Proc. Natl Acad. Sci.
USA
Vol. 80, pp. 3129-3132, May 1983
Chemistry
Multielectron storage and hydrogen generation with
colloidal semiconductors
(energy conversion/charge transfer/semiconducting particles/amphiphilic viologens/photoreactions)
MICHAEL GRATZEL AND JACQUES MOSER
Institut de Chimie Physique, Ecole Polytechnique FMderale, CH-1015 Lausanne, Switzerland
Communicated by Melvin Calvin, January 17, 1983
ABSTRACT Multielectron storage and hydrogen generation
by light is achieved in aqueous dispersions of ultrafine TiO2 par-
ticles (120-A diameter) when the amphiphilic viologen derivative
N-tetradecyl-N'-methyl-4,4'-dipyridinium dichloride (CM4MV21)
is used as an electron relay. Consecutive reduction of C14MV2+
to the radical ion (C14MV+) and neutral (C14MV0) was observed
after band-gap excitation of the semiconductor particle. Through
surface adsorption of the relay, these electron-transfer reactions
can occur very rapidly and are completed within less than 100 pisec
(pH 11). Two-electron reduction of C14MV2+ can be coupled with
H2 generation in alkaline medium in the presence of Pt catalyst
codeposited onto the TiO2 particle. Electron-relay-free systems
are 1/15th as efficient in producing H2 at the same pH.
Colloidal semiconductors have several advantageous features
(1-7) that make them attractive candidates to be used as light-
harvesting units in solar energy devices. The idea of using col-
loidal semiconductors in photoconversion devices has been dis-
cussed by Nozik (8, 9). The concept of photoelectrochemical
reactions on semiconductor particles dates back to the discov-
eries of Emil Baur (10). For a recent review, see ref. 11.
Particularly intriguing is the possibility of surface modifi-
cation of the semiconductor particle by chemisorption, deriv-
atization, or catalyst deposition to achieve light-induced charge
separation (12) and subsequent fuel-generating dark reactions.
The present study illustrates successful molecular engineering
with such systems. By using aqueous dispersions of ultrafine
TiO2 particles in conjunction with the amphiphilic redox relay,
CH3-(CH2)l- Q--H3 (C14MV2+),
striking electron storage and hydrogen generation effects are
demonstrated.
MATERIALS AND METHODS
Colloidal solutions of TiO2 were prepared by slowly adding 5
g of TiC14 (Fluka purissimum) distilled under vacuum to 200 ml
of water at 0°C. The solution was dialyzed until the pH reached
a value of ca. 3. Precise determination of the TiO2 content was
carried out as described (5). Application of electron microscopy
and quasielastic light-scattering technique showed that the sol
consisted of 110-A-diameter particles. At pH > 3, poly(vinyl
alcohol) (PVA) was used to stabilize the colloidal particles. Com-
mercial PVA (Mowiol 98110, Hoechst, Federal Republic of
Germany) was pretreated by UV light (5) to remove impurities
that absorb 347.1-nm light. Laser photolysis experiments were
carried out with 347.1-nm pulses (10-nsec duration) of a JK-2000
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3129
ruby laser. An Osram XBO 450-W Xe lamp equipped with a
water jacket was used for continuous illuminations. C14MV2+
was synthesized as described (13).
RESULTS AND DISCUSSION
Illumination of an aqueous TiO2 sol containing C14MV2+ with
light of wavelength A > 300 nm results in the immediate ap-
pearance of a blue color, which can be attributed to formation
of viologen cation radicals (C14MV+) (Fig. 1). However, this
color does not persist under continuing exposure to light. A
striking and rather rapid change from blue to intense yellow is
noted. The resultant spectrum, also shown in Fig. 1, exhibits
a weak absorption at 500 nm and a strong peak at 380 nm.
Whereas the former absorption can be attributed to viologen
dimer radicals (C14MV+)2 (14) present at low concentration, the
latter was identified as doubly reduced viologen-i.e., 1-methyl-
1'-tetradecyl-4,4'-bipyridylene (C14MV0). The two-electron re-
duction of the analogous compound methylviologen by chem-
ical (15, 16) and electrochemical (17, 18) means yields dimethyl-
bipyridylene with similar spectral features [solvent, acetoni-
trile: Ama, 404 nm, 340 sh, 315 nm (19); solvent, cyclohexane:
Amax 348 nm (log E = 4.77), 377 nm (log e = 4.66) (20); Ama 400
nm, 376 sh (16)].
To substantiate the assignment of the 380-nm peak to C14MV0,
two-electron reduction of C14MV2+ was performed chemically
by using dithionite as a reductant (16) and aqueous micellar so-
lutions of Triton X-100 as a reaction medium. The spectrum of
the product obtained has features (Fig. 2) identical with those
of the photoproduct shown in Fig. 1 except that the absorption
maximum of the bipyridylene is at 400 instead of 380 nm. We
attribute this shift of the absorption maximum to adsorption of
the doubly reduced viologen to the surface of the TiO2 parti-
cles. Spectral shifts due to adsorption onto mineral supports
have been shown for a large number of chromophores including
Ru(bipy)2+ (21) and other transition metal ion complexes (22).
Independent experiments involving oxygen confirmed the
two-electron nature of the C14MV2' reduction in the colloidal
TiO2 dispersion. When a solution containing the yellow product
of C14MV2+ photoreduction by colloidal TiO2 is exposed to air,
the blue color of C14MV2+ is formed first, which subsequently
fades to yield colorless C14MV2+. (This reduction-reoxidation
cycle can be repeated many times.) Apparently the reoxidation
of C14MV0 occurs in two distinct steps,
C14MV0 + 02 -* C14MV+ + 02 [1]
C14MV+ + 02 - C14MV2 + - [2]
Interestingly, the first reaction was found to occur much less
rapidly than the second one, showing that C14MV0, despite its
more reducing nature, is less reactive towards 02 than is C14MV+.
Abbreviation: PVA, poly(vinyl alcohol).
3130 Chemistry: Gratzel and Moser Proc. Nad Acad. Sci. USA 80 (1983)

pH = 11.0, I
= 602nm
2.0
l
_A I I___ A

_. __ I___
___ 0.8

LASER 0.6
PULSE
1.0

0.4
Irradiation lamp 450W, 1min 30sec
.____ Irradiation lamp 450W, 10sec

0.2

0.0
400 500
k [nm] 600 700

FIG. 1. Spectral changes observed upon illumination (A > 300 nm) of a solution of TiO2 (500 mg/liter) containing C14MV2+ (0.2 mM) and PVA
(1 g/liter; Mowiol 10-98). -, Left ordinate scale; right ordinate scale. A solution of TiO2 (500 mg/liter; pH 11) was used in the reference
---,

light beam. (Inset) Laser flash photolysis (347.1 nm) of the preirradiated (1 min, 30 sec) solution: temporal behavior of the 602-nm absorption of
the C14MV+ radical. All solutions were flushed with nitrogen prior to irradiation.

The mechanism of light-induced C14MV0 formation involves
band-gap excitation of TiO2 particles generating electron-hole
pairs (Fig. 3). Conduction band electrons, eCB, reduce C14MV2+
first to the radical cation
ki
ecB + C14MV2+ -C14MV+ [3]
and subsequently to the bipyridylene
k2
C14MV+ + ecB C14MV0. [4]
Adhesion of the amphiphilic relay to the surface of TiO2 par-
ticles allows both electron-transfer processes to occur at a very
rapid rate. Application of the laser photolysis technique yields
for pH 11 the rate constants k1 = 10' sec-1 and k2 = 5 x 104
sec 1.* Therefore, two-electron reduction is completed in less
than 100 ,usec. This contrasts sharply with the behavior of sim-
ple methylviologent which at comparable light intensity and
* Because the reduction of ec( with C14MV2+ (C14MV+) occurs on in-
dividual TiO2particles, it fits in the general framework of fast electron-
transfer processes in colloidal aggregates, which has been elaborated
upon previously (23). Similar to intramicellar electron-transfer pro-
cesses, such intraparticle reactions follow first-order kinetics. The ob-
served rate constant is expressed in units of sec- and is expected to
increase with C14MV2+ association of the particle until saturation of
surface sites available to the electron relay is reached. Under our ex-
perimental conditions (temperature, pH, TiO2 concentration), the sat-
uration is practically reached at 0.2 mM C14MV2+.
t Simple methylviologen is not adsorbed to the TiO2 surface (2). The
rate of electron transfer in this case is limited by the diffusional ap-
proach of the reactants. For both C14MV2' and MV2', the quantum
yield of radical ion formation is approximately 1.
concentration does not appear to undergo two-electron reduc-
tion at pH ' 12.5. Only at high alkalinity does slow formation
of doubly reduced product become apparent. Apart from ki-
netic reasons, there are thermodynamic reasons for this drasti-
cally different behavior of the two electron relays. The second
reduction of methylviologen requires a potential of -0.83 V
(vs. the normal hydrogen electrode). Taking into account that
the conduction-band position of the TiO2 particle changes with
pH according to ECB = -0.11-0.059 pH (2), one predicts that
a pH of at least 12 is required to render this process thermo-
dynamically feasible. In the case of the amphiphilic viologen,
adsorption to the surface of TiO2 apparently shifts the potential
of the C14MV+/Cl4MV0 redox couple by more than 100 mV,
facilitating the second reduction step. Blank photolysis exper-
iments with solutions of C14MV2' did not lead to appearance
of C14MV0 or C14MV+, showing that light absorption by TiO2
particles produces the electron-transfer events.
As to the valence-band process occurring in parallel with the
reaction of conduction-band electrons, it is indicated in Fig. 2
that this comprises oxidation of water to oxygen, competing with
hole-scavenging by the PVA polymer used to stabilize the sol.
However, the latter process has been shown to be rather in-
efficient on TiO2 colloids (5). Therefore, hole reaction with water
prevails even in the presence of PVA. [TiO2 acts as an oxygen
carrier. From our own experiments (unpublished data), we
conclude that the capacity of the carrier is ca. 20 ,ul of 02 per
mg of TiO2.] However, it cannot be excluded that intermedi-
ates from the water oxidation attack subsequently the protec-
tive polymer. So far we have not analyzed these processes in
more detail, our main interest being the storage of conduction-
band electrons by the adsorbed relay.
 Chemistry: Gratzel and Moser Proc. Natl. Acad. Sci. USA 80 (1983) 3131

0.8 F

0.6 F
CH3- (OH, )13- N~tN - CH3

0.4 1-

0.2 h

0.0
400 500 600 700
AS [nm]
FIG. 2. UV/visible absorption spectrum of doubly reduced C14MV2" in Triton X-100 micellar solution.

A third valence-band process, which sets in once a major viologen radical:

fraction of C14MV2" has undergone two-electron reduction, is
reoxidation (hV = holes) of the doubly reduced product to the h+ + C14MV0 -> C14MV+. [5]
Laser photolysis technique was applied to preirradiated
Colloidal particle 00 C"4 MV2+ C14MV2+/TiO2 solutions in order to monitor this reaction. Fig.
Ti 02 \
1 Inset shows the temporal behavior of the absorption at 602
2e
> C14 MV nm. The sharp rise in the signal after the laser pulse is due to
, C14MV+ formation by reaction 5, whereas the subsequent ab-
,' . sorption decay indicates the time course of C14MV+ reduction
....... by conduction-band electrons (Eq. 4). In accordance with this
I..........
I.......
..........
.....
interpretation, one finds that the 380-nm absorption behaves
as the exact mirror image of the optical events at 602 nm: rapid
I.....

bleaching after the laser pulse is followed by recovery of the

(PVAt)1O + 2H ' original absorption, which obeys the same time law as the 602-
2 2
nm decay. One concludes that, under illumination of TiO2/
C14MV2+ solutions, a state is approached where cyclic electron
transfer (i.e., the sequence of reactions 4 and 5) occurring on
(PVA) individual TiO2 particles maintains the electron relay in the
doubly reduced form.
Attempts to exploit this two-electron storage system to achieve
light-induced hydrogen generation in alkaline aqueous medium
(C14 MV ) C14 H29-N N -CI 13
gave very encouraging results. TiO2 particles (500 mg/liter)
loaded with 1.5% Pt by a published procedure (2) were used in
|e E° (N H E) - 0.446 V these experiments. The solution volume was 5 ml, and the pH
was adjusted to 12 with NaOH. Vigorous hydrogen generation
(Cl4MV ) C14 H29- Nc N-CH E3 (0.5 ml/hr) was observed in C14MV2+-containing samples, while
blank experiments with TiO2/Pt dispersions in the absence of
&e E' (NHHE) 0.820 V C14MV2+ yielded only 35 ,ul of H2 per hr. Apparently, the co-
operation of functional electron relay and catalyst on the sur-
(C14MV0) C14 H29- N N - CH3 face of the semiconductor particle gives much better yields of
hydrogen than do catalyst deposits alone.
FIG. 3. Scheme for two-electron reduction of C14MV2"; the redox In conclusion, we have illustrated two-electron storage and
potentials given refer to simple methylviologen (MVh). CB, conduc- hydrogen generation by light in colloidal semiconductor dis-
tion band; VB, valence band; NHE, normal hydrogen electrode. persions, using an amphiphilic viologen as an electron relay.
3132 Chemistry: Gratzel and Moser
This work was supported by Swiss National Science Foundation and
Ciba Geigy, Basel, Switzerland.
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