO2/Ce2O3) ? % 2000 °C (3632 °F)

Hybrid sulfur cycle (HyS) 43 % 900 °C (1652 °F)

Sulfur iodine cycle (S-I cycle) 38 % 900 °C (1652 °F)

Cadmium sulfate cycle 46 % 1000 °C (1832 °F)

Barium sulfate cycle 39 % 1000 °C (1832 °F)

Manganese sulfate cycle 35 % 1100 °C (2012 °F)

Zinc zinc-oxide cycle (Zn/ZnO) 44 % 1900 °C (3452 °F)

Hybrid cadmium cycle 42 % 1600 °C (2912 °F)

Cadmium carbonate cycle 43 % 1600 °C (2912 °F)

Water splitting 5

Iron oxide cycle (Fe3O4/FeO) 42 % 2200 °C (3992 °F)

Sodium manganese cycle 49 % 1560 °C (2840 °F)

Nickel manganese ferrite cycle 43 % 1800 °C (3272 °F)

Zinc manganese ferrite cycle 43 % 1800 °C (3272 °F)

Copper-chlorine cycle (Cu-Cl) 41 % 550 °C (1022 °F)

Patents
• Vion, U.S. Patent 28793 [29], "Improved method of using atmospheric electricity", June 1860.

See also
• Photocatalytic water splitting
• Water gas shift reaction

References
[1] Patent Database Search Results: ttl/"water splitting" in US Patent Collection (http:/ / patft. uspto. gov/ netacgi/ nph-Parser?Sect1=PTO2&
Sect2=HITOFF& u=/ netahtml/ PTO/ search-adv. htm& r=0& p=1& f=S& l=50& Query=ttl/ "water+ splitting" & d=PTXT)
[2] Electrolysis of Water (http:/ / www2. uni-siegen. de/ ~pci/ versuche/ english/ v21-2. html)
[3] 2001-High pressure electrolysis - The key technology for efficient H.2 (http:/ / www. fz-juelich. de/ scientific-report-2001/ docs/ patente/
26_11600. pdf?web_session=e4af90eba1518be519b2c1b61fa42cfb)
[4] 2003-PHOEBUS-Pag.9 (http:/ / www. fz-juelich. de/ ief/ ief-3/ datapool/ page/ 214/ solar energy 75 469-478. pdf)
[5] Electrode lights the way to artificial photosynthesis (http:/ / technology. newscientist. com/ article/
dn14441-electrode-lights-the-way-to-artificial-photosynthesis. html)
[6] Solar-Power Breakthrough: Researchers have found a cheap and easy way to store the energy made by solar power (http:/ / www.
technologyreview. com/ Energy/ 21155/ ?a=f)
[7] http:/ / swegene. com/ pechouse-a-proposed-cell-solar-hydrogen. html
[8] DOE 2008 Report 25 % (http:/ / www. hydrogen. energy. gov/ pdfs/ progress08/ ii_f_2_melis. pdf)
[9] Int J Hydrogen Energy 26: 185ff. 2001.
[10] http:/ / www. dis. anl. gov/ ceeesa/ documents/ NuclearHydrogen_ANL0530Final. pdf
[11] http:/ / www. dlr. de/ en/ desktopdefault. aspx/ tabid-1/ 86_read-14380/
[12] http:/ / www. h2powersystems. com
[13] Belitskus, David (August 1970). "Reaction of Aluminum with Sodium Hydroxide Solution as a Source of Hydrogen" (PDF). Journal of The
Electrochemical Society (Pennington, New Jersey: ECS) 117 (8): 1097–1099. doi:10.1149/1.2407730. ISSN 0013-4651
[14] Soler, Lluís; Macanás, Jorge; Muñoz, Maria; Casado, Juan (2007). "Aluminum and aluminum alloys as sources of hydrogen for fuel cell
applications" (http:/ / www. scopus. com/ record/ display. url?eid=2-s2. 0-34248401100& view=basic& origin=inward&
txGid=7tmJ4r3OwfBeSG1wyiRAiCi:4). Journal of Power Sources (Elsevier) 169 (1): 144–149. doi:10.1016/j.jpowsour.2007.01.080.
[15] Wang, H.Z.; Leung, D.Y.C.; Leung, M.K.H.; Ni, M. (2008). "A review on hydrogen production using aluminum and aluminum alloys"
(http:/ / www. scopus. com/ record/ display. url?eid=2-s2. 0-60049096697& view=basic& origin=inward&
txGid=7tmJ4r3OwfBeSG1wyiRAiCi:2). Renewable and Sustainable Energy Reviews (Elsevier) 13 (4): 845–853.
doi:10.1016/j.rser.2008.02.009.
[16] Amendola, Steven C.; Binder, Michael; Kelly, Michael T.; Petillo, Phillip J.; Sharp-Goldman, Stefanie L. (2000) "A Novel Catalytic Process
for Generating Hydrogen Gas from Aqueous Borohydride Solutions" in Grégoire Padró, Catherine E.; Lau, Francis Advances in Hydrogen
Energy New York: Kluwer Academic Publishers pp. 69–86 doi:10.1007/0-306-46922-7_6 ISBN 978-0-306-46922-0
[17] http:/ / www. sc. doe. gov/ bes/ hydrogen. pdf
[18] Soler, Lluís; Macanás, Jorge; Muñoz, Maria; Casado, Juan (2007). "Synergistic hydrogen generation from aluminum, aluminum alloys and
sodium borohydride in aqueous solutions" (http:/ / www. scopus. com/ record/ display. url?eid=2-s2. 0-36549086695& view=basic&
origin=inward& txGid=7tmJ4r3OwfBeSG1wyiRAiCi:6). International Journal of Hydrogen Energy (Elsevier) 32 (18): 4702–4710.
doi:10.1016/j.ijhydene.2007.06.019. ISSN 0360-3199.
[19] Stockburger, D.; Stannard, J.H.; Rao, B.M.L.; Kobasz, W.; Tuck, C.D. (1992) Corrigan, Dennis A.; Srinivasan, Supramaniam eds. Hydrogen
storage materials, batteries, and electrochemistry Pennington, New Jersey: ECS pp. 431–444 ISBN 9781566770064 OCLC 25662899
[20] Strategies for the Development of Visible-light-driven Photocatalysts for Water Splitting Akihiko Kudo, Hideki Kato1 and Issei Tsuji
Chemistry Letters Vol. 33 (2004) , No. 12 p.1534
[21] (http:/ / www. eurekalert. org/ pub_releases/ 2008-08/ mu-mtl081408. php)
Water splitting 6

[22] Kostov, M. K.; Santiso, E. E.; George, A. M.; Gubbins, K. E.; and Nardelli, M. Buongiorno (2005) (PDF). Dissociation of Water on
Defective Carbon Substrates (http:/ / scitation. aip. org/ getpdf/ servlet/ GetPDFServlet?filetype=pdf&
id=PRLTAO000095000013136105000001& idtype=cvips& prog=normal). Physical Review Letters. . Retrieved 2007-11-05.
[23] 353 Thermochemical cycles (http:/ / www. hydrogen. energy. gov/ pdfs/ review06/ pd_10_weimer. pdf)
[24] UNLV Thermochemical cycle automated scoring database (public) (http:/ / shgr. unlv. edu/ stchNew/ source/ login. asp)
[25] Development of solar-powered thermochemical production of hydrogen from water (http:/ / www. hydrogen. energy. gov/ pdfs/ review05/
pd28_weimer. pdf)
[26] Naoptek (http:/ / www. nanoptek. com/ )
[27] http:/ / www. treehugger. com/ files/ 2008/ 07/ hydrogen-production-breakthrough-from-mit-a-giant-leap. php
[28] Development of solar-powered thermochemical production of hydrogen from water (http:/ / www. hydrogen. energy. gov/ pdfs/ review05/
pd28_weimer. pdf)
[29] http:/ / www. google. com/ patents?vid=28793
Article Sources and Contributors 7

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