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SOLAR HYDROGEN PRODUCTION THROUGH PHOTOBIOLOGICAL,

P H O T O C H E M I C A L A N D P H O T O E L E C T R O C H E M I C A L ASSEMBLIES
II'AMAR WILLNER and B I I . t t A S T E I N I , I F R G I : . R - W I I . I . N I - Z R

Department of Organic Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel

( Received forpublication 18 May 1988)

Abstract--H, evolution by photochemical transformation that uses solar light is accomplished by pholobiologicul
systems, photochemical assemblies and photoelcctrochemical ceils. Semiconductor particles providc
microphotoetcctrochemical cells for walcr photolysis. Hybrid systems can be designed where dye compounds and
semiconductor particles act cooperatively in He evolution. Photoreduction of CO2 to formate allows the production
of hydrogen storage products.

INTRODUCTION evolution through photoredox transformations (Scheme

I). The first involves photobiological systems that apply
The production of hydrogen from cheap raw materials
thylakoid membranes as light harvesting units and
like water is a challenging project that could provide
H2-evolution enzymes as catalysts for photolysis of
future energy needs. Among the different approaches
water. The second approach employs synthetic molecu-
are electrolysis, plasmolysis, magnetolysis and mag-
lar assemblies as the photoactive sites that effect elec-
malysis. Photochemical means that utilize solar light for
tron transfer processes. Proper design of organized
photolysis of water to hydrogen fuel are an important
microenvironments that couple the redox photopro-
option for the world's future fuel needs [1]. Research
ducts with artificial catalysts results in the cyclic cleavage
activities in the area of photochemical conversion and
of water. The third approach bridges the photocatalytic
storage of solar energy with specific efforts towards
activity of semiconductor materials withphotoconver-
water photolysissystems have grown extensively in recent
sion and storage systems. The electron-hole pair formed
years [2-5]. The subject has turned into an interdisciplin-
upon the excitation of the semiconductor material
ary area that involves photochemistry, electrochemis-
provides the basic redox configuration for the photolysis
try, catalysis, biochemistry and photobiology.
of water through photoelectrochemically based cells.
Plant photosynthesis provides a system for the conver-
These materials could be used either as bulk electrodes
sion of solar light energy into fuel products (carbohy-
or in suspended particulate forms. The objectives of this
drates). The primary events of the natural device involve
review article are to evaluate the three approaches in
photoredox reactions where visible light induces redox
conjunction with water photodecomposition, to high-
reactions. The intermediate redox photoproducts ulti-
light the present accomplishments and to discuss existing
mately yield net useful fuel products.
difficulties. Special emphasis will be given to hybrid
Photolysis of water to H_, fuel could be envisaged by
systems where counterparts of the three different
the use of artificially designed systems that duplicate approaches are united into assemblies that effect water
functions of the natural process. This concept is outlined
photodecomposition.
in Fig. 1, where a light harvesting compound S induces
an electron transfer reaction upon absorbence of visible LIMITING EFFICIENCIES OF SOLAR
light. The redox products could then mediate, in the PHOTOLYSIS OF WATER
presence of proper catalysts, H2 and 02 evolution, thus
The solar spectrum is rather diffuse and covers a
establishing cyclic water photolysis systems. Three diffe-
broad range of wavelengths, 350-1400 nm. This implies
rent approaches are presently examined to effect H~
that in photochemical transformations that use visible
light (350-700 nm) a substantial amount of the incident
t ~r,=r=r.~=ex Tr=ns~er..--.=:iCnS I solar radiation is lost (=52%). The photoredox trans-
formations are also thermodynamically controlled by

Sys:e,-,.s ~----~ Sys~.,,ms , 5ysT; m~.

I I I _.. f 0 + . . , F s -%.._
. . . . L yC_,o,ys,
[ I.- . . . . . . . . . . . . . . J i ~20Z+211 +'4~" ~" D ~ ~S ÷'~" "~P"A - ~ ~ 211+
1- . . . . . . . . . . . . . . . . . . . . . . ...a

Scheme 1. Approaches for x~ater photolysis through photo- Fig. 1. Scheme for photolysis of water by a sensitizer-acceptor
redox transformations. donor and catalysts assembly.
593
594 I. WILLNER AND B. STEINBERGER-WILLNER
the endoergenicity of the specific process [6-8]. For
photolysis of water (equation 1) by a single photon, a
threshold photon energy of kg~<611 nm is required. If N~
(k) is the incident solar photon flux at wavelength k and
e(X) is the absorption coefficient of the light absorbent,
the absorbed flux,.Je, in the threshold region is given by
equation (2):
-F/
g 5o

~z0~ / A-,,.
H20-'+ He + 1/2 O2 AG°=l.23V, (1)
Je = ~.fkg N~(J.) ~(X)dk (2)

The available solar power E Wm -2 is given by :~0 ~ ICO0 14C0

equation (3) and the fraction of incident solar power, ~,g (nm)
~/E, that could initiate the photoconversion process is
given by equation (4): Fig. 2. Plots of conversion efficicnccs as a function of threshold
active wavelength (k,.). (a) Plot of ~h.. (b) Plot of ~/<,,~laS~ltlllitlg
hc gin energy loss of 0.8 cV.
E = & -- (3)

E P H O T O B I O L O G I C A L H2-EVOLUTION
(4) SYSTEMS
tie -oj~E(;k)dX,
Photobiological processes that produce hydrogen can
where be designed by the separation of chloroplasts from
plants and exclusion of the enzymes involved in CO,
,, J'~° E(X)dL
fixation. These isolated chloroplasts contain the natural
represents the total solar incident power. Figure 2 shows light harvesting unit of chlorophyll centers and are
the calculated curve of photoconversion efficiency, r IE. capable of inducing the photosensitized electron trans-
as a function of irradiance wavelength and implies a fer (Fig. 3) [9]. Addition of bacterial extracts that
maximum efficiency of 47% at ~ 1000 nm. This ideal contain the hydrogen-activating enzyme, hydrogenase.
conversion efficiency is controlled by thermodynamic can utilize the electrons tunnelled by the photoredox
and kinetic drops that have been estimated by Ross, process and effect H2 evolution. Chloroplasts isolated
Bolton and others, to be in the range of 0.6-1.0 eV per from spinach when irradiated in the presence of hyd-
absorbed photon. These energy drops reduce the max- rogenase isolated from Clostridium bacterium and an
imum conversion efficiency to =21% at a threshhold artificial electron carrier such as N,N'-dimethvl-4,4'-
energy of 750 nm. In practice, the overall solar energy bipyridinium, methylviologen, MV 2+, generate hyd-
storage efficiency, 'llstorage, is governed by several rogen [10]. The artificial electron carrier mediates the
efficiency factors (equation 5): transfer of electrons from chloroplasts to the enzyme
hydrogen evolution active site. Although significant
'l]storag e = lqahs 'l](p ]]E lqchem 'l]coll.
(5) progress has been made in developing this system, the
instability of chloroplasts towards continuous illumina-
r/er/~i,~,m is the thermodynamically and kinetically li- tion and towards oxygen limits the system for H~
mited photoconversion efficiency (=0.21): ~/:a,~corres- production.
ponds to the fraction of solar photons absorbed beyond Photobiological H2 production can be cffected bv
the threshold energy (),~;tg); rl,,., the quantum yield of intact organisms [!1]. Both, blue-green algae [12],
the photoreaction process, and r/c,,u is the fraction of cyanobacteria and eucaryotic green algae [13] possess
separated products that can be stored. Using optimal two photosystems analogous to those in green plants, as
wdues for the latter efficiency factors (=0.9), the well as the He-evolution enzyme, hydrogenase. The
maximum solar energy storage efficiency is envisaged to great advantage of using cyanobacteria for biosolar H~
be in the range of 12-15%. production is their adaption to aerobic environment

light electron

2H" ÷ t/202 -qK.,

H20 ~ "-2""

Fig. 3. Photolysis of water by chloroplasts in the presence of hydrogcml~c.

 SOLAR HYDROGEN PRODUCTION 595
conditions and protection of the oxygen labile hyd- kd kei
rogenase enzyme. Various blue-green algae species S* + A k-d (S'.-. A) ~ (S+.,.A -)
have been immobilized on solid matrices such as alginate k-et
gel beads, polyurethane and polyvinyl foams [14, 15],
and continuous H2 evolution has been accomplished
upon illumination. Yet, the approach of whole cell
application for H2 production is not free of limitations.
The H2-production process competes with other phy- S +A S++A -
siological cellular reactions such as nitrogen fixation. Scheme I I. Kinetic scheme of photosensilizcd electron transfer
Methods that ignore cellular H, evolution include reactions.
modification of microorganism growth conditions, reg-
ulation of the formation of the competitive enzyme rcvicwed [17-23]. The aims of this chapter are to
nitrogenase, and nitrogen starvation of cells prior to highlight some of the accomplishments and to dclnons-
illumination [16]. Other approaches such as isolation of tralc that various disciplines connect into the organiza-
new strains and design of selected mutants merit future lion of such molecular assemblies for solar H2 produc-
exploitation. tion.
The overall photosensitized electron transfer process
comprises of the sequence of steps outlined in Scheme
II. it involves the formation of the excited sensitizer-
S Y N T H E T I C M O L E C U L A R A S S E M B L I E S FOR relay complex, electron transfer and formation of an
WATER PHOTOLYSIS encounter complex of photoproducts and either recom-
bination or separation of this labile cage structure of
Design of artificial molecular assemblies for photo-
photoproducts. Kinetic analysis of this scheme [24]
lvsis of water to hydrogen and oxygen gained substantial
yields the observed rate constant for product formation
research activities in recent years [2-51. A simplified
given in equation (8).
scheme of a molecular asseml~ly for water photolysis is
displayed in Fig. 1 and includes a light absorbent, S, an kd
electron relay compound, A, and an electron donor, D. kohs --
The excited photosensitizer effects the electron transfer kb k-d (1 + k_~, + kh ) (81
1 + ~ + ~ k~ k,
process to the relay and generates the redox photopro-
ducts S + and A - . The added electron donor recycles the
Numerous theoretical and experimental studies have
light harvesting compound and completes the trans-
attempted to relate the free energy of activation ~ G '~:to
formation of visible light energy into redox potential.
the change of free energy, AG", associated with the
Selection of components that exhibit the proper thermo-
electron transfer reaction. The relationship given in
dynamic redox potentials for the reduction and oxida-
equation (9):
tion of water to H2 and O2 could establish a cyclic water
photolysis system. AG °
The organization of such assemblies for generation of AG* z = A G * ( 0 ) (1 + 4AG,:z(0 ) ) (9)
solar hydrogen involves various aspects. For effective
conversion and storage of solar light energy to a fuel, the where AG*(0) is the free energy of reorganization when
formation of redox products from the excited species A G = 0 . describes the process well. It implies that the
should be efficient. Thus, it is essential to define suitable electron transfer rate constant, k~,, is close to diffusion
sensitizer-relay systems. Yet, the thermodynamic redox controlled at small negative A G ° values, while the rate
properties of the redox products (Fig. 4) imply that constant decreases when AG~>0 or when A G ° exhibits
spontaneous back electron transfer should occur (equa- large negative values.
tions 6 and 7), a process that degrades the energy storage
process. Slondord
Polenliol
S+ + A - ~ S + A (6)
EO(S*/S+) -
E°( A IAm ) --

D++A ---~ D + A (7) Eo(211t/Hz) - /

/

/
It is therefore essential to develop means that stabilize /

the photoproducts against these degradative pathways. hv /

/ Recombinolion
Finally photolysis of water by redox products that meet / / of Pholop~oducls
E°(Oz/1120) - /
the proper thernlodvnamic potentials turn out to be
kincticalh sluggish reactions. Thus. development of E°(D~ID) -
Eo(s+IS) ~/S+A
catalysts capable of the utilization of the photoproducts
in the rcdticIioll and oxidation of water is Cl-ticlal.
Substantial cfforts to rcsolxc the various aspects have Fig. 4. Thermodynamic redox properties of photoproducts for
bccn made cind each of the stlb CCtShas been cxtensi\'elv water photolysis.
596 1. WILLNER AND B. STEINBERGER-WILLNER
2+
( ~ - ' ~ N _ _ _Ru/__ _ N / ' - ' ~ t
k=/-- ,", ,
2/
1
R
N N m
R = S03
R
3
A wide variety of photosensitizers that are capable of
inducing electron transfer reactions has been characte-
rized. These include organometallic complexes amongst
which Ru(II)-tris-bipyridine [25], Ru(bpy)~ + (1), metal-
[oporphyrins [26,. 27], such as Zn(II)-meso-
tetramethylpyridinium porphyrin, Zn-TMPyP 4+ (2),
Zn(ll)-phthalocyanine tetrasulfonate, Zn-PcTS 4 (3),
organic dyes [28] such as acridine orange (4) or proflavin
(5) are noteworthy examples.
Electron relay compounds that have been widely
examined in photoinduced H2 evolution include N,N'-
dialky[-4,4'-bipyridinium salts such as methylviologen
(6) [29, 30], N , N - d ' a l k y l - 2 , 2 ' - b p y r i d ' n i u m salts [31],
i.e. (7), organometallic complexes such as Rh(IIl)-tris-
bipyridine, Rh(bpy)) ~ [32] or Co:(lll)-scpulchurate (8)
Co(sepul) 3+ [33, 34], and metal ions such as Eu ~+, or
V 3+ [35]. Although the reduced forms of these relay
systems exhibit the suitable thermodynamic potential
CIIj + N ~ - ~ N +-"'~Ctt 3
R
R R R =
R
( C H s ) z N ~ N ( C H 3 ) 2
4
H2N NH2
for H, evolution from water, the introduction of
catalysts to effect the process is mandatory.
Metals such as Pt, Ag, Rh, Os and Ib,u, or metal
oxides, i.e. PrO2 or IrO2, have been widely applied as
redox catalysts for H~ evolution. In order to obtain
maximum rates of electron carrier mass transfer to the
electrode surface, it is important to design metal
catalysts with high surface areas. Colloidal metal parti-
cles that exhibit high surface areas have been prepared
by various means. For such colloidal particles the rate
constant for interaction bctwccn the reduced relay and
the metal particles is given by equation (lfl), where r is
the particle radius, D is the diffusion coefficient of the
electron carrier and N the density number of colloid
particles.
kob ~ = 4 ~ N D r (1(I)
Photosensitized H, evolution has been extensively
3+
N\ t,.N--
7
 SOLAR HYDROGEN PRODUCTION 597

Table 1. Hydrogen evolving photosystcms*

Photosensitizer Electron Electron Quantum

(S) relay (A) donor (D) efficiency ("H2)

Ru(bpy)3 + methyl viologen EDTA 0.26

acridine yellow methyl viologen EDTA 0.32
Zn-TMPvP 4+ methyl viologen EDTA 0.60
Zn-TPPS "~ methyl viologen EDTA 0.I)2

*In all systems Pt colloids are used as catalysts.

Table 2. Oxygen evolving photosystems

Photosensitizer Electron Relay Catalyst Quantum efficiency

(S) (A) (q>V202)

Ru(bpy)~ + Co(NH3)sCI 2+ RuO~ colloid 0.2

Ru(bpy)~ + Co(NH3)sCI 2+ RuO2-TiO2 O. 12
Ru(bpy)3 + S_-O~ RuO2-TiO2 0.24
Ru(bpy)~ + S,O~- lrO~ 0.14

examined in sacrificial systems that include a degradable
electron donor that recycles the light active compound.
Figure 5 represents schematically such sacrificial systems
where methyl viologen acts as electron relay that
mediates H2 evolution in the presence of colloidal Pt
that acts as catalyst. Sacrificial electron donors common-
Iv applied for the regeneration of the photosensitizer
include ethvlenediaminetetraacetic acid (EDTA),
triethanolamine, (TEOA), ascorbic acid and thiols, i.e.
cvsteine. Numerous investigations have examined the
effects of various sensitizers, structural modifications of
the electron relay, different electron donors and various
metal colloids on the quantum efficiencies of H2 evolu-
tion (qHz). Table 1 summarizes the quantum efficien-
cies of some of these photosensitized H2-generation
systems.
For cyclic photolysis of water, O,-evolution catalysts
must be developed. A similar approach to that described
for H2-evolution catalysts has been successfully applied
to the development of oxygen evolving photosystems.
This approach involves the application of sacrificial
electron relays that allows the selective characterization
of O,-evolution catalysts. It has been found that metal
efficiencies of several oxygen evolving photosystems
that have been observed with various sacrificial electron
relays.
The various catalysts that were developed for the
separated processes (H 2 evolution and O2 evolution)
exhibit effective redox catalysis properties and could be
combined into a single unit that effects cyclic light
induced cleavage of water. This concept is exemplified in
Fig. 6 where the compounds of highest activity in the
separated H 2 and O2 photosystems are united: a TiO2
colloid is used as the carrier for the redox catalysts and is
loaded with RuO2 and Pt as 02 and H 2 evolution
catalysts respectively. The photosensitizer, Ru(bpy) 2*,
and methyl viologen, MV 2+, acting as charge relay are
included as the light harvesting compound and the
electron carrier substrate respectively. The interaction
of the redox photoproducts with the proper catalysts is
anticipated to result in the cyclic cleavage of water and
the regeneration of the photosensitizer and electron
Ru(bpy)~÷+MVZ+ hu • Myt ÷Ru(bpyl;+
1 . 1 2 ~ 21+ l / i 120

/
oxides such as RuO2 or IrO2 act as effective O2-
evolution catalysts [36, 37]. Recently, homogeneous
[Ru(ll) and Mn(IIl) complexes, i.e. [(NH3)sRu-O-
Ru(NH3)5] 4.. have been applied as water oxidation
catalysts [38, 39]. Table 2 summarizes the quantum

21| 2
2:'1"+9zOz~ -

o~ ~s*~." "~c,@~_c.3J "~.*

Fig. 6. Cyclic photo-decomposition of water by a
Fig. 5. H)drogen c'olution through photoredox transforma- photosensitizer-electron acceptor assembly in the presence of a
tion using sacrificial electron donors. heterogeneous TiO2 bifunctional cata]yst.
59S I. WILLNER ,AND B. STEINBERGER-WILLNER

relay compound. Primary attempts to follow this scheme Substantial progress has been accomplished in recent
have been reported by Gr~tzel and colleagues to lead to ,,,,ears in the organization of microheterogeneous en-
the cyclic photolysis of water, although at low quantum vironments that are capable of controlling photoinduced
efficiencies. Later studies have controversed these re- electron transfer reactions and effecting the stabilization
sults and have implied limitations of such catalysts of the photoproducts against recombination processes.
configurations. Organized microenvironments composed of micelles
The problems in designing photosystems that simul- [40], microemulsions [41], charged colloids [42. 43 I,
taneously evolve H, and O: originate from poor selecti- vesicles [44.45] or molecular cvclodextrin receptors [40]
vities of the catalysts towards the specific processes, provide means to retard the back electron transfer
poor kinetic properties and non-adequate configuration reactions. In these organized microenvironments spe-
that results in degradative recombination of the desired cific electrical repulsion and attraction of the photo-
products: generated products from charged microheterogeneous
interfaces, or the selective association of one of the
(i) The oxygen evolution catalyst, RuO2, is not a reactive photoproducts to a micro-hydrophobic phase
selective O2-evolving catalyst, and acts also as present in the continuous aqueous phase, result in the
catalyst for H 2 evolution. Consequently, recom- separation of products and their subsequent stabiliza-
bination of hydrogen and oxygen occurs on the tion against recombination processes. For example, the
metal oxide• Similarly, immobilization of the H,- photosensitized reduction of N,N'-dipropvlsulfonato-
• . '~+

and O.-evolution catalysts on the same carrier 2,2'-bipyridimum (9), DQS, using Ru(bpy)~ as photo-
results in a destructive effect as a result of rapid sensitizer and T E O A as sacrificial electron acceptor has
recombination of H? and O2 bound to the carrier been examined in a microheterogeneous system that
surface. Thus, efforts should be directed towards includes SiO2 colloids (Fig. 7) [47]. In the absence of
the development of specific O, evolution catalysts SiO, particles, no net photoreduction of DQS occurs
and towards the design of compartmentalized sys- due to rapid recombination of the photoproducts. In the
tems where the catalysts are separated but transport presence of SiO2-co[loid, however, effective photore-
of the electron carriers is still available. duction of DQS proceeds and the electron carrier
(ii) The sacrificial systems omit the kinetic behaviour of mediates H2-evolution in the presence of colloidal Pt.
the redox catalyst since one of the photoproducts is Detailed analysis has revealed that the negatively
irreversibly decomposed. Consequently, high quan- charged SiO: colloid selectively associates, as a result of
tum efficiencies are possible even with poor kinetics electrostatic attraction, the photosensitizer and the
of the redox catalyst. In cyclic water phototysis oxidized photoproduet. The stabilization of the reduced
systems the thermodynamically favoured back elec- photoproduct allows subsequent electron transport to
tron transfer reaction of the intermediate photopro- the Pt-catalyst and H, evolution takes place.
ducts (equations 6 and 7 and Scheme II) is dominant A related noteworthy system that applies electrostatic
and is close to a diffusion controlled process. Thus, and hydrophobic interactions as a means to retard back
the activities of the redox catalysts should be electron transfer reactions of the intermediate photo-
sufficiently high to intercept kinetically with the products and enhance subsequent H~ evolution, has
recombination processes. This implies that the H,- been exemplified by Grfitzel and his colleagues [20].
and O~-evolution catalysts must be active in the Photoreduction of N-dodecadecyI-N'-met hyl-4,4'-
microsecond time domain. An alternative approach bipyridinium ClaMV 2'+, (10), acting as charge relay, has
might involve the design of organized photosystems been exam ned in aqueous media using Ru(bpy)5 ~- as
where the photoproducts are stabilized against photosensitizer and a sacrificial electron donor, The
recombination reactions as a result of system- charge relay, Cl4MV 2+ is bydrophilic in character and
environmental effects. does not interact with micellar aggregates. Yet, its

Sacrificial
producls hv
0-

Ru(bpy)1 <',~,'/ ~ P,-DQ S~ . / ~2H*

o- TEOA

DQS°:

Fig. 7. Control of photosensitized transformations and subsequent tt,-evolution by means of charged

SiO,-colloids.
 SOLAR HYDROGEN PRODUCTION 599

Ru( bpy~Z+ + Cl4MV2L,.__~..Ru(bpy):~'+CI4MV +. o)

~/202+2H+

Ha0 2H
~'tr 1' c,,~",c,,, ~ c , , ~ , , c,,, n-lype [
photoonode [
Fig. 8. Scheme for specific interactions of Cj.~MV* with a
polysoap Pt-catalyst resulting in He-evolution.
b)
reduction product. C.4MV + . exhibits amphyphitic C.B. - H2
properties and is associated with hydrophobic micellar
microenvironments and specifically with positively + ZH++u20
charged micelles. Consequently, photoinduced electron ~B.
• . hae
.I I "2H
transfer to the relay substrate, CI4MV 2÷ , (equation 11)
in the presence of positively charged micelles results in
association of CI4MV + and in electrostatic repulsion of
the oxidized photoproduct Ru(bpy).~ +. C.B,

Ru(bpy)3 + + Cj~MV 2+ h--orRu (bpy).~ + + C l a M V +. C)

(11) F V.B

These selective associative and repulsive interactions

retard the degradative recombination of the photopro-
ducts. These concepts and properties of CI4MV + couple
have been utilized in relay and a Pt-colloid stabilized on
the polysoap poiyvinylpyridinium with Cu, pendent
groups, PCP-Cj6 (Fig. 8). In the absence of the polysoap
the primary photoproducts recombine with a diffusion
controlled rate constant, kb = 4 × l0 9 M - I S -~. In the
presence of the polysoap and exclusion of the Pt-colloid
the recombination rate is retarded due to the selective
association of C14MV + to the hydrophobic polysoap
core and concomitant repulsion of Ru(bpy)~ +, kb = 8 ×
l0 s M - ~ S -I. This stabilization of the photoproducts
results in effective subsequent He-evolution in the
presence of the Pt catalysts sites.
PHOTOELECTROCHEMICAL H,-EVOLUTION
SYSTEMS T H R O U G H W A T E R PHOTOLYSIS
Electrode based H_,-evolution systems
Photolvsis of water by photoelectrochemical systems
has evoked extensive research activities since 1972,
when it was shown that substitution of the anode in a
water electrolysis cell by an illuminated semiconductor
type TiO: electrode could substantially reduce the
electrical energy, for water electrolysis [48]. As the
subject has been extensively reviewed [49-53], only
fundamental aspects of photoelectrochemical H:-
evolution systems will be considered here with specific
emphasis to correlate these systems to the other
approaches discussed in this paper.
Figure 9 represents three schematic configurations of
photoelectrochemical cells, where semiconductor
(S.C.) electrodes are used. Figure 9(a) represents a cell
where the S.C. electrode acts as photoanode. Photoex-
citation of the semiconductor with light energy greater
r;:zo":oo. ::ZO:o
)hotocathode
Fig. 9. Schematic configurations of photoeleetrochemical semi-
conductor based cells. (a) n-type semiconductor photoanode
cell. (b) p-type semiconductor cell. (c) Photodiode cell com-
posed of n- and p-type semiconductor electrodes.
than the band gap, results in an electron-hole pair in the
conduction band (C.B.) and valence band (V.B.) re-
spectively. While electrons are tunnelled to the counter-
electrode where H2 evolution occurs, oxidation of water
at the S.C. electrode takes place. In Fig. 9(b) an
alternative configuration is shown and the p-type S,C.
electrode acts as photocathode. Photoexcitation of the
S.C. results in the reduction of protons to H2 while the
holes are carried to the counter electrode where oxida-,
tion of water to oxygen proceeds. The third configura-
tion, Fig. 9(c), represents a combined system composed
of two S.C. photoactive electrodes. The n-type S.C.
photoanode effects the oxidation of water while the
p-type S.C. acts as the He evoluton photocathode and
the circuit is completed by electrons carried from the
photoanode to V.B. holes of the photocathode.
The solar energy conversion efficiency (rl) of a
photoelectrochemical cell is given by:
Vma× imax
(12)
q = , , f ~E(k)d)~
where Vm.× and im~,xare the photogenerated maximum
cell potential and the photocurrent density respectively,
600 I. WILLNER AND B. STEINBERGER-WILLNER

effective in the light driven process. Consequently, the

solar energy conversion efficiency is low. = 1%.
-i.0 -J Often, deposition of catalysts on the S.C. electrodes
assist the reduction or oxidation reactions occurring at
H÷/H2 these electrodes. An example where a catalyst effected
0 ~,,,, . . . . . . . . . . . . . . . . . . .
efficient H2 production was demonstrated in a photo-
electrochemical cell that applied p-type lnP as photo-
02/0H" cathode is given in Fig. 9(b) [55, 56]. InP has an ideal
band gap for solar energy conversion (EBo = 1.34 eV).
Deposition of metals such as Pt or Rh on the photo-
cathode catalyses the H2-evolution process and the
o quantum efficiencies were drastically increased. Such
photoelectrochemical cells operate at a rather high solar
to fuel conversion efficiency that corresponds to ~] =
÷4.0~ (~ C~ 13.3%. The structure of the S.C. immobilized catalyst

l affects substantially the effectiveness of the photoelec-

Fig. 10. Relative band edge potentials of some metal-oxide
semiconductor materials. Standard potentials for H, and 02
evolution are also indicated on this scale.
while the denominator is the solar incident power.
Numerous materials show S.C. photoactivities. These
include metal oxides such as TiO2, Fe203, SnO2, WO3 or
SrTiO3, sulphides (dichalcogenides) such as CdS, MoS~
or WSe2, and phosphides such as lnP or GaP p-type
photocathodes. Figure 10 shows the valence and con-
duction band edge potentials of some transition metal
oxides. It is evident that valence band holes are thermo-
dynamically capable of oxidizing water to oxygen while
only SrTiO3 and TiO2 in this series exhibit a C.B.
potential that allows H2-evolution.
For example, n-type SrTiO3 based photoelectroche-
mical cells drive the photoinduced splitting of water to
H2 and 02 [54]. The SrTiO3 electrode acts as a photo-
anode where oxidation of water occurs while C.B.
electrons are driven to the counter Pt-electrode where
He evolution proceeds (Fig. 9a). This cell results in
efficiencies of 25-30%. However, since the band gap of
SrTiO3 corresponds to 3.2 eV, only near U.V. light is
trochemical cells. For example, a uniform 50 ,~,-thick
layer of Pt on InP reflects and absorbs ca 50% of the
useful photons of the solar spectrum. To avoid this loss,
the catalyst must be deposited in the form of islands with
diameters smaller than the useful wavelengths of the
solar spectrum.
A photo-diode electrochemical assembly (Fig. 9c)
that effects the photolysis of water has been demon-
strated by Somorjai and his colleagues [51]. In this
configuration a Si-doped Fe203 electrode acts as photo-
anode and a Mg-doped Fe203 electrode acts as photo-
cathode. Upon illumination of the two electrodes O:-
evolution occurs at the photoanode while H2-evolution
proceeds at the photocathode and the circuit is com-
pleted by electrons carried from the photoanode to
vacant V.B. holes in the photocathode. The efficiency of
the iron oxide p/n assembly is low, c a 0.1%, but it
operates in the visible light region of the solar spectrum.
Table 3 summarizes the band gaps, Eg, and the solar
energy conversion efficiencies, ~1, for water photoelec-
trolysis using various representative semiconductor
electrode materials.
Several limitations are encountered in the operation
of photoelectrochemical cells. The quantum efficiency
of these units is maximum when all incident photons that
exceed in their energy the band gap energy produce

Table 3. Solar conversion efficiencies in the photoelectrolysis of water

with representative semiconductor electrode materials

Semiconductor Eg (eV) q("/o)

SrTiO3 3.2 1(20)*

KTaO3 3.5 >0. l('4~)t
n-TiO2 3.0 [).4~:
Si-Fe203/Mg-Fe20~ 2.2 0. I
InP 1.34 13.3
MoSe2 1.4 4-5§

*In brackets conversion efficiency in the region of maximum electrode

photosensitivity.
+Ref. [85].
~:Ref. IS61.
§Photocurrent efficiency, i.e. Ref. [87].
 SOLAR HYDROGEN PRODUCTION
electron-hole pairs that lead to the desired anodic and
cathodic products. It is common to all photoelectroche-
mical cells that losses due to recombination of photo-
generated electron-hole pairs, leakage of the 'wrong'
carrier across the barrier, reflection of photons from the
S.C.-solution interface and absorption and reflection of
photons by S.C. immobilized catalysts, reduce the
quantum efficiencies and conversion yields. Yet, the
most severe limitation of photoelectrochemical cells
relates to the deterioration of the S.C. electrodes.
Photoanodes are generally susceptible to photodegrada-
tion of the electrode surface by oxidation of the S.C. by
holes (equations 13 and 14). Photocathodes exhibit
inherent superior stability towards reductive degrada-
tion. Although reduction of the S.C. surface by C.B.
electrons is thermodynamically feasible by a reaction
such as equation (15), such processes have not been
observed.
n-GaAs + 6h + + 10 O H - ~ GaO 2- 4- AsO 3- 4- 5H20
(13)
n-CdS + 2h + ~ Cd 2÷ 4- S (14)
p-InP + 3e- + 3H ÷ ~ In + PH3 (15)
Powder and colloidal semiconductor systems
Suspended S.C. particles in solution constitute a
collection of microphotoelectrochemical cells. Illumina-
tion of such S.C. particles results in the formation of a
cathode and anode sites on the particle assembly (Fig.
11).
Immobilization of proper 02- and H2-evolution
catalysts could provide a route to the cyclic photodecom-
position of water. Several n-type suspended semicon-
ductors such as TiO2 [57-60], SrTiO3 [61, 62] and CdS
[63, 64] have been examined as microcells to accomplish
water photolysis. Illumination of wide band gap semi-
conductor powders such as n-TiO2, n-SrTiO3 and n-CdS
in aqueous media results in the evolution of hydrogen.
Immobilization of SrTiO3 (EBG = 3.2 eV) with H2- and
O~_-evolution catalysts, i.e. Pt and RuOz, forms a
photocatalytic assembly that decomposes water upon
illumination [63]. With platinized n-TiO2 effective H2
evolution occurs but the complementary oxidation pro-
cess leads to the oxidation of surface bound Ti-OH
v o--h+ t- / oxidized dye in solution. Electrons carried through the
H20
Fig. 11 Photoelectrolysis of water by suspended S.C.--catalysts
assembly.
N)I
groups, rather than oxygen evolution. Although subse-
quent O2-evolution by proper treatment of the Ti-
OH oxidation products might be advantageous in re-
spect to separation of H2 and O2 it introduces further
complications in the photoprocess.
The use of suspended inorganic S.C. powders is
certainly attractive in view of the high-surface area
active in the photoprocess and the simplicity of the
systems. Yet, low efficiencies due to light reflection,
recombination of photogenerated electron-hole pairs
and utilization of wide band gap S.C. that are only active
in the near U.V. region are serious disadvantages. The
average transport time (x) for a carrier from the interior
part of a spherical particle to its surface is given by
equation (16), where ro is the spherical aggregate radius
and D is the diffusion coefficient for electron or hole in
the S.C.
fo 2
.~ = (16)
~D
Thus, the time of charge transport to the surface is
shorter as the particle radius decreases. This suggests
that appliction of colloidal S.C. aggregates might elimin-
ate light scattering phenomena and enhance the efficien-
cies of the photoprocesses by improving charge trans-
port to the surface, where the redox reactions occur.
Various methods for the preparation of S.C. colloids
were developed in recent years. These include stabiliza-
tion of colloid aggregates by polymers [65], vesicles [66],
and recently, molecular cyclodextrin receptors [67].
H2 evolution has been accomplished upon illumina-
tion of Pt-loaded TiO2 colloids [68, 69] and cyclic
photolysis of water using n-CdS colloids that contain
immobilized Pt and RuO2 catalysts have been reported
to proceed with a quantum efficiency of 0.2% [70].
H Y B R I D H2-EVOLUTION SYSTEMS
The three different approaches discussed in this
article to accomplish the photolysis of water describe
efforts of various disciplines to develop systems for the
conversion of solar energy to fuel products. Accomplish-
ments achieved in the various disciplines allow us to
design hybrid systems, where principles of the three
approaches are united to He-evolution systems.
An approach to switch the activity of wide band gap
S.C. into the visible absorption region involves the
photosensitization of semiconductors by dye molecules
[71, 72]. The concept is outlined in Fig. 12, where the
S.C. particle is loaded with the H2-evolution catalyst
(Pt). Excitation of the photosensitizer (dye), S, results in
electron injection into the S.C. conduction band and the
C.B. effect H2-evolution while the oxidized dye could
mediate the oxidation of water in the presence of proper
catalysts, i.e. RuO2. Various dye compounds such as
rhodamine B, Methylene Blue and Erythrosine [73--75],
or organometaltic complexes such as phthalocyanines,
the hydrophobic complex Ru(II)-(b/s-pyridine)
602 I. WILLNER AND B. STEINBERGER-WILLNER

been reported from isolated chloroplasts in the presence

2+2"*
2H+~ Lk V.B. //)OyeLn~
H20
Fig. 12. Scheme for water photolysis through dye sensitization
of S.C.-catalysts assemblies.
(4,4'tridecyl-2,2'-bipyridine) or Pt(II) and Ir(III)-8-
hydroxyquinoline complexes [76, 66] have been re-
ported to photosensitize wide band gap S.C. such as
ZnO, TiO2 or SrTiO3 and subsequently yield H2 evolu-
tion.
Most of the studied Hz-evolution systems through
charge injection involve sacrificial electron donors for
the regeneration of the dye. For example, using E D T A
as electron donor and Ru(bpy)z(4,4'-tridecyl-2,2'-
bpy) 2+ as photosensitizer Hz-evolution occurs in the
presence of Pt loaded TiO; at a rate of 0.8 m1-1 upon
illumination with visible light (L>435 nm) [77].
Hz-evolution has been reported from systems where
the natural enzyme hydrogenase is included as catalyst
in artificially designed photosensitizer assemblies [78--
80]. Using various sacrificial electron donors such as
triethanolamine or thiols, the photosensitized reduction
of N,N'-dimethyl-4,4'-bipyridinium, MV 2+, (6), has
been derived with Ru(bpy) 2÷ or Zn(II)-porphyrins
acting as photosensitizers. The reduced photoproduct,
MV +, mediates H 2 evolution in the presence of the
enyme hydrogenase rather than with heterogeneous
metal catalysts. Similarly, photoproduction of He has
of heterogeneous Pt-colloids in the presence of bipyridi-
nium charge relays acting as electron carriers [81].
P H O T O P R O D U C T I O N OF F O R M A T E - - A N
H2-STORAGE SUBSTRATE
The concomitant production of hydrogen and oxygen
through direct photolysis of water suffers from the basic
disadvantage that photoproducts recombine on the
common heterogeneous catalyst applied in these sys-
tems. This limitation will certainly effect the efficiencies
of cyclic water photolysis devices. Also transportation
and storage of H2 might introduce constraints. Thus,
photoproduction of a non-volatile low molecular weight
substrate that is inert towards oxygen, and capable of H
evolution in a subsequent controlled reaction, might be
advantageous. Formate, HCO2-, meets these criteria,
and in the presence of heterogeneous Pd based catalysts
is decomposed in a dark process to hydrogen (equation
17). Thus, photoreduction of CO2 to formate in aqueous
media (equation 18) might be a source for hydrogen and
a model system for natural photosynthesis to utilize the
same reactants for solar conversion.
Pal-catalyst
HCO2H ' H~ + CO,_ (17)
CO2 + H20 h v HCO, H + 1/2 02 (18)
Photochemical assemblies composed of Ru(bpy)~ ÷ as
sensitizer, one of the electron relays, N,N'-dimethyl-
4,4'bipyridinium, MV -~+, (6), or N,N'-trimethylene-
2,2'-biyridinium, DT 2+, (11), and cysteine as sacrificial
electron donor, yield, upon illumination, formate in the
presence of the enzyme formate dehydrogenase (FDR)
[82]. This photosensitized transformation, schematically
presented in Fig. 13(a), proceeds with a quantum

hi,/

Cysleine~ ~ Ru(bpy)~'.~.-/ "~-t,.DTT~ ~CO2+2H'oN..~

~--~-
DT2*: -l~J-
hu

CO2HJ" MdRFI+'W~" "i" MVt ~J" ~HCO~ ~N,

I

CO2H dRFI: N ~ ~ NN

Fig. 13. Cyclicscheme for photosensitized reduction ofCoJHCO~ - to formate (HCO= . a. Using formate
dehydrogenase (FDR) as catalyst, b. Using deazaribollavin as photosensitizer and a Pd-cyclodextrin as
catalyst.
 SOLAR HYDROGEN PRODUCTION
efficiency of 0.016%. A closely related InP photoelec-
trochemical cell has also been developed. In this system
M V 2+ is p h o t o r e d u c e d at the S.C. electrode, and
M V + mediates formate production in the presence of
F D R [83]. Very recently, an artificial photochemical
asembly that reduces CO2/bicarbonate with unit quan-
tum efficiency, has been d e v e l o p e d (Fig. 13b) [84]. A
h e t e r o g e n e o u s Pd-colloid stabilized by cyclodextrins
acts as the reduction catalyst. As photosensitizer,
deazariboflavin, dRFI. (12), is used, MV 2+ acts as
charge relay and oxalate is the sacrificial electron donor.
The reduced relay, M V + , mediates C O 2 / H C O 3 - photo-
reduction in the presence of the Pd-catalyst.
CONCLUSIONS AND OUTLOOK
We have addressed three disciplines for the photolysis
of water to H,-fuel by means of solar energy. Man-made
assemblies c o m p o s e d of photosynthetic cells and bacter-
ia, synthetic dyes and s e m i c o n d u c t o r materials, together
with p r o p e r redox catalysts could provide the organiza-
tion of light harvesting and subsequent fuel generation
systems. A t present, bulk photoelectrolysis of water is a
viable alternative for solar hydrogen production. Yet,
the intensive research activities in the various areas open
future perspectives where new redox catalysts, colloidal
semiconductors, immobilized enzymes and functional
organization will provide means of large-scale solar
energy harvesting and conversion. Future efforts to
produce solar hydrogen fuel are anticipated to merge
through the indirect photoreduction of COz. D e v e l o p -
ment of such artificial photosynthetic devices might be of
e x t r e m e importance not only as fuel generation systems,
but as a means to dispose of CO2 that is a growing
e n v i r o n m e n t a l concern.
A cknowledgements--The support of our energy projects by the
National Council for Research and Development, Israel; the
Kernforschung Anlage Juelich, Germany; the Belfer Founda-
tion and the Singer Foundation: is gratefully acknowledged.
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