ENERGY CARRIERS AND CONVERSION SYSTEMS WITH EMPHASIS

ON HYDROGEN
Tokio Ohta
Yokohama National University, Japan
T. Nejat Veziroglu
Clean Energy Research Institute, University of Miami, USA
Keywords: Energy conservation law, entropy increasing law, fossil fuels, nuclear energy,
renewable energy, mechanical energy, potential energy, electric energy, photon energy,
chemical energy, energy resources, nuclear and solar hydrogen energy systems, hydrogen
production from water, electrolysis, photolysis, thermochemical water-splitting, solid polymer
electrolysis, photochemcial and photoelectrochemical water-splitting, fuel cells,
metalhydrides, heat pump, development of hydrogen energy system safety.
Contents
1. Energy Resources
2. Proposed Systems and the Elementary Technologies
3. Metal Hydrides and Hydrogen
4. Safety
Related Chapters
Glossary
Bibliography
Biographical Sketches

Summary
This theme level article introduces the background and outline of hydrogen energy systems
and the relevant elementary technologies. The most significant points are as follows:
Energy, energy resources, and energy carriers are defined. The merits and the demerits of
every energy resource are pointed out. It is emphasized that the combination of every
traditional system with hydrogen systems must be considered.
Hydrogen energy systems are introduced as an important option of future energy systems,
and the elementary technologies are reviewed. The most important fundamental is how to
produce hydrogen using renewable energy resources. However, it is too expensive to be
realized at the present stage.
Feasibilities for realizing the proposed application technologies are promising. Therefore, if
hydrogen fuel can be produced at low cost and safely distributed, our energy systems will
tend to move gradually towards the hydrogen energy systems.
Recently, environmental demands for clean fuel for driving vehicles have been promoting the
application of PEMFC to cars to a practical level. A new age for hydrogen energy is coming
now.

1. Energy Resources
1.1. Energy, Energy Resources, and Energy Carriers
The term "conversion system," which often appears in the contexts of energy essays, has two
meanings. The first is scientific and technological as in the example of: "mechanical energy
conversion to electric energy has high efficiency, whereas thermal energy can be converted to
mechanical energy with somewhat limited efficiency."
The second meaning is economical and political as in the example of "conversion of the main
systems of energy carriers from coal to oil have been going on since the 1960s." The term
"conversion system" used in the present case has the second connotation. Putting this in
concrete terms, "the present systems of energy carriers may be converted to advanced carrier
systemsthe hydrogen energy systemsin the twenty-first century."
Energy is defined as a capacity for motion, which is sometimes equivalent to work. Work is
scientifically defined by the physical quantity that is given to a body when it is moved a
distance by a force. The general meaning of energy includes every quantity that is equivalent
to work as defined above. There are two kinds of energy: dynamic and static. Examples of the
former are kinetic energy, electric current, photon, and sensible heat. The latter includes
potential energy, electro- (magneto) static potential energy, latent heat, and chemical cohesion.
We shall next define the concepts of energy source, resource (the primary energy), and energy
carrier (the secondary energy). Let us consider a domestic refrigerator. The cold generated by
a conventional refrigerator is due to the adiabatic expansion of a heat medium that has been
compressed with the use of a compressor and motor. Energy is provided to the latter in the
form of electricity from an electric power plant, operates the compressor. The electric power
plant gets the electric energy from a steam-power station where fuel oil is burnt. In this
system, the oil is called the energy resource and electricity is called the energy carrier. Strictly
speaking, the electricity provided to the refrigerator is called the energy source on the spot,
and the initial provider of energy, the fuel oil in this case, is called the energy resource.
An innovative refrigeration energy conversion system is possible if the energy resource is a
solar-hydrogen energy system (a system of hydrogen produced by solar energy), the energy
carrier is hydrogen, and a metal hydride refrigeration system replaces the mechanical
compressor system.
There are several kinds of energy carriers in present energy systems, for example, gasoline,
kerosene, electricity, city gas, LNG, and LPG. Some advanced energy carriers, making use of
hydrogen, laser beams, and microwave power transmission in space, may be realized in the
near future.
The basic principles of energy are noted in the following paragraphs. First, "energy is
conserved overall in the universe," where the term energy means the sum of conventional
energy and mass, because mass is equivalent to conventional energy, that is to say, a mass of
m kg can be converted to the conventional energy of mc2 kJ, where c is the velocity of light in
a vacuum. This equivalence is due to Einsteins special relativity. One important energy
resource today, nuclear energy, is the result of precisely this equivalence. There are only
negligible amounts of nuclear energy conversions globally, so that the energy conservation
law holds among the conventional energies, kinetic energy, potential energy, electric energy,
chemical energy, photon energy, and thermal energy.
Let us consider the case of lighting. If the energy resource is oil, the following conversion
systems are realized:
 from oil (chemical energy) to burner (heat)
from heat to heat energy (mechanical energy + waste heat)
from mechanical energy to electric generator (electric energy +
waste energy)
from electric energy to light bulb (light energy + waste energy),
where all the waste energies are converted finally to waste heat.
Less than 8.5 percent of the oil energy is used in the illuminating energy of the fluorescent
lamp.
It should be noted that "energy is conserved," but the useful (available) energy decreases at
every step of energy conversion. Therefore, we obtain the second main principle: "available
energy decreases whenever it is converted." This principle is called the second law of
thermodynamics: the law of increasing entropy. This is why energy is not always ability of
work as indicated above; for example energy may be energy at ambient temperature.
Expressing the total energy (enthalpy), Gibbss free energy, entropy, and the absolute
temperature, by E, G, S, and T, respectively, we arrive at the well-known formula:
G = E TS (1)
Free energy is the energy which can be converted to mechanical energy directly rather than
via a heat engine; it has a higher value than heat energy, which is expressed by the term TS.
Equation (1) shows that the useful energy G decreases as entropy increases. The lost heat q
divided by T is the entropy increment in the energy conversion process.
It is understood that dynamic energy (kinetic energy and sensible heat) tends to generate
entropy much more easily than static energy (potential energy and latent heat). Therefore, for
energy storage, static energy systems become indispensable. Coal, oil, fuel gas, wood, and
uranium are the materials wherein cohesive potential energies are stored stably. These
materials are often called "energy media," and are equivalent to energy carriers (secondary
energy). One must be careful to use the term energy media, because all matter, even void
space, can be the energy propagation medium.
1.2. Fossil Fuels
1.2.1. Coal
The ancient remains of plants that were subjected to a dry distillation under geothermal heat
and great geological pressures several hundred thousand years ago, in due course became
coal, of which the major constituent is carbon. Coal has been one of the most important
energy resources since the Industrial Revolution in the eighteenth century. The kinds of coal
are anthracite, bituminous, sub-bituminous, and lignite; however only anthracite and
bituminous are used in practice, because they higher more energy density (about 32,400
kJ/kg) and are cleaner (with a sulfur component of about 3 percent) than the others. The world
has very large coal reserves in the world are very large, with a lifetime estimated at 230 years
in 1998. Moreover, these resources are fairly evenly distributed around the world. The major
problem with coal utilization is the air pollution caused by coal combustion, which gives off
more than three times the amount of sulfur oxide gas than is produced by oil combustion, and
more than twice the amount of carbon dioxide gas, which is the main cause of the greenhouse
effect. Other obvious economic disadvantages are that coal is not readily compatible with
automatic combustion systems or with a pipeline transportation system. However, it is highly
probable that the use of coal will be revived when oil resources are depleted in about sixty-
four years time.
It is obvious that the disadvantages of coal can be overcome if it can be liquefied or gasified.
The simplest way of getting liquefied coal is to mix oil with powdered coal. It is necessary to
add a surfactant (surface active agent) to avoid the precipitation of the coal powder. This
energy carrier is called COM (coal oil mixture), and is often used in order to save oil.
1.2.2. Coal and Hydrogen
The well-known and traditional coal fluidization technologies are coal liquefaction and coal
gasification, which involve the addition of hydrogen to coal under high pressure and at high
temperatures. If the added hydrogen can be supplied from the solar hydrogen energy system,
then the energy quantity of the liquefied coal fuel will be comparable to that of oil, and the
lifetime of the fuel will be greater than 230 years. This fuel could be one of the leading fuels
in the post petroleum era.
1.2.3. Oil
Accumulated masses of ancient remnants of plankton were subjected to dry distillation under
geothermal heat and high geological pressure about a billion years ago, resulting in the
production of oil (petroleum). Oil is a stable liquid energy carrier with high energy density.
For example, the energy density of kerosene is 40,850 kJ/kg, of burner oil 42,680 kJ/kg, and
heavy oil 45,740 kJ/kg. Oil is believed to be the most practical energy carrier in human
history. More than 30,000 oil-producing wells have been drilled so far. They produced, for
example, 3.82 billion kl of oil in 1979 (this is a remarkable record). The vast amounts of oil
produced lowers its price, and not only energy but everything in human civilization has
benefited from oil. Today is said to be the golden age of oil.
There are three major problems with oil energy: the depletion of reserves, uneven distribution
around the world, and pollution.
Depletion of Reserves: The most serious of these problems concern the world reserve of oil.
The ultimate reserve is roughly estimated to be about 2 T barrel, (T = 1012; 1 barrel = 0.159
kl). The production rates and global reserves of every energy resource are usually a function
of time elapsed. For example, oil data for 1985 indicate a production rate of 3.48 T l/Y and
total global reserves of 318 T l. Assuming a constant consumption rate, the total life of the
reserve can be easily estimated. If oil is consumed at a constant rate, then it will be exhausted
in ninety-one years from 1985. However, we know that the situation is not so simple. The
production rate is sensitive to the global economy and the demands of exporting and
importing countries. Since oil first began to play an important role in the economy, the
production rate has been steadily increasing (although it is relatively stable at present). On the
other hand, it is expected that the rate will decrease at some point, when about half of the
reserves have been consumed. In order to express this trend, and to study the resource life
cycle more exactly, we shall study a model.
M. K. Hubbert proposed a life-cycle model for oil in 1956. This is shown in Figure 1, where
the horizontal axis and vertical axes represent the oil production rate and the year,
respectively. The model is based on the following three assumptions:
The total initial oil reserve is 2 T barrel = 318 T l.
 The production rate increases to a maximum and then stabilizes
for a short time before decreasing.
The behavior of the production rate is predicted by an extension
of empirical data and is assumed to be symmetrical with respect to
the time when the production rate becomes maximum.

Figure 1. Hubberts model for lifetime of oil reserve

Note: dM / dt is the production rate.
We extended the empirical data taken from 1910 to 1955 by Hubbert to 1985. The hump in
the oil production is due to the oil crisis. Assuming a production rate increase of 2 percent
every year, the production rate reaches a peak in 2010 and is estimated to be 5.22 T l/Y. In
1955 Dr Hubbert predicted that oil would be depleted in 2042. According to a recent
publication by Deffeyes (2001) the depletion time has shifted to the beginning of 2100.
There are several other predictions about the year of the maximum production:
20005; F. Bernable, ENI SOA, 1998
200010; C. Campbell and J. Laherrere, Petroconsultants, 1998
200714; J. Makenzie, World Resources Institute, 1996
201020; OECDs International Energy Agency, 1998
2020; J. Edwards, University of Colorado, 1997
After 2020; DOEs Energy Information Administration, 1998.
Geographical Distribution of Oil: The second problem is the uneven distribution of oil
around the world, which can cause global economical confusion, as in the "oil crisis" of 1973
to 1980. According to a recent research report in Science (August 21 1998), about 50 percent
of the initial total reserves of oil have been consumed, and the confirmed remaining reserves
of 1.0376 T barrel (=164.91T l) is distributed as follows:
North America: 12.18 T l
South & Central America: 13.7 T l
Europe: 3.2 T l
former Soviet Union: 10.4 T l
Middle East: 107.6 T l
Asia Pacific: 6.725 T l
Africa: 11.1 T l.
The Middle East contains 65.23 percent of the worlds oil reserves. This situation is very
different from coal distribution.
Pollution: The third problem of oil is related to polluting emissions. When oil is burned, it
emits as many kinds of gases as the number of elements it contains. Most of the gases are
oxides: NOx, SOx, COx, and H2O. Carbon dioxide (CO2) has been recognized, for a long time,
as a non-noxious gas resulting from fossil fuel combustion. However, the huge amount of CO2
gas accumulated in the atmosphere year by year poses a serious problem for the global
environment.
Figure 2 shows the change in global surface air temperatures. The standard level (0.0) is the
average from 1950 to 1979. The tropical rain forests and seaweeds have very active
photosynthetic actions in summer, and so the amount of CO2 to the atmosphere decreases in
that season.
 Figure 2. Global surface air temperature
Note: The standard (0.0) is the average temperature from 1950 to 1970
Source: University of East Anglia.
The global damage due to the increase of surface air temperatures is obvious: rise of sea
levels, enlargement of desert areas, changes of climate, and so on. All of these effects affect
the sustainable development of human lives. Agenda 21 was issued in 1992, setting out the
aim of reducing carbon dioxide emissions to a level agreed by every country of the world.
However, the underdeveloped countries such as China tend to increase their use of oil rather
than coal. Thus, the developed countries will have to yield more of the oil reserve to the
underdeveloped countries, and will have to develop and utilize more natural gas, nuclear
energy, and pollution free fuels such as hydrogen generated from water by renewable energy
sources.
1.2.4. Oil and Hydrogen
Crude oil contains some noxious elements, among which sulfur (S) is the most serious,
because SOx (SO, SO2, S2O3), the reactants of sulfur, are noxious to human health. They also
react with water vapor to become acid rain, which is very harmful to every plant on earth.
In order to avoid this hazard, the sulfur contained in oil must be removed. Here hydrogen
plays an important role. When oil is charged with hydrogen, under high pressure and at high
temperatures, the sulfur contained in the oil reacts with hydrogen to yield hydrogen sulfide
(H2S), which is extracted. More than 7 Nm3 of hydrogen gas is necessary to remove the sulfur
from 1 t of oil, if the density of sulfur in the oil is 1 percent (usually the density is between 1
and 3 percent). This process is called "desulphurization," and is also used to remove H2S gas
from coal.
It should be noted that a large amount of hydrogen is used for desulphurization of oil and
coal. If 6 Gt of oil and coal are subjected to this process, more than 7.2 GNm3 hydrogen gas
must be supplied (assuming that the average sulfur content is 2 percent). In practice,
desulphurization demands more hydrogen because the process efficiency is only about 50
percent).
1.2.5. Methane
The confirmed world reserve of methane gas as of the beginning of 2001 is estimated at about
149T Nm3 which is equivalent to 149 T l of oil, a quantity roughly equal to the confirmed
reserves of oil. Methane gas is believed to be better fuel than coal and oil in future, because
(1) methane gas is a little more evenly distributed .
Methane gas, the proved reserves as of the end of 2004 (BP statistical review of world energy
2005)

Region TNM3 ( %)

(i) Middle East: 72.83 TNM3 (40.6 )

(ii) Europe and Eurasia: 64.02 (35.7)

(iii) Asia Pacific: 14.21 (7.9)

(iv) Africa: 14.21 (7.9)

(v) North America: 7.32 (4.1)

(vi) South & Central America: 7.10 (4.0)

Second, the quantity of CO2 produced from methane combustion is only about half of that
from oil for the equivalent generated calories. The production rate of methane gas was 1.7 T
Nm3 in 1985 (not much different than from today), so that a simple estimation of the lifetime
is 58.8 years as measured from 1985 (the estimated life time in 1998 was 62 years, because
more reserves had been discovered).
1.3. Nuclear Energy
1.3.1. General Survey
As mentioned in the beginning of this chapter, the principle of "mass equivalence of energy"
is expressed by:
E = mc2 (2)
Where c is the velocity of light in a vacuum. According to Equation (2) mass is converted to
energy as follows:
1 g = 57.03 T J (3)
The energy density of burner oil is 42680 J/g, so that the mass of 1 g is converted to generate
energy that is equivalent to 1.34 M t of the burner oil. This is the splendid result of modern
physics. Actually, the application of this principle to the nuclear fission of U235 has been put
into practical use since the World War II (1945). The first experiment for electric power
generation by nuclaer heat by the use of U235-fission was undertaken on 20th of December,
1951 at Argonne National Laboratory. In order to save oil fuels by the principle, one gram of
U235 generates about 2 B cal ", each industrially developed country has tried to install
nuclear plants for generation electric power. In 1982, there were 302 nuclear plants, of which
total output capacity of electric power was about 200 BW. The share of nuclear energy of
some conspicuous countries as of the end of 2005 is as follows:

Country GW

(i) U.S.A.: 10.275

(ii) France: 6.602

(iii) Japan: 4.822

(iv) Russia: 2.356

(v) Germany: 2.137

(vi) Korea: 1.722

(vii) Canada: 1.342

(viii) Ukraine: 1.282

The world reserve of uranium (U235), which is more evenly distributed than oil, is a little more
than that of oil in calorie equivalence, and the lifetime is estimated to be roughly seventy
years from 1998. However, both the quantity and the lifetime are functions of technology,
which is quite versatile, and depend upon the acceptability of nuclear power among different
nations.
Another prospective source of nuclear energy is nuclear fusion. For example, the masses of
the proton and the neutron are 1.007825 amu and 1.008655 amu, respectively, (where amu is
defined as 1 amu x Avogadros number = 1 g) so that two of each nucleon comprises 4.03296
amu. On the other hand, the mass of helium 4 is only 4.00260 amu; the difference, 0.03036
amu, will be released from a nuclear reaction that combines two pairs of proton-neutron to
produce one helium 4 atom. This mass defect is equivalent to 28.2665 erg, so that we have:
1 g of deutron = 2728 T J
Until now, nuclear fusion technology has been applied only in the hydrogen bomb, not yet in
electric power generation. Large-scale research projects on power generation by nuclear
fusion are underway. The merits of nuclear energy (fission and fusion) will be covered in a
separate theme, and we shall point out some difficulties and a new idea, nuclear hydrogen
energy system, later in this article.
1.3.2. Difficulties of Nuclear Power Utilization
Most citizens are unwilling to accept the presence of a nuclear facility near where they live.
This is because they remember the tragic accidents of the nuclear plants in Three-Mile Island
(1979) and Chernobyl (1986). In order to overcome the citizens uneasiness, we must consider
every possible defect in nuclear power plant systems. The main challenges are:
The safety of the nuclear fuel-systems must be ensured. Every
process from the mining of uranium ore to the final disposal of
radioactive waste material could give rise to radioactivity. Even in
the countries where the use of nuclear energy is appreciably large,
complete cycle systems for nuclear fuels have not been established
yet.
The safety of the total systems of plants, subsystems, elemental
machines, and materials must be carefully investigated, and safety
software and training must be provided. However, it is very
difficult to predict the damage to materials due to fatigue or other
stresses caused by aging in the high temperature environment of
reactor cores.
Present technologies for nuclear plants have not yet matured. For
example, control of the fission process to meet fluctuating demands
for output power cannot be achieved yet. Thus the nuclear plant is
operated at a constant rate of output power, even when the demand
of power supply becomes extremely low. This is very different
from thermal plants, in which fossil fuels are burnt and the fuel
supply can be stopped if no output is needed. In other words, the
fuel economy of nuclear plants is worse than that of conventional
thermal plants(and also to the hydraulic power generation stations).
There must be strict adherence to the international protection
regulations for the safekeeping of plutonium, the reactant of the
nuclear reactions, which can be the raw material of atomic bomb.
Large amounts of plutonium are produced from nuclear plants.
Hence, it becomes an important task to use plutonium as a new
fuel. This new system is called a Pluthermal system. However,
Pluthermal systems need much stricter controls, because plutonium
is one of the most poisonous materials ever produced.
1.3.3. Nuclear-Hydrogen Energy Systems
The conventional nuclear-electric energy system is shown diagrammatically in Figure 3, and
an innovative nuclear-hydrogen energy system is proposed, as shown in Figure 4. A
comparison of the two systems is given below:
 Figure 3. Conventional nuclear energy system

Figure 4. An advanced nuclear energy system

Fuel Economy: The present nuclear plants cannot vary their output to reflect fluctuations in
demand, and effective electric power storage is not possible. Hence, some of the generated
power is wasted when demand decreases. What is worse, the radioactive waste materials
increase. The systems fuel economy decreases as the capacity of nuclear plants increases, and
the difference between the maximum and the minimum power supply increases.
On the other hand, hydrogen can be produced at a constant rate in nuclear plants, and the
evolved hydrogen gas can transported by pipe line to gas storage tanks or vessels, which can
be combined with city gas systems. Thus the generated hydrogen gas is stored without
wastage.
Conversion Efficiency: The output temperature of conventional reactors is about 600 K, and
the thermal efficiency of power generation is about 34 percent. A hydrogen production plant,
however, can be operated at an input temperature of about 1,300 K or higher (this level of
temperature can be produced in high temperature gas reactors), and the thermal efficiency of
hydrogen generation can be about 40 percent or more.
Energy Transport Economy: Which is more economical, energy transmission by electrical
power-line or energy transport by gas pipeline? This question has been the subject of debate,
and the conclusion is that the gas-pipeline is more advantageous above distances of 1,600 km.
The energy losses by power-line transmission are due to Ohm heat losses incurred in
transforming and transmission, and vary between 7 and 12 percent depending on the
circumstance where the power cable is installed.
On the other hand, there is very little loss in the case of pipeline hydrogen transport, because
the viscosity of hydrogen gas is so small that the friction loss generated between the pipeline
walls is very small. Accordingly, the energy needed to operate the compressor to pressurize
the hydrogen gas is as little as 1 percent or less.
Energy Storage Systems: It is very difficult to store large amount of electric power. The only
method now in use is pumped up hydroelectric storage, in which off-peak power is used to
raise water in a lower pond into a higher reservoir (upper dam). During periods of peak
demand, this water is then used to operate hydrogenerators to produce electric power. There
are few sites suitable for the installation of pumping dams in most industrialized countries.
This is one of the most serious problems in the present electric power system.
In contrast, hydrogen can be stored in many ways, such as in pressurized vessels, metal
hydride systems, and in liquid form. The size of these storage facilities ranges from small
domestic applications to industrial levels.
Diversified Utilization: Electric power is an important energy for modern civilization. It can
operate electric trains, electric machines in factories, electric lamps, refrigeration systems, air-
conditioning systems, electronic machines, TVs, radios, computers, telephones, clocks,
elevators, escalators, medical equipment, robots, and a host of other devices. There are no
alternatives for many applications. However, it is not practical for trucks, ships, or airplanes.
Battery-driven electric vehicles have been developed. Their batteries are charged at night,
when the demand for electric power decreases, using the electric power surplus caused by
nuclear power generation. As has been mentioned, in nuclear reactors the output of electric
power cannot be varied with demand cannot be controlled, so one useful option for the
nuclear energy economy is to expand the use of battery cars. One should note that battery cars
emit no carbon dioxide, but on the other hand, radioactive waste materials are produced in
electricity generation.
Compared with electric generation, nuclear-hydrogen systems are more meritorious and offer
valuable options. Hydrogen from storage vessels can be utilized not only as important
chemical agent in the chemical and metal refining industries, but also as clean fuel that can
drive transport. We have no alternative fuel for rockets secondary engines.
Let us compare hydrogen cars with the battery cars mentioned above. There are two types of
hydrogen car: one running on the conventional internal combustion engine modified slightly
for hydrogen fuel, and the other using an electric motor, whose electric energy is supplied
from fuel cells on board. Metal hydride hydrogen vessels or liquefied hydrogen cryogenic
vessels can be used for fuel storage. The metal hydride must be as light as possible, and the
waste cold evolving from the cryogenic vessels could be used for air conditioning and/or for
refrigeration.
At present, the possibilities of nuclear fusion reactors are being researched. However, even if
a practically stable power output is attained, there remain the problems of the heat-resisting
materials that compose the reactor, the energy conversion system at extremely high
temperatures, and the associated safety problems, which have not yet been resolved.
However, it can safely be said that hydrogen production systems using direct decomposition
of water at the temperatures as high as T* = 4125 K will certainly be introduced in nuclear-
fusion energy systems. The critical temperature T* is given by the equation:
T* = E / (S So) (4)
Where E is the energy needed to split a water molecule into two hydrogen atoms and one
oxygen atom, S and So are the entropies at T = T* and at ambient temperature, respectively.
1.4. Renewable Energy Systems
1.4.1. General Survey
1.4.1.1. Classification of Natural Energies: Natural energy is sometimes called "renewable
energy," because the lifetimes of these energy resources are more than 10 billion years.
"Natural energy" signifies the energy that drives, or activates natural phenomena. We can
classify natural energies into three categories:
Solar energy, which drives more than 99.9 percent of the natural
phenomena on the earths surface.
Earths internal energy, which comes from the high temperature
crust and is carried to the surface by underground water. The first
geothermal power plant was established in 1904, in Italy.
Tidal energy derived from the lunar gravitational force exerted on
the oceans. Use of the energy of ocean tides has a long history,
since it was first harnessed in 1960 in France.
1.4.1.2. Amount of Resources
Solar Energy: The nuclear fusion reactions of pairs of protons and neutrons into a helium
atom in the sun yield a huge amount of energy, which is estimated at 3.47 T of T kW. This
value is comparable to the revolving kinetic energy of the moon around the earth. Of this huge
amount of energy, only 50 p (pico) is irradiated onto the earth's surface. The useful amount of
solar energy on the earth is 40 T kW, which is more than ten thousands times of the energy
consumed by human beings. Both photon and heat energies are available, but the total output
wattage of solar cells, the most advantageous use of direct solar photon, has very small
amount, e.g., only 65 GW were produced in 1998. Yet it is fast growing presently.
The top 8 cumulative capacities of solar cells are as of the end of 2002 is (IEA/PUPS)

Country MW (%)

(i) Japan: 636.8 (48.5)

(ii) Germany: 277.3 (21.1)

(iii) U.S.A.: 212.2 (16.2)

(iv) Australia: 39.1 (3.0)

(v) NL: 26.3 (2.0)

(vi) Italy 22.0 (1.7)

(vii) Switzerland: 19.5 (1.5)

(viii) France: 17.2 (1.3)

Hydro Power Energy: Rainfall is gathered in dams (mountain dams and river dams) and
converted to electric energy when the water flows down from them. It is estimated that the
total amount of the rainfall on the earths surface is, on average, 25.13 T t per year. If this
amount of water falls from a height of 1 km, then a kinetic energy of 1,062 P J is given to the
earths surface every year. The worlds reserve of hydropower for both types of power
generating dam systems are estimated to be about 2 TW, only about 10 to 15 percent of which
have yet been developed.
Wind Energy: Most of sunshine is absorbed in the atmosphere and is converted to heat . The
temperatures are not uniform, so that the air streams occur to give rise of wind blowing. Thus,
large part of solar energy falling the earth converted to wind energy. The total amount of the
wind energies on the earth's surface are huge, however it is distributed so widely that the
energy density is not large, except for hurricanes, typhoons, and tornados. The wind energy is
not always available (intermittent) and has moderate density.
According to fluid dynamics, the conversion of wind energy by windmills to useful energy is
propotional to the cube of wind speed and the squire of the wheel diameter of windmill.
Top 8 cumulative installed capacities as of the end of 2005 are (Global Wind Energy
Council):

Country MW (%)

(i) Germany 18,428 MW (31 )

(ii) Spain 10,027 (16.9)

(iii) U.S.A. 9,149 (15.4)

(iv) India: 4,430 (7.5)

(v) Denmark: 3,122 (5.3)

(vi) Italy: 1,717 (2.9)

(vii) U.K. 1,353 (2.3 )

(viii) China 1,260 (2.1)

The total amount of output wattages in the world was ca. 5,2000MW. This capacity is
equivalent to that of more than 80 conventional nuclear power plants, but the electric energy
generated per year is less than that of a few nuclear plants, because of the intermittent
operation of the wind power stations. However, it is obvious that wind power stations can
compete with nuclaer plants in countries where winds are strong.
Ocean Energy: This can be divided into four kinds: lunar tidal energy, wave energy, ocean
thermal energy, and ocean current energy.
Lunar tidal energy. The periodical movements of the ocean caused by the lunar gravitational
force are known as tides or tidal phenomena. The difference between the sea levels at ebb tide
and high tide varies from coast to coast. Although there are huge amounts of tide energy
resources, the only practical power station that has yet been built is the Rance power plant in
France, where the largest head is 13.5 m and the maximum difference comes every 6 hours
and 12 minutes. This station was installed in 1966, and generates 548 GWh of electric power
every year. There are many suitable sites in Canada, Northern Europe, and Northern Russia.
However, the investment cost is so high that no country has undertaken to construct a new
tidal power station.
Wave energy. The energy density of ocean waves can reach 1 MW/m of the coastline, and is
proportional to the square of the wave height. The merit of wave energy is that the density of
water is about 800 times greater than that of air. On the other hand, the intermittence and
strength variations are so large that the economical installation of power plants is very
difficult.
Ocean thermal energy. There are two kinds of ocean currents, one being hot on the ocean
surface, and the other cold in the deep sea. A heat medium gas such as ammonia and CFC
(chlorofluorocarbon) can be cooled to a liquid state by deep-seawater at a temperature of 510
C; the liquid is then vaporized by the surface seawaters at temperatures of 15 to 25 C. The
resulting vapor pressure is used to drive a gas turbine. This system is called OTEC (Ocean
Thermal Energy Conversion). OTEC has two drawbacks: one is that the thermal efficiency is
very small (as little as 7 percent); the other is that the amount of water that must be pumped is
huge.
It must be mentioned that there are difficulties in transmitting generated electrical power, so
that the power could be used to generate hydrogen gas by electrolysis, with storage at the
plant site. This system is called OTEC-Hydrogen System.
Ocean current energy. It would be necessary to build a huge installation to convert ocean
current to an energy carrier. There are currently no large-scale experiments, and we have
rather low scientific expectations of the practicability of this energy resource.
Geothermal Energy: Geothermal resources are abundant and estimated to be 400 E J. We
currently use a capacity of more than 5 G W, and some 100 electric power plants have been
installed. Suitable sites for geothermal power plants are along volcanic zones, where magma
comes up near the earths surface. These mountainous regions have fine landscapes and are
often designated as National Parks, so that development is almost impossible. It should be
noted that pipeline installation for hydrogen transport also faces many difficulties, so a
"geothermalhydrogen energy system" has many hurdles to overcome.
1.4.2. Feasibilities of Renewable EnergyHydrogen Systems
We have mentioned the possibilities of natural energyhydrogen systems. Although there exist
no large artificial hydrogen systems combining with natural energy, we know that
innumerable natural micro-solar hydrogen energy systems are working on the earths surface.
Photosynthesis has generated about 1220 E g of oxygen in total since green plants first
appeared on the earths surface. Photosynthesis has been absolutely fundamental to every
living thing on earth. We shall investigate whether any large artificial system similar to
photosynthesis is feasible.
1.4.2.1. Preliminary Requirements for Hydrogen Energy Systems: The conventional
assumption is that very large land areas must be progressively dedicated to the solar energy
system if, in fact, we are to make major use of solar energy. However, much of the land area
of the world is simply not suitable for solar energy power installations, because of climate,
terrain, and other land-use commitments. For the more promising regions, typically the semi-
tropical and tropical arid areas such as the great Sahara in Africa and the US Southwest
region, it is not yet clear that the land use will meet the approval of governments, local
citizens, conservationists, and environmentalists. These areas may to be given over to solar
cell stations if the conditions are satisfied.
The most significant point to be observed is quite fundamental. Most high-energy-use
industrialized countries have little or no sizable, favorably insulated region within their
national boundaries.
Another condition for hydrogen energy systems is that the system needs a great amount of
hydrogen, which can be used as an alternative to part of the secondary energies in the relevant
industries. Therefore, very large amounts of hydrogen would have to be produced by solar-
hydrogen energy systems, so that the scale of facility and the sunlit areas needed are large.
Each natural energy system has its appropriate site: the wind power system is suited to windy,
dry plateaus, dam power systems to rainy mountain valleys, geothermal plants to the
geothermal zones, solar-cell power stations to deserts. Where is the proper site for the
hydrogen energy system?
1.4.2.2. World Energy Network Systems: The Japanese government launched a major
project called WE-NET (World Energy Network) in 1993. This is based upon the idea of
importing electrolytic hydrogen generated in the countries blessed with abundant hydraulic
power such as Canada, Brazil, and China. Hydrogen could be transported in supertankers
carrying liquefied hydrogen or chemical materials such as methanol (CH4O), ammonia (NH3),
and cyclohexane (C6H12). These materials can be used not only as energy sources but also as
chemical agents. The relevant technologies have been extensively studied in the WE-NET
project.
A similar project named EURO-QUEBEC had already been set up, in 1989. This was a joint
project of Europe and the Canadian province of Quebec, but the key technologies are the
same as those for WE-NET.
1.4.2.3. Ocean Raft Systems for Hydrogen Energy: Characteristic "maximum insolation"
isopleths congregate for various months of the year in a Central Pacific region with an area of
about 0.5 M km2, centered on 13 W and 8 S. Large amounts of intense sunlight fall onto the
surface of this region, so very few living things exist because even plankton cannot survive;
that is to say, this area is like "an ocean desert."
A clear advantage of ocean basing is the ready availability of an unlimited low temperature
source of water for cooling purposes. If it is also possible to generate high temperatures by
concentrating solar radiation, electric power generation can be achieved.
The first Plan for an Ocean Raft System for Hydrogen Energy (PORSHE) had its origins in
this idea. Feasibility studies were undertaken by W. J. D. Escher and T. Ohta, and by T. Ohtas
group, beginning in 1974. The first requirement is to get high temperature heat sources using
solar collectors based on floating rafts; the heat can then be used to operate heat engine to
generate electric power. Thus one can generate electrolytic hydrogen. The principle is quite
simple, but there are many problems, such as stability of raft systems, control of solar
collectors, desalination of seawater, and transportation of hydrogen. The feasibility study has
been completed, and the conclusion is that the hydrogen fuel generated in this way is more
than twenty times as expensive as methane, if evaluated on a per unit energy basis.
The second version of the PORSHE project utilizes solar cells, and the structure is much
simpler than the first version. The hydrogen fuel produced by this raft system is between
twelve and eighteen times more expensive than methane. The cost is mainly due to the rafts
and solar cells, so that the price of solar-hydrogen could be competitive with methane fuel if
the rafts were multipurpose and the price of the solar cells could be reduced. In addition,
photo-bioproduction of hydrogen, which has been studied since 1942, could be one element of
PORSHE.

2. Proposed Systems and the Elementary Technologies

2.1. Combined Energy Systems of Electric Power with Hydrogen
2.1.1. Primary Energies
The simplest energy system that has been proposed (by T. Ohta in 1973) is shown in Figure 5.
Many kinds of energy resources are used to produce not only electric power but also
hydrogen. Natural energy sources have low energy densities and cannot easily generate high
temperature heat. Therefore they are applied either for electric power generation (by solar
cells) or for hydrogen evolution (by biological methods). In contrast, nuclear energy is able to
generate temperatures so high that multistage energy conversions in series are possible. For
example, the temperatures higher than 1,000 C are applied to split water, and the waste heat,
with temperatures lower than 300 C, is used to drive a steam turbine for generating electric
power. Such systems as this are called "co-generation," and are very popular in supplying
both steam and electricity from the power facilities of buildings, and in the combined cycles
of gas and steam turbines in LNG thermal plants. Co-generation and combined cycle systems
need more capital investment, but can save energy resources.
 Figure 5. Co-generation energy system
2.1.2. Secondary Energies
Electric power and hydrogen are secondary energies in the proposed system. Each of these
can very efficiently be converted to the other. Electric power can produce hydrogen by
electrolysis, a long-standing and well-developed technology. Electric power generation from
hydrogen is also possible by the use of fuel cells, which have been developed recently. These
two conversion systems are especially important for energy systems and will be described
further in later sections.
There are also many other important technologiesfor example, metal hydrides for hydrogen
storage and heat pumping, liquid hydrogen for hydrogen storage and transportationsome of
which will be introduced later.
2.1.3. Tertiary Energy sSystems (Utilization Systems)
One of the aims of introducing hydrogen assisted electric power systems is to save energy,
and savings can be achieved in the utilization systems as well. In the proposed system, electric
power is to provided to industries and facilities where no alternative to electric power is
available, such as communication systems, computer systems, illumination system, TV, radio.
Hydrogen is to be supplied to various chemical plants as a chemical agent, to semiconductor-
refining plants, to city gas systems for mixing with other fuels, vehicle fuel, and so on.
When electric power is in surplus (in off-peak times), hydrogen can be evolved by
electrolysis; when electric power is required (in peak time), hydrogen is converted to electric
power by fuel cells. Thus the proposed energy system can be very flexible.
2.2. Hydrogen Production from Water
The most important thing in hydrogen energy systems is how to generate economically large
amounts of hydrogen from water using renewable energies. Small-scale experiments on
innovative technologies have been conducted and attained good results, and pilot plants have
been operated in some cases. However, there are no practical working plants yet. On the other
hand, the traditional technologies are still actively employed.
Outlines of both technologies will briefly be reviewed below.
2.2.1. Thermodynamics of Water-Splitting and Sources for Free Energies
The total energy (enthalpy) E of a water splitting system is composed of the Gibbs free
energy G and the thermal energy Q and expressed by:
E = G + Q with Q = TS, (5)
which is nothing but Equation (1), with the thermal energy Q expressed by the entropy S
multiplied by the absolute temperature T. If we want to split water in a liquid state into a
gaseous state of hydrogen and oxygen under the condition that the temperatures and pressures
of the initial and final states are the same, we have to have the increment of total energy E,
which is composed of the free energy increment G and that of thermal energy Q:
E = G + Q with Q = T (S So) (6)
where S and So are the entropies at the final and the initial states of the system, respectively.
Two important facts should be noticed about Equations (5) and (6). The first is that the
sources of free energy are:
electrical energy
chemical energy
photon energy.
Any of these can activate the binding electrons of water molecules and separate hydrogen and
oxygen. Among these three sources, electric energy can be considered as unstable in the
natural world, chemical energy is stored in fossil fuels, while photon energy is plentifully
available in sunlight. Therefore, it seems reasonable to utilize solar photon energy to split
water, just as nature uses it in the photosynthesis of plants.
The second fact is that if higher temperatures are available, then less free energy is needed.
This is the fundamental basis of high temperature water electrolysis and thermo-chemical
water splitting.
The numerical values for the thermodynamic parameters in Equation (6) are,
E = 285.57 kJ / mol, G = 244.82 / mol, S = 149.2 / mol (7)
The initial and the final states are assumed to be the normal state, namely, T = 298.15 K and
the pressure = 101.3251 kPa. These values show that more than 85 percent of the energy
needed to split water at normal state is due to free energy; this is the reason why electrolysis
has been the best-known method of producing hydrogen from water.
2.2.2. Diagram of Water-Splitting and Direct Thermal Decomposition
Figure 6 shows the diagram of water splitting by plotting the total energy (enthalpy) E needed
against the absolute temperature T. E is positive in the upper half of the figure, and the water
molecule is in the split gaseous state, H2 and (1/2) O2, on the upper part of the oblique line
that passes the point where T = 0. E is negative in the lower half space, and the water is in a
stable liquid state. The distance between the two oblique lines is E, the necessary energy to
split water, of which G and Q are the free energy and thermal energy, respectively. At the
characteristic temperature T*, which is defined by Equation (4), the lower oblique line crosses
the temperature axis, so that no free energy is needed and all the energy to split water is
provided by thermal energy. According to the numerical values shown in Equation (7), T* is
calculated to be 4,125 K. This temperature is too high to be realized by normal fuel
combustion, but can be realized in solar-collector systems using Fresnels lens.

Figure 6. Enthalpy (total energy) vs. temperature curves for water splitting
Note: Total energy needed to split water is given by E = G0 + Q0 = Qc
Water vapor at such high temperatures is a mixture of hydrogen, oxygen, and hydroxide-
molecular gases. In addition it contains the atomic and ionic forms of these components. It is
possible, in principle, to get only hydrogen by separating hydrogen from the mixture with the
use of a palladium membrane. However, operations at such high temperatures are difficult to
achieve, and hence direct thermal decomposition of water will not be feasible.
Strictly speaking, the two oblique lines in Figure 6 are not straight lines, because the entropy
is weakly dependent on temperature. However, the analysis described above is a good
approximation.
2.2.3. Principle of Thermochemical Decomposition
It is readily understood from Figure 6 that less free energy is required at higher temperatures.
Therefore, two approaches are possible: electrolysis at high temperatures, or a combination of
chemical energy (a kind of free energy) with thermal energy. The latter is a new method of
water splitting and has been studied since 1970s.
Let us consider, for example, one set of three chemical equations:
(i) X + Y + H2O = XH2 + YO,
(ii) XH2 = X + H2, (8)
(iii) YO = Y + (1/2) O2,
Where X is an oxidizing agent and Y is a reducing agent. The key reaction is the first one in
Equation (8), which splits H2O into XH2 and YO. This means that chemical energy provides
most of the necessary free energy. The remaining two reactions can be advanced by thermal
energy. It is obvious, in the set of three reactions of Equation (8), that the catalysts X and Y are
not consumed, but H2O is split into H2 and O2. Hence this method is called "Thermo-chemical
Water Decomposition." Most of the concrete cycles are operated at temperature ranges lower
than 1,000 C, which is a much higher temperature than that of thermal plants for electric
power generation. The merit is that no electric energy is required. However, if one of the
reactions in Equation (8) is readily achieved by electrolysis (with less electric energy that that
used by direct electrolysis), then the hybrid cycle of thermo-chemical process with
electrolysis becomes more feasible.
Thermo-chemical decomposition technology is being challenged by high temperature
electrolysis combined with an electricity generator combined with high efficiency turbines
(the input temperature of modern gas turbine is as high as 1,300 C, so that the efficiency
becomes 40 percent or more). Therefore the efficiency of the thermo-chemical cycle needs to
be more than 40 percent, which seems to be difficult to attain.
2.2.4. Electrolysis
Electrolytic production of hydrogen and oxygen from water is a traditional technology that
has been known since the eighteenth century. Faradays law of electrolysis was discovered in
1933. We shall review the development of essential points for the traditional as well as
innovative water-electrolysis below.
2.2.4.1. Principle of Electrolysis and Traditional Technology: When two electrodes are
inserted into a glass vessel, containing a solution of potassium hydroxide (KOH) or dilute
sulfuric acid (H2SO4), hydrogen and oxygen evolve at the cathode and anode respectively,
when a direct electric current is applied.
Figure 7 shows a schematic diagram of this electrolyzer. The notations A, C, and S represent
the anode, cathode, and separation membrane respectively. In order to prevent the evolved
gases from mixing, a membrane is installed between A and C. When DC power is applied, the
reaction at the cathode is 2OH = H2O + 2e + (1/2) O2, and at the anode 2K+ + 2H2O + 2e- =
2KOH + H2 occurs, so that oxygen and hydrogen evolve.
 Figure 7. Schematic diagram for water electrolysis
Note: A, C, and S are cathode, anode, and separating membrane, respectively.
The required electric energy is dG of Equation (6), which is expressed by:
G = qV = Ivt (9)
The notations q, V, I, and t represent electric charge, applied voltage, electric current density,
and the applied time of electric current density respectively. The relationship: q = It holds.
The applied voltage is of two parts:
V = Vo +V* (10)
Where Vo = 1.23 V is the theoretically estimated voltage, and V* is an excess value called
"over voltage," which depends on temperature, current density, and the type of electrodes.
Every possible step is taken to reduce V*. The values of over voltage in conventional
electrolyzers range from 1 to 0.5 V, so that the electrolytic voltage must be at least 2 V. The
energy efficiency is quite high, reaching more than 60 percent.
According to Equation (6), additional heat energy must be supplied to the electrolyzer in order
to save electric energy. Electrolysis at high temperature and under high pressure has been
investigated since the 1970s. The important point is that it is not necessary to provide
additional external thermal energy, because the Joulian heating of RI2, where R and I are the
resistance of the electrolyte and the current density respectively, increases the temperature of
the electrolysis. However, a heat insulating wrapping around the electrolyzer is necessary. In
addition the high temperatures cause high vapor pressures, so that a strong container structure
is also needed.
Assuming that a conventional electrolyzer has 60 percent efficiency at 80 C and 101.37 kPa
(=1 atmospheric pressure), an increase of the temperature to 100 C and of pressure to 2.075
MPa (= 20 atmospheric pressure) results in about 70 percent efficiency. Examples of the
former and the latter are the elctrolyzers of NORSK Hydro and of Julichs KFA, respectively.
2.2.4.2. Solid Polymer Electrolyte (SPE): The most advanced electrolyser in operation is
equipped with a solid polymer electrolyte, called "Nafion," which has been developed by Du
Pont. No liquid electrolyte such as KOH or H2SO4 is needed; the protons generated can pass
through the solid polymer electrolyte. Note that a hydroxide ion is the charge carrier in the
conventional electrolyte.
Figure 8 shows the polymer structure of Nafion. The proton, which is loosely bound to SO3-
anion, can move through the polymer.

Figure 8. Structure of Nafion

Figure 9 shows a schematic diagram of SPE. The notations A, B, C, and F indicate anode,
battery, cathode and filter, respectively. The water is ionized and is composed of OH and H+,
and when DC electric power is applied, the following reactions occur:
Cathode reaction: 2H+ + 2e = H2
Anode reaction: 2OH = H2O + (1/2)O2 + 2e
The protons generated at the anode A move to the cathode C through SPE, since C has a
positive charge, and combine with the electrons from the electric circuit to generate hydrogen
molecules. The hydroxide decomposes into water, oxygen, and electrons. Electrons move to
the anode through the electric circuit.
The SPE has very strong acidity, so the electrode materials must be acid resistant; carbonates
of Ta, Zr, Mo, and Ti are used. The energy efficiency is more than 85 percent under the
conditions of T = 423 K and I = 10000 A/m2.
 Figure 9. Schematic diagram of a solid polymer electrolyte
Note: A, B, C, and F represent anode, battery, cathode, and filter, respectively
2.2.4.3. Solar Cell-Electrolysis Systems: A simple but reasonably effective hydrogen
evolution system is to combine the DC output of solar cells with an electrolyser. DC voltage
from a solar cell is about 1 V. Hence, two solar cells in series could supply about 2V electric
power to the electrolysis system, and this voltage is adequate for water electrolysis.
Many use of solar cell-electrolysis systems (SCES). For example, SWB (SolarWasserstoff
Bayern GmbH) in Germany has built a facility to produce hydrogen at a total rate of 47
Nm3/h, using mono-crystalline and polycrystalline Si solar cell panels to generate 135 kW and
131 kW respectively. The former and the latter are supplied to the conventional electrolyser
with 111 kW and 100 kW, respectively.
If the efficiency of solar cells is 10 percent, the system efficiency of SCES is estimated to be
about 6 percent, which is about the same value as the maximum efficiency of plant
photosynthesis.
2.3. Photo Electrochemical Systems
Professors K. Honda and A. Fujishima discovered an innovative method of hydrogen
generation, in 1969, which will be introduced, in detail, by Fujishima in a separate article of
EOLSS on-line. A brief introduction is presented here.
The SCES is composed of two subsystems:
i) [semiconductor pn junction] + photons = electric power
ii) electric power + water-electrolysis = hydrogen + oxygen.
The unification of these two systems may be possible by:
[Semiconductor electrode vs. electrolyte junction] + water = hydrogen and oxygen.
This discovery by Honda and Fujishima is known as a Photo Electrochemical System (PECS).
Figure 10 shows a schematic diagram of a PECS, where E, M, S, and R represent the metal
electrode, separation membrane, semiconductor electrode (photo electrode), and external
circuit respectively. When an efficient photon beam irradiates S, two pairs of electrons and
positive holes (h+) are created, and then the following processes take place:
Photo electrode reaction: 2h+ + H2O = 2H+ + H2O +(1/2) O2
Metal electrode reaction: 2e + 2H+ = H2
The protons generated at the photo electrode go to the metal electrode, and the electrons move
to the counter electrode, and combine with each other to produce hydrogen.

Figure 10. Schematic diagram of a photo electrochemical system

There are very limited numbers of true photo semiconductors, as they must satisfy certain
strict conditions. They must be stable in the electrolyte under ultraviolet irradiation, and the
width of forbidden band of semiconductor must match the solar spectrum, the potential
erecting effect at the interface between semiconductor and electrolyte must be large, and so
on. The semiconductors TiO2 (which was used by the discoverers), SrTiO3, Fe2O3, and MOS2,
among others, have been under investigation.
Although PECS is an innovate system, the efficiency cannot be greater than that of solar cell-
electrolysis system. This is because these devices, that work with liquids, generally have more
difficulties than systems where the liquid and the solid parts are separated.
2.3.1. Photochemical Cycle Systems
If the key reaction (i) of Equation (8) is produced by photon energy, the water splitting cycle
is called a photochemical cycle system. One of the simplest photochemical cycle systems
proposed by a MIT group headed by Professor L. Heidt in the 1950sis the Ce4+/Ce3+ redox
system. The sensitized oxidation of water by the Ce3+ ion is carried out under irradiation of
light with wavelength shorter than 253.7 nm, i.e.:
(i) Ce4+ + (1/2) H2O = Ce3+ + (1/4)O2 + H+,
(ii) Ce3+ + H2O = Ce4+ + (1/2)H2 + OH (11)
where both of the reactions advance by ultraviolet photons. However, the efficiency is very
small (lower than 1 percent) because the back reactions associated with Equations (11) (i) and
(ii) cancel the effective density of the useful ions. A similar photochemical cycle system using
Fe2+ and Fe3+ was proposed by a Yokohama National University group in 1973. However, the
efficiency could hardly be improved, unless the catalyst, which initiates the back reaction, is
not applied.
A considerable number of studies have been carried out on photochemical cycle systems using
metal-organic complexes. Such a system is shown schematically in Figure 11, and illustrates
the use of coupled redox catalysts such as ruthenium dioxide, RuO2, and colloidal platinum
Pt. Incident light with wave lengths longer than 300 nm is absorbed by the sensitized Ru
(bipy)2+/3 (where bipy = bipyridine, a dye). Then the sensitizer transfers electrons to methyl
viologen MV2+. The products are Ru (bipy)3+/3 and MV+, which tend to revert to their original
states in a back reaction. However, the back reaction is suppressed in the presence of the
catalysts RuO2 and Pt. Hydrogen production is due to the following two reactions:
(i) nMV+ + Pt = nMV2+ + Ptn+,
(ii) Ptn+ + nH+ = Pt nH (abs) = Pt + mH2 (12)
Ru (bipy) is reduced on the surface of RuO2 particles, and oxygen evolves by this process.

Figure 11. Photochemical cycle system using metal-organic complexes

2.3.2. Mechano-Catalytic Water-Splitting
Dr K. Domens group in the Tokyo Institute of Technology discovered in 1998 that
simultaneous H2 and O2 evolution can be achieved by simply stirring a common metal-oxide
powder such as Cu2O, NiO, Co3O4, or Fe3O4 in distilled water at room temperature. Rubbing
the powder with a stirring rod in water resulted in the catalytic decomposition of water, a
process known as mechano-catalysis.
2.4. Fuel Cells
2.4.1. Principle
A fuel cell is an electric power generator, in which the stored chemical energy of fuel is
converted directly to electric energy. "Directly" means not via a heat engine. Fuel cells do not
go through the thermal regime and the conversion from fuel to electric energy is not subject to
the limit of Carnots rule of efficiency, which states that the maximum thermal efficiency of a
heat engine is given by (Th-Tl)Th, where Th and Tl are the higher and lower temperatures,
respectively. On the contrary, the efficiency of a fuel cell becomes higher as the operating
temperature decreases. The electrons of fuel are converted directly to oxygen (air) via an
external circuit. Therefore, entropy production is small and the amount of available energy is
much greater. For these reasons, considerable interest has been generated and much effort has
been invested in the development of this system.
2.4.2. HydrogenOxygen (Air) Fuel Cells
The hydrogenoxygen (air) fuel cell is a typical and practical example of fuel cells. The cell is
composed of a cathode, anode, and electrolyte (usually, potassium hydroxide, KOH, or
phosphoric acid, H3PO4). Hydrogen and oxygen (air) are fed to the cathode and the anode,
respectively.
Figure 12 shows a schematic diagram of a hydrogenoxygen fuel cell, where A, C, E, and R
represent the anode, cathode, electrolyte, and external circuit respectively. The following
reactions occur:
Cathode reaction: (Pt) + = 2H+ + 2e,
with 2OH + 2H+ = 2H2O
Anode reaction: 2e + (1/2) O2 + H2O = 2OH
Hydrogen fed into the cathode is split into protons and electrons by the catalytic reaction of Pt
embedded in cathode. The electrons go to the cathode via an external circuit (an electric
current is generated) and the cathode reaction advances. The product of hydroxide moves in
the electrolyte toward the cathode, where the second reaction occurs. We can get water in
addition to electric power, as the chemical equations show.
 Figure 12. Schematic diagram of hydrogen-oxygen fuel cell
Note: A, C, E, and R represent anode, cathode, electrolyte, and resistance, respectively.
If it is possible to find a good catalyst, any fuel can be fed to the cathode of a fuel cell. The
open circuit voltage differs according to the fuel. Some examples of theoretical values are as
follows: hydrogen 1.23 V, methane 1.2 V, propane 1.09 V, carbon monoxide 1.33 V, and
gasoline 1.21 V.
2.4.3. Proton Exchange Membrane (PEM) Fuel Cells
The principle of a PEM fuel cell is the reverse of SPE. A schematic diagram of a PEM cell is
shown in Figure 13 Its heart comprises a solid polymer electrolyte (S) with, typically, a 0.1
mm thick proton-conducting membrane. The film is coated with a metal catalyst (M, e.g. Pt)
and an electrode made of gas-permeable graphite-paper (A and C). Gas channels are milled on
both sides of bipolar graphite-plates. H2 and O2 are fed into the anode side and the cathode
side respectively.
 Figure 13. A schematic diagram of a PEM cell
Then the reaction, H2 = 2H+ + 2e, is initiated by the catalyst at the anode side, of which H+
goes through the permeable film, so that the anode (A) acquires a negative charge (e), which
is provided to the external load (R). The reaction, 2H+ + 2e + (1/2) O2 = H2O occurs at the
cathode (C), where the electrons are provided from the load (R). Thus we obtain, first, electric
power, second, heat generated by the proton conduction, and third, water (at about 80 C). A
single cell generates about 1V with the current density about 1A/cm 2. Serial and parallel
connections increase the output voltage and the current density respectively, so that an
adequate stack can be designed. A practical bus named NEBUS (H: 2.5 m, W: 3.5 m, L: 12 m,
14 t)produced in 1998 by Daimler Benzhas 10 PEMFC stacks, each with an output of 72
V and 25 kW.
2.4.4. Next and Third Generations of Fuel Cells
The next generation of fuel cells works without noble catalysts such as Pt or noble metal
alloys such as AgNi alloy. An example of this type is the molten carbonate fuel cell (MCFC),
whose fuel could be carbon monoxide, hydrogen, coal gas, or other substances. The electrode
is LiC and the operating temperature is about 650 C. The advantage is that there are plenty of
carbon resources (coal) and there is no need for pure noble metals.
The third generation of fuel cell is the solid electrolyte fuel cell (SOEC). Ceramics of
zirconium are used as the electrolyte and the fuel could be carbon monoxide, hydrogen, coal
gas, and so on. It works at temperatures as high as 1,000 C.
The characteristic features of fuel cells are:
silent operation
no pollutants if hydrogen is the fuel
on-site generation
 suitable for vehicles (especially for electric cars)
cogeneration of electricity and heat
very high efficiency.
Fuel cells are, undoubtedly, at the frontiers of energy conversion.

3. Metal Hydrides and Hydrogen

3.1. Properties of Metal Hydrides
Some metals and alloys can absorb as much as 700 to 1,000 times their own volume of
hydrogen atoms in their interior body. This phenomenon was discovered by T. Graham (1805
1869) more than a century ago.
Metals or alloys (M) that absorb hydrogen and dissociate it reversibly are called "metal
hydrides" (MH). The reaction of a M to MH is:
H2 + 2M = 2MH + Q (13)
Where Q is the reaction heatabout 1720 kJ/mol.H2, in most cases.
In order to discuss the characteristics of metal hydrides, three thermodynamic parameters are
necessary. The first is the numerical ratio of hydrogen atoms to metal atoms, which is denoted
by C at constant temperature; the second and third are the pressure (P) and the temperature
(T). The pressure Pi charging hydrogen into the metal and the pressure Pd for discharging
hydrogen from the metal are not equal to each other at the same temperature; Pi is higher than
Pd. Three parameters P, C, and T determine the characteristic of a metal hydride and this is
called the "PCT-curve."
Figure 14 shows the PCT-curves for LaNi5Hx, a representative metal hydride. The dissociation
pressure is sensitive to temperature, and hysteresis phenomena are appreciable. The upper and
lower curves correspond to the charging and discharging cases, respectively.
 Figure 14. PCT-curves for LaNi5Hx
We note that the P vs. x curves are flat, except for the initial and final parts, which indicates
that hydrogen gas is effectively stored under constant pressure. Metal hydride systems having
a flat pressure characteristic are classified into three categories:
i) Titaniumiron alloys (TiFe: Pd = 10000 hPa, at T = 50 C, Q =
5.5 kcal/mol)
ii) Lanthanumnickel alloys (LaNi: Pd = 4000 hPa, at T = 50 C, Q
= 7.2 kcal/mol)
iii) Magnesiumnickel alloys (Mg2Ni: Pd = 1000 hPa, at T = 250
C, Q = 15.4 kcal/mol)
More than one hundred metal hydrides have been manufactured in order to examine their
characteristics.
3.1.1. Graphite Nanofibers
Graphite nanofibers consist of very small graphite platelets, 30500 A in width, which are
stacked in a perfectly arranged conformation. It was reported in 1998 that such material is
capable of absorbing and retaining in excess of 2,000 N cm3 of hydrogen per atom of carbon
when the nanofibers are exposed to the gas at pressures of 12 MPa (120 atm) at 25 C, a value
that is one magnitude higher than that of conventional metal hydride hydrogen storage
systems.
However, it is not clear whether graphite nanofibers can replace metal hydrides or not,
because no mass production method for nanofibers has yet been devised.
3.2. Applications
3.2.1. Hydrogen Storage and Heat Storage
To store hydrogen in a metal hydride, a small value of Q in Equation (13) is first required
because cooling (for absorption) and warming (for desorption) need energy. Next, the flat
portion in the P vs. C plot at room temperature must be long enough to store hydrogen.
Finally, the metal hydride should be light enough to be carried by vehicles driven by hydrogen
fuel. FeTi alloy, one of the common metal hydrides, has a ratio of hydrogen weight to the total
weight of 1.86 percent, which is not so favorable as that of pressure vessels with the hydrogen
pressure 150 atm that have a hydrogen weight of 47.1 percent under 15.2 MPa (150 atm), but
storage in metal hydrides is much safer.
As shown in the reversible Equation (13) and Figure 14, the metal hydridemetal cycle can be
applied not only to store hydrogen and heat energy but also to store mechanical energy. When
heat energy is in surplus, it is used to drive out hydrogen from the metal hydride (which is
cooled) and the hydrogen is stored in another vessel (which may be another type of metal
hydride). When heat is needed, the hydrogen stored in the vessel is charged to the original
metal hydride, and thermal energy is generated. This is the principle of the long-term stable
storage of heat energy.
When the alloy absorbs hydrogen, this process can be regarded as storing mechanical energy,
because if the alloy is warmed up, high-pressure hydrogen gas evolves. This process is
utilized as a compressor and an actuator of robots.
3.2.2. Heat Pumps
Most air-conditioners use freon gas as a heat medium but, since freons are known to destroy
the ozone layer in the stratosphere, regulations limiting their use have been imposed in
industrialized countries. Alternative heat media and refrigeration systems are urgently
required.
Figure 15 shows a schematic diagram of metal hydride air-conditioning and heating
mechanisms. Metal hydride M1H is cooled by the lower room temperature and then more
capacity to absorb hydrogen from another metal hydride M2H. When absorbing hydrogen,
M1Htemperature rises, evolving reaction heat that is emitted from M1H into the room.
 Figure 15. Schematic diagram of metal hydride air-conditioning
Note: M1 and M2 are different kinds of metal alloy.
The refrigeration mechanism is similar (shown at the left hand side of the figure). Ambient
cold air cools M2H, which then has the capacity to absorb hydrogen from another metal
hydride M1H. As the M1H loses hydrogen, it absorbs heat from the room, which is thus
refrigerated. Some test heat pumps have been in operation in industrialized countries such as
Japan.

4. Safety
Like any other fuel or energy carrier, hydrogen poses risks if not properly handled and
controlled. The risks of hydrogen, therefore, must be considered in relation to common fuels
such as gasoline, propane, or natural gas. The specific physical characteristics of hydrogen are
quite different from those common fuels. Some of these properties make hydrogen potentially
less hazardous, while others could theoretically make it more dangerous in certain situations.
Since hydrogen has the smallest molecule, it has a greater tendency to escape through small
openings than do other liquid or gaseous fuels. Given such properties of hydrogen as density,
viscosity, and diffusion coefficient in air, the propensity of hydrogen to leak through holes or
joints of low pressure fuel lines may be only 1.26 to 2.8 times faster than a natural gas leak
through the same hole (and not 3.8 times faster as is frequently assumed when only the
diffusion coefficients are taken into account). Experiments have indicated that most leaks
from residential natural gas lines are laminar. Since natural gas has over three times the
energy density per unit volume, a natural gas leak would result in more energy release than a
hydrogen leak.
For very large leaks from high-pressure storage tanks, the leak rate is limited by sonic
velocity. Due to its higher sonic velocity (1,308 m/s), hydrogen would initially escape much
faster than natural gas (the sonic velocity of natural gas is 449 m/s). Again, since natural gas
has more than three times the energy density than hydrogen, a natural gas leak will always
contain more energy.
Some high-strength steels are prone to hydrogen embrittlement. Prolonged exposure to
hydrogen, particularly at high temperatures and pressures, can cause these steels to lose
strength, eventually leading to failure. However, many other construction, tank, and pipe
materials are not affected in this way so, given the proper choice of materials, hydrogen
embrittlement should not contribute to hydrogen safety risks.
If leaks should occur for whatever reason, hydrogen will disperse much faster than any other
fuel, thus reducing the hazard level. Hydrogen is both more buoyant and more diffusive than
gasoline, propane, or natural gas. Table 1 compares some properties and leak rates for
hydrogen and natural gas.

Table 1. Properties and leak rates of hydrogen and natural gas

Hydrogen Methane

Diffusion coefficient (cm2 /s) 0.61 0.16

Viscosity (.poise) 87.5 100

Density (kg/m3) 0.0838 0.651

Sonic velocity (m/s) 1,308 449

Laminar flow 1.23 1

Turbulent flow 2.83 1

Sonic flow 2.91 1

Table 1. Properties and leak rates of hydrogen and natural gas

A hydrogen/air mixture can burn in relatively wide volume ratios, between 4 and 75 percent
of hydrogen in air. The other fuels have much lower flammability ranges: natural gas 5.3 to 13
percent, propane 2.1 to 10 percent, and gasoline 1 to 7.8 percent. However, the range has little
practical value. In many actual leak situations the key parameter that determines if a leak
would ignite is the lower flammability limit, and hydrogens lower flammability limit is four
times higher than that of gasoline, 1.9 times higher than that of propane, and slightly lower
than that of natural gas.
Hydrogen has a very low ignition energy (0.02 mJ), about one order of magnitude lower than
other fuels. The ignition energy is a function of fuelair ratio, and for hydrogen it reaches a
maximum at about 25 to 30 percent. At the lower flammability limit hydrogens ignition
energy is comparable to that of natural gas.
Hydrogen has a flame velocity seven times faster than that of natural gas or gasoline. A
hydrogen flame would therefore be more likely to progress to a deflagration or even a
detonation than other fuels. However, the likelihood of a detonation depends in a complex
manner on the exact fuelair ratio, the temperature and particularly the geometry of the
confined space. Hydrogen detonation in the open atmosphere is highly unlikely.
The lower detonability fuelair ratio for hydrogen is 13 to 18 percent, which is twice that of
natural gas and twelve times higher than that of gasoline. Since the lower flammability limit is
4 percent, an explosion is possible only under the most unusual scenario; for example
hydrogen would first have to accumulate and reach a concentration of 13 percent in a closed
space without ignition, and only then would an ignition source have to be triggered
Should an explosion occur, hydrogen has the lowest explosive energy per unit of stored
energy in the fuel, and a given volume of hydrogen would have twenty-two times less
explosive energy than the same volume filled with gasoline vapor.
Hydrogen flame is nearly invisible, which could be dangerous because people in the vicinity
of a hydrogen flame may not even know there is a fire. This can be remedied by adding
chemicals that will provide the necessary luminosity. The low emissive power of hydrogen
flames means that nearby materials and people will be much less likely to catch fire and/or be
hurt by radiant heat transfer. The fumes and soot from gasoline fire pose a risk to anyone
inhaling the smoke, while hydrogen fires produce only water vapor (unless secondary
materials begin to burn).
Liquid hydrogen presents another set of safety issues, such as risk of cold burns, and the
increased duration of leaked cryogenic fuel. A large spill of liquid hydrogen has some of the
characteristics of a gasoline spill, but will dissipate much faster. Another potential danger is of
a violent explosion caused by the liquid boiling and expanding as vapor in the case of a
pressure relief valve failure.
In conclusion, hydrogen appears to poses risks of the same order of magnitude as other fuels.
In spite of public perception, in many ways hydrogen is actually a safer fuel than gasoline or
natural gas. As a matter of fact, hydrogen has a very good safety record, as a constituent of the
"town gas" widely used in Europe and the United States in the nineteenth and early twentieth
centuries, as a commercially used industrial gas, and as a fuel in space programs. There have
been accidents, but nothing that would characterize hydrogen as more dangerous than other
fuels.
One of the most notorious accidents involving hydrogen was the Hindenburg dirigible disaster
of 1937. However, hydrogen did not cause that accident, and the hydrogen fire did not directly
cause any casualties. The accident appears to have been caused by a discharge of static
electricity, and it was the balloons lining that caught fire first. The hydrogen with which the
 balloon was filled for buoyancy (instead of the helium specified in the original design) then
ignited, as any fuel is supposed to. However, the hydrogen flames went straight up and it did
not radiate heat, so the people in the gondola underneath the balloon were not burned or
suffocated. As a matter of fact, fifty-six survivors walked out of the gondola once it landed
after all the hydrogen and balloon structure had burned out. Therefore, even in a worst-case
scenario, hydrogen proved to be a safe fuel.
The safety aspects of fuels involve their toxicity on the one hand and their fire hazard
properties on the other. In addition to the toxicity of their combustion products, the fuels
themselves can be toxic. This toxicity increases as the carbon to hydrogen ratio rises.
Hydrogen and its main combustion product, water or water vapor, are nontoxic. However,
NOx, which can be produced by the flame combustion of hydrogen (as well as through the
combustion of fossil fuels), displays toxic effects.
Table 2 lists the characteristics of fuels related to fire hazards. Lower density makes a fuel
safe, since it increases the buoyancy that makes for speedy dispersal of fuel in case of a leak.
For the same reason, higher diffusion coefficients are helpful. Higher specific heat also causes
a fuel to be safer, since it slows down the temperature increases for a given heat input. Wider
ignition limits, lower ignition energies, and lower ignition temperatures make the fuels less
safe, as they increase the limits in which a fire could occur. Higher flame temperature, higher
explosion energy, and higher flame emissivity also make a fuel less safe, since its flames
would be more damaging.
Table 2. Characteristics related to fire hazard
Notes: * At normal temperature and pressure
** Theoretical maximum; actual 10 percent of theoretical

Table 2. Characteristics related to fire hazards

Gasolene Methane Hydrogen

Density* (kg/m3) 4.40 0.65 0.084

Diffusion coeff. in air (cm2/s) 0.05 0.16 0.610

Specific heat at const. pressure** (J/gK) 1.2 2.22 14.89

Ignition limits in air (vol. %) 1.07.6 5.315.0 4.075

Ignition energy in air (mJ) 0.24 0.29 0.02

Ignition temperature in air (C) 228471 540 585

Flame temperature in air (C) 2 197 1 875 2 045

Explosion energy (gTNT/kJ) 0.25 0.19 0.17

Flame emissivity (%) 3443 2533 17.25

Notes:
* At normal temperature and pressure.
** Theoretical maximum; actual 10 percent of theoretical.

Table 3 compares the safety of fuels. For each of toxic element and fire hazard characteristics,
it ranks the fuels from 1 to 3, 1 being the safest and 3 the least safe.

Table 3. Safety ranking of fuels.

Gasolene Methane Hydrogen

Toxicity of fuel 3 2 1

Toxicity of combustion
3 2 1
(Co, SOx, NOx, HC, PM)

Density 3 2 1

Diffusion coefficient 3 2 1

Specific heat 3 2 1

Ignition limit 1 2 3

Ignition energy 2 1 3

Ignition temperature 3 2 1

Flame temperature 3 1 2

Explosion energy 3 2 1

Flame emissivity 3 2 1

Totals 30 20 16
 Safety factor 0.53 0.80 1.00

Table 3. Safety ranking of fuels

These rankings have been totaled for each fuel in order to arrive at an overall ranking. The
total rankings have been pro-rated to obtain the safety factors, defined as the ratio of the total
ranking for hydrogen to that of a given fuel. It can be seen that hydrogen emerges as the safest
fuel, while gasoline is the least safe, with methane in between the two.

Related Chapters
Click Here To View The Related Chapters

Glossary
Biochemical hydrogen : Hydrogen production from biomass.
production
Biological hydrogen : Hydrogen production with use of living plants such as algae
production and bacteria.
Coal-oil mixture (COM) : Coal powder mixed with oil is an oil-saving fuel.
Direct water-splitting : Water vapor is split into hydrogen and oxygen at a very high
temperature (4,250 K).
FC : Fuel cell.
Hydrogen energy systems : Hydrogen made from water is a clean and undepletable fuel.
(HES) Hydrogen is also an indispensable chemical feedstock, so HES
will replace the petroleum energy system in the near future.
Hydrogen fueled vehicle : A vehicle whose engine can be driven by hydrogen fuel. The
engine can also be replaced by fuel cells.
Liquefied natural gas :Methane gas is liquefied at 111.8 K under the atmospheric
(LNG) pressure.
Liquefied petroleum gas : Ethane, propane, and n-butane are liquefied at 184.2 K, 273.1
(LPG) K, and 272.7 K, respectively.
Ocean-based hydrogen : Systems of hydrogen production from seawater using solar
production energy and/or the available onsite energy sources.
Ortho- and para- hydrogen : If the two directions of spin of the two component atoms in
hydrogen molecule are parallel, it is called ortho-hydrogen,
and if they are antiparallel, it is called para-hydrogen.
OTEC : Ocean thermal energy conversion.
Photo- chemical effect : The chemical reactions caused by photon irradiation.
(PCE)
Photo- electro-chemical : Some semiconductors irradiated by photons emit electrons
effect (PECE) and positive holes, and cause a chemical reaction.
Pluthermal (Plutonium use : The plutonium extracted from the used nuclear fuel (ash) can
in thermal neutron reactor) be applied to the fuel of high breeder reactor, and to the fuel of
thermal neutron reactor.
Proton exchange membrane : A film made of a solid polymer such as Nafion is proton
(PEM) conducting, and is applied, as an electrolyte, to a highly
efficient water electrolyzer and a fuel cell.
Solar hydrogen energy : Energy systems, of which the primary and secondary energies
systems are solar energy and hydrogen respectively.
Solid electrolyte fuel cell : Solid electrolyte such as ceramics of zirconium is applied to
(SOFC) fuel cell.
Solid polymer electrolysis : Fuel cell using PEM.
(SPE)
Therm-ochemical water : Both thermal and chemical energies are applied to split water.
splitting For example, if the chemical agents A and B are dissolved in
water, then AH2 and BO are produced. Water can be split by
decomposing these compounds by thermal energy, and no
agent is consumed.
List of Prefixes
(Prefixes are used in the text for the simplicity.)

exa E 1018 deci d 101

peta P 1015 centi c 102

tera T 1012 mili m 103

giga G 109 micro 106

mega M 106 nano n 109

kilo k 103 pico p 1012

hecto h 102 femto f 1015

deca da 10 atto a 1018

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Biographical Sketches
Tokio Ohta was born in 1925 in Japan. He studied at the Department of Physics, University of Kyoto obtaining
a Ph.D. in Solid State Physics. He has taught at the University of Kyoto, Portland State University of Oregon,
USA, and the University of Tokyo, and served as Dean of the Faculty of Engineering, Yokohama National
University (19858), and as the President of Yokohama National University (198894) He has been appointed as
Superintendent of the International Network University since 1999, a member of the Staff Committee of Science
and Technology to the Prime Minister (197494), and of the Staff Committee of the Minister of International
Trade and Industry (19949). He has published some 160 papers and sixty books on solid state physics and
energy systems. He has been elected as Vice President of the International Association for Hydrogen Energy, and
is the Founding Past President of the Hydrogen Energy Systems Society of Japan.

T. Nejat Veziroglu was born in 1924 in Istanbul, Turkey. He received an A.C.G.I. Degree in Mechanical
Engineering from the City and Guilds Institute of London, a B.Sc. in Mechanical Engineering from the
University of London, a D.I.C. in Advanced Studies from Imperial College, London, and a Ph.D. in Heat
Transfer from the University of London. He has served as Chair of the Department of Mechanical Engineering,
University of Miami (19715), and as Associate Dean of Engineering Research, University of Miami (19759);
he is presently the Director of the Clean Energy Research Institute, the University Miami. Dr Veziroglu has
published some 250 scientific reports and papers, edited 170 volumes of proceedings, and is the Editor-in-Chief
of the monthly scientific journal, the International Journal of Hydrogen Energy. He is the Founding President of
the International Association for Hydrogen Energy.

To cite this chapter

Tokio Ohta, T. Nejat Veziroglu, (2004/Rev.2006), ENERGY CARRIERS AND CONVERSION SYSTEMS
WITH EMPHASIS ON HYDROGEN, in ENERGY SCIENCES, ENGINEERING AND TECHNOLOGY
RESOURCES , [Ed. Willie O.K. Grabow], in Encyclopedia of Life Support Systems (EOLSS), Developed under
the Auspices of the UNESCO, Eolss Publishers, Oxford ,UK, [http://www.eolss.net] [Retrieved May 8, 2007]