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INNOVATIVE HYDROGEN PRODUCTION FROM WATER

Tokio Ohta
Yokohama National University, Japan
Keywords: Innovative method, renewable energy, Gibb free energy, thermal energy,
thermolysis, electrolysis, thermochemical cycle, photoelectrochemical method, mechano-
catalytic method, photobiochemical method, fermentation
Contents
1. Definition of "Innovative Technology"
2. Renewable Energy Resources
3. Five Innovative Hydrogen Production Technologies
4. Algae and Bacteria Hydrogen Systems
5. Hydrogen Production from Biomass
Related Chapters
Glossary
Bibliography
Biographical Sketch
Summary
"Innovative technology" is defined as unconventional technology that promotes efficiency
and/or sustainability. The water-splitting method utilizing renewable energy is emphasized.
Available renewable energy resources are reviewed. Solid polymer electrolysis, the
thermochemical cycle method, photoelectrochemical method, and mechano-catalytic method
are reviewed. Hydrogen production by the photobiochemical method and by fermentation are
mentioned.
1. Definition of "Innovative Technology"
a. Technology quite different from the conventional one; for example, the
electrolyte in an electrolytic cell is, conventionally, a liquid. However, if
an efficient solid polymer takes the place of the liquid, the technology is
innovative. The changes should be "sustainable," "economical" (cost
down), "energy saving," "ecological," "material saving," "safety," "non-
pollutant," "recycle," "beneficial to human beings and environments."
Hydrogen energy systems are innovative.
b. Energy conversion technology that applies a renewable energy resource.
For example, if fossil fuel is used to produce hydrogen, the hydrogen
energy systems are, in principle, not "innovative," because the utilization
of fossil fuel is contradictory to the catchwords listed in (a).
2. Renewable Energy Resources
2.1. Solar Energy
Solar energy coming onto the earth is divided into the following branches.
Direct reflection: 52 PW (30%).
Converted to heat: 81 PW (47%).
 Vaporization (e.g., rainfall): 40 PW (23%).
Wind, ocean wave, ocean flow, ocean convection etc.: 0.378 PW (0.37%).
Photosynthesis: 40 TW (0.023%).
Direct photons onto the earths surface: approximately 1 kW m2.

2.2. Tide Energy and Geothermal Energy

Tide energy: 3 TW.
Geothermal energy: 0.3 TW.

On the other hand, the total primary energy consumed in 1999 was 8.5 Gt (in oil equivalent
ton). Therefore, the wattage is
Wattage of world energy supply = 8.5 Gt Y = 9.056 TW (1)
It is not easy to provide this amount of energy by renewable energies.
The defects of renewable energies are (1) the low energy density and (2) the intermittence. A
very large surface area is required to overcome these defects. Therefore, the condensed forms
are preferable. The energies of moving fluid such as hydraulic power, ocean wave, and wind
are examples, among which the wasted hydraulic power must be developed more, because the
energy density is given by

Energy density aV 3 (2)

where r and V denote air density and velocity respectively. The utilization of rapidly moving
liquid is more profitable. If innovative technology such as mechano-catalytic water splitting is
applied, hydrogen can be obtained from even the faucet of the waterworks.
3. Five Innovative Hydrogen Production Technologies
As the statistics in the article Statistics on Hydrogen Production and Consumption show,
hydrogen production today is almost always based on the splitting of fossil fuel. This is not
always sustainable.
First, the principles of water splitting are briefly reviewed. The total energy (the enthalpy
change) necessary to split water is the sum of the Gibbs free energy and the thermal energy.
The free energy can be given by electrical energy, mechanical energy, chemical energy, and
photon energy. Therefore, these energies as well as thermal energy must be provided from
renewable energies in order to make the production system sustainable.
The sustainable and the innovative methods of hydrogen production are summarized below.
3.1 Solid Polymer Electrolysis
A water electrolyzer with high performance using solid polymer, where proton conducts
charge, has been invented. This is called SPE (solid polymer electrolyzer) and the typical
material is Nafion. Water vapor with high temperature can be applied to SPE with less free
energy.
SPE combined with renewable energy can be sustainable. Practical examples are the
combinations with photovoltaic generation and wind power generation.
3.2 Ideal Water-splitting Process
Water thermolysis (pyrolysis) means the water-splitting system that utilizes thermal energy.
Figure 1 shows the temperature (T)entropy (S) diagram for an ideal thermolysis. The water
vapor in A-state (gaseous H2O at T1K) changes to B-state (mixed gas of H2 and O2 at T2K) by
the thermal energy (Qi) from the outside. B-state changes to C-state (separated gases of H2 and
O2 at T2K) by obtaining the external free energy (Wi). Thermal energy (Qo) is recovered by the
cooling transition from C-state to D-state (separated gases of H2 and O2 at T1K). Free energy
returns by the process from D-state to A-state, which is realized, for example, by the fuel cell.
If the input thermal energy (Qi) is equal to the output thermal energy (Qo) and the input free
energy (Wi) is equal to the output free energy (Wo), this cycle is reversible and Carnot
efficiency is attained.
If no thermal energy is utilized, the water-splitting process is reversible, so that the efficiency
is 100%. For example, water electrolysis, water photolysis, and mechano-catalytic water
splitting, may have 100% efficiency, if the Joulian heat and other energy losses are neglected.
3.3 Thermochemical Cycle Method
Chemical energy is applied as the free energy. For example, if a reduction agent X is mixed
with water at high temperature, the two reactions H2O + X =X O + H2, XO =X + (1/2)O2 may
split water. No agent is consumed. Figure 1 shows this cycle as an example of thermolysis.
The thermal energy (at about 1000 K) may be provided by the solar collector.
 Figure 1. Temperature (T)entropy (S) diagram for an ideal thermolysis, using the
thermochemical cycle as an example.
3.4 Photoelectrochemical Method
The photovoltaic generation system combined with water electrolysis can effectively evolve
hydrogen. In the same way, if an appropriate semiconductor and platinum (Pt) are inserted as
the cathode and the anode, respectively, in an electrolyte of a cell, H2 and O2 evolve at anode
and cathode, respectively, when a solar beam irradiates upon the semiconductor. This direct
photolysis was discovered in 1969 in Japan. Details of the method will be introduced by the
discoverer in (Photochemical and Photoelectrochemical Water Splitting).
The transition from the starting state A (H2O (liquid) + X +Y, where X and Y are chemical
agents, at T1 K) to the state B (XH2 + YO, at T2 K) is realized from the external heating.
By applying some free energies, the decompositions of the hydride and the oxide are
achieved, and then the state C (separated gases H2, O2 and X, Y, at T2 K) is attained. X and Y
are recovered and the separated H2 and O2 returns via the proper method. This is the process
from D to A. Thus Carnot efficiency is obtained.

Figure 2. Experimental arrangement for the mechano-catalytic water-splitting by Domens

group. GC, gas chromatography. Magnetic stirrer is applied. The reaction cell and the stirrer
are made of Pyrex glass and Teflon, respectively. The density of the slurry: 0.1 g per 200
cubic centimeters of water. The stirring speed is 1500 revolutions per minute. The gas
evolution rate is 26 mol/h, at most.
3.5 Mechano-catalytic Method
Water-splitting methods have been studied since Michel Faraday. However, one cannot expect
that mechanical energy can be applied directly to the free energy, which is useful to water
splitting. In the beginning of 1998, a research group at the Tokyo Institute of Technology
discovered that simultaneous hydrogen and oxygen evolutions can be achieved by simply
stirring a powder of a p-type semiconductor, such as NiO or Cu2O, in distilled water at room
temperature. Frictional rubbing of the stirring rod onto the bottom of the glass vessel is an
important condition. The experimental arrangement is shown in Figure 2. The theory is due to
the present author (2000), who attributes this effect to the frictional electricity in water.
4. Algae and Bacteria Hydrogen Systems
The photobioproduction of hydrogen by intact cells was discovered in algae by H. Gaffron
and J. Rubin in 1942, and in photosynthetic bacteria by H. Gest and M. D. Kamen in 1949.
The present introduction of these biological and biochemical hydrogen production systems is
due to A. Mitsuis
excellent article published in the book Solar-hydrogen Energy Systems (edited by T. Ohta,
1979).
There are two types of photobioproduction of hydrogen. One is due to living cells, and the
other due to cell free systems (see, Hydrogen from Biomass parts (1) and (2)). In order to
produce photobio hydrogen, a pond with a transparent roof is constructed, which is filled with
seawater rich in algae or the bacteria. The evolved hydrogen gas is separated from air, and
compressed. The theoretical maximum efficiency for hydrogen production by intact cells is
estimated at 12%, but the observed efficiencies are about 2.5%. Although the production
efficiency is not large, the expenditures necessary for the plant are less than for Plan of Ocean
Raft Systems for Hydrogen Economy (PORSHE). In addition, it will be possible to site the
facilities in bays or inlets, and we may expect no serious objections against siting since algae
and bacteria hydrogen systems are essentially agricultural systems without pollution.
5. Hydrogen Production from Biomass
Biomass can be a renewable feedstock for hydrogen production. Hydrogen can be produced
from biomass by gasification of biomass followed by its conversion into hydrogen.
Thermochemical conversion, biomethanation, and hydrothermal treatment are the typical
technologies.

Related Chapters
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Glossary
Biomethanation :A method of hydrogen production from biomass using a
fermentation process.
Direct water splitting :Water vapor at higher than the critical temperature splits into
hydrogen and oxygen.
Hydrothermal treatment :A kind of fermentation.
Mechano-catalytic water :Mechanical system of hydrogen evolution by stirring the
splitting powder of an oxide semiconductor in pure water while
keeping the stirring rod in contact with the wall of the vessel.
Photobiochemical water :Algae and bacteria with photosynthesis function or cell free
splitting biomass can produce hydrogen on solar irradiation.
Photoelectrochemical water :Applying a photo-semiconductor to the cathode of the cell,
splitting water splits into hydrogen and oxygen on irradiating violet
light onto the cathode.
Renewable energy resources :Solar energy (direct and converted), tide, and geothermal
 energy.
SPE :Solid polymer electrolysis. A high performance electrolysis.
Thermochemical cycle :A combination of several chemical equations at about 100 K
results in water splitting without consuming the chemical
substances.
Thermochemical hydrogen :Decomposition of biomass compounds at a temperature of
production from biomass around 1000 K.
Bibliography

Domen K., Ikeda S., Takata T., Tanaka A., Hara M., and Kondo J. N. (2000). Mechano-catalytic water-splitting
into hydrogen and oxygen on some metal oxides, Energy Systems: Adaptive Complexity (ed. T. Ohta), pp. 159
179. Oxford: Elsevier Science. [The details of the discovery experiments are introduced of mechano-catalytic
water-splitting.]

Fujishima A. and Honda K. (1972). Electrochemical photolysis of water at a semiconductor electrode. Nature
238, 37. [The discovery of photoelectrochemical water-splitting using TIO2 electrode.]

Funk J. E. and Reinstrom R. M. (1966). Energy requirements in the production of hydrogen from water. I & EC
Process Design and Development 5(3). [This is the first paper that proposed the thermochemical water splitting
in the order of energy requirement.]

Mitsui A. (1979). Biological and biochemical hydrogen production. Solar-hydrogen Energy Systems, Chapter 8
(ed. T Ohta), 264 pp. Oxford: Pergamon Press. [Comprehensive explanation of biological and biochemical
hydrogen production. The author is the pioneer in this field.]

Ohta T., ed. (1979). Solar-hydrogen Energy Systems, 264 pp. Oxford: Pergamon Press. [Collections of the
pioneering researches on solar production of hydrogen.]

Ohta T. (1999). Energy Technology, Sources, Systems and Frontier Conversions, 235 pp. Oxford: Pergamon
Press. [Energy systems and their elemental technologies are introduced and evaluated from the view point of
efficiency and the global environment.]

Ohta T. (2000). Energy Systems: Adaptive Complexity, 230 pp. Oxford: Elsevier Science [The first book on
energy systems as approached from the adaptive complexity.]

Sato S. (1979). Thermochemical hydrogen production. Solar-hydrogen Energy Systems, Chapter 5 (ed. T. Ohta),
264 pp. Oxford: Pergamon Press. [Detailed and concrete description of thermochemical cycles for water
splitting.]

Biographical Sketch

Tokio Ohta, born November 3, 1925, in Japan, received his education from the Department of Physics,
University of Kyoto with a Ph.D. degree in Solid State Physics; he has taught at the University of Kyoto,
Portland State University of Oregon, USA, and at the University of Tokyo, and served as the Dean of Faculty of
Engineering, Yokohama National University (19851988), and President of Yokohama National University
(19881994). Since 1999 he has been Superintendent of the International Network University; other
appointments include the Committee Staff of Science and Technology to the Prime Minister (19741994) and the
Committee Staff of the Minister of International Trade send Industry (17941999). He has published some 160
papers and 60 books on solid state physics and energy systems. He has been elected Vice President of the
International Association for Hydrogen Energy, and is the Founding Past President of the Hydrogen Energy
Systems Society of Japan.

To cite this chapter

Tokio Ohta, (2004), INNOVATIVE HYDROGEN PRODUCTION FROM WATER, in Energy Carriers and
Conversion Systems , [Ed. Tokio Ohta], in Encyclopedia of Life Support Systems (EOLSS), Developed under the
Auspices of the UNESCO, Eolss Publishers, Oxford ,UK, [http://www.eolss.net] [Retrieved April 12, 2007]