Selective Photocatalytic Oxidation of Aniline to Nitrosobenzene by Pt Nanoparticles Supported on TiO 2 under Visible Light Irradiation
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1 Selective Photocatalytic Oxidation of Aniline to Nitrosobenzene by Pt Nanoparticles Supported on TiO 2 under Visible Light Irradiation Yasuhiro Shiraishi,*, Hirokatsu Sakamoto, Keisuke Fujiwara, Satoshi Ichikawa, and Takayuki Hirai Research Center for Solar Energy Chemistry, and Division of Chemical Engineering, Graduate School of Engineering Science, Osaka University, Toyonaka , Japan. Institute for NanoScience Design, Osaka University, Toyonaka , Japan. shiraish@cheng.es.osaka-u.ac.jp SUPPORTING INFORMATION CONTENTS Page Figure S1. Diffuse reflectance UV vis spectra of catalysts..... S2 Figure S2. TEM images and size distributions of Pt particles on Pt 2 /TiO 2 catalysts.. S3 Figure S3. Results of aerobic oxidation on various Pt/TiO 2 catalysts. S4 Figure S4. XPS chart for catalysts.. S5 Figure S5. IR spectra for aniline in the absence and presence of base... S5 Figure S6. TEM images and size distributions of Pt particles on Pt 2 /P25 catalysts... S6 Figure S7. XRD patterns of catalysts prepared at different calcination temperature... S7 S1
2 M 2 /P25 (M = Au, Ag, Pd, Pt) 4 Ag 2 /P25 Au 2 /P25 F(R ) 2 Pd 2 /P25 Pt 2 /P25 Pt x /P25 (x =.5, 1, 2, 3, 4 wt %) Wavelength / nm F(R ) 4 2 x / wt % P Wavelength / nm Pt 2 /P25 prepared at different temperatures (673, 773, 873 K) 4 F(R ) K 873 K P K Wavelength / nm Figure S1. Diffuse-reflectance UV-vis spectra of catalysts. S2
3 Pt 2 /anatase ±.6 nm Pt 2 /rutile ±.6 nm Figure S2. Typical TEM images of catalysts and size distribution of Pt particles. S3
4 Pt 2 /JRC TIO 1 Pt 2 /ST 21 Pt 2 /anatase (Wako) Pt 2 /P25 Pt 2 /JRC TIO 6 Pt 2 /NS 51 <.1 Pt 2 /PT 11 <.1 nitrosobenzene azobenzene 5 1 Amounts / µmol Properties of the supports used Catalyst Supplier crystalline phase particle size / nm a S BET / m 2 g -1 b JRC TIO 1 Catalysis Society of Japan anatase ST 21 Ishihara Sangyo Co., Ltd. anatase anatase (Wako) Wako anatase P25 Catalysis Society of Japan anatase/rutile (83/17) JRC TIO 6 Catalysis Society of Japan rutile NS 51 Toho Titanium Co., Ltd. rutile 22 7 PT 11 Ishihara Sangyo Co., Ltd. rutile a Hydrodynamic diameter of particles determined by a Horiba LB 5 dynamic light scattering particle size analyzer. b BET surface area determined by N 2 adsorption/desorption measurements at 77 K using an AUTOSORB 1 C/TCD analyzer (Yuasa Ionics Co., Ltd.). Figure S3. Amounts of (white) nitrosobenzene and (black) azobenzene produced by aerobic oxidation of aniline on anatase or rutile TiO 2 loaded with Pt particles under visible light irradiation (λ >45 nm). The reaction conditions are identical to those in Figure 3 (manuscript). S4
5 Pt 4f 5/2 Pt 4f 7/ Pt 2 /JRC TIO Pt 2 /ST Pt 2 /anatase(wako) Pt 2 /P25 Pt 2 /JRC TIO Pt 2 /NS 51 Pt 2 /PT Binding energy / ev Figure S4. XPS results for respective catalysts. Transmittance (au) ν anti ν sym Wavenumber / cm 1 Figure S5. IR spectra of aniline (2 mm) measured in the (black) absence and (blue) presence of triethylamine (3 equiv) in CCl 4. S5
6 Pt.5 /P ±.4 nm Pt 4 /P ±.4 nm Pt 2 /P25 prepared at 873 K ± 2.9 nm Figure S6. Typical TEM images of Pt/P25 catalysts and size distribution of Pt particles. S6
7 P25 A/R 82/18 Pt 2 /P25 (673 K) Pt 2 /P25 (773 K) Pt 2 /P25 (873 K) 81/19 81/19 75/25 anatase rutile Figure S7. XRD patterns of Pt 2 /P25 catalysts prepared at different calcination temperature. The anatase (A) and rutile (R) contents were determined with the equation; A (%) = I A (11) / [I A (11) + 1.4I R (11)] 1 (Ramis, G.; Busca, G.; Cristiani, C.; Lietti, L.; Forzatti, P.; Bregani, F. Langmuir 1992, 8, ). S7
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