i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 1 2 4 6 e1 1 2 5 7

Available at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/he

Solar hydrogen production: A comparative performance

assessment

Anand S. Joshi*, Ibrahim Dincer, Bale V. Reddy

Faculty of Engineering and Applied Science, University of Ontario Institute of Technology, 2000 Simcoe Street North, Oshawa,
ON L1H 7K4, Canada

article info abstract

Article history: Hydrogen is a sustainable fuel option and one of the potential solutions for current energy
Received 31 August 2010 and environmental problems. Its eco-friendly production is really crucial for better envi-
Received in revised form ronment and sustainable development. In this paper, various solar hydrogen production
23 November 2010 methods are discussed. A comparative performance assessment study of solar thermal and
Accepted 26 November 2010 photovoltaic (PV) hydrogen production methods is carried out. It is found that the solar
Available online 13 January 2011 thermal hydrogen production via electricity production is an environmentally benign
method and possesses higher exergy efficiency than PV hydrogen production. However,
Keywords: the latter is better in a way that it does not involve any moving parts. PV hydrogen
Hydrogen production production suffers lower exergy efficiency because of low PV efficiency.
Solar energy Copyright 2010, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
PV reserved.
Electricity
Efficiency
Exergy

1. Introduction sources for example, solar energy. Solar energy is abundant

Hydrogen, undoubtedly, is future fuel and energy carrier. It is
carbon free and hence environmentally friendly. Although
hydrogen is naturally present on Earth in combined state in
both organic and inorganic compounds for example, as
hydrocarbons, water and other substances, but it is scarcely
present in the free and molecular state, therefore, the
elemental hydrogen is artificially produced and hence its safe
and environmentally benign production is most important.
Electrolysis of water is one of the many techniques by which
hydrogen can be produced. An electrolyser unit uses electricity
and breaks water into hydrogen and oxygen. While hydrogen
can be considered as a direct energy source like fuel in auto-
mobiles, oxygen can be considered as a safe by-product.
Production of electricity can be done by using renewable
source of energy that is freely and immensely available all over
the globe and can be used for electricity production using two
different routes namely, PV and solar thermal via concen-
trating collector systems. Some difficulties associated with the
intermittent nature of solar energy, cloudy and no sunshine
conditions are successfully encountered by using a storage
system. Storage system in PV hydrogen production system is
a battery bank where as in thermal system it can be a hot water
storage tank or phase change materials. The estimated
potential of the direct capture of solar energy is enormous.
When solar energy strikes the Earths atmosphere, approxi-
mately 30% gets reflected. After reflection by the atmosphere,
Earths surface receives around 3.9
1024 MJ incident solar
energy per year which is almost 10000 times more than current
global energy consumption. Thus, the harvesting of less than

* Corresponding author.
E-mail addresses: anandsj75@rediffmail.com (A.S. Joshi), ibrahim.dincer@uoit.ca (I. Dincer), bale.reddy@uoit.ca (B.V. Reddy).
0360-3199/$ e see front matter Copyright 2010, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2010.11.122
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 1 2 4 6 e1 1 2 5 7 11247

1% of photonic energy would serve all human energy needs [1].
PV system, as discussed above, is a novel approach to the
electricity generation as it uses solar energy which is freely
available. Though the intermittent nature of solar radiation
limits the use of this technology up to some extent, still for off
sunshine periods the stored energy in a battery bank can be
used. PV systems can not only be used as standalone systems
but also as connected to grid to supply continuous electricity
throughout a day. The efficiency of the solar cell can range
from 12 to 15% typically for the silicon solar cell. However, it is
as high as 25e30% for GaAs solar cells. The cost of the former is
less as compared to the latter which is used mostly for space
applications. The efficiency of the PV system can also be
calculated by taking the product of the efficiencies of its various
components like solar cell, module, battery, etc. From a health
perspective, the potential benefits of solar energy applications
seem very desirable. The two disadvantages of the PV tech-
nology can be low conversion efficiency and high cost of the
solar cells but it can be overcome by intense research in the
same. On the other hand, solar thermal technology is at its
maturity stage. Depending upon the temperature needed
different types of solar collectors can be used. Table 1 gives

Table 1 e Different types of solar collectors (adapted from Ref. [2]).

Flat plate collector C1
T < 200  C
P < 1 MW(th)

Vacuum tube collector C3

T < 300  C
P < 1 MW(th)

Concentrating solar collector C 40e80

T < 350  C
P < 50 &MW(e)

Field mirror collector C 200e700

T < 1500  C
P < 150 &MW(e)

Parabolic collector C 1000e2500

T < 2500  C
P < 100 kW (th)/Einh.
11248 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 1 2 4 6 e1 1 2 5 7
information about different solar collectors, their tempera-
tures, concentration factors and power capacities.
The flat plate collector is the simplest one on which solar
radiation incident on a flat transparent surface which trans-
mit these radiation to an equal size absorbing/collecting
surface generally made up of Cu or Al metals. Cu or Al metals
are preferred because of high thermal conductivity (Cu) and
comparatively reasonable cost (Al) of the material. Point to be
noted here is that the incident solar flux directly gets absorbed
on the receiver surface. Larger the area of receiver surface
larger would be the thermal energy available. The concen-
tration factor of a FPC is 1 and a thermal power up to 1 MW can
be generated for a temperature range up to 200  C by con-
necting flat plate collectors in series. The other collectors
shown are concentrating collectors. Their concentration
factor, power and the operating temperature are higher. The
application of solar energy in hydrogen production is dis-
cussed in the subsequent sections. The various hydrogen
production methods are also discussed in brief.
2. Solar hydrogen production systems
Various solar hydrogen production systems are summarized
in Table 2. The main four types of systems are as follows: (1) PV
(2) photoelectrochemical (3) photobiological and (4) solar
thermal. The PV-based hydrogen production is mainly asso-
ciated with an electrolyser unit that utilizes the DC electricity
produced by the PV panels to electrolyze water into hydrogen
and oxygen. In solar thermal, the thermal power of solar
energy is utilized to produce hydrogen. Solar thermal energy
can be utilized in two ways; low temperature and
high temperature application also called concentrated solar
energy. PV, photoelectrolysis and biophotolysis are low
temperature application where as thermolysis, thermochem-
ical cycles, gasification, reforming and cracking are high
temperature applications of concentrated solar thermal
energy. The details of each hydrogen production method are
presented in the following sections.
Table 2 e Various solar hydrogen production systems with their types, processes, process description and end products.
Solar H2 production systems Type Processes
PV Low temperature Electrolysis
Photoelectrochemical Photoelectrolysis
Photobiological Photobiolysis
Concentrated solar thermal High temperature Thermolysis
Thermochemical
cycles
Gasification
Cracking
Steam-reforming
Electrolysis
2.1. PV hydrogen production via electrolysis
The hydrogen production by electrolysis of water using the
electricity produced by the PV cells was started in the begin-
ning of 70s [3e6]. The electrolysis of water can be carried out
by a current generated by the PV cells. From the economic and
ecological viewpoints, the most effective production method
is considered the application of a photovoltaic current source
(PCS) as a result of transforming radiant solar energy directly
into electrical energy. When the efficiency of modern photo-
converters (i.e. PVs) and electrolysers is about 20% and 80%,
respectively [7], the total efficiency of solar radiant energy
transformed to chemical hydrogen energy is nearly 16% [6].
The schematic diagram of a hydrogen production system that
uses PV unit is shown in Fig. 1. The electrolysis of distilled
water using electricity produced by the PV panel takes place in
electrolyser unit and produces hydrogen and oxygen as the
end products as shown in same figure. Joshi et al. [8] have
analyzed a PV-based solar hydrogen production and found the
exergy efficiency is ranging between 3.68 and 4.84% and
concluded that the efficiency is low because of low PV effi-
ciency [9]. This technology is not cost effective as the PV
technology is costly therefore needs a higher and extensive
research in this area. Some advantages of PV technology are
that it does not emit greenhouse gases during the operation
and since it does not involve any moving part its maintenance
is simple and easy and it does not cause any noise pollution
during operation.
2.2. Solar photoelectrochemical hydrogen production
system
Another method to convert sunlight into hydrogen is by
photoelectrolysis of water that uses photoelectrochemical
light collecting systems (PEC e photoelectrochemical cell) to
power the electrolysis of water. Recently, Kelly and Gibson [10]
conducted some tests on two simple and inexpensive photo-
electrochemical (PEC) reactors namely teardrop shaped
plastic-film bag reactor, and acrylic spherical tank reactor
Process description End
products
Water electrolysis H2, O2
Photoelectrolysis of water H2, O2
Plant and algal photo-synthesis H2
Thermal dissociation of water H2, O2
Thermochemical cycles using H2, O2
metal oxides
Steam-gasification of coal and other solid H2, CO2
carbonaceous materials
Thermal decomposition of natural gas H2, C
(NG), oil, and other hydrocarbons
Steam-reforming of NG, oil, and H2, CO2
other hydrocarbons
High temperature water electrolysis and H2, O2
water electrolysis via solar
thermal electricity generation
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 1 2 4 6 e1 1 2 5 7
Fig. 1 e Schematic of a PV hydrogen production system.
capable of producing hydrogen via water electrolysis using
solar energy and found that the latter had the best light-
focusing properties, with up to a factor of 3.7 increase in the
solar energy (and thus hydrogen production) for PEC cells
mounted at the optimal point within the reactor electrolyte.
They concluded that by increasing the solar irradiance on the
PEC photoelectrode, the hydrogen production increases and
also it can help to reduce the system cost. A schematic of their
spherical tank reactor is shown in Fig. 2. The positive and
negative terminals of the PV modules were connected to
anode and cathode, respectively, which are separated by
a chamber divider. The tank was filled with the 5 M KOH
electrolytic solution. When sunlight falls on PV module it
produces electricity which further negotiates the chemical
reaction and produces hydrogen on cathode and oxygen on
anode side of the system respectively. The spherical shape of
the rector is helpful to focus solar radiation on the PV module
by properly orienting the PV module towards the sun or
simply by tilting the reactor so the PV cells face the sun
thereby increasing the hydrogen output per unit area. Since
the electrolyte solution takes the shape of its curved
container, the reactor acted as a convex lens that focused the
solar radiation onto the PV cells at an increased intensity.
Further it is possible to focus light onto the PV cell by
a combination of light-focusing properties of the reactor
together with that of lenses such as Fresnel lenses. Another
advantage of having the PV module dipped inside the KOH
Fig. 2 e A schematic of spherical tank reactor (adopted from
[10]).
11249
solution is that the performance of the solar cells in terms of
electrical efficiency would not be affected by the thermal
energy (heat) of the solar radiation. In other words, the KOH
solution would cool down the solar cells if the concentrated
solar radiations try to increase the temperature of the solar
cells of the PV module.
Fujishima and Honda [11] also proposed a photo-
electrochemical hydrogen production system that uses
a single PEC. When exposed to sunlight, a semiconductor
photoelectrode (anode or cathode), submerged in an aqueous
electrolyte, generates sufficient voltage to split water mole-
cules; typically the other electrode is a metal [12]. Photons
with energies greater than the semiconductor band gap can be
absorbed by the semiconductor, creating electron-hole pairs
which are split by the electric field in the space-charge region
between the semiconductor and the electrolyte. The electric
field reflects the band bending of the conduction and valence
band edges at the semiconductor surface and is necessary to
supply the free carriers to the appropriate electrode. The
overall cell reaction then becomes [13]:
2hy H2 Ol/1=2O2 g H2 g (1)
where h is the Plancks constant, n is the frequency.
Photoelectrolysis integrates solar energy absorption and
water electrolysis into a single photoelectrode. The device
does not require a separate power generator and electrolyser
[14]. The maximum theoretical efficiency is about 35% [15]. In
current research, it has been seen that photoelectrolysis
systems reached first-law of thermodynamic efficiency of
about 18% [16]. However, this efficiency was obtained for only
a very small amount of hydrogen production. The solar-to-
hydrogen conversion efficiency of the materials has not yet
met requirements for practical use due to the limitation of
usable solar spectrum. It is expected that technological
advancement and speedy commercialization will make such
systems feasible and practical. Although photoelectrolysis
cells are simple and do not require the complex
manufacturing steps necessary in the formation of p/n and
n/p PVs, they require high land space and semiconductor
requirements. Its lifetime is also extremely low, and some
operational/technical details are unknown [17]. Moreover,
they suffer from material problems.
2.3. Solar photobiological hydrogen production
Photobiological hydrogen production uses the processes same
as plant and algal photosynthesis, for hydrogen production.
The biological hydrogen production can be classified into two:
(1) light dependent and (2) light independent process. First
process includes direct or indirect biophotolysis and photo-
fermentation whereas the second one includes dark fermen-
tation [18]. Plant and algal photosynthesis results in the
splitting of water into oxygen and a reducing agent strong
enough to reduce CO2, or protons, to carbohydrates or
hydrogen, respectively. Photobiological production of hydrogen
from water (biophotolysis), involves an efficient biological
converter, microalgae, and a photobioreactor. Microalgae are
suitable for such processes, as they exhibit hydrogen evolution
under some conditions, and they can be cultured in closed
11250 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 1 2 4 6 e1 1 2 5 7
systems that can permit hydrogen capture. Microalgal strains
must be developed that exhibit high hydrogen production rates
and photosynthetic efficiencies in dense cultures at full solar
intensities. The photobioreactor must expose the H2 producing
cultures to sunlight, while allowing recovery of the gas [6]. One
advantage of biological processes is to be catalyzed by micro-
organisms in an aqueous environment at ambient temperature
and pressure [18]. Biological methods for solar hydrogen
production have not yet been developed for commercial use,
except for the laboratory stage and small (<10 m2) outdoor
demonstration scale systems [19]. This technology is still under
development stage because of relatively low efficiency of
photosynthesis as trees and agricultural crops convert sunlight
at efficiencies less than 1% [20].
2.4. Concentrated solar thermal hydrogen production
Various thermochemical methods for solar hydrogen
production are given in Table 2. The chemical source of
hydrogen that is, water for the solar thermolysis and the solar
thermochemical cycles, fossil fuels for the solar cracking, and
a combination of fossil fuels and H2O for the solar reforming
and solar gasification are also given in the same table. Since all
these methods involve endothermic reactions, they make use
of thermal energy of concentrated solar radiation as the
energy source of high-temperature process heat. Various
hydrogen production methods involving concentrated
thermal energy are described in brief as follow:
2.4.1. Solar thermolysis
The single-step thermal dissociation of water is known as
water thermolysis and can be given as
H2 O/H2 1=2O2
As discussed above, the reaction requires a high-tempera-
ture heat source at above 2500 K to have a reasonable degree
of dissociation, and by the need of an effective technique for
separating H2 and O2 to avoid ending up with an explosive
mixture. Among many, effusion separation [21e23] and elec-
trolytic separation [24,25] are two ways to separate the
hydrogen from products. Kogan [23] and Diver et al. [26] have
tested semi-permeable membranes based on ZrO2 and other
high-temperature materials at up to 2500 K, but these
ceramics usually fail to withstand the severe thermal shocks
that often occur when working under high flux solar irradia-
tion. Some simple and workable methods are rapid quench by
injecting a cold gas [27], by expansion in a nozzle, or by
submerging an irradiated target in liquid water [28], but the
quench causes a significant drop in the exergy efficiency and
produces an explosive gas mixture. The very high tempera-
ture required by the process (e.g. 3000 K for 64% dissociation at
1 bar) pose severe material problems and can lead to signifi-
cant re-radiation from the reactor, thereby lowering the
absorption efficiency.
2.4.2. Solar thermochemical cycles
Water-splitting thermochemical cycles have an upper edge on
thermolysis as it does not have the H2/O2 separation problem
and further allow operating at relatively moderate upper
temperatures (1200 K). An efficient 2-step thermochemical
cycle using metal oxide redox reactions can be given as,
1st step (solar):
y
Mx Oy /xM O2 (3)
2
2nd step (non-solar):
xM yH2 O/Mx Oy yH2 (4)
where M denotes a metal and MxOy the corresponding metal
oxide. The first, endothermic step is the solar thermal disso-
ciation of the metal oxide to the metal or the lower-valence
metal oxide. The second, non-solar, exothermic step is the
hydrolysis of the metal to form H2 and the corresponding
metal oxide. The net reaction is (H2O H2 1/2O2), but since
H2 and O2 are formed in different steps, the need for high-
temperature gas separation is thereby eliminated.
2.4.3. Decarbonization of fossil fuels
Hydrogen can be produced from fossil fuels by using solar
thermochemical processes. Three solar thermochemical
processes are: solar cracking, solar reforming, and solar gasi-
fication. The process of solar cracking can be explained by the
thermal decomposition of NG, oil, and other hydrocarbons,
and can be represented by the simplified net reaction:
y
Cx Hy /xCgr H2 (5)
2
The steam-reforming of NG, oil, and other hydrocarbons,
and the steam-gasification of coal and other solid carbona-
ceous materials can be expressed by the simplified net
reaction:
y 
Cx Hy xH2 O/ x H2 xCO (6)
2
(2)
Depending on the reaction kinetics and on the presence of
impurities in the raw materials, other compounds may also be
formed. Reaction (5) produces a carbon-rich condensed phase
and a hydrogen-rich gas phase. The carbonaceous solid product
can either be sequestered without CO2 release or used as material
commodity or reducing agent under less severe CO2 restraints.
The product of reaction (6) is syngas. The CO content present in
the syngas can be shifted to H2 via the catalytic water-gas shift
reaction (CO H2O H2 CO2), and the product CO2 can be
separated from H2 using, for example, the pressure swing
adsorption technique. Some of these processes that are already
on industrial scale use the heat supplied by burning the feedstock
as the process heat which further results in either the contami-
nation of the gaseous product in case of internal combustion or in
a reduced thermal efficiency due to irreversibility associated
with indirect heat transfer in case of external combustion.
Some advantages of using solar energy for process heat are
the discharge of pollutants can be avoided, the gaseous
products are not contaminated and the calorific value of the
fuel is upgraded by adding solar energy in an amount equal to
the enthalpy change or total energy required by the reaction.
The steam-reforming/gasification method requires additional
steps for shifting CO and for separating CO2 whereas the
thermal cracking accomplishes the removal and separation of
carbon in a single step. On the contrary, the major drawback
of the thermal decomposition method is the energy loss
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 1 2 4 6 e1 1 2 5 7
associated with the sequestration of carbon. Thus, the solar
cracking may be the preferred option for NG and other
hydrocarbons with high H2/C ratio. For coal and other solid
carbonaceous materials, the solar gasification via reaction (6)
has the additional benefit of converting a solid fuel tradi-
tionally used to generate electricity in Rankine cycles into
a cleaner fluid fuel, i.e. hydrogen. This may be achieved in two
ways: firstly it is produced by using solar process heat that can
be used in highly efficient fuel cells, and secondly, it is free
from carbon as carbon dioxide is separated and sequestrated.
2.4.4. Solar thermal hydrogen production via electricity
generation and electrolysis
A schematic of solar thermal system can be described as
shown in the Fig. 3. The system comprises of four main units:
concentrating collector, heat engine, generator and electro-
lyser. Thermal heat storage unit can also be added to the
circuit to ensure the continuous supply of thermal energy to
heat engine. When solar radiation strikes the concentrating
collector it gets concentrated on the absorber surface with
which heat engine is attached. Heat engine uses part of this
thermal energy and converts it to mechanical (shaft) work.
Remaining thermal energy escapes into the atmosphere and
hence called heat loss. The shaft work is then utilized to
generate electricity by using an electrical generator. The
electricity generated is then supplied to electrolyser unit
which electrolyses water into hydrogen and oxygen. The
system involves moving parts for example, heat engine,
generator etc., therefore, requires more maintenance as
compared to others (e.g. PV hydrogen production system).
3. Analysis of PV AND Solar Thermal
Hydrogen Production Systems
In this section, the analysis of the PV and solar thermal
hydrogen production systems is done. The two different routes
are shown in Fig. 4. In PV route, DC electricity is generated first
by PV panes and then stored in a battery bank. The DC elec-
tricity can be converted to AC electricity by using an inverter
and then this electricity is further used to run an electrolyser.
In solar thermal route, the thermal energy of solar radiation is
Fig. 3 e Schematic of a solar thermal hydrogen production system.
11251
first collected and concentrated using a concentrating solar
collector. Thermal storage system may also be used to ensure
the continuous supply of thermal energy. Then by using a heat
engine the thermal energy is converted into mechanical shaft
work and by coupling a generator to heat engine the shaft work
is converted into electricity. This electricity is used by an
electrolyser for water electrolysis.
3.1. Energy and exergy efficiencies
The energy and exergy efficiencies of the system can be
calculated by considering the efficiencies of each component
of the system. Here is a brief calculation for each component.
To calculate the collector efficiency, the heat available on the
collector surface is an important parameter that can be
calculated by Hottler Whiller equation as [29],


Q_ FR AA rR aA It C  UL TA  Ta  es T4A  T4a (7)
where rR is the reflectivity of the reflector surface; aA is the
absorptivity of the absorber surface; It is the intensity of total
solar radiation (W/m2); AA is the area of absorber surface (m2); C
is the concentration factor; UL is the heat transfer coefficient
from absorber surface to ambient (W/m2 K); TA is the absorber/
receiver surface temperature ( C); Ta is the ambient temperature
( C); e is the emissivity of the absorber surface; s is the
StefaneBoltzmann constant (5.67
108 W/m2 K4); FR is the
efficiency factor.
Useful heat available at the receiver surface is limited by the
Carnot efficiency of a fictitious heat engine working between
the temperature of the receiver and the ambient temperature
and can be given as,
 
Ta
Q_ u Q_ 1  (8)
TA
The energy efficiency of the concentrating collector can be
defined as the ratio of thermal energy available at the receiver
surface to the incident solar energy on the concentrator and
can be expressed as,
Q_
hC (9)
It AC
where Ac Area of collector (m2).
11252 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 1 2 4 6 e1 1 2 5 7

efficiency of the electrical generator/alternator is limited by

Solar Energy
iron loss, copper loss and the voltage drop in the diode bridge
and it is between 50e62% [31]. The final expression for exergy
Solar Thermal PV efficiency of electrical generator/alternator becomes,

PE VI VI
jGEN (14)
Solar Collector PM s
u s
2p
rpm
60
PV Panels
where s is torque (Nm), u is the rotations per minute (rpm), V is
Thermal Storage the voltage (V) and I is the current (A).
Battery Bank The energy efficiency of electrolyser can be calculated as [6],
Heat Engine _ H2 HHVH2
m
hEL (15)
Pin
Generator Electrolyser Inverter The exergy efficiency of electrolyser can be calculated as [6],

_ out Ex
Ex _ H Ex _ O
Solar Hydrogen jEL 2 2
(16)
Pin Pin

Fig. 4 e Two routes of solar hydrogen production. Once all the above said efficiencies of each unit are known,
the overall energy efficiency of solar thermal hydrogen
production system can be calculated as,
The exergy efficiency of the concentrating collector can be h hC
hHE
hGEN
hEL (17)
defined as the ratio of the useful thermal energy available at
the receiver surface to the incident solar exergy on the Similarly the overall exergy efficiency of the solar thermal
concentrator and can be expressed as, hydrogen production system becomes,

j jC
jHE
jGEN
jEL (18)

Q_ u
jC   (10)
It 1  TTaS AC Similarly, the overall energy efficiency of a PV hydrogen
production system can be calculated as
The exergy of the solar radiation incident on the collector
surface as expressed in the denominator of the Eq. (10) can be h hPV
hCR
hIN
hEL (19)
defined as the product of intensity of solar radiation, area of where
the collector surface and the Carnot cycle efficiency of a ficti-
tious heat engine between ambient and Sun temperatures Voc Isc
hPV (20)
[30]. The mechanical work (shaft work) of a heat engine can be It A
calculated as, Here, Voc is the open circuit voltage (V) Isc is the short circuit
current (A).
_ hHE Q_ u
W (11) And the overall exergy efficiency of PV hydrogen produc-
where tion system becomes,
j jPV
jCR
jIN
jEL (21)
Ta
hHE 1  (12)
TA where JPV is the exergy efficiency of PV panel, JCR is the
Note that the efficiency of heat engine (hHE) is the Carnot exergy efficiency of charge regulator, and JIN is the exergy
cycle efficiency that limits the maximum usage/application of efficiency of inverter.
thermal energy by any heat engine. In other words, no heat The exergy efficiency of PV panel can be given as,
engine can perform better than its Carnot cycle efficiency. FFVoc Isc VI
jPV     (22)
Therefore the exergy efficiency of the heat engine is less than It 1  TTSa A It 1  TTaS A
the Carnot cycle efficiency. Once mechanical work is
produced, electricity can be generated by coupling an elec- where the fill factor (FF) is the ratio of electrical output to the
trical generator/alternator with the heat engine. It can also be maximum possible electrical output from a PV cell. Fill factor
calculated by taking the ratio of electrical power generated to can be expressed as
solar energy incident on the collector area. Hence the energy VI
FF (23)
efficiency of the electrical generator can be calculated as, Voc Isc

PE
hGEN (13)
PM
3.2. Sustainability index
where PE is the electrical power (W) and PM is the mechanical
power (W). Once the exergy efficiency of the system is known, the
The exergy efficiency of electrical generator/alternator can sustainability index can be calculated. The relation between
also be considered same as the energy efficiency because the exergy efficiency (J) and the sustainability index (SI) can be
electrical output and mechanical input remains the same. The given as [32]:
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 1 2 4 6 e1 1 2 5 7 11253

Table 3 e Energy and exergy efficiency parameters for Table 5 e Energy and exergy efficiencies of photovoltaic
solar concentrating collector [29]. hydrogen system components (modified from [6]).
Parameter Value Parameter Value Components Energy Exergy e
efficiency (%) fficiency (%)
rR 0.9 FR 0.9
aA 0.9 e 0.9 PVs 11.2e12.4 9.8e11.5
AA 0.8 m2 AC 80 m2 Charge regulators 85e90 85e90
C 100 UL 8 W/m2K Inverter 85e90 85e90
Electrolyser 56 52

1
j1 (24) areas of absorber surface and collector, concentration ratio
SI
and overall heat loss coefficient have been modified and are
where given in Table 4. To analyze the solar concentrator perfor-
1 mance based on energy and exergy efficiencies four different
SI (25) cases are adopted which are described in brief as follows.
DP
Case 1: it uses the data of Tyagi et al. [29] as given in Table 3.
and Dp is the depletion factor/number defined by [33] as the Case 2: it uses the data same as Case 1 except for the value
ratio of exergy destruction rate to the input exergy rate of the of emmisivity.
system and can be given as Case 3: it uses the data same as Case 1 except for the values
_ D of absorptivity and emmisivity.
Ex
DP (26) Case 4: it uses the modified data as given in Table 4.
_ in
Ex
The above four cases are discussed with their explanation in
detail and the different climatic parameters in the next section.
3.3. Case study
For the analysis of PV hydrogen production system, the
data of Yilanci et al. [6] as presented in Table 5 is adopted.
For a case study, the analysis presented in the previous
section is applied to PV and solar thermal hydrogen produc-
tion systems. The case study is divided into three parts. First
4. Results and discussion
part deals with the efficiency analysis of concentrating
collector for solar thermal hydrogen production system.
The analysis and data presented in the previous section are
Second part deals with the overall energy and exergy effi-
applied to solar thermal and PV hydrogen production systems
ciency analysis of the thermal and PV hydrogen production
and the results and their pertinent discussion for all the three
systems whereas the third part deals with the sustainability
parts as described in the beginning of case study are presented
index analysis of the above two systems.
as follows.
To analyze the solar thermal hydrogen production system,
the energy and exergy efficiency analysis of concentrating
4.1. Efficiency analysis for concentrating collector
collector is very important as this component is responsible to
convert solar energy to concentrated thermal energy and is
For solar thermal hydrogen production system, first the energy
affected by climatic parameters such as intensity of solar
and exergy efficiencies of solar collector are evaluated by using
radiation and ambient temperature and the physical param-
Eqs. (7)e(10) and the data of Tyagi et al. [29] (Table 3). The effect
eters of the concentrator such as reflectivity of reflector
of variation in solar radiation on the energy and exergy effi-
surface, absorptivity and emmisivity of absorber surface,
ciencies of concentrated collector is also calculated and is
areas of absorber surface and collector, concentration ratio
shown in Table 6 and Fig. 5, respectively. The effect of
and overall heat loss coefficient, etc. For the energy and exergy
absorptivity and emmisivity of the absorber surface on energy
analysis of concentrating collector of solar thermal system,
and exergy efficiencies is also shown in the same table. Table 6
the data of Tyagi et al. [29] is adopted and presented in Table 3.
It should be noted that they have assumed the absorptivity
and emmisivity of the absorber surface each equal to 0.9. To
have a more realistic analysis and for comparison purposes, Table 6 e Effect of solar radiation, absorptivity and
some data of Tyagi et al. [29] such as absorptivity, emmisivity, emmisivity on the energy and exergy efficiency of a solar
concentrating collector.
It , Case 1, Case 2, Case 3, Case 4a,
W/m2 aA 0.9, aA 0.9, aA 0.8, aA 0.8,
Table 4 e Modified parameters for the evaluation of e 0.9 e 0.1 e 0.2 e 0.2
energy and exergy efficiency of solar concentrating
collector (modified from [29]). hC JC hC JC hC JC hC JC
Parameter Value Parameter Value (%) (%) (%) (%) (%) (%) (%) (%)

rR 0.9 FR 0.9 500 23.9 16.07 60.74 40.79 48.04 32.26 51.76 34.76
aA 0.8 e 0.2 750 40.25 27.03 64.79 43.51 53.62 36.01 56.14 37.7
AA 0.0079 m2 AC 1.96 m2 1000 48.41 32.51 67 44.87 56.42 37.89 58.33 39.18
C 250 UL 25 W/m2K a For Case 4, complete data is shown in Table 4.
11254 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 1 2 4 6 e1 1 2 5 7
Energy Efficiency Case 1
Exergy Efficiency Case 2
Energy Efficiency Case 4
70
Energy & Exergy Efficiency (%)
60
50
40
30
20
10
500
Fig. 5 e Variation of energy and exergy efficiency with solar radiation.
shows four cases for energy and exergy efficiencies of the solar
concentrating collector and they are described as follows: Case
1 that uses the data of Tyagi et al. [29], Cases 2 and 3 use
modified data from Tyagi et al. [29]. It should be noted that
Tyagi et al. [29] have assumed the absorptivity and emmisivity
of the absorber surface each equal to 0.9 (Case 1). To minimize
the radiation losses the emmisivity is reduced in Cases 2, 3 and
4. In Case 3, the absorptivity and emmisivity are taken as 0.8
and 0.2, respectively. Case 4 shows the effect of concentration
factor, areas of absorber and collector surface and the overall
heat loss coefficient on the efficiencies of the collector. The
modified data for Case 4 is shown in Table 4. It should be noted
that the absorber area is reduced to reduce the heat loss due to
radiation and the concentration factor is increased to have
more thermal energy available at absorber surface. More
realistic value of overall heat loss coefficient (25 W/m2 K) is
considered as at higher absorber temperatures for example,
823 K, the heat transfer coefficient is also high [34]. For calcu-
lations, three different solar intensities, i.e., 500, 750 and
1000 W/m2 are considered and ambient and the absorber
temperatures are assumed as 298 and 823 K, respectively.
Fig. 5 shows the variation of energy and exergy efficiencies
of a solar concentrating collector. It is clear from the same
figure that energy efficiency is higher than the exergy effi-
ciency in all four cases. This is because the exergy efficiency
also called second law efficiency, incorporates the losses due
Table 7 e Energy and exergy efficiencies of solar thermal
hydrogen system components [6,30].
Components Energy
efficiency (%) fficiency (%)
Solar collector 58.33
Heat engine 63.8
Generator 50e62
Electrolyser 56
Exergy Efficiency Case 1 Energy Efficiency Case 2
Energy Efficiency Case 3 Exergy Efficiency Case 3
Exergy Efficiency Case 4
750 1000
2
Solar Radiation (W/m )
to irreversibility and hence gives more realistic analysis.
Energy and exergy efficiencies increase with the increase in
solar radiation because higher solar radiation is responsible
for high thermal energy available at absorber surface. There-
fore it can be said that the higher the intensity of solar radi-
ation, higher would be the energy and exergy efficiencies of
the concentrating collector. Further, comparing Cases 1 and 2
it can be said that the energy and exergy efficiencies of former
are lower because of higher emmisivity. Comparing Cases 2
and 3 it can be said that the efficiencies of Case 2 is higher
because of low emmisivity and high absorptivity. Comparing
Cases 3 and 4 one may get that the efficiencies of Case 4 are
higher because of higher concentration factor. The area of
absorber surface is reduced to reduce the heat losses due to
radiation.
4.2. Overall efficiency analysis for solar thermal and PV
hydrogen production systems
Once the solar concentrating collector efficiency is evaluated,
the overall energy and exergy efficiencies of solar thermal
hydrogen production system can be calculated by using Eqs.
(11)e(18), however, for present case study, the energy and
exergy efficiency data for other components (except for
storage system) (Table 7) of the solar thermal hydrogen
production system as shown in Fig. 4 is considered. It is found
that the overall energy and exergy efficiencies of solar thermal
hydrogen production system range between 10.42e12.92%
and 3.06e6.31%, respectively, as shown in Fig. 6. The
minimum overall energy and exergy efficiencies are calcu-
lated by taking least values of individual components and
Exergy e
maximum value is calculated considering maximum values of
the same. Note that the energy efficiency of the heat engine is
39.18 calculated as 63.8% by using Eq. (12) which is also the Carnot
30e50
cycle efficiency working between the higher (823 K) and lower
50e62
52
(298 K) temperatures and exergy efficiency of the heat engine
is assumed as ranging between 30 and 50% which is less than
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 1 2 4 6 e1 1 2 5 7 11255

PV Hydrogen Production System 10

Theoretical
14 Solar Thermal Hydrogen Production System 9 Concentrating Collector
System
12 8 Heat Engine
Overall Efficiency (%)

Generator
10 7

Sustainability Index
Electrolyser
8 6

6 5

4 4

2 3

0 2

Energy Efficiency Energy Efficiency Exergy Efficiency Exergy Efficiency 1

(Minimum) (Maximum) (Minimum) (Maximum)
0
0 10 20 30 40 50 60 70 80 90 100
Fig. 6 e Overall energy and exergy efficiency range for PV Exergy Efficiency (%)
and solar thermal hydrogen production systems.
Fig. 7 e Variation of sustainability index with exergy
efficiency of a solar thermal hydrogen production system.

that of the Carnot cycle efficiency and are also given in Table 7.
The energy and exergy efficiencies of solar concentrating
collector are taken from Case 4 corresponding to the solar
radiation of 1000 W/m2. It is to be noted that the above
calculations are based on theoretical data therefore, gives
a theoretical analysis of energy and exergy efficiencies of
a solar thermal hydrogen production system.
The overall efficiencies of PV hydrogen production system
are also shown in Fig. 6. The exergy and energy efficiencies of
different components as given in Table 5 are considered to
evaluate the overall exergy and energy efficiencies of the PV
hydrogen production system. However, this can also be done
by calculating each components efficiency by using Eqs. (15),
(16) and (19)e(23). Referring Table 5 and by using Eq. (19), the
energy efficiency of the PV hydrogen production system is
calculated as ranging between 4.53 and 5.62% (Fig. 6). Similarly
the exergy efficiency of the PV hydrogen production system is
calculated by using Eq. (21) as ranging between 3.68 and 4.84%
(Fig. 6). It can be seen from Tables 5 and 7 that the energy and
exergy efficiencies of individual components of the systems
are higher as compared to the overall energy and exergy effi-
ciencies of the system because latter is the product of former
and some components namely solar concentrating collector
and PV panels have lower efficiencies.
An interesting point worth mentioning in Fig. 6 is that the
minimum exergy efficiency of the solar thermal hydrogen
production system is lower than the PV hydrogen production
system. It may be because at low operating conditions, for
example, in the morning time of the day, the intensity of solar
irradiance is low and the ambient temperature is also low.
exergy efficiency level as compared to PV hydrogen produc-
tion system which suffers the lower electrical efficiency
because of high operating temperatures.
4.3. Sustainability index analysis of solar thermal and
PV hydrogen production systems
The sustainability index for solar thermal hydrogen produc-
tion system is calculated based on the overall exergy effi-
ciency of the solar thermal hydrogen production system and
by using Eqs. (24)e(26) and are shown in Fig. 7. It is clear from
the same figure that sustainability index ranges between 1.03
and 1.07. A curve based on theoretical calculation of sustain-
ability index is also shown just to have a clear understanding
of the variation of it with exergy efficiency. The relation
between sustainability and exergy efficiency is given by Eq.
(24). Here sustainability is measured in terms of sustainability
index (SI). It is clear from Fig. 7 that the sustainability index
increases with increasing exergy efficiency. A system is said to
be more sustainable if its sustainability index is higher. It is
possible only when its exergy efficiency is also higher [35,36].
The sustainability index of each component is also shown in
the same figure. It is understood easily that although the
10
Theoretical
9 PV array
8
System
Inverter
Charge Regulator
7
Sustainability Index

This affects adversely to the exergy efficiency of the former as Electrolyser

6
the heat engines efficiency drops due to insufficient thermal
5
energy available due to low thermal gradient. However these
4
conditions are favorable for the PV system to maintain its
electrical efficiency for the same solar irradiance. On the other 3

hand, when the operating conditions are high, for example, in 2

the noon time of the day, the intensity of solar irradiance and 1
the operating temperature both are higher therefore 0
0 10 20 30 40 50 60 70 80 90 100
producing higher thermal energy/gradient to the heat engine
Exergy Efficiency (%)
and obviously the heat engines thermal efficiency gets better
this time and hence the performance of the solar thermal Fig. 8 e Variation of sustainability index with exergy
hydrogen production system is higher at the maximum efficiency of a solar PV hydrogen production system.
11256 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 1 2 4 6 e1 1 2 5 7

PV Hydrogen Production System  Both PV and solar thermal hydrogen production systems are
1.08 Solar Thermal Hydrogen Production System environmentally benign.
1.07  The energy and exergy efficiencies of concentrating
Sustainability Index

1.06 collector increase with increasing solar radiation.

1.05  Energy efficiency of the systems is higher than the exergy
1.04 efficiency as expected.
1.03  Higher the exergy efficiency of the system, higher would be
1.02 the sustainability index.
1.01  Solar thermal hydrogen production system has higher
Minimum Max imum sustainability index because of higher exergy efficiency as
compared to the PV hydrogen production system.
Fig. 9 e Comparison of sustainability index for solar
thermal and PV hydrogen production systems.

Acknowledgement

The authors acknowledge the financial support provided by

sustainability index of each component is higher individually the Natural Sciences and Engineering Research Council of
but the sustainability index of the overall system is lower. It is Canada in Canada.
because of the fact that the exergy efficiency of the overall
system is lower as it is the product of the exergy efficiencies of
the different components of the system. The low sustain- Nomenclature
ability index of the system is a consequence of low overall
exergy efficiency of the system.
The sustainability index corresponding to the exergy A area, m2
efficiency of PV hydrogen production system is calculated as C concentration factor
ranging between 1.04 and 1.05, and is shown in Fig. 8. A lower DP depletion factor
value of sustainability index can be seen in same figure. It is _
Ex exergyrate, W
due to the lower value of exergy efficiency of the system FF fill factor
which in turn is a result of low exergy efficiency of PV unit. It FR efficiency factor
is clear from Figs. 7 and 8 that to improve the sustainability HHVH2 higher heating value of Hydrogen, 39.4 kWh/kg
index one has to improve the exergy efficiency of the system. I current, A
It can be done by system modifications and proper imple- It intensity of total solar radiation, W/m2
mentation and use of a particular technology. A comparison m _ mass flow rate, kg/s
of sustainability index of both systems is shown in Fig. 9. It is P power, W
clear from the same figure that the sustainability index of Q_ thermal energyrate, W
solar thermal hydrogen system is higher as compared to the SI sustainability index
PV hydrogen production system as former has higher exergy T temperature,  C
efficiency. UL heat transfer coefficient from absorber
surface to ambient, W/m2 K
V voltage, V
W_ shaft work, W
5. Conclusions
Greek letters
In the present study, various types of solar hydrogen a absorptivity
production systems are discussed. Two routes of hydrogen e emmisivity
production namely PV and solar thermal systems are studied h energy efficiency, %
for their performance based on energy and exergy analysis r reflectivity
and sustainability index. A case study is presented to apply s StefaneBoltzmann constant, 5.67
108 W/m2 K4
the analysis to evaluate the above said parameters. The s torque, Nm
exergy efficiency of the concentrating collector is an impor- J exergy efficiency, %
tant parameter to evaluate the exergy efficiency of the solar u rotations per minute, rpm
thermal hydrogen production system as it fluctuates with the
intensity of solar radiation. Similarly, the exergy efficiency of Subscripts
PV panel also fluctuates with the intensity of solar radiation a ambient
and ambient temperature, therefore making it a critical A absorber
parameter for the exergy efficiency calculation of the PV C collector
hydrogen production system. Design modifications and CR charge regulator
proper implementation and use of respective technologies D destruction
may enhance the exergy efficiency of the system. Some EL electrolyser
concluding remarks are as follows. E electrical
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 1 2 4 6 e1 1 2 5 7 11257

GEN generator [16] Licht S, Wang B, Mukerji S, Soga T, Umeno M, Tributsch H.

HE heat engine Over 18% solar energy conversion to generation of hydrogen
H2 hydrogen fuel; theory and experiment for efficient solar water splitting.
Int J Hydrogen Energy 2001;26:653e9.
IN inverter
[17] Murphy OJ, JOBockris M. Photovoltaic electrolysis: hydrogen
in input and electricity from water and light. Int J Hydrogen Energy
M mechanical 1984;9(7):557e61.
O2 oxygen [18] Kotay SM, Das D. Biohydrogen as a renewable energy
oc open circuit resource e prospects and potentials. Int J Hydrogen Energy
out output 2008;33:258e63.
[19] Luzzi A, Bonadio L, McCann M, editors. In pursuit of the
PV photovoltaic
future e 25 years of IEA research towards the realisation of
R reflector
hydrogen energy systems. International Energy Agency;
s sun 2004. Hydrogen implementing agreement.
sc short circuit [20] Benemann JR. Feasibility analysis of photobiological
u useful hydrogen production. Int J Hydrogen Energy 1997;22:
979e87.
[21] Fletcher EA, Moen RL. Hydrogen and oxygen from water.
references Science 1977;197:1050e6.
[22] Bilgen E. Solar hydrogen production by direct water
decomposition process: a preliminary engineering
assessment. Int J Hydrogen Energy 1984;9:53e8.
[1] Markandya A, Wilkinson P. Electricity generation and health.
[23] Kogan A. Direct solar thermal splitting of water and onsite
Lancet 2007;370(9591):979e90.
separation of the products. II. Experimental feasibility study.
[2] Friberg R. A photovoltaic solar-hydrogen power plant
Int J Hydrogen Energy 1998;23:89e98.
for rural electrification in India. Part 1: a general survey of
[24] Ihara S. On the study of hydrogen production from water
technologies applicable within the solar-hydrogen concept.
using solar thermal energy. Int J Hydrogen Energy 1980;5:
Int J Hydrogen Energy 1993;18(10):853e82.
527e34.
[3] Hollmuller P, Joubert JM, Lachal B, Yvon K. Evaluation of a 5
[25] Fletcher EA. Solar thermal and solar quasi-electrolytic
kWp photovoltaic hydrogen production and storage
processing and separations: zinc from zinc oxide as an
installation for a residential home in Switzerland.
example. Ind Eng Chem Res 1999;38:2275e82.
Int J Hydrogen Energy 2000;25:97e109.
[26] Diver RB, Pederson S, Kappauf T, Fletcher EA. Hydrogen and
[4] Bilgen E. Solar hydrogen from photovoltaic-electrolyser
oxygen from water e VI. Quenching the effluent from a solar
system. Energy Convers Manage 2001;42:1047e57.
furnace. Energy 1983;12:947e55.
[5] Lehman PA, Chamberlin CE, Pauletto G, Rocheleau MA.
[27] Lede J, Villermaux J, Ouzane R, Hossain MA, Ouahes R.
Operating experience with a photovoltaic-hydrogen energy
Production of hydrogen by simple impingement of
system. Int J Hydrogen Energy 1997;22(5):465e70.
a turbulent jet of steam upon a high temperature zirconia
[6] Yilanci A, Dincer I, Ozturk HK. A review on solar-hydrogen/
surface. Int J Hydrogen Energy 1987;12:3e11.
fuel cell hybrid energy systems for stationary applications.
[28] Olalde G, Gauthier D, Vialaron A. Film boiling around
Prog Energy Combustion Sci 2009;35(3):231e44.
a zirconia target. Application to water thermolysis. Adv
[7] Rzayeva MP, Salamov OM, Kerimov MK. Modeling to get
Ceram 1988;24:879e83.
hydrogen and oxygen by solar water electrolysis. Int J
[29] Tyagi SK, Wang S, Singhal MK, Kaushik SC, Park SR. Exergy
Hydrogen Energy 2001;26:195e201.
analysis and parametric study of concentrating type solar
[8] Joshi AS, Dincer I, Reddy BV. Exergetic assessment of solar
collectors. Int J Therm Sci 2007;46:1304e10.
hydrogen production methods. Int J Hydrogen Energy 2010;
[30] Joshi AS, Dincer I, Reddy BV. Development of new solar
35(10):4901e8.
exergy maps. Int J Energy Res 2009;33:709e18.
[9] Joshi AS, Dincer I, Reddy BV. Performance analysis of
[31] Crouse WH, Anglin DL. Automotive mechanics, 3rd ed., Tata
photovoltaic systems: a review. Renew Sustain Energy Rev
McGraw-Hill Publishing Company Limited. 375-385.
2009;13(8):1884e97.
[32] Rosen MA, Dincer I, Kanoglu M. Role of exergy in increasing
[10] Kelly NA, Gibson TL. Solar energy concentrating reactors for
efficiency and sustainability and reducing environmental
hydrogen production by photoelectrochemical water
impact. Energy Policy 2008;36:128e37.
splitting. Int J Hydrogen Energy 2008;33(22):6420e31.
[33] Connelly L, Koshland CP. Two aspects of consumption: using
[11] Fujishima A, Honda K. Electrochemical photolysis of water at
an exergy-based measure of degradation to advance the
a semiconductor electrode. Nature 1972;238:37e8.
theory and implementation of industrial ecology. Resour
[12] Nowotny J, Sorrell CC, Bak T, Sheppard LR. Solar-hydrogen:
Conserv Recycl 1997;19:199e217.
unresolved problems in solid-state science. Solar Energy
[34] Toolbox e the engineering toolbox. URL: http://www.
2005;78:593e602.
engineeringtoolbox.com/overall-heat-transfer-coefficient-d_
[13] Photoelectrochemical cell (PEC). URL: http://emat-solar.lbl.
434.html [accessed: May 2010].
gov/research/PEC.html [accessed: April 2010].
[35] Dincer I. Environmental and sustainability aspect of
[14] Yamada Y, Matsuki N, Ohmori T, Mametsuka H, Kondo M,
hydrogen and fuel cell systems. Int J Energy Res 2007;31:
Matsuda A. One chip photovoltaic water electrolysis device.
29e55.
Int J Hydrogen Energy 2003;28:1167e9.
[36] Rosen MA, Dincer I. Exergy as the confluence of energy,
[15] Dincer I. Technical, environmental and exergetic aspects of
environment and sustainable development. Exergy, an Int J
hydrogen energy systems. Int J Hydrogen Energy 2002;27(3):
2001;1(1):3e13.
265e85.