Supporting Information Photon Energy Threshold in Direct Photocatalysis with Metal Nanoparticles Key Evidence from Action Spectrum of the Reaction Sarina Sarina, a Esa Jaatinen, a Qi Xiao, a,b Yi Ming Huang, a Philip Christopher, c Jin Cai Zhao, d Huai Yong Zhu a, * a School of Chemistry, Physics and Mechanical Engineering, Queensland University of Technology, Brisbane, QLD4001, Australia b CSIRO Manufacturing, Bayview Avenue, Clayton, VIC 3168, Australia c Department of Chemical & Environmental Engineering, University of California, Riverside, Riverside, California 92521, United States d Key Laboratory of Photochemistry, Institute of Chemistry, the Chinese Academy of Sciences, Beijing 100190, China. *Corresponding author: Prof. Dr. Huai-Yong Zhu, E-mail: hy.zhu@qut.edu.au
Contents Experimental section Figure S1 TEM images of metal nanoparticle photocatalysts supported on ZrO 2 Figure S2 The digital photograph of the LED lamps setup used in the wavelength experiments
Experimental Preparation of catalysts Au NP@ZrO 2 : ZrO 2 powder (1.0 g) was dispersed in a HAuCl 4 (13mL, 0.01 M) aqueous solutions under magnetic stirring at room temperature. An aqueous solution of lysine (3 ml, 0.1 M) was then added to the mixture with vigorous stirring for 30 min, and the ph was 8 9. To this suspension was added a freshly prepared aqueous solution of NaBH 4 (2 ml, 0.35 M) dropwise. The mixture was aged for 24 h, and then the solid was separated by centrifugation, washed with water (three times) and ethanol (once), and dried at 60 C in a vacuum oven for 24 h. The same procedure is applied to other monometallic NPs, Ag, Pt, Pd, Rh and Ir onto ZrO 2 powder by reducing the corresponding metal salt with NaBH 4 in the presence of ZrO 2 powder. Au-Pd alloy NP@ZrO 2 : 2.0 g ZrO 2 powder was dispersed into 15.2 ml of 0.01 M HAuCl 4 aqueous solution and 28.3 ml of 0.01 M PdCl 2 aqueous solution were added while magnetically stirring. A total of 20 ml of 0.53 M lysine was then added into the mixture with vigorous stirring for 30 min. To this suspension, 10 ml of 0.35 M NaBH 4 solution was added dropwise in 20 min, followed by an addition of 10 ml of 0.3 M hydrochloric acid. The mixture was aged for 24 h and then the solid was separated, washed with water and ethanol, and dried at 60 C. Characterization of Catalysts The sizes, morphologies, and compositions of the catalyst samples were characterized by TEM using a JEOL 2100 transmission electron microscope equipped with a Gatan Orius SC1000 CCD camera and an Oxford X-Max EDS instrument. TEM images are provided in Figure S1. Photocatalytic Reaction conditions For all reactions: A 20 ml Pyrex glass tube was used as the reaction container with seal of a rubber septum cap. The reaction mixture was stirred magnetically and irradiated using Light-emitting diode (LED) lamps (Tongyifang, Shenzhen, China, setting image is given in Figure S2) with wavelengths of
365±5, 400±5, 470±5, 530±5, 590±5, and 620±5 nm. After reaction 0.5 ml aliquots were collected at given irradiation time intervals and filtered through a Millipore filter (pore size 0.45 µm) to remove the catalyst particulates. Then flask was purged with argon again for more than 3 min to remove air and then sealed. The filtrates were analyzed by an Agilent 6890 gas chromatograph with HP-5 column. An Agilent HP5973 mass spectrometer was used to determine and analyze the product compositions. Reaction condition of data collection in Figure 1 and 2. Aryl iodide (1 mmol), alkyl alkyne (1.2 mmol), photocatalysts (50 mg), cetyltrimethylammonium bromide (CTAB) (1 mmol), and K 3 PO 4 (2 mmol) were added to 10 ml of H 2 O. The reaction temperature was 45±2 C, under a 1 atm argon atmosphere, with a reaction time of 24 h. Reaction condition of data collection in Table 1. Entry 1 and 2: 1 mmol of reactant, 50 mg (containing 3% of metals) of catalyst in CH 3 CN solvent at 45 C and 1 atm of O 2, reaction time 48h. Entry 3: 2 mmol of the reactant, 50 mg (containing 3% of metals) of catalyst in trifluorotoluene solvent at 45 C and 1 atm of O 2, reaction time 5h. Entry 4 and 5: 1 mmol nitrobenzene in 2 ml isopropyl alcohol (IPA), 0.3 mmol KOH, and 50 mg of catalyst were added to the reaction tube, and the reaction was run at a required temperature under a 1atm argon atmosphere for a reaction time of 18 h. Reaction condition of data collection in Table 2. Entry 1 and 4: 100 mg catalyst, the metal content is 3 wt%; 0.5 mmol reactant in 5 ml triflourotoluene solvent; 1atm Ar atmosphere. Oxygen was removed from the reaction mixture prior to introducing Ar and the reaction proceeded 48 h for all catalysts under irradiation of various light and in the dark at 45±2ºC. Entry 2 and 3: 1 mmol of reactant, 50 mg (containing 3% of metals) of catalyst in CH 3 CN solvent at 45 C and 1 atm of O 2, reaction time 24h. Entry 5 and 6: catalyst 50 mg, iodobenzene 0.1 mmol, styrene 0.12 mmol, N,N-Dimethylformamide (DMF) 2 ml, 1 atm Ar, sodium acetate (AcONa) 50 mg, reaction time 17 h, temperature for (a) 50 ± 2 C.
Figure S1 TEM images of metal nanoparticle photocatalysts supported on ZrO 2.
Figure S2 The digital photograph of the LED lamps setup used in the wavelength experiments.