Catalysis Science & Technology
Paper
supplied by Catalysis Society of Japan. WO
3
(x)/TiO
2
catalysts
D. W. Bahnemann, Chem. Rev., 1995, 95, 69–96;
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9
were prepared as follows: TiO
2
(1 g) was stirred vigorously in
an ammonia solution (1 M, 50 mL) containing an appropriate
amount of H WO at 353 K. The obtained dry powders were
2
4
ꢀ
1
calcined at 673 K for 2 h under O flow (0.5 L min ), affording
2
3
white powders of catalysts. WO was purchased from Kojundo
Chemical Laboratory Co. and used as a reference. Analytical
9
procedures were described in our previous paper.
concentration was determined by titration with KMnO
2 2
H O
4
(detec-
2
1
tion limit: 0.25 mmol).
4.2 Photoreaction procedure
(e) Y. Shiraishi and T. Hirai, J. Jpn. Pet. Inst., 2012, 55,
Each respective catalyst (5 mg) was suspended in MeCN (5 mL)
containing the substrate within a Pyrex glass tube (f 10 mm;
capacity, 20 mL). The tube was sealed using a rubber septum
cap. The catalyst was dispersed by ultrasonication for 5 min
287–298.
3 J.-M. Herrmann, Top. Catal., 2005, 34, 49–65.
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175–179.
and O
2
was bubbled through the solution for 5 min. The
solution was photoirradiated under magnetic stirring using a
2
2
2
kW Xe lamp (USHIO Inc.), and filtered through a Pyrex glass
saturated with water to give light wavelength of l > 300 nm. The
ꢀ
2
light intensity at 300–400 nm was 2.2 mW cm . After photo-
irradiation, the gas-phase product was analyzed by GC-TCD
(
Shimadzu; GC-14B). The catalyst was recovered by centrifuga-
5 (a) R. A. Sheldon and J. K. Kochi, Metal-Catalyzed Oxidations
of Organic Compounds, Academic Press, New York, 1981;
(b) C. L. Hill, Activation and Functionalization of Alkanes,
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tion and washed with MeCN (5 mL). The combined solution
was analyzed by GC-FID (Shimadzu; GC-1700), where the sub-
strate and product concentrations were determined using
authentic samples. Identification of the products was per-
formed by GC-MS (Shimadzu; GCMS-QP5050A).
4
.3 ESR measurement
ESR spectra were recorded at the X-band using a Bruker EMX-
0/12 spectrometer with a 100 kHz magnetic field modulation at a
microwave power level of 10.5 mW, where microwave power
7
8
(a) R. L. Brutchey, I. J. Drake, A. T. Bell and T. D. Tilley,
Chem. Commun., 2005, 3736–3738; (b) F. Wang, J. Xu, X. Li,
J. Gao, L. Zhou and R. Ohnishi, Adv. Synth. Catal., 2005, 347,
1
23
1987–1992; (c) J. Lv, Y. Shen, L. Peng, X. Guo and W. Ding,
saturation of the signals does not occur. The magnetic field
was calibrated using a 1,1 -diphenyl-2-picrylhydrazyl (DPPH) as
standard. The measurement was carried out as follows: each
catalyst (1.0 g L ) was suspended in MeCN containing toluene
0
Chem. Commun., 2010, 46, 5909–5911.
(a) M. Fujihira, Y. Satoh and T. Osa, Nature, 1981, 293,
9
ꢀ1
206–208; (b) C. Bouquet-Somrani, A. Finiels, P. Geneste,
ꢀ
1
ꢀ1
P. Graffin, A. Guida, M. Klaver, J. L. Olive and
A. Saaedan, Catal. Lett., 1995, 33, 395–400; (c) H. Rezala,
H. Khalf, J. L. Valverde, A. Romero, A. Molinari and
A. Maldotti, Appl. Catal., A, 2009, 352, 234–242;
(
10 mmol L ) and DMPO (100 mmol L ) and dispersed well by
ultrasonication. The 100 mL of the suspension was introduced to a
was
flat ESR cell [10 mm ꢂ 20 mm ꢂ 0.3 mm (path length)], and O
2
bubbled through the solution for 1 min. The cell was placed on an
ESR sample cavity and photoirradiated using a 500 W Xe lamp
through a glass filter to give light wavelengths of l > 300 nm at
room temperature. After photoirradiation for 90 s, the irradiation
was turned off, and the measurement was started immediately.
(d) S. Ouidri and H. Khalaf, J. Photochem. Photobiol., A,
2009, 207, 268–273.
9
D. Tsukamoto, M. Ikeda, Y. Shiraishi, T. Hara,
N. Ichikuni, S. Tanaka and T. Hirai, Chem.–Eur. J., 2011,
1
7, 9816–9824.
0 (a) S. A. Larson and J. L. Falconer, Catal. Lett., 1997, 44,
7–65; (b) P. Pichat, Catal. Today, 1994, 19, 313–334.
1
Acknowledgements
5
This work was supported by the Grant-in-Aid for Scientific 11 (a) F. Hilbrig, H. E. Gobel, H. Kn o¨ zinger, H. Schmelz and
Research (No. 23360349) from the Ministry of Education,
Culture, Sports, Science and Technology, Japan (MEXT).
B. Lengelr, J. Phys. Chem., 1991, 95, 6973–6978;
(b) S. Yamazoe, Y. Hitomi, T. Shishido and T. Tanaka,
J. Phys. Chem. C, 2008, 112, 6869–6879.
1
2 H. P. Maruska and A. K. Ghosh, Solar Energy, 1978, 20,
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276 Catal. Sci. Technol., 2013, 3, 2270--2277
This journal is c The Royal Society of Chemistry 2013