Dye-sensitizer effects on a Pt/KTa(Zr)O3 catalyst for the photocatalytic splitting of water

Article abstract of DOI:10.1002/anie.200503316

(Figure Presented) Back to the elements: The activity of Pt/K _0.95Ta_0.92Zr_0.08O₃ for the photocatalytic splitting of water into H₂ and O₂ is greatly improved by dye sensitization (see picture). Among the organic dyes examined, the highest photocatalytic activity is obtained with cyanocobalamin (vitamin B₁₂) as a sensitizer.

Full text of DOI:10.1002/anie.200503316

Communications
have been investigated for this reaction.[1,2] Recently, how-
ever, various Ta-based oxides reported by Kato and Kudo
et al. have attracted interest as new photocatalytic materials
because of their fairly high activity for the photocatalytic
splitting of H2O.[3–5] In addition, Zou et al. have found that Ni-
doped InTaO4 can decompose H2O upon activation with
visible light,[6] as can the mixed SrTiO3/WO3 compound
reported by Sayama et al.[7,8] In a previous study we found
that Zr-doped KTaO3 exhibits a high activity, splitting H2O
into almost stoichiometric amounts of H2 and O2.[9,10] How-
ever, these photocatalysts mainly consist of oxide semi-
conductors combined with a metal or metal oxide such as Pt
or NiO. On the other hand, dye-sensitized solar cells are
attracting a great deal of interest because of their simple
structure and high efficiency.[11,12] In these cells a free electron
is excited in the organic dye and passes through a TiO2
electrode to the counter electrode. Although the structure
of these solar cells is simple, a high energy conversion up to
11% can be achieved, and the electron-transfer step resem-
bles that in photocatalysis. Indeed, the application of dye-
sensitized solar cells to the photolysis of water has also been
reported,[12] therefore a dye-sensitized TiO2 electrode should
also function as a photocatalyst for the splitting of water into
H2 and O2.
Photocatalysts sensitized by various organic dyes have
been investigated, and it has been reported that hydrogen
forms under visible-light irradiation of Pt/TiO2 in the
presence of bipyridyl–ruthenium complex, albeit in a small
amount.[13,14] However, the splitting of pure water by a dye-
sensitized oxide semiconductor has not yet been achieved.
This study reports the sensitizing effects of porphyrinoids on
the photocatalytic splitting of H2O into H2 and O2 by Pt/
KTa(Zr)O3 and shows that the addition of porphyrinoids to
KTaO3 increases the activity of this compound.
Photocatalysis
DOI: 10.1002/anie.200503316
Dye-Sensitizer Effects on a Pt/KTa(Zr)O3
Catalyst for the Photocatalytic Splitting of
Water**
Figure 1 shows a TEM image of K0.95Ta0.92Zr0.08O3 coated
with tetraphenylporphyrinatochromium(iii). The surface of
Hidehisa Hagiwara, Naoko Ono, Takanori Inoue,
Hiroshige Matsumoto, and Tatsumi Ishihara*
The development of an active catalyst for the photocatalytic
decomposition of pure water into H2 and O2 is urgently
required from an energy-saving viewpoint. Various semi-
conductor oxides, mainly TiO2- and Nb-based mixed oxides,
[*] H. Hagiwara, H. Matsumoto, Dr. T. Ishihara
Department of Applied Chemistry
Faculty of Engineering
Figure 1. TEM image of Pt-loaded K0.95Ta0.92Zr0.08O3 sensitized by Cr–
TPP (rough, thin surface layer).
Kyushu University
Motooka 744, Nishi-Ku, Fukuoka, 819-0395 (Japan)
Fax: (+81)92-802-2871
E-mail: ishihara@cstf.kyushu-u.ac.jp
the particle is covered with an amorphous film of the
chromium complex. Therefore, the KTaO3-based oxide is
encapsulated with the organic dye and good electronic
contact between the oxide semiconductor and organic dye
seems to have been achieved. The prepared KTaO3 also
appears to have good crystallinity since the lattice image is
also observed. The UV/Vis spectrum of the prepared catalyst
N. Ono, T. Inoue
Department of Applied Chemistry
Faculty of Engineering
Oita University
Dannoharu 700, Oita, 870-1192 (Japan)
[**] The authors are grateful for financial support from the Nissan
Science Research Foundation.
1420
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 1420 –1422

Angewandte
Chemie
is the sum of those of KTaO3 and tetraphenyl-
porphyrinatochromium(iii) (Cr–TPP). This also supports the
uniform distribution of organic dye on the KTaO3-based
oxide.
cyanocobalamin, this result is to be expected. A further study
examined the dye-sensitizer effects of cyanocobalamin.
Figure 2 shows the rate of formation of H2 and O2 with
different amounts of cyanocobalamin added for
Table 1 summarizes the photocatalytic activity of the
KTaO3 catalyst sensitized by various organic dyes. The
observed formation rate of O2 is almost half that of H2, and
Table 1: Photocatalytic splitting of waterinto
K
H
and O2 by
2
0.95Ta0.92Zr0.08O3 sensitized by various organic dyes.[a]
Organic dye
Formation rate
[mmolgÀ1 hÀ1
]
H2
O2
Pt/K0.95Ta0.92Zr0.08O3
Pt/cyanocobalamin
Cyanocobalamin/K0.95Ta0.92Zr0.08O3
2.1
4.5
6.1
0.7
trace
0.5
Pt/organic dye/K0.95Ta0.92Zr0.08O3
Tetraphenylporphine tetrasulfonic acid (TPPS)
Tetrakis(4-carboxyphenyl)porphine (TCPP)
Zn–TPP dimer[b]
Co–phthalocyanine
Cr–phthalocyanine
376.8
404.2
365.2
22.3
106.0
95.6
152.0
9.3
Figure 2. Rate of formation of H2 and O2 as a function of amount of
added cyanocobalamin forK 0.95Ta0.92Zr0.08O3.
52.0
25.1
Co–tetraphenylporphyrin (Co–TPP)
Cr–tetraphenylporphyrin (Cr–TPP)
Chlorophyll a
145.3
512.6
371.5
575.0
44.8
257.0
122.6
280.4
K
0.95Ta0.92Zr0.08O3. It can be seen that the rate of formation
Cyanocobalamin
of H2 and O2 increases upon increasing the amount of
cyanocobalamin, with the highest formation rate achieved at
0.6 wt.%. Since the light absorbed by cyanocobalamin cannot
reach the central part of the photocatalyst (KTaO3), addition
of a large excess of cyanocobalamin only serves to lower the
activity of the catalyst. Therefore an optimum cyanocobala-
min load was achieved with 0.8 wt.%.
[a] Pt was added forall catalysts except forcyanocobalamin/
0.95Ta0.92Zr0.08O3 , and the Pt load and the amount of organic dye are
K
0.2 and 0.8 wt.%, respectively. Photolysis was performed at pH 11.
[b] Pentamethylene bis[4-(10,15,20-triphenylporphin-5-yl)benzoate]di-
zinc(ii).
the lowest formation rate of H2 is 2.1 mmolhÀ1 gÀ1 for Pt/
Figure 3 shows the amount of H2 and O2 formed by Pt/
K
0.95Ta0.92Zr0.08O3. It can also be seen that almost no H2 or O2
K0.95Ta0.92Zr0.08O3 sensitized by cyanocobalamin after various
was formed with Pt/cyanocobalamin (vitamin B12) or cyano-
cobalamin/KTaO3. The formation rate of H2 and O2 was
greatly increased relative to that for Pt/K0.95Ta0.92Zr0.08O3 by
addition of various porphyrinoids. The formation rate of H2
increases as follows: TPPS < TCPP < Co–TPP ! Cr–TPP <
TMPyP < cyanocobalamin. Although the rate of formation
of H2 is slightly larger than that of O2, almost stoichiometric
amounts of H2 and O2 are formed with respect to H2O
splitting with the various dye-sensitized catalysts studied. In
particular, the rate of formation of H2 is almost twice as large
as that of O2 on Cr–TPP-sensitized Pt/KTaO3. The metal
cation of the porphyrin complex also has a large influence on
the rate of formation of H2 and O2, as can be seen by
comparing the results for catalysts sensitized with Co–TPP
and Cr–TPP. Among the porphyrinoids examined, cyanoco-
balamin shows the strongest effect on the photocatalytic
splitting of water. Although it would be difficult, changing the
central cation of cyanocobalamin from Co2+ to Cr3+ should
greatly improve the photocatalytic activity. In any case, the
formation rate of H2 and O2 with this cyanocobalamin-based
catalyst is the highest obtained in this study (575.0 and
280.4 mmolgÀ1 hÀ1, respectively). Almost no H2 and O2 were
observed with Pt/cyanocobalamin as the photocatalyst
(Table 1), therefore cyanocobalamin is a promoter rather
than a photocatalyst. In view of the narrow bandgap of
Figure 3. Amount of H2 and O2 formed by cyanocobalamin-sensitized
Pt/K0.95Ta0.92Zr0.08O3 as a function of reaction time.
reaction times. Formation of H2 and O2 occurs immediately
upon irradiation, and although the rate of formation
decreases slightly from the initial rate, it is sustained over
the time period examined (9 h). The total amount of H2
evolved during these 9 hours was 1370 molar times larger
than that obtained with cyanocobalamin supported on
KTaO3, therefore cyanocobalamin is a promoter rather than
Angew. Chem. Int. Ed. 2006, 45, 1420 –1422
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
1421

Communications
a sacrificial agent. The estimated apparent quantum yield of
Experimental Section
the catalyst for this experiment is 12.2% with 300-nm light,
which is smaller than that reported for La-doped NaTaO3,
although it is known that this catalyst exhibits a high quantum
yield with UV light.
To identify the effect of the sensitizer, the photovoltaic
behavior of Pt/KTa0.92Zr0.08O3 with and without added Cr–
TPP was studied as a function of time. Figure 4 shows the
decay curve of the photovoltaic potential after irradiation
The KTaO3 catalyst was prepared by calcination of a mixture of
Ta2O5, K2CO3, and ZrO(NO3)2·6H2O at 1173 K in air for 10 h.
Commercially available organic dye, mainly porphyrin, was used in
this study after exchanging the metal center. The various metal
porphyrins were prepared by refluxing with the appropriate metal
chloride in pyridine. Loading of the dye sensitizer onto the obtained
KTaO3 was performed by an impregnation method with pyridine as
solvent. Pt was also loaded by an impregnation method with an
aqueous solution of [Pt(NH3)4(NO3)2]. The photodecomposition of
water was performed in a conventional closed circulating system with
a dead volume of about 500 mL. The catalyst (100 mg) was suspended
in 30 mL of pure water pre-saturated with Ar. KOH was used to
adjust the pH to pH 11. The quartz reaction cell was irradiated by an
external light source (500-W Xenon lamp, Ushio). During the
photodecomposition the water and catalyst were mixed with a
magnetic stirring bar. Argon at a pressure of 10.67 kPa was used as the
circulating carrier gas. The H2 and O2 formed were measured with a
TCD gas chromatograph (Shimadzu GC-8APT) connected to the
circulating line with a sampling valve.
Received: September 19, 2005
Published online: January 20, 2006
Keywords: dyes/pigments · heterogeneous catalysis ·
.
photolysis · porphyrinoids · sensitizers
[1] S. Moon, H. Mametsuka, E. Suzuki, M. Anpo, Chem. Lett. 1998,
117 – 118.
[2] T. Takata, A. Tanaka, M. Hara, J. N. Kondo, K. Domen, Catal.
Today 1998, 44, 17 – 26.
[3] H. Kato, A. Kudo, Catal. Today 2003, 78, 561 – 569.
[4] A. Kudo, H. Kato, Chem. Phys. Lett. 2000, 331, 373 – 377.
[5] H. Kato, K. Asakura, A. Kudo, J. Am. Chem. Soc. 2003, 125,
3082 – 3089.
[6] Z. Zou, J. Ye, K. Sayama, H. Arakawa, Nature 2001, 414, 625 –
627.
Figure 4. Decay curve of the photovoltaic potential of KTaO3 with and
without Cr–TPP sensitization after irradiation for 8–10 ns with a 263-
nm laser.
[7] K. Sayama, K. Mukasa, R. Abe, Y. Abe, H. Arakawa, Chem.
Commun. 2001, 2416 – 2417.
[8] K. Sayama, K. Mukasa, R. Abe, Y. Abe, H. Arakawa, J.
Photochem. Photobiol. A 2002, 148, 71 – 77.
[9] T. Ishihara, H. Nishiguchi, K. Fukamachi, Y. Takita, J. Phys.
Chem. B 1999, 103, 1 – 3.
[10] C. Mitsui, H. Nishiguchi, K. Fukamachi, T. Ishihara, Y. Takita,
Chem. Lett. 1999, 1327 – 1328.
[11] T. Renouard, R.-A. Fallahpour, M. K. Nazeeruddin, R.
Humphry-Baker, S. I. Gorelsky, A. B. P. Lever, M. Grꢀtzel,
Inorg. Chem. 2002, 41, 367 – 378.
[12] M. Grꢀtzel, Chem. Lett. 2005, 34, 8 – 13.
[13] E. A. Malinka, G. L. Kamalov, S. V. Vodzinskii, V. I. Melnik,
Z. I. Zhilina, J. Photochem. Photobiol. A 1995, 90, 153 – 158.
[14] R. Abe, K. Sayama, H. Arakawa, Chem. Phys. Lett. 2003, 379,
230 – 235.
with a 8–10-ns pulse from a 263-nm Nd-YAG laser. When Pt/
KTa0.92Zr0.08O3 was irradiated, the photovoltaic potential was
observed over 4.0 ms with an estimated half-life of 11.2 ms. It is
evident from this figure that the half-life of the photovoltaic
potential is increased upon addition of Cr–TPP. This suggests
that the lifetime of the photo-excited electron and hole can be
increased by coating with Cr–TPP. Therefore the positive
effects of porphyrinoids can be explained by the improved
efficiency of charge separation. In light of the small bandgap
of the organic dye, it is likely that the excited free electron in
the KTaO3-based oxide passes to the organic dye, where it is
excited again, and then passes to Pt, which is the effective site
for H2 formation, in analogy to photosynthesis. This is
because the photovoltaic potential increases upon irradiation
with a 263- and 526-nm mixed-laser compared with that of a
single 263-nm laser. As previously discussed, TEM observa-
tion suggests that the KTaO3 oxide semiconductor is encap-
sulated by the organic dye, therefore the electron in KTaO3
can easily transfer to the organic dye, resulting in the efficient
separation of hole and electron.
This study has demonstrated that the photocatalytic
splitting of water by KTaO3 can be greatly improved by
addition of an organic dye as sensitizer and that cyanocoba-
lamin is the most effective dye in this respect.
1422
www.angewandte.org
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 1420 –1422