Table 1 Physicochemical Data of Au Catalysts and the Results for the Aerobic Oxidation

Support information

ETS-10 Supported Au Nanoparticles for Solvent-Free Oxidation of 1-Phenylethanol with Oxygen

Jiajia Xu · Yueming Liu · Haihong Wu · Xiaohong Li · Mingyuan He ·Peng Wu

Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry, EastChinaNormalUniversity, 3663 North Zhongshan Rd., Shanghai 200062, China. e-mail: ; .cn

Experiment Methods

Hydrothermal Synthesis of ETS-10. The details for the synthesis of ETS-10 were as follows.For preparation Ti source, 14.401 gof Ti(SO4)2was dissolved in 5.160 gof H2SO4and60.064 gof deionized water under stirring.17.763 gof NaOH and 10.727 gof KF·2H2O were dissolved in 74.116 gof deionized water to form a clear solution, into which then 62.4 gof colloidal silica (30 wt %) was added and stirred to be homogeneous. Thereafter, the Ti source solution was mixed with the silica gel, resulting a white synthetic gel. The crystallization was carried outstaticallyin 150mL Teflon-lined stainless steel autoclaves at 473 K for 2 days.The solid products were filtered, washed with deionized water for several times, and dried overnight at 363 K in ambient air.

Synthesis of Au Precursor. 15.0 mL of chloroauric acid solution containing 0.05 g of Au was supersaturated by 18.0 g NH4NO3. To this solution, ammonia solution(25 wt%) was added until pH≈7 over an ice water bath. A white precipitate of crystallized tetrammine gold(III) nitrate was formed in the reaction mixture.The product was collected by filtration, washing with cooled ethanol, and then dried at 353 K overnight.

DP Method.1.0 gof ETS-10 powder was added to 30 mL of HAuCl4 solution, which contain different amounts of Au, the pH value was adjusted to 10 by using 1 wt % NaOH solution. After stirring for 2 h, then the samples were filtered, washed with deionized water, dried at 353 K and calcined in air at 573 K.

IW Method.1.0 gof ETS-10 powder was added into 0.5 mL of HAuCl4 solution containing different amount of Au. After stirring for 2 h, the mixture was dried up at 353 K and calcined in air at 573 K.

Fig. S1 X-ray powder diffraction patterns of (a) ETS-10 as synthesized, (b) Au-ETS -10(1.2%), (c) Au-ETS-10(0.2%,573 K), (d) Au-ETS-10(0.8%,573 K), (e) Au-ETS-10(1.2%,573 K), (f) Au-ETS-10(1.8%,573 K), (g) Au-ETS-10(4.1%,573 K).

The as-synthesized ETS-10 proved to be a pure phase, which showed a XRD pattern identical to that reported in literature(Fig.S1a). With 1.2 % Au content sample as an example, the structure of ETS-10 was maintained after the cation exchange (Fig. S1b). The weak acidity of [Au(NH3)4](NO3)3 solution may affect the structure of ETS-10, but which is not serious because of a relative high stability of the ETS-10 framework. After a further calcination at 573 K for 2 h, the Au-ETS-10 samples with different Au loadings still maintained the crystalline structure (Fig. S1c-g). The calcination induced the decomposition of the Au complex and subsequentlythe self-reduction to Au NPs. The Au particles gives the reflection peaks at 2θ of 38.1˚and 44.6˚ assignedthe (111) and(311) planes, respectively.The Au NPs-related reflections become distinct only when the Au loading reached 4.1 wt % (Fig. S1e). The results indicated that the Au particles were highly dispersed for the Au-ETS-10 samples with a lower Au content.