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SCIENTIFIC REVIEWS

Can Water Splitting into Hydrogen as a Renewable Energy Source

Meet Humanity’s Energy Needs?
Advances in Photoelectrical and Electrocatalytic Methods for Water Splitting
Athanasios Valavanidis
Department of Chemistry, University of Athens,
University Campus Zografou, 15784 Athens, Greece
e-mail: valavanidis@chem.uoa.gr

ABSTRACT
The Sun is the primary and abundant form of energy in the Solar System, and the
fundamental factor in the development and survival of life systems on Earth. The human
civilization, in the primitive or modern form, was intrinsically connected with the
transformation of energy sources into useful forms of energy (fire, wind-powered machines,
mineral fuels for heat and energy, nuclear power, etc.) and the technological management
of storage, transport and use of energy for every aspect of human civilization. The excessive
use of non-renewable sources of mineral fuels in the last decades (coal, petroleum, natural
gas) caused a series of environmental pollution problems and especially the greenhouse
effect and climatic changes. Inevitably, scientists and technologists initiated many decades
ago the use of renewable energy sources which are environmentally friendly. Sunlight is by
far the most plentiful renewable energy resource, providing Earth with enough power to
meet all of humanity's needs several hundred times over. However, it is both diffuse and
intermittent, which presents problems regarding how best to harvest this energy and store it
for times when the sun is not shining.
Devices that use sunlight to split water into hydrogen and oxygen could be one solution to
these problems, because hydrogen is an excellent fuel. However, if such devices are to
become widely adopted, they must be cheap to produce and operate. Therefore, the
development of electrocatalysts for water splitting that comprise only inexpensive, earth-
abundant elements is critical. In this review, we included the most recent papers and
reviews on water splitting and the progress towards such electrocatalysts, with special
emphasis on how they might be incorporated into photoelectrocatalytic water-splitting
systems and the challenges that remain in developing these devices. Despite the intensive
research projects of the last decades and the promising technologies the development of
practical applications for splitting economically water and the production of hydrogen as a
renewable alternative fuel is lacking. The hydrogen can be stored and then oxidized to
release energy giving a carbon-neutral fuel production and consumption cycle.
www.chem-tox-ecotox.org/scientificreviews May 2017

Introduction
Historians on the development and evolution of human civilization agree that control,
storage and use of energy played a key role in last centuries on planet Earth. The
development of our modern civilization can be seen as especially dependent on energy and
many characteristics of human society (increased population, poverty, technological
advances, sustainable development, plentiful nutritious diet, transport) are supported by
available energy resources, especially electricity. This is the natural context of the
development of Homo sapiens, the most energy-using species the world has ever known.
Societal complexity, affluence and differences between developed and developing countries
are related to levels of energy consumption. Also, energy production and use remained for
the last centuries key factors in understanding the impact of human society on the Earth’s
environment (pollution), climate change (emissions of CO2 and other air pollutants) and the
direction of sustainable development within the limited fossil energy resources.1-4

Figure 1. Wind, running river water and wood have been sources of power generation for the
human civilization for more than 5000 years. Fossil fuels during the industrial revolution
replaced other forms of energy. Today, 70% of electricity in developed countries is produced
from fossil fuels (about 50% from coal, and 20% from natural gas).

Despite all the negative environmental consequences, the main energy sources (coal, oil,
natural gas, hydroelectric power, nuclear energy) are expected to continue growing as a
result of human civilization energy needs. But it is well known from past lesson, that
sustainable civilizations require sustainable development and sustainable energy resources.
The closer human societies come to the limits of mineral energy resources, the more will
become apparent that renewable energy sources must expand to replace fossil fuels.
Sustainable energy technologies include renewable energy sources, such as hydroelectricity,
solar energy, wind energy, wave power, geothermal energy, tidal power and also
technologies designed to improve energy efficiency. Most of these technologies are now
economically competitive with other sources and effective government policies support
investors in renewable energy technologies. In the last 20 years considerable progress is
being made in the energy transition from fossil fuels to ecologically sustainable energy
systems.5,-8
In 2011 fossil fuels made up 83% of the world’s energy use. Fossil fuels contain so much
energy that they provide a remarkable return on investment even when used inefficiently.
When coal is burned to drive dynamos, for example, only 35% of its energy ultimately
becomes electricity. Nevertheless, an amount of electricity equal to the energy used by a
person who works all day, burning up 1,000 calories worth of food, can be bought for less

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than ten cents. The abundant, cheap energy provided by fossil fuels has made it possible for
humans to exploit a staggering variety of resources, effectively expanding their resource
base. In particular, the development of mechanized agriculture has allowed relatively few
farmers to work vast tracts of land, producing an abundance of food and making possible a
wild growth of population. The problem is that fossil fuels are non-renewable energy
sources. They are limited in supply and will one day be depleted with increasing demand for
humanity’s needs. There is no escaping this conclusion and only investment in alternative
renewable sources of energy must be the future prospect for human civilization. Fossil fuels
supply the vast majority of USA energy needs, including more than 2/3 of U.S. electricity
generation. But their production and use have significant health and environmental impacts
and in addition causes the dangerous global warming of the Earth. According to the
Environmental Protection Agency (EPA), the burning of fossil fuels was responsible for 79%
of U.S. greenhouse gas emissions in 2010. 9-11

Figure 2. Global energy resources for 2010. Despite the dramatic increase of renewable
energy sources, fossil fuels are predominant (83%). Petroleum 37%, Natural gas 25%, Coal
21%. The total renewable energy in 2010 was only 8%. The increase in renewable energy
sources it is hoped by 2050 (do not generate greenhouse gases) will be supplying 40% of the
world's energy, as to 13% today (solar 6%, wind 12%, hydro 12%, 8% nuclear, 1% other
renewables).

Every day, the Sun in the solar system sends out an enormous amount of energy which is a
renewable energy. It radiates more energy each day than the world uses in one year. Like
most stars in the galaxy, the Sun is made up mostly of H2 and Helium (He) atoms in a plasma
state because of the very high temperatures. At the core of the Sun gravitational attraction
produces immense pressure and temperatures which can reach more than 27 million
degrees Fahrenheit (or 15 million degrees Celsius). The chromosphere, the next layer of the
sun's atmosphere is a bit cooler, at about 7,800 degrees Fahrenheit (or 4,320 degrees
Celsius). Hydrogen atoms get compressed and fuse together, creating He called nuclear
fusion. During nuclear fusion, the high pressure and temperature in the sun’s core cause
nuclei to separate from their electrons. Hydrogen nuclei fuse to form one helium atom.
During the fusion process, radiant energy is released. It can take 150,000 years for energy in
the sun’s core to make its way to the solar surface, and then just a little over eight minutes
to travel the 93 million miles to Earth. The radiant energy travels to the Earth at a speed of
300,000 km/sec, the speed of light. In addition to supplying a large amount of energy
directly, the Sun is also the source for many different forms of energy on Earth. Solar energy

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powers the water cycle, drives wind formation and plants use solar energy in the process of
photosynthesis. Biomass can trace its energy source back to the sun. Even fossil fuels
originally received their energy from the sun. 12-14

Figure 3. Energy released during fusion is related to Albert Einstein’s Equation (E = mc2) and
by the Law of Conservation of Energy. During a fusion reaction Hydrogen is converted into
Helium along with a highly energetic neutron. A Fusion Reaction typically happens at high
temperatures. Formation of Helium & the highly energetic neutron is accompanied by release
of a large amount of energy. [http://www.solarenergyexplorer.com/nuclear-
fusion.html#ixzz4Ws9GVEINhttp://www.solarenergyexplorer.com/nuclear-
fusion.html#ixzz4Ws8fFWT3 ].

Green Technologies and Future Prospects for Renewable Energy Sources

The latest edition of the flagship publication World Energy Outlook (International Energy
Agency) in its latest 2016 edition predicts major transformations in the global energy system
that will take place over the next decades. Renewable energy sources (solar, wind, etc) and
natural gas are the big winners in the race to meet energy demand growth until 2040. The
IEA predicts that the clear winners for the next 25 years will be the natural gas (CH4) and
especially wind and solar energy. These renewable will replace the champion of the previous
25 years, coal and petroleum. Similar predictions are published in the other prestigious
publication of World Energy Outlook 2016 of BP. The fossil fuels will decline from 85% to
60% of energy in 2035. Renewable energy sources will grow rapidly, almost quadrupling by
2035 and supplying a 33% of the growth in power generation.15,16
The new report (2017) from the Grantham Institute at Imperial College London and the
Carbon Tracker suggested that falling costs of electric vehicles and solar panels could halt
worldwide growth in demand for oil and coal even by 2020. The prediction uses a scenario
that takes into account the latest cost reduction projections for the green technologies, and
countries’ pledges to cut emissions. Taking into account these changes scientists predict that
solar power and electric vehicles are “gamechangers” that could leave fossil fuels stranded.
A number of low-carbon technologies about to achieve critical mass since the cost of solar
panels has fallen 85% in 7 years and could supply 23% of global power generation by 2040
and 29% by 2050, entirely phasing coal out. By 2035, electric vehicles could make up 35% of
the road transport market, and 2/3 by 2050, when it could displace 25m barrels of oil per

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day. Under such a scenario, coal and oil demand could peak in 2020, while the growth in gas
demand could be curtailed. It could also limit global temperature rises to between 2.4oC and
2.7oC above pre-industrial levels, while more ambitious action by countries than currently
pledged, along with falling costs of solar and electric vehicles, could limit warming to 2.1 oC
to 2.3oC.17

Figure 4. World Energy Outlook 2016 for the period until 2040 by International Energy
Agency. Despite the big increases in renewable energy sources by 2040 will be lower than
fossil fuels but will be able to supply 30% of energy demands by 2015.

Sunlight as Renewable Source to Meet Humanity’s Energy Needs

Solar energy is plentiful radiating out an enormous amount of energy each day. The amount
of daily solar energy that falls on Earth is more than the human civilization is using only in
one year. Solar energy is the cleanest and most abundant renewable energy source
available. Modern technology can harness this energy for a variety of uses, including
generating electricity, providing light or a comfortable interior environment, and heating
water for domestic, commercial, or industrial use. As our reliance on renewable energy
grows, there will be an increasing need to store solar energy for times when the Sun is
not shining and the wind is not blowing all the time. There are several ways to harness
solar energy: photovoltaics (also called solar electric), molten salt power plants, artificial
photosynthesis, solar heating and cooling, concentrating solar power (typically built at
utility-scale), and passive solar. The United Nations Development Programme (UNDP) in its
2000 World Energy Assessment estimated that the annual potential of solar energy was
1,575–49,837 exajoules (EJ) [The exajoule is equal to one quintillion (1018) joules], which is
several times larger than the total world energy consumption, which was estimated at 559.8
EJ in 2012. 18,19
One of the most attractive options for storing this solar energy is to use it as a renewable
power by splitting water into hydrogen and oxygen according to equation 1. The
hydrogen can be stored and then oxidized to release energy and regenerate water, giving
a carbon-neutral fuel production and consumption cycle.

2H2O → O2 + 2H2 (1)

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The reaction in equation 1 is a thermodynamically uphill process and requires an energy

input of 286 kJ mol−1 at room temperature and pressure. Electrochemical methods are
viewed as efficient and scalable means to effect this conversion, which would simply
require inputs of water and electricity to produce hydrogen. Historically, the cost of
manufacturing renewable H2 as an alternative fuel has been higher than the cost of the
energy used to make it. This is the dilemma of the Hydrogen Economy, which is defined as
the industrial system in which one of the universal energy carriers is H2 (the other is
electricity) and H2 is oxidized to water that may be reused by applying an external energy
source for dissociation of water into its component elements hydrogen and oxygen.
Hydrogen is a gas high in energy. NASA has used liquid hydrogen since the 1970s to propel
the space shuttle and other rockets into orbit. Hydrogen fuel cells power the shuttle's
electrical systems, producing a clean by-product—pure water.20,21
Scientists working on renewable energy sources think that H2 in the future will form the
basic energy infrastructure that will power future societies. They see a new hydrogen
economy to replace our current energy economies. Hydrogen has an excellent safety record
and is as safe for transport, storage and uses. Nevertheless, safety remains a top priority in
all aspects of hydrogen energy. The vision of building an energy infrastructure that uses
hydrogen as an energy carrier is considered the most likely path toward a full commercial
application of hydrogen energy technologies.22,23

Rifkin J. The Hydrogen Economy: The Creation Ball M, Wuetschel M (Eds). The Hydrogen
of the Worldwide Energy Web and the Economy. Opportunities and Challenges.
Redistribution of Power on Earth. Tarcher Cambridge University Press, Cambridge, 2009.
Perigee, NY, 2003.

Figure 5. Recent publications on “Hydrogen Economy” provide a strong overview of the

issues surrounding hydrogen energy systems, valuable reference data for researchers, policy
makers and others. The books contain detailed discussions of the methodological issues
surrounding large infrastructure systems, distribution of hydrogen storage, etc.

The International Energy Agency (IEA, Paris), has established a Hydrogen Co-ordination
Group and in 2006 published a review of priorities and gaps in hydrogen production and
storage R&D. The Hydrogen Implementing Agreement (HIA) is the R&D co-operation
programme on hydrogen technologies established by IEA member countries in 1977 under
the IEA framework for international collaboration on energy technology. For more than 25
years, the HIA has been working to promote international co-operation and to carry out

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innovative research, development and demonstration (RD&D) of hydrogen technologies

with the aim of accelerating widespread utilisation of hydrogen as a clean energy carrier.
The first task was completed with the publication by the IEA Secretariat of the report
Hydrogen and Fuel Cells: National R&D Programmes (2004), which built on the information
provided by HCG members on the R&D and policy programmes of IEA member countries.24

The Best Methods of Splitting Water to Produce Hydrogen

The technological question in splitting water is if there is an economically viable way to
separate H2 from H2O. The hydrolysis of water is seen thermodynamically unfavorable
because the amount of energy consumed is far greater than that obtained by burning
hydrogen as a renewable fuel. In the last decades there was lot of research in splitting water
by methodologies that use metals as catalysts and other methods (high pressure, high
temperature, photocatalytic, nanotechnological devices, etc). The best methods of
decomposition of water to separate hydrogen until now are:
1) Electrolysis of Water for the decomposition of water into oxygen and hydrogen gas has
been used by passing an electric current through the water in an electrolyser. In chemistry
and manufacturing, electrolysis is a method of separating chemically bonded elements and
compounds. Hydrogen production via electrolysis may offer opportunities for synergy with
variable power generation, which is characteristic of some renewable energy technologies.
25

2) High Pressure Electrolysis. When water is pressurized and then electrolysis is conducted
at those high pressures, the produced H2 gas is pre-compressed at around 120–200 bar. By
pre-pressurising the H2 in the electrolyser energy is saved as the need for an external
hydrogen compressor is eliminated, the average energy consumption for internal
compression is around 3%. Ultrahigh-pressure electrolysis is HPE operating at 34–69
megapascals (5,000–10,000 psi). At ultra-high pressures the water solubility and cross-
permeation across the membrane of H2 and O2 is affecting hydrogen purity, modified PEMs
(proton exchange membrane) are used to reduce cross-permeation. 26,27
3) High-temperature Electrolysis. Hydrogen can be generated from energy supplied in the
form of heat and electricity through high-temperature electrolysis (HTE). Because some of
the energy in HTE is supplied in the form of heat, less of the energy must be converted twice
(from heat to electricity, and then to chemical form), and so potentially far less energy is
required per kilogram of hydrogen produced. While nuclear-generated electricity could be
used for electrolysis, nuclear heat can be directly applied to split hydrogen from water. High
temperature (950–1000 C) gas cooled nuclear reactors have the potential to split hydrogen
from water by thermochemical means using nuclear heat. Hydrogen production via high
temperature steam electrolysis is a promising technology as it involves less electrical energy
consumption compared to conventional low temperature water electrolysis, as consequence
of the more favourable thermodynamic and electrochemical kinetic conditions for the
reaction. 28,29
4) Photoelectrochemical Water Splitting. Using electricity produced by photovoltaic
systems potentially offers the cleanest way to produce H2 from water. The electrical energy
is obtained by a photoelectrochemical cell (PEC) process which is named artificial
photosynthesis. The PEC water splitting process uses semiconductor materials to convert
solar energy directly to chemical energy (H2) which are similar to those used in photovoltaic
solar electricity generation. In the case of PEC applications the semiconductor is immersed in
a water-based electrolyte, where sunlight energizes the water-splitting process. PEC reactors
can be constructed in panel form as electrode systems or as slurry-based particle systems,

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each approach with its own advantages and challenges. To date, panel systems have been
the most widely studied. Continued improvements in efficiency, durability, and cost are still
needed for market viability for PEC. Ongoing research and development of PEC materials,
devices, and systems is making important strides, benefiting from strong synergies with
contemporary national and international research efforts in photovoltaics, nano-
technologies, and computational materials.30-34

Hydrogen production, High Temperature Electrolysis

Ultrahigh-pressure electrolysis is high-pressure (HTE). Developed for solid oxide fuel cells. Vast
electrolysis operating at 34–69 megapascals improvement of efficiency over using a conventional
(5,000–10,000 psi). electric current through water.

Figure 6. High-pressure electrolysis and high-temperature electrolysis methods have been

developed in recent years. These technological systems are well established and operati ng
in many countries.

5) Photocatalytic Water Splitting. Photocatalytic Hydrogen production via water

dissociation has been an attractive scientific and technological goal. Although tremendous
efforts have been made, hydrogen production by a robust and highly efficient water splitting
system driven by visible light still remain a difficult scientific and technological challenge.35
A typical research effort is the use of TiO2 under various forms. For example, Nano-sized TiO2
photocatalytuc water-splitting technology has been developed in the last decade. The
method has great potential for low-cost, environmentally friendly solar-hydrogen production
to support the future hydrogen economy. Presently, the solar-to-hydrogen energy
conversion efficiency is too low for the technology to be economically sound. The main
barriers are the rapid recombination of photo-generated electron/hole pairs as well as
backward reaction and the poor activation of T i O 2 by visible light. In response to these
deficiencies, many investigators have been conducting research with an emphasis on
effective remediation methods. The scientific literature has many studies with metal ion-
implantation and dye sensitization which more effective to extend the activating spectrum
to the visible range.36

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Figure 7. Photoelectrochemical (PEC) water splitting, a process that uses solar light energy to
split water molecules into hydrogen and oxygen.

6) Photoelectrochemical Water Splitting. Photoelectrochemical (PEC) water splitting has

been considered to be a promising route for sustainable H2 production from the solar
energy. However, owing to the suitable potential required for such process, the external bias
is usually indispensable on the PEC cell, which hinds its wide application. Using electricity
produced by photovoltaic systems potentially offers the cleanest way to produce H2. In this
case water is split into H2 and O2 by electrolysis, but the electrical energy is obtained by a
photoelectrochemical cell process. The system is also named artificial photosynthesis. Also,
hydroelectric power generator can be integrated for water splitting.37
Conventional photoelectrochemical (PEC) tandem devices for unassisted solar water
splitting systems (consisted of a front photoelectrode for water splitting and a rear
photovoltaic cell) have been exposed to the scientific literature. In the last years a variety
of studies have been reported and various photoanode combinations have been tested to
optimize the performance and efficiency. Nevertheless, the efficiency must be further
improved to greater than 10% to reach a viable level for commercialization. 38

Figure 8. Van de Krol R, Gratzel M (Eds). Photoelectrochemical Hydrogen Production.

Electronic Materials: Science and Technology, Springer Scincer + Business Media, New
York, 2012. Alkire RC, Kold A, Lipkowski J, Ross PN (Eds). Phooelectrochemical Materials and
Energy Conversion Processes. Vol. 12, Wiley-VCH, Verlag GmbH &Co, 2010.

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7) Photocatalytic Water Splitting. Photocatalytic hydrogen production technologies have

been developed in the last decades. The main groups of photocalysts used in therse
methods are titanium oxide (TiO2), cadmium sulfide (CdS), zinc oxide/sulfide (ZnO/ZnS) and
other metal oxide-based photocatalyst. Photocatalytic water splitting has been attracting
significant interest in the recent literature because it uses two of the most abundant
sources, clean, renewable and natural energy sources available to us. The prospective
benefits of photocatalytic water splitting can be listed as economic and environmental
advantages because the process uses solar energy and produce hydrogen in a clean way.
Experimental results showed that among individual photocatalysts, on average, Au–CdS has
the best performance when band gap, quantum yield and hydrogen production rates are
considered. From this perspective, TiO2–ZnO has the poorest performance. Among the
photocatalyst groups, CdS have the best average performance, while other metal oxides
show the poorest rankings, on average. In the past five years, there has been significant
progress in water splitting photocatalysis, especially in the development of co-catalysts and
related physical and materials chemistry. Numerous state of the art reviews on the subject
of photocalysts and future challenges have been published.39-41

Figure 9. Water splitting using solar energy in the presence of semiconductor photocatalysts
has long been studied as a potential means of clean, large-scale fuel production. In general,
overall water splitting can be achieved when a photocatalyst is modified with a suitable co-
catalyst with increasing efficiency of hydrogen production.

8) Photobiological Water Splitting. Biological hydrogen can be produced in an algae

bioreactor. In the late 1990s it was discovered that if the algae are deprived of sulfur it will
switch from the production of oxygen (normal photosynthesis) to the production of
hydrogen. It seems that the production is now economically feasible by surpassing the 7–
10% energy efficiency (the conversion of sunlight into hydrogen) barrier with a hydrogen
production rate of 10-12 ml per liter culture per hour. Hydrogen photoproduction by micro-
organisms combines the photosynthetic properties of oxygenic and non-oxygenic microbes
with the activity of H2-producing enzymes in nature: hydrogenases and nitrogenases. The
overall efficiency of the process depends on the separate efficiencies of photosynthesis and
enzymatic catalysis. 42-44
Laboratory-scale measurements suggest that photobiological hydrogen production rates
could yield more energy than current crop-based biofuel productivities. Major challenges,
such as inhibitory amounts of oxygen produced during oxygenic photosynthesis and
inhibition of H2-producing nitrogenase by ammonia, are being overcome through genetic
engineering. Genetic engineering, co-culturing, and bioreactor designs making use of
immobilized cells have the potential to increase conversion efficiencies of light energy to H2

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and to decrease the land area needed for photobiological H2 production. Overall, production
of commercially viable algal fuels in any form, including biomass and biodiesel, is
challenging, and the very few systems that are operational have yet to be evaluated.
Scientists contact experimental projects for the necessary conditions for economical
production of H2 and discuss the necessity for further progress needed to achieve
commercially viable large-scale H2 production.45,46

Figure 10. The biological hydrogen production with algae is a method of photobiological
water splitting which is done in a closed photobioreactor based on the production of
hydrogen as a solar fuel by algae (in sulfur-deprived Chlamydomonas reinhardtii, a green soil
alga). Microalgae in large scale biofuel farms are used for the production of biodiesel.

9) Thermal Decomposition of Water. Thermal decomposition, also called thermolysis, is

defined as a chemical reaction whereby a chemical substance breaks up into at least two
chemical substances when heated. At elevated temperatures water molecules split into their
atomic components hydrogen and oxygen. For example, at 2,200oC about 3% of all H2O
molecules are dissociated into various combinations of hydrogen and oxygen atoms, mostly
H, H2, O, O2, and OH. Other reaction products like hydrogen peroxide H2O2 or HO2 remain
minor. At the very high temperature of 3,000oK more than half (50%) of the water molecules
are decomposed. For example, at 3,000oK and 1 bar, the degree of dissociation is 64%. One
of the challenges of this production method is the separation of the gases H2 and O2. In
order to separate the two gases a semi-permeable membrane can be used at temperatures
up to 2.500oK. Therefore, the mixture needs to be cooled down before sent to the
separation process. Experiments showed that if the gases are rapidly cooled in few
milliseconds to 1500-2000Ok. At such temperatures the recopmbinatio0n of H2 and O2 can be
avoided. Effective H2 separation is another problem and can be achieved by using palladium
membranes.47
10) Solar Thermal Splitting of Water. The high temperatures necessary to split water can be
achieved through the use of concentrating solar power. An experimental station for splitting
water with solar power is the Hydrosol-II (from 2008) is a 100-kilowatt pilot plant at the
Plataforma Solar de Almería in Spain which uses sunlight to obtain the required 800 to
1,200oC to split water. The design of this 100-kilowatt pilot plant is based on a modular
concept. As a result, it may be possible that this technology could be readily scaled up to
megawatt range by multiplying the available reactor units and by connecting the plant to
heliostat fields (fields of sun-tracking mirrors) of a suitable size. Also, an interesting

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approach to solar thermal hydrogen production is proposed by H2 Power Systems. The

method involves application of solar energy with high flux density focused by a dish-type
concentrator for single-step thermal dissociation of water at temperature levels above 2,000
K and separation of hydrogen from the resulting gas mixture. Dissociation however is partial,
(Equation 1) and its extent is a function of reaction temperature and pressure.
(1)
The low dissociation rate of water despite the high temperature and the risk of
recombination of hydrogen and oxygen back to water duely emphasise the importance of
reaction—gas separation as the main feature of the process.48

Figure 11. Hydrosol-II and H2 Power Systems. The H2 Power Systems (H2PS) holds and
exploits the patents to the H2P Technology for hydrogen and oxygen production from
thermal water splitting. The company has produced H2 enriched steam from thermal water
splitting in 2011, and pure H2 and O2 in 2012 in laboratory generators.

*Hydrosol–II, Solar Hydrogen via Water Splitting in Advanced Monolithic Reactors for Future Solar
Power Plants to investigate the possibility of making hydrogen from two renewable resources: water
and sunlight. This cutting-edge research, coordinated by the Centre for Research and Technology
Hellas (CERTH), has culminated in the development of a technologically advanced reactor, which can
turn ordinary water and sunlight into hydrogen. Concentrated solar radiation is used to heat water;
the resulting steam traverses a thermo-chemical reactor, where hydrogen and oxygen are separated
at high temperature by oxidation reduction. Under the Framework Programme the EU has spent
some EUR 29 million for the development and implementation of CSP (Concentrate Solar Power)
technologies [ http://ec.europa.eu/research/energy eu/index_en.cfm?pg=research-csp-support ].

Presently, a commercial-scale or a pilot-scale solar thermal water decomposition plant does

not exist. So far, the process of direct thermal decomposition of water was studied from an
engineering perspective thermodynamically and economically. The experimental solar
thermolysis of water study conducted by Baykara achieved 90% of the equilibrium at a
residence time of 1 ms and temperature of 2500oK. The results also show that if the product
gases are rapidly cooled to 1500–2000oK (in few milliseconds); recombination of H2 and O2
can be avoided by effective hydrogen separation with the use of palladium membranes.49

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11) Water Splitting Through Efficient Water Oxidation by Coordination Complexes.

Water oxidation (2H 2O → 4H+0 + 4e¯0 +O2) with the use of coordinated metal catalysts can
be an important step providing the necessary electrons and protons for the next step for
proton reduction in which hydrogen production takes place. Metal catalysts like Cobalt
(Co), Nickel (Ni) and Iron (Fe) are cheap and earth abundant elements which can play an
economically viable energy conversion role in these types of reactions. 50,51

−1
2H2O + hʋ → 2H2 + O2 ∆G°=4.92eV (113 kcal mol )
+ −
4H + 4e → 2H2
+ −
2H2O → 4H +4e +O2

These water splitting techniques require, among many things, highly active noble metal-free
hydrogen evolution catalysts to make the water splitting process more energy-efficient and
economical. Several important kinds of heterogeneous non-precious metal electrocatalysts,
including metal sulfides, metal selenides, metal carbides, metal nitrides, metal phosphides,
and heteroatom-doped nanocarbons are used for catalysis. At present there are numerous
examples of electrocatalysts that can serve as efficient co-catalysts for promoting direct
solar-to-hydrogen conversion in both photochemical and photoelectrochemical water
splitting systems, when combined with suitable semiconductor photocatalysts.52,53
Water splitting in photosynthesis. Photosynthesis is an important biological process used by
plants and other living organisms to convert light energy into chemical energy which fuels
organisms for their needs. In nature, the solar energy is converted to chemical energy by the
process of photosynthesis producing energy essential for the survival of life on earth.
Photosynthesis works with two photosystems: Photosystems I (P700) and Photosystem II
(P680). When the photosystem I is excited electron transfer reactions gets initiated, which
results in reduction of a series of electron acceptors, eventually reducing NADP+ to NADPH
and PS I is oxidized. The oxidized photosystem I captures electrons from photosystem II
through a series of steps involving agents like plastoquinone, cytochromes and
plastocyanine. The photosystem II then brings about water oxidation resulting in evolution
of oxygen, the reaction being catalyzed by CaMn4O5 clusters embedded in complex protein
environment; the complex is known as oxygen evolving complex.54,55

Figure 12. In nature, the solar energy is converted to chemical energy by the process of
photosynthesis producing energy essential for the survival of life on earth. Photosynthesis
works with photosystem I and photosystem II. Scientists were inspired by photosynthesis to
promote coordination complexes as catalysts in splitting water (Berg JM, Tymoczko JL, Stryer
L. Biochemistry, 7th revised international edition, Freeman & Co, New York, 2011.)

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Water splitting by coordination complexes got its inspiration from the natural
photosynthesis. These coordination complexes are used as catalysts in water splitting or
water oxidation and hence being called water oxidation catalysts (WOCs). Research in the
last 20 years produced a number of promising synthetic metal complexes used for this
purpose.
12). Water Oxidation Catalysts (WOCs). Ruthenium (Ru) Complexes. In the last decade
numerous research projects promoted efficient Water Oxidation Catalysts (WOCs) by using
various metals. One of the most successful metal complexes proved to be Ruthenium (Ru).
Ruthenium based complexes exhibited high turnover numbers in catalytic activity. A number
of mononuclear Ru catalysts have been reported in the scientific literature to be efficient
water oxidation catalysts.56
One of the major scientific challenges for the whole water splitting process is the lack of
methods to immobilize water oxidation catalyst on electrode surface for potential device
making. By using efficient molecular water oxidation catalyst, scientists have in recent years
successfully demonstrated a universal method, by which molecular water oxidation catalysts
can be firmly immobilized on conductive carbon nanotubes. A high turnover frequency (TOF)
of 7.6 s−1 together with a high catalytic current density of 2.2 mA/cm2 was successfully
obtained at an overpotential of 480 mV after 1 h electrolysis, which is much higher than
similar systems reported in literature.57

Figure 13. University Kungl Tekniska Högskolan (KTH), Stockholm, Sweden, School of
Chemical Sciences Engineering. Dpt of Chemistry, Laboratory of Prof. Licheng Sun. Solar Cells
and Solar Fuels. [ https://www.kth.se/en/che/divisions/orgkem/research/lichengsun ]. The
research team used efficient molecular water oxidation catalysts of Ruthenium complexes
which was firmly immobilized on conductive carbon nanotubes [F. Li et al, Chem. Commun.
2014, 50, 13948-13951], which is much higher than similar systems reported in the scientific
literature.57

Mastering the light-induced four-electron oxidation of water to molecular oxygen is a key

step towards the achievement of overall water splitting to produce alternative solar fuels. A
recent research project used rugged molecular pyrazolate-based diruthenium complexes
that efficiently catalyze visible-light-driven water oxidation.

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Figure 14. Structures of WOCs and dyes (RuPS) used in this work. For clarity, the
nomenclature used for 1(H2O)2−, 2(H2O)2−, and m3(H2O)23+ refers to all of the protonation
states of these complexes.[ Berardi S, et al. 2015].58

These complexes were fully characterized both in the solid state (by X-ray diffraction
analysis) and in solution (spectroscopically and electrochemically). Benchmark performances
for homogeneous oxygen production have been obtained for both catalysts in the presence
of a photosensitizer and a sacrificial electron acceptor at pH 7, and a turnover frequency of
up to 11.1 s−1 and a turnover number of 5300 were obtained after three successive catalytic
runs. Under the same experimental conditions with the same setup, the pyrazolate-based
diruthenium complexes outperform other well-known water oxidation catalysts owing to
both electrochemical and mechanistic aspects.58
Scientists have the ambition to imitate the ingenuity of nature (exploiting the billions of
years of natural selection that developed numerous effective biochemical conversions, such
as photosystem II of photosynthesis). However, an inability to replicate the elegance and
efficiency of the oxygen-evolving complex of photosystem II (OEC-PSII) in its oxidation of
water into O2 is a significant bottleneck in the development of a closed-loop sustainable
energy cycle. A research team presented in 2016 an artificial metallosupramolecular
macrocycle that gathers three Ru(bda) centres (bda = 2,2′-bipyridine-6,6′-dicarboxylic acid)
that catalyses water oxidation. The macrocyclic architecture accelerates the rate of water
oxidation via a water nucleophilic attack mechanism, similar to the mechanism exhibited by
OEC-PSII. 59 The same group of scientists overcame solubility problems by incorporating a
Ru(bda)(bda = 2,2′-bipyridine-6,6′-dicarboxylate, as a water oxidation catalyst, into a
trinuclear metallosupramolecular macrocycle. This leads to increased stability and activity
compared to the mononuclear reference system. 60

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Figure 15. A trinuclear metallosupramolecular macrocycle of Ruthenium. Scientists tried to

overcome solubility problems of such large structures in water and the need for large
amounts of organic co-solvents.60

13) Water Splitting by Cobalt Complexes. Cobalt salts can be used as WOCs, but their water
oxidation capability decreases with the passage of time because of the precipitation of the
salt from the homogenous solutions, resulting in turbidity.
The well known scientists Kanan and Nocera (Dpt of Chemistry, MaIT, Prof. Nocera moved
from 2012 at Harvard University) have demonstrated the formation of a dark thin film over
the surface of indium tin oxide which was used an electrode, along with bubbling in the
solution. These bubbles were confirmed to be of oxygen. Co-WOCs have been shown to
work very efficiently at a pH 7.0. The realization of artificial systems that perform “water
splitting” requires catalysts that produce oxygen from water without the need for excessive
driving potentials.61
The Nocera Group (D. G. Nocera, initially in MIT, now is Patterson Rockwood Professor of
Energy, in the Chemistry Dpt of Harvard University from 2012) is a well known university
group with advanced research on chemical issues of pertinence to energy conversion. The
Nocera group discovered Cobalt (Co) and Nickel (Ni) catalysts that duplicate the solar fuels
process of photosynthesis outside of the leaf. The catalyst self assemble from water to form
a partial cubane structure, they are self-healing and they split water to H2 and O2 using light
from neutral water at atmospheric pressure and room temperature. The catalyst operates at
100 mA/cm2 at 76% efficiency, which is very high.61
The discoveries enabled the construction of inexpensive water splitting devices that may be
coupled to either photovoltaic panel or coupled directly to the surface of a semiconducting
substrate. The Nocera group has recently accomplished a solar fuels process that captures
many of the elements of photosynthesis and translated this science to produce the artificial
leaf, which was named by Time magazine as Innovation of the Year for 2011. He has since
achieved solar-to-hydrogen efficiency of greater than 10%. He has also demonstrated a path
to liquid fuels using a bio-engineered bacterium, Ralstonia eutropha to efficiently convert
carbon dioxide, along with hydrogen produced from the artificial leaf, into biomass and fusel
alcohols.62
The construction of an artificial leaf by the Nocera group comprised of earth-abundant
elements by interfacing a triple junction, amorphous silicon photovoltaic with hydrogen- and

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oxygen-evolving catalysts made from a ternary alloy (NiMoZn) and a cobalt–phosphate

cluster (Co-OEC), respectively. The latter captures the structural and functional attributes of
the PhotoSystem II-OEC. Similar to the PSII-OEC, the Co-OEC self-assembles upon oxidation
of an earth-abundant metal ion from 2+ to 3+, may operate in natural water at room
temperature, and is self-healing. The NiMoZn alloy may be used in place of Pt to generate
H2. To stabilize silicon in water, its surface is coated with a conducting metal oxide onto
which the Co-OEC may be deposited. The net result is that immersing a triple-junction Si
wafer coated with NiMoZn and Co-OEC in water and holding it up to sunlight can effect
direct solar energy conversion via water splitting. 63,64

Figure 16. The Nocera experiment. One face of the artificial leaf generates H2 and the other
O2. It is a cheap catalyst that rips electrons from water to produce oxygen, protons and
electrons. This catalyst covers one side of the silicon solar cell, with a layer of indium tin oxide
or fluorine tin oxide in between to protect the cell from the oxygen generated. [ Kanan MW,
Nocera DG. In situ formation of an oxygen-evolving catalysts in neutral water containing
phosphate and Co2+. Science 321:1072-1075, 2008].

Many scientific projects focused on Co as a most versatile non-noble metal catalyst for
splitting water. In natural systems the active sites of enzymes involved in water-splitting
processes (namely hydrogenases and photosystem II), use metals such as iron (Fe), nickel
(Ni), and manganese (Mn) ions. But from experimental results in the last decade emerged
that Cobalt (Co) was the most versatile non-noble metal for the development of synthetic H2
and O2 evolving catalysts. These metal catalysts can be further coupled with photosensitizers
to generate photocatalytic systems for light-induced hydrogen evolution from water. In the
last 5 years a series of new Co catalysts proved to be very efficient in splitting water and
producing H2. 65-67
14) Water splitting by Iron complexes. In recent decades, tremendous efforts have been
devoted by chemists to develop efficient, cost-effective catalytic methods (Co, Mn, Fe and
Cu) for solar-driven water oxidation for the production of hydrogen (H2). Among the first-
row transition metals, iron (Fe) is probably the most desirable to be used in WOCs because it
is the most abundant and relatively nontoxic. In a recent report scientists used iron(III)
complex bearing a tetraamido macrocyclic ligand (FeIII-TAML) to catalyze water oxidation by
CeIV at approximately pH 1 with a turnover number (TON) of 18 and turnover frequency
(TOF) of greater than 1.3s−1. In another research paper it was reported that a number of iron
complexes bearing tetradentate N-donor ligands can catalyze water oxidation at low pH with
TON>350 and >1000 using CeIV and IO4−, respectively.68

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Fillol and Costas et al., also reported that a number of iron complexes bearing tetradentate
N-donor ligands can catalyze water oxidation at low pH with TON>350 and >1000 using
CeIV and IO4−, respectively.69 A paper in 2013 reported that chemical and light-driven water
oxidation catalyzed by a number of iron complexes and iron salts at pH 7–9 in borate buffer
showed evidence that at this pH range, trioxide of iron Fe2O3 particles are produced, which
are the actual catalyst for water oxidation.70
15) Water splitting by Iridium complexes. Iridium (IV) oxide (Ir-O2) is a stable bulk WOC
catalyst with low overpotential. McDaniel and other co-workers synthesized analogues of
[Ir(ppy)2(OH2)2]+ (ppy = 2-phenylpyridine) with high turnover numbers, but low catalytic
rates. Replacing ppy of the complex with Cp* (C5Me5) resulted in an increase in the catalytic
activity but decreased the turnover number.71
Iridium complexes have been proved efficient water oxidation catalysts. A new family of
octahedral Ir(III) complexes with a resilient and electronically tunable tetradentate
bis(pyridine-2-sulfonamide) (bpsa) ligand scaffold was synthesized and investigated as a
robust and efficient water oxidation catalyst platform. Experimental results showed that
these complexes were capable of catalyzing water oxidation processes electrochemically and
chemically with Ceric ammonium nitrate, a one-electron oxidant. The molecular nature of
these catalysts was confirmed by dynamic light scattering experiments as well as
electrochemical quartz crystal microbalance studies.72
In the last decade there are numerous applications for patents of various metal complexes
and organo-metal catalysts in aqueous solution for the purpose of hydrogen production. 73-76

Figure 17. The electrochemical studies were complemented by work on chemically driven
water oxidation, where the catalytic activity of the iridium complexes was studied upon
exposure to Ceric ammonium nitrate, a strong, one-electron oxidant. Variation of the catalyst
concentrations helped to illuminate the kinetics of these water oxidation processes and
highlighted the robustness of these systems.

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Intensification Technologies for Water Splitting and Hydrogen Production

The need for alternative energy sources at a global scale is part of the ongoing research and
development in research institutes and university laboratories in the last decade. The water
splitting is a promising solar-to-hydrogen pathway for hydrogen production, offering the
potential for high conversion efficiency at low operating temperatures using cost-effective
thin-film and/or particle semiconductor materials. Experimental results showed continued
improvements in efficiency, durability, and cost which are still needed for market viability.
New technologies, new catalysts, advanced materials, devices, and systems are making
important strides. The promising signs are benefiting from strong synergies with
contemporary research efforts in photovoltaics, nano-technologies, and computational
materials. Efficiencies are being improved through enhanced sunlight absorption and better
surface catalysis. Durability and lifetime are being improved with more rugged materials and
protective surface coatings. Hydrogen production costs are being lowered through reduced
materials and materials processing costs.
The scientific literature in the last years is rich with new research papers and improved
technological achievements. A recent paper (2016) described the production of clean and
“green energy” through electrochemical water splitting aided by a simple bifunctional
electrocatalyst. The anodic and cathodic catalysts comprised of a nickel seleno-based
coordination complex, [Ni{(SePiPr2)2N}2], containing a tetrahedral NiSe4 core, exhibiting
exceptionally high activity towards both oxygen evolution and hydrogen evolution reactions
in alkaline solution at very low overpotentials, and enabling water electrolysis at a cell
voltage of 1.50 V. The high efficiency is attributed to the specific coordination environment
around the catalytic site.77
In October 2016, researchers in Washington State University (USA) have found a way to
more efficiently create hydrogen from water. The researchers, led by professors Yuehe Lin
and Scott Beckman in the School of Mechanical and Materials Engineering, have developed a
catalyst from low cost materials. It performs as well as or better than catalysts made from
precious metals that are used for the process. The work is published in the journal
Advanced Energy Materials (http://onlinelibrary.wiley.com/doi/10.1002/
aenm.201601555/full ). Cobalt-based bimetallic phosphide encapsulated in carbonized
zeolitic imadazolate frameworks has been successfully synthesized and showed excellent
activities toward both hydrogen evolution reaction (HER) and oxygen evolution reaction. For
their catalyst, the research team added nanoparticles of relatively inexpensive copper to a
cobalt-based framework. The new catalyst was able to conduct electricity better than the
commonly used precious metal catalysts. It produced oxygen better than existing
commercial catalysts and produced hydrogen at a comparable rate.78
The SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering
in Stanford University (USA) are experimenting with many artificial methods of making
hydrogen from splitting water. But the main obstacles in these processes were that
materials are very expensive and require too much energy. Also, devices break down too
quickly in real-world conditions (acidic electrolytes). Professor Thomas Jaramillo and his
collaborators sought to develop catalysts that will split water faster, with less energy and at
low cost. Their experimental results were published in various journals (Nature
communications, Science, ACS Energy Letters, 2016). The research team presented an
oxygen and hydrogen evolution catalyst that worked in harsh conditions, beat in efficiency
all of its competitors, and was stable under acidic conditions. The key benchmarks is the
overpotential, or the amount of electricity needed to drive the reaction of splitting water.
The catalyst was a thin film crystal, grown to be as flat as possible, with one layer made from
iridium oxide and another layer made from strontium iridium oxide. With a flat, thin crystal,
researchers had a better standard of comparison for their simulations.79-82

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Conclusions
Splitting water molecules into hydrogen and oxygen using solar energy—called photcatalytic
water splitting—is a promising technology, capable of providing high-energy yield without
polluting byproducts. In the process, energy is used to separate hydrogen and oxygen atoms
to produce a zero-emissions fuel. Exciting advancements in photocatalytic water splitting
are underway. The latest experimental results according to some scientists are milestones
which bring the scientific community much closer to a sustainable and practical process to
use water-splitting as a storage technology. Improving efficiency of splitting water and
producing hydrogen has a remarkable impact on lowering costs. But for the moment there is
a highly successful breakthrough. Scientists must continue researching on finding more ways
to lower the costs to compete with conventional fuels. In the USA these research efforts are
supported by the Department of Energy’s National Renewable Energy Laboratory (NREL)
which recently formed a team of national laboratories called HydroGEN Advanced Water
Splitting Materials Consortium. HydroGEN is being funded by the Energy Department’s Fuel
Cell Technologies Office in the Office of Energy Efficiency and Renewable Energy (EERE).
Approximately $10 million per year will support photocatalytic research in water splitting
and the production of hydrogen [https://energy.gov/eere/fuelcells/hydrogen-advanced-
water-splitting-materials-consortium ].
COST is the longest-running European framework (EU) supporting trans-national
cooperation among researchers, engineers and scholars across Europe (from 1971).The
project ERSPECT-H2O [CMST COST Action CM1202] will enable spectroscopy/theory guided
design of supramolecular photocatalysts for water splitting, and hence the generation of
molecular hydrogen as a renewable fuel. The network will integrate leading European
groups and national research centers, focusing on a central theme of contemporary research
in homogeneous photocatalysis and integration of supramolecular photocatalysts towards
the construction of functional materials. The Action combines synthetic chemistry,
photophysics and photochemistry, electrochemistry, and theory aiming at a detailed
molecular mechanistic understanding of photoinduced reaction steps in supramolecular
photocatalytic water [ http://www.cost.eu/COST_Actions/cmst/CM1202 ].

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