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Solar Hydrogen: Fuel of the Near Future

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DOI: 10.1039/B923793N

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PERSPECTIVE www.rsc.org/ees | Energy & Environmental Science

Solar hydrogen: fuel of the near future

Mario Pagliaro,*a Athanasios G. Konstandopoulos,*b Rosaria Ciriminnaa and Giovanni Palmisanoa
Received 11th November 2009, Accepted 19th January 2010
First published as an Advance Article on the web 8th February 2010
DOI: 10.1039/b923793n

Renewable hydrogen produced using solar energy to split water is the energy fuel of the future.
Accelerated innovation in both major domains of solar energy (photovoltaics and concentrated solar
power) has resulted in the rapid fall of the solar electricity price, opening the route to a number of
practical applications using solar H2. Referring to several examples as well as to new technologies, this
article provides insight into a crucial technology for our common future.

Introduction solar hydrogen. In general, hydrogen cleanly reacts with oxygen

in an highly exothermic reaction giving pure water as the unique
Hydrogen generated by solar energy induced water splitting is exhaust by-product (eqn (1) and Fig. 1):
the fuel, alternative to fossil fuels, capable of replacing fossil fuels
and ultimately cease our dependence (or ‘‘addiction’’,1 to quote 2 H2 (g) + O2 (g) / 2 H2O (l) + 572 kJ (286 kJ mol1) (1)
the former US president) on fossil oil and gas, abating the carbon
dioxide emissions in the atmosphere causing global warming.
Hydrogen gas has an enormous volume: 1 kg of H2 at ambient For practical reasons, fuel cells are usually operated with air
temperature and atmospheric pressure has a volume of 11 m3 so rather than pure oxygen and low amounts of nitrogen oxides are
that hydrogen storage basically implies a reduction in volume, formed among the actual exhaust products. PEM and SOFC
generally accomplished by increased pressure (in gas cylinders (high temperature) fuel cells emit trace amounts of NOx as shown
with a maximum pressure of 80 MPa) or by lowering the by extensive tests at Georgetown University.†
temperature.2 Hydrogen must be generated by extracting it from hydrogen
In the last ten years, much hype has been associated with the sources. Today most of the hydrogen we use comes from
hydrogen topic. Romm,3 for instance, has questioned the idea hydrocarbons which clearly contributes to the overall CO2
that hydrogen is an economically viable fuel for transportation emissions and thus to global warming. Once available, however,
because of the cost and greenhouse gases generated during it is an excellent fuel that can replace hydrocarbons with
production, the low energy content per volume and weight of the numerous advantages, including a specific heat capacity 3 times
container, the cost of the fuel cells, and the cost of the infra- higher than that of our best fossil fuel (natural gas, or methane).
structure. Yet, the price of solar electricity in the last 3 years has For example, in 2009, Italy’s power company Enel started
fallen to such an extent, and the pace of innovation in both fields operating a 12 MW H2-powered electricity plant in Venice’s
of solar energy has been so intense, that a number of unexpected industrial zone of Porto Marghera, uniquely fuelled by hydrogen
practical applications have emerged that are indeed based to by-products from local petrochemical industries (Fig. 2). The
turbines were specially designed to resist embrittlement from
hydrogen, but in any case the only emission of hydrogen
a
Istituto per lo Studio dei Materiali Nanostrutturati, CNR, via U. La Malfa combustion is water.
153, 90146 Palermo, Italy. E-mail: mario.pagliaro@ismn.cnr.it
b
Aerosol and Particle Technology Laboratory (APTL), CERTH / CPERI,
P.O. Box 369, 57001 Thermi-Thessaloniki, Greece. E-mail: agk@cperi.
certh.gr † http://fuelcellbus.georgetown.edu/overview3.cfm

Broader context
Renewable hydrogen produced using solar energy to split water is the energy fuel of the future. Accelerated innovation in both major
domains of solar energy (photovoltaics and concentrated solar power) has resulted in the rapid fall of the solar electricity price,
opening the route to a number of practical applications using solar H2. New thermochemical water splitting using concentrated solar
power (CSP) as well as CSP coupled to electrolysis has the potential to convert and store solar energy into clean hydrogen using
a tiny fraction of the world’s desert area to meet our present and future global energy needs. Photovoltaics, in turn, has the versatility
required for supporting the creation of a distributed energy generation infrastructure in developing countries especially now that the
price of PV solar electricity has fallen to unprecedented low levels. In all these cases, solar H2 will be used to store energy and release
it on demand either for fuel cells (to power homes and boats) or internal combustion engines and turbines (for powering cars, trucks
and in thermoelectric power units). Referring to several examples as well as to new technologies, this article provides insight into
a crucial technology for our common future.

This journal is ª The Royal Society of Chemistry 2010 Energy Environ. Sci., 2010, 3, 279–287 | 279
 Fig. 2 First in the world to operate on such a scale, the 12 MW
combined cycle plant in Venice’s industrial zone of Porto Marghera
fuelled by hydrogen by-products from local petrochemical industries.
(Photo courtesy of Enel).

In contrast to fossil fuel deposits that are a concentrated

source of high-quality energy, commonly extracted with power
densities—the rate of energy production per unit of the earth’s
Fig. 1 The only emission of Frauscher’s Riviera 600 hydrogen-powered area—of 102 or 103 W m2 for coal or hydrocarbon fields,
boat is clean water, whilst H2 is cleanly obtained by photovoltaic elec- biomass energy production has densities well below 1 W m2,
trolysis of water. (Photo courtesy of Fronius). while densities of electricity produced by photovoltaic generation

Mario Pagliaro, a scholar at Rosaria Ciriminna is a research

Italy’s Research Council based chemist at Palermo’s CNR
in Palermo, is the founder and Institute of nanostructured
director of Sicily’s Photovoltaics materials. Her interests span
Research Pole. His research from catalysis and green chem-
interests are in materials chem- istry, to natural products and
istry, solar energy, science sol–gel materials for advanced
methodology and management. applications. She has co-auth-
Mario is the author of a large ored more than 60 research
body of research papers and papers on these topics and was
scientific books. His joint invited to present her work at
achievements include the several international confer-
commercialization of several ences.
Mario Pagliaro new chemical technologies. Rosaria Ciriminna

Athanasios G. Kon- Giovanni Palmisano is a chem-

standopoulos, founder and ical engineer currently working
Director of APT Lab at on dye solar cells at Italy’s
CPERI/CERTH and a member CHOSE research center. He has
of the faculty of Aristotle co-authored 30 research papers
University of Thessaloniki, on this and other chemistry and
Greece, is the coordinator of the materials science topics. Gio-
European "Hydrosol" projects. vanni is also an entrepreneur in
He is an expert in aerosol/ the field of the solar energy
nanoparticle technologies and business.
multifunctional structured reac-
tors with applications in
combustion engine emission
Athanasios G: Konstandopoulos control, solar hydrogen/fuels Giovanni Palmisano
production and biotechnology.
He is the recipient of many awards, including the 2006 Descartes
Prize of the European Commission.

280 | Energy Environ. Sci., 2010, 3, 279–287 This journal is ª The Royal Society of Chemistry 2010
 where F is the Faraday constant measuring 1 mol of electricity
(96 485 C). Once locally available, hydrogen can be used to
generate electricity by the reverse of reaction 2:

H2 + ½O2 / H2O + 2F (3)

which is the process that occurs in an H2–O2 fuel cell. Indeed, the
same cell can work as a fuel cell or as an electrolyzer, depending
on the operating conditions, which is not the case with other
competing reactions for the production of H2. Overall, the
process is able to locally create the required amount of hydrogen
needed to power a house or a small boat’s engine, such as in the
case of the commercial electric boat powered by an H2–O2 fuel
cell shown in Fig. 1.
Hydrogen can also be burnt in air within an internal
Fig. 3 Power densities for renewable fuels and energy consumers. Power combustion engine (ICE) such as in the case of the BMW
density is the rate of energy production per unit of the earth’s area, Hydrogen 7 automobile equipped with a hydrogen tank. Like
expressed in watts per square meter (W m2). (Reproduced from ref. 4, gasoline, hydrogen is highly flammable. Yet, Fig. 4 shows that
with permission). due to the buoyancy of hydrogen (14.4 time lighter than air,
rising at 20 m s1 rate), the flame shoots up vertically, whereas
is around 20 W m2 at peak power. Fig. 3 shows that the energy gasoline is heavy and spreads beneath the vehicle.
supply chain of today’s fossil-fuelled civilisation works by The solar method to generate H2 from water, better suited to
producing fuels and thermal electricity with power densities that addressing the energy-intensive needs of modern society, relies
are one to three orders of magnitude higher than the common on CSP and is a catalytic thermochemical process that makes use
power densities with which our buildings and cities use of concentrated solar radiation to create a large surplus of
commercial energies.4 hydrogen suitable for energy-intensive applications. Such solar
Solar energy is the only renewable energy source with the technology not only produces hydrogen but employs entirely
versatility to meet both intensive production needs (through renewable and abundant energy sources and raw materials: solar
concentrated solar power, or CSP) and localized energy distri- energy and water, respectively, without any CO2 emissions.
bution demands (through onsite installed photovoltaic (PV) Finally, one can use the CSP technology to produce large
modules), whose price in the last 18 months has fallen by 75% amounts of electricity and then store it as pure hydrogen through
(from 6 to less than 1.5 V/W). electrolysis. The convenience of this option will depend on the
In the past three decades, computers and telephones have
become decentralized and wireless. Solar energy will do the same
for the energy industry. In other words, PV distributed on a small
scale,5 instead of on today’s industrial-size electricity grids, will
begin to compete with the economies of scale that Edison’s
electricity transmission created over the last century. As the price
of solar electricity approaches that of fossil energy, developing
nations will adopt distributed solar generation as they did with
mobile phones, jumping over fixed-line phones. Hence, in place
of big fossil fuel power stations and a national electric grid, both
fixed infrastructures with large costs, these nations will develop
distributed generation.
Similarly, in wealthy nations where electricity costs are rapidly
rising, citizens and companies can greatly benefit from solar
energy, thanks to the now low upfront cost, and extremely low
ongoing costs, and whose overall cost of finance amortized over
the life of the equipment/capital investment vastly enhance the
economics of solar energy.
In this context of rapid change, H2 is an excellent storage
option for storing the excess energy during the day for night time
Fig. 4 On the left is a vehicle with a hydrogen tank, and on the right
and cloudy days uses. Two complementary methods exist which
a vehicle with a standard gasoline tank. Both tanks have been deliberately
rely on the two main solar energy technologies, namely photo-
punctured and ignited. The top panel shows the two vehicles 3 s after
voltaics (PV) and concentrated solar power (CSP). The first ignition. The bottom panel shows the two vehicles 60 s after ignition. The
technology is water electrolysis using a photovoltaic current hydrogen supply has burned off and the flame is diminished, whereas the
(eqn (2)): gasoline fire has accelerated and has totally engulfed the vehicle on the
right. (Photo courtesy of the University of Miami, reproduced from
H2O + 2F / H2 + ½O2 (2) Physorg.com).

This journal is ª The Royal Society of Chemistry 2010 Energy Environ. Sci., 2010, 3, 279–287 | 281
specific application. This article thus aims to provide insight into Table 1 Experimental parameters in alkaline electrolysis. (Reproduced
a crucial technology for our common future. from ref. 7).

H2O / H2 + ½O2
Water electrolysis Electrolyte: 25–30% KOH
DV ¼ 1.65–2.00 V, j ¼ 1–10 kA m2
The splitting of water into gaseous H2 and O2 by the action of Energy consumption: 4–4.9 kW h m3
Current yield: 98–99.9%
electricity is definitely an entirely clean process since no polluting H2 purity: >99.8%
by-products are formed provided that electricity is produced
using either photovoltaics, hydroelectric, geothermal or aeolian
power.6 In general, the product yield of reaction 2 is 100%,
Fig. 6 shows that conventional (alkaline) electrolyzers show
namely no electrical energy is wasted; and since the cost of water
high overpotential and a relatively small production rate,
is negligible, eqn (2) shows that the entire economics of the
whereas membrane and advanced alkaline electrolyzers display
process is driven by the cost of electricity. An electrolyte is dis-
a very similar performance, with lower overpotential and much
solved in water to enhance conductivity and thus the overall rate
higher production rates.
of the process of water electrolysis.
Typically, a commercial alkaline electrolyzer produces H2 by
In current commercial electrolyzers, the solution employed is
consuming 4.49 kW h m3 of electricity with current yield and
a 30% KOH at 80  C (alkaline electrolysis) and the electrolyte
hydrogen purity both close to 100% (Table 1).7
can be recovered and re-used. Alkaline electrolysis systems have
In 2009 the Austrian companies Fronius, Bitter and Frauscher
efficiencies of 55–75% and make use of a ceramic microporous
successfully presented Riviera 600: the first electric boat powered
separator, whereas the electrodes are usually made of nickel, with
by solar hydrogen fuel cells. The concept is that of a self-con-
the cathode coated in platinum and the anode coated in
tained energy supply provided by hydrogen simply obtained by
manganese oxide or tungsten oxide. Remarkably, the use of
photovoltaic electrolysis of water. The fuel cell makes it possible
intermittent PV electricity results in two shortcomings: (i) its
to use the solar power made available as H2 when the (weather)
activity decreases with time, and (ii) shutdown of industrial cells
conditions are optimal and to store the excess power so that it
provokes Ni dissolution at the cathode since this electrode is
can be made available for later use as required. Extracted from
driven to more positive potentials by short-circuit with the
water using photovoltaics and electrolysis, H2 is oxidised in the
anode. These shortcomings can be alleviated if Ni cathodes are
fuel cell and the only emission is clean water (Fig. 1), completing
activated, i.e. if they are coated with a thin layer of more active
a zero emission energy production cycle. The necessary invest-
and more stable materials (Fig. 5).
ment for the hydrogen infrastructure gains more economic
profitability with an increasing number of boats. The team
‘‘Future Project Hydrogen’’8 has created budget calculations for
the generation of hydrogen on site by use of photovoltaics under
the premises of 10 boats for commercial use, for example, within
a boat rental.
With a range of 80 kilometres with a full hydrogen tank and
having been awarded a safety certificate by Germany’s TUV, € the
boat is 6 m long, 2.2 m wide and weighs 1400 kg. Its 4 kW
continuous power electric motor has twice the range of conven-
tional battery-powered boats. The 47% efficiency of the noise-
free fuel cell engine should be compared to the 18%–20%
Fig. 5 Variation of overpotential (inversely proportional to activity) for
O2 evolution as a function of time for continuous and intermittent elec-
trolysis. Under the latter conditions, Ni-based cathodes need protection
by a thin layer of more active and more stable materials. (Reproduced
from ref. 6, with permission).

Fig. 7 Re-fuelling of the 600 Riviera Frauscher boat is done in 5 min

using a standard 350 bar filler coupling on the one hand plus a simple
Fig. 6 Range of performance of different water electrolyzers. (Repro- exchange of an empty cartridge for a full one on the other. (Reproduced
duced from ref. 6, with permission). from Frauscherboats.com, with permission).

282 | Energy Environ. Sci., 2010, 3, 279–287 This journal is ª The Royal Society of Chemistry 2010
efficiency of a conventional (steel) internal combustion engine. installation is simple thanks to the ‘‘container construction’’
The main economic advantage compared with conventional design and can be carried out simply and quickly at many
electric boats is the fact that no time has to be spent charging the different locations. The station comprises electricity power
batteries. For conventional electric boats, 6–8 h of charging gives charger, hydrogen and payment units (Fig. 8). For comparison,
just 4–6 h of use. The hydrogen-powered electric boat requires storing power in batteries over long periods of time is linked to
only the time that it takes to change the cartridge: 5 min. The huge losses due to self-discharge (5–10% per month), while the
boat’s fuelling system consists of a 20 kg cartridge that can be energy density is a fraction of that for hydrogen, which means
charged with up to 0.7 kg of hydrogen kept at 350 bar. Re- that by storing energy in the summer in a battery of the same
fuelling is done using a standard filler coupling on the one hand capacity, one would have no more energy available in winter.9
plus a simple exchange of an empty cartridge for a full one on the Another example that shows that photovoltaic renewable
other (Fig. 7). hydrogen is far from being solely a research topic is given by the
The energy filling (‘‘Clean Power’’) station makes use of PV world’s first underground pipeline supplying H2 to customers in
modules integrated in a 250 m2 flat roof, and further connected to the Italian city of Arezzo (Fig. 9).10 At present, the pipeline serves
an electrolytic cell. Even at Austria’s cold latitudes the station is 4 companies and the HydroLAb with a main channel of around
capable of affording an annual yield of 823 kg hydrogen, 600 m where the whole network is around 1 km.
equivalent to 1100 cartridges with a 27 200 kW h energy content, Four goldsmith companies use it for industrial and energy
namely enough hydrogen to run a boat for 80 000 km. Its needs via four 5 kW fuel cells and two 1 kW fuel cells at the
HydroLAb, the laboratory for hydrogen and renewable energies
(Fig. 10).11
The aim was to set up a completely off-grid testing lab for
technologies in the renewable energy sector, collecting data to
test solar energy technologies linked with hydrogen production
and use. Hence, solar panels provide electricity, solar thermal
vacuum tube panels provide heat for room heating and feed
a 5 kW solar cooling machine (Fig. 10) in order to get zero-
emission air conditioning in summer. Waste water is completely

Fig. 8 The Clean Power Station makes use of a 250 m2 flat roof equipped
with PV modules whose electric power output feeds an electrolyzer
splitting water molecules. (Image courtesy of Fronius).

Fig. 10 The HydroLAb is completely off-grid since photovoltaic solar

panels provide electricity and solar thermal vacuum tube panels provide
heat for room heating and feed a solar cooling machine (5 kW, the
smallest in Italy) in order to get air conditioning at zero emission in
summer. (Photo courtesy of La Fabbrica del Sole).

Fig. 9 Made of passivated steel and 1 km long, the first hydrogen Fig. 11 Sun and wind provide all the energy needed to power the
pipeline in the world has been built in the Italian city of Arezzo and HydroLab in Italy, and solar hydrogen is used to store the intermittent
delivers pure H2 at 3.5 bar to the fuel cells installed in 4 goldsmith energetic supply of solar irradiation. (Image courtesy of La Fabbrica
companies. (Photo courtesy of La Fabbrica del Sole). del Sole).

This journal is ª The Royal Society of Chemistry 2010 Energy Environ. Sci., 2010, 3, 279–287 | 283
recycled through a fito remediation dry technique and rain is
collected and stored (Fig. 11). The technologies implemented are
continuously monitored, with the aim of further optimization in
view of widespread commercial application in the building
industry.
Today, when solar panels generate more electricity than
a home is using, the excess is simply fed back into the grid,
essentially subtracting from the homeowner’s utility bill. In an
off-grid application, the excess is put into batteries. But fuel cells
are more versatile and their price is rapidly declining.
Existing electrolyzers are expensive. Hence, the challenge is
devising a system that is efficient enough to make energy inex-
pensively. In general, however, PV electricity should be used as
such, for electricity is the highest quality energy available; but
this will require in its turn the introduction of new generation
batteries able to recharge rapidly with large amounts of energy. Fig. 12 Scheme for the solar thermo-chemical water splitting cycle.
Yet, the idea to use the PV energy to crack water molecules into (Reproduced from hydrosol-project.org, with permission).
hydrogen and oxygen and used later in a fuel cell to make elec-
tricity when the sun is not shining is general. The concept is water-splitting materials that are heated by concentrated solar
a closed-loop system in which hydrogen oxidized with air in the radiation using a set of mirrors that is used to concentrate the
fuel cell creates water, which is captured and used again. solar energy, increasing the temperature in the reactor (Fig. 12).
A promising alternative process to split water into its elements In the first step of water-splitting, the activated redox reagent
is a based on a cobalt phosphate catalyst developed by Nocera (usually the reduced state of a metal oxide) is oxidized by taking
and co-workers which can operate in plain water at atmospheric oxygen from water and producing hydrogen, according to
pressure mimicking photosynthesis.12 The system makes use of reaction (4):14
a traditional anode (positively charged electrode in an electro- MOx1 þ H2 OðgÞ/MOox þ H2 exothermic (4)
lytic cell) consisting of indium tin oxide for the splitting of water
by electrolysis upon which the ‘‘cobalt phosphate’’ solid catalyst During the second step the oxidized state of the reagent is
is absorbed when current is passed through a solution containing reduced, to be used again (regeneration), delivering some of the
Co2+ cations and HPO42 anions. The catalyst forms in situ as the oxygen of its lattice according to reaction (5):
amount of charge passed during the course of an 8 h electrolysis MOox /MOx1 þ ½O2 endothermic (5)
far exceeds what could be accounted for by stoichiometric
oxidation of the Co2+ in solution. The researchers, however, have The advantage is the production of pure hydrogen and the
worked only on one half of the problem (the anode) and at removal of oxygen in separate steps, avoiding the need for high-
present this solution offers no alternative to the platinum-based temperature separation and the chance of explosive mixture
cathode. A company (Sun Catalytics) was established to formation. The active redox material is in fact capable of water-
commercialize this new versatile, and affordable catalyst that splitting and regeneration, so that complete operation (water-
splits water into oxygen and hydrogen fuel. Despite the advan- splitting and redox material regeneration) is achieved in a closed
tages, water electrolysis and hydrogen/oxygen fuel cell tech- solar reactor.
nology still face challenges. For instance, the electrodes used in The concept has been proven experimentally for pairs of
water electrolysis are currently coated with platinum, which is oxides of multivalent metals or metal/metal oxide systems (for
not a sustainable resource, and researchers are currently inves- example, in the case of the highly promising ZnO/Zn system
tigating the employment of nanomaterials with a large reduction studied by Steinfeld and co-workers).15 However, even though
on the amount of precious metal needed. Indeed, the main water splitting is taking place at temperatures lower than 700  C,
advantage of Nocera’s catalyst that splits the water molecules material regeneration (i.e. reduction) takes place at much higher
using cobalt phosphate is that it is far cheaper and more abun- temperatures (>1600  C). In addition, despite basic research with
dant compared to expensive metals such as platinum. respect to active redox pairs, solar reactors reported in the
literature are based on particles fed into rotating cavity reactors,
concepts that are complicated and costly to operate.
Thermochemical water splitting
The uniqueness of the HYDROSOL approach is based on the
On the larger scale required to make solar-based H2O splitting combination of two novel concepts: nanoparticle materials with
using only the energy of the sun a practical technology in terms of very high water-splitting activity and regenerability (synthesised
quantity and cost, the thermochemical redox-cycle process using by novel routes such as aerosol processes, combustion techniques
a simple and robust materials is necessary, with manufactur- and reactions under controlled oxygen pressure) and their
ability on a large scale at competitive costs developed in the incorporation as coatings on special refractory ceramic mono-
context of the EU-funded Hydrosol project.13 The process—an lithic reactors whose geometry first emerged from traditional
endothermic reaction that requires an energy input—employs chemical engineering with its most familiar application to auto-
a multichannel ceramic honeycomb reactor resembling the mobile catalytic converters. The solar thermo-chemical reactor
familiar catalytic converter of automobiles, coated with active for the production of hydrogen from water splitting is

284 | Energy Environ. Sci., 2010, 3, 279–287 This journal is ª The Royal Society of Chemistry 2010
 temperature processes will be a viable way to produce large
amounts of hydrogen at a reasonable cost without any green-
house gas emissions, paving the way for a purely renewable solar
hydrogen economy. Further scale-up of the technology and its
effective coupling with solar concentration systems are in prog-
ress to demonstrate large-scale feasibility of a solar hydrogen
production plant.18

Outlook and perspectives

In a recent perspective paper based on order of magnitude
calculations,19 without referring to environmental arguments but
focusing on economic convenience only, Abbott has suggested
that sunlight is the scalable source of power on which our future
Fig. 13 The monolith channels are coated with active water-splitting energy needs must rely, based on low-tech CSP in place of
materials capable of splitting water vapor passing through the reactor photovoltaic electricity. Smil, on the other hand, suggests that
by ‘trapping’ its oxygen and leaving hydrogen in the effluent gas stream
even if a non-fossil world may be highly desirable, many decades
as product pure. (Reproduced from hydrosol-project.org, with permis-
will be needed for solar energy to capture substantial market
sion).
shares on the global market, because of the enormity of requisite
technical and infrastructural requirements. Yet, as Nocera puts
constructed from special refractory ceramic thin-wall, multi- it, the shift to a distributed power distribution infrastructure
channeled (honeycomb) monoliths (Fig. 13) that absorb solar where each home can produce and store enough electricity from
radiation. the sun to be self-sufficient (Fig. 15) is necessary because as
The reactor contains no moving parts, and with an overall billions of people in countries of Africa or of Asia start using
efficiency of about 70%, the water vapour is cleanly converted higher amounts of energy compared to today’s consumption, the
into hydrogen.16 The hydrogen produced is indeed clean and world’s energy needs will continue to explode in the coming
ready for use. Multi-cyclic solar thermo-chemical splitting of years. H2 is the fuel of the future because it solves the intermit-
water was successfully demonstrated on a pilot solar reactor tency of supply of free solar energy, meeting one key requirement
(Fig. 14) achieving constant hydrogen production exclusively at of modern societies: the continuous flows of energy. Of course,
the expense of solar energy. Single-phase doped spinel (AxBy)- human activity and energy usage correlates significantly with the
FezO4 (where A and B denote the bivalent dopant metals Ni, Mn delivery of radiation from the sun, making solar hydrogen an
or Zn, obtained by aerosol spray pyrolysis of a solution of the excellent load-following clean technology.
metal precursor salts) exhibited both the highest water conver- A hydrogen economy makes sense, even if there are efficiency
sion and hydrogen yield, being capable of splitting water at losses in liquefying and delivering H2,20 because the available
relatively low temperatures (800  C) with water conversions of
up to 80% and hydrogen being the only reaction product.17
The first 100 kW/reactor continuous pilot plant scale was
inaugurated on the Plataforma Solar de Almerı́a, Spain, on
March 31st 2008, being the first ever, closed solar-only, ther-
mochemical cycle for hydrogen production. Up to 40 cycles of
constant H2 production were operated in a row in a two-day
continuous production of hydrogen. Operation has demon-
strated that the combination of CSP facilities coupled with high

Fig. 14 In March 2008, a 100 kilowatt reactor for producing hydrogen

through water splitting using solar energy was put into commission at the
Plataforma Solar in Almerı́a as part of the Hydrosol project. The reactor Fig. 15 During the day PV modules power the home. At the same time,
is located inside the tower on the right. (Reproduced from hydrosol- excess energy is used to split water into H2 and O2 for storage and
project.org, with permission). subsequent usage in fuel cells. (Adapted from MIT, with permission).

This journal is ª The Royal Society of Chemistry 2010 Energy Environ. Sci., 2010, 3, 279–287 | 285
solar power is virtually unlimited and the collector technology is In Iceland, where abundant geothermal energy is freely
low-cost. As the sun delivers 5000 times our present global power available and the country is facing a most serious economic crisis,
needs, as little as a 500 by 500 km2 area is needed to supply the H2 manufactured by water electrolysis is increasingly used to
world’s energy needs (a tiny fraction of the world’s desert area); power private cars, public buses and boats with the aim of
using mirrors, focused sunlight can viably heat water for gener- expanding its use in the large fishing fleet of the country.25 And in
ating electricity via a conventional steam turbine. As put by Berlin there are two hydrogen filling stations open to the public.
Abbot: In general, the required infrastructure to support the use of
‘‘The point about solar energy is that there is so much of it hydrogen as a fuel will have to be developed.26
that you only have to tap 5% of it at an efficiency as tiny as 1% Bettiol argues that renewable energy will be a local, hi-tech
and you already have energy over 5 times the whole world’s business with a global impact.27 And it is remarkable to see how
present consumption. There is so much solar that all you have in practice this is occurring. For example, all three companies
to do is invest in the non-recurring cost of more dishes to drive involved in the ‘‘Future Project Hydrogen’’ are based in Austria,
a solar-hydrogen economy at whatever efficiency it happens very close to each other. Scientific and technical advice was
to sit at.’’ provided by the Technical University of Graz, whereas the
For Abbott, pure H2 (ready for combustion) should be project was realized with support of the European Union regional
preferred to both electric batteries and hydrogen fuel cells as the programs and further funding from one of Austria’s regions. The
latter are not scalable due the use of expensive membrane tech- first 600 Riviera boat is commercialized at 150 000 V, with the
nology as well as the expensive metal catalysts (platinum) or first exemplars to be delivered to customers in early 2010.
conducting metal ions (lithium), respectively. As the number and reach of similar successful projects
With the same logic, solar energy concentration systems inte- implemented worldwide grows, the huge potential of solar energy
grated with systems capable of directly splitting water will have in both developing countries endowed with ample solar energy
an immense impact on energy economics, as they require no like China as well as in wealthy countries such as the US or
electrolysis to provide affordable, renewable solar hydrogen with Australia will become self-evident. We add to this our idea that
virtually zero CO2 emissions. Such plants can offer new oppor- further progress will increasingly make use of alternative forms
tunities to regions of the world that have a huge solar potential, of financing whose ethical core on financing socially and envi-
like countries of Maghreb, that can become important local ronmentally sound projects will naturally have a great impact on
producers of clean hydrogen. the solar energy business. This will further accelerate adoption of
The intrinsic versatility and the fall of the price of PV elec- solar hydrogen and solar electricity until when solar energy will
tricity supports the option to use solar PV stations to locally be the most economically and technically convenient option,
produce electricity as well as relatively small amounts of H2 to replacing our dependency on fossil fuels.
power cars or boats powered by fuel cells. If a 250 m2 solar
station like the one shown in Fig. 8 in Austria can produce 823 kg
Acknowledgements
of pure H2 per year, in European regions like Sicily where PV
electricity has already reached the grid-parity,21 this figure should Thanks to Derek Abbot, University of Adelaide, for his insight on
be doubled at a fraction of the cost. Furthermore, new genera- the first version of this manuscript. Stefano Trasatti, University of
tion batteries and fuel cells will be nanotechnology-based,22 Milan, has shared valued information on water electrolysis. We
requiring ever less amounts of ‘‘exotic’’ metals and ensuring owe Claudia Bettiol for a grandiose vision on the future of
unprecedented performance in terms of power delivered or rate renewable energy. Special thanks are due to all the members of the
of charge. HYDROSOL team that made possible the project’s achieve-
But when will our global energy needs likely be met with the sun ments. This paper is dedicated to the children of all the world,
using solar farms distributed throughout the world?23 Very who will reap the benefits of massive adoption of solar energy.
shortly, we argue and namely within the next decade. And this is
based on pure economic and national security reasons. What is,
for example, the interest of a country like the US, the world’s
References
largest economy, to go ahead with a dependence on foreign oil 1 G. W. Bush, State of the Union Address, 2006, www.whitehouse.gov/
when it owns huge desertic regions that are exceptionally suited to stateoftheunion.
2 A. Z€ uttel, Materials for Hydrogen Storage, in Catalysis for
a massive adoption of solar energy?24 Despite the 2008–2009 (and Sustainable Energy Production, ed. C. Bianchini and P. Barbaro,
continuing) global economic recession in which the world’s Wiley-VCH, Weinheim, 2009, pp. 235–269.
manufacturing output dropped by 30%, the price of oil remains 3 J. J. Romm, The Hype about Hydrogen: Fact and Fiction in the Race to
Save the Climate, Island Press, Washington D. C., 2004.
>70 $/barrel. This can only accelerate the transitions to solar
4 V. Smil, 21st century energy: Some sobering thoughts, OECD
energy as many countries have the urgent need to reduce the Observer, 2006, 258/59, 22.
public debt that exploded following the public bailout of the 5 T. Bradford, Solar Revolution The Economic Transformation of the
financial system. Hence, they need to reduce the import of foreign Global Energy Industry, MIT Press, Boston, 2006.
6 E. Guerrini and S. Trasatti, Electrocatalysis in Water Electrolysis, in
oil and natural gas that even in a relatively small country like Italy Catalysis for Sustainable Energy Production, ed. C. Bianchini and
costs 60 billion V/year. Similarly, other oil-free semidesertic P. Barbaro, Wiley-VCH, Weinheim, 2009, pp. 235–269.
countries such as Jordan, Israel or Morocco have no interest to 7 H. Wendt and G. Kreisa, Electrochemical Engineering, Springer,
continue their dependence on foreign fossil fuels. Indeed, all the Berlin, 1999.
8 www.zukunftsprojektwasserstoff.at.
latter countries have announced detailed plans for adoption of 9 www.zukunftsprojektwasserstoff.at/typo/fileadmin/user_upload/
large-scale solar energy projects. download/FAQ_fuel_cell.pdf.

286 | Energy Environ. Sci., 2010, 3, 279–287 This journal is ª The Royal Society of Chemistry 2010
10 P. Fulini and E. Cecchini, Hydrogen Project for Arezzo. Build up an 18 A. G. Konstandopoulos, Solar Hydrogen from Thermochemical
underground hydrogen pipeline testing fuel cells in industrial areas. Water-Splitting: The HYDROSOL process and beyond, in The Fuel
Hydrolab – The link between hydrogen and renewable energies, Cells and Hydrogen Joint Technology Initiative, Stakeholders
World Hydrogen Technologies Convention, Montecatini Terme, General Assembly, Brussels, 2009. http://ec.europa.eu/research/fch/
Italy, 2007, http://www.lafabbricadelsole.it/wp/wp-content/uploads/ pdf/konstandopoulos.pdf#view¼fit&pagemode¼none.
file/WHTC2007.pdf. 19 D. Abbott, Proc. IEEE, 2010, 98, 42.
11 www.idrogenoarezzo.it. 20 U. Bossel, Proc. IEEE, 2006, 94, 1826. This paper does not consider
12 (a) M. W. Kanan and D. G. Nocera, Science, 2008, 321, 1072; (b) the case of using sun to generate the hydrogen.
M. W. Kanan, Y. Surendranath and D. G. Nocera, Chem. Soc. 21 W. Hoffmann, president of the European Photovoltaic Industry
Rev., 2009, 38, 109. Association, commenting the study SET For 2020, 2009. See also:
13 Co-ordinated by the Greek Aerosol and Particle Technologies http://greeninc.blogs.nytimes.com/2009/06/22/industry-group-says-
Laboratory, the consortium consisted of; the German Aerospace solar-to-become-cost-competitive-in-italy-next-year/.
Centre, Stobbe Technical Ceramics from Denmark and Johnson 22 M. Pagliaro, Nano-Age, Wiley-VCH, Weinheim, 2010.
Matthey Fuel Cells from the UK. www.hydrosol-project.org. 23 N. Armaroli and V. Balzani, Angew. Chem., Int. Ed., 2007, 46, 52.
14 C. Agrafiotis, M. Roeb, A. G. Konstandopoulos, L. Nablandian, 24 This is the aim of the Desertec project first conceived in Germany and
V. T. Zaspalis, C. Sattler, P. Stobbe and A. M. Steele, Sol. Energy, now being advanced by a consortium of German enterprises: http://
2005, 79, 409–421. www.desertec.org.
15 L. Schunk, P. Haeberling, S. Wepf, D. Wuillemin, A. Meier and 25 http://www.newenergy.is.
A. Steinfeld, J. Sol. Energy Eng., 2008, 130, 021009. 26 S. Pogutz, A. Russo and P. Migliavacca, Innovation, Markets and
16 http://ec.europa.eu/research/star/index_en.cfm?p¼22_main. Sustainable Energy: The Challenge of Hydrogen and Fuel Cell,
17 C. C. Agrafiotis, C. Pagkoura, S. Lorentzou, M. Kostoglou and Edward Elgar, Cheltenham, 2009.
A. G. Konstandopoulos, Catal. Today, 2007, 127, 265. 27 C. Bettiol, Il Futuro, Seminar ‘‘Marcello Carapezza’’, CNR, Palermo, 2009.

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