Supporting Information A Rational Solid-state Synthesis of Supported Au-Ni Bimetallic Nanoparticles with Enhanced Activity for Gas-phase Selective Oxidation of Alcohols Wuzhong Yi, a Wentao Yuan, b Ye Meng, a Shihui Zou, a, b Yuheng Zhou, a Wei Hong, a Jianwei Che, a Mengjia Hao, a Bin Ye, a Liping Xiao, a Yong Wang, b Hisayoshi Kobayashi, c Jie Fan*, a a Key Lab of Applied Chemistry of Zhejiang Province, Department of Chemistry, Zhejiang University, Hangzhou 310027, China b School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China c Department of Chemistry and Materials Technology, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan E-mails: jfan@zju.edu.cn S-1
Table S1. Solvent-free aerobic oxidation of alcohols over different catalysts. Entry Catalysts Substrate Temp 1 a Ag/SBA-15 Benzyl alcohol o C Sel. % STY c Kg g metal h -1 2 a Pt/FeO Benzyl alcohol 270 99 0.50 2 3 b Pd/TiO 2 Benzyl alcohol 100 54 0.33 3 Ref. 240 97 0.19 1 4 b Au-Pd/TiO 2 Benzyl alcohol 100 95 0.35 3 5 a Nanoporous Au Benzyl alcohol 240 95 0.052 4 6 a Au/EP-FDU-12 Benzyl alcohol 230 100 0.12 5 7 b Au/SiO 2 Benzyl alcohol 280 98 0.86 6 8 a NiO x @Au/Ti-fiber Benzyl alcohol 250 99 0.42 7 9 b Au/MgCuCr 2 O 4 ethanol 200 99 0.30 8 10 a Nanoporous Au Methanol 80 97 0.002 9 11 a Au/EP-FDU-12 Cyclohexanol 230 100 0.12 10 12 b Au@PION-1 Cyclohexanol 140 99 0.98 11 13 a Au/SiO 2 1-propanol 250 100 0.87 12 14 b Pt/HT 1-octanol 100 84 2.04 13 15 b Ru/Al 2 O 3 1-phenylethanol 150 98 0.40 14 a, gas-phase reaction; b, liquid-phase reaction; c, space time yield (STY) of benzyl aldehyde (BAD). S-2
Figure S1. O 2 adsorbed structure on a) Au 50 and b) Au 30 Ni 20 clusters; BA adsorbed structure on c) Au 50 and d) Au 30 Ni 20 clusters. Table S2. Adsorption energies of O 2 and BA and the O-O bond length on Au 50 and Au 30 Ni 20. a Model E (O 2 ) E (BA) O-O Length Au 50-1.117 ev -1.248 ev 1.327 Å Au 30 Ni 20-2.286 ev -1.046 ev 1.389 Å S-3
Figure S2. TEM images and particle size distribution of a-c) AuNP and d) PdNP seeds. S-4
Figure S3. HAADF STEM picture of Au 1 Ni 1-700 o C NP. S-5
Figure S4. HAADF STEM mappings of row A) Au 3 Ni 1-500 o C, B) Au 2 Ni 1-500 o C, C) Au 1 Ni 1-500 o C and D) Au 1 Ni 2-500 o C. S-6
Figure S5. XRD patterns of samples with different Au/Ni feeding ratio after annealing at 500 o C (5.1 ± 0.2 nm AuNPs as seeds). S-7
Table S3.The metal contents of different samples calcinated at 500 o C determined by ICP-MS analysis. Sample Seeds size Metal loading (wt%) nm Ni Au Ni - 0.31 - Au 5.1 ± 0.2-1.05 Au 3 Ni 1 5.1 ± 0.2 0.12 1.03 Au 2 Ni 1 5.1 ± 0.2 0.26 1.02 Au 1 Ni 1 5.1 ± 0.2 0.32 1.03 Au 1 Ni 2 5.1 ± 0.2 0.61 1.04 Au 1 Ni 1 3.2 ± 0.3 0.31 0.98 Au 1 Ni 1 7.8 ± 0.5 0.32 0.96 S-8
Figure S6. Nitrogen sorption isotherms of different samples calcinated at 500 o C. a-b) 5.1 ± 0.2 nm AuNPs as seeds, c) 3.2 ± 0.3 nm AuNPs as seeds and d) 7.8 ± 0.5 nm AuNPs as seeds. Table S4. Pore volume and BET surface area of different samples calcinated at 500 o C. Sample Seeds size Pore volume S BET nm cm 3 g -1 m 2 g -1 EP-FDU-12-0.90 513 Ni - 0.89 504 Au 5.1 ± 0.2 0.87 497 Au 3 Ni 1 5.1 ± 0.2 0.87 496 Au 2 Ni 1 5.1 ± 0.2 0.85 489 Au 1 Ni 1 5.1 ± 0.2 0.84 499 Au 1 Ni 2 5.1 ± 0.2 0.86 483 Au 1 Ni 1 3.2 ± 0.3 0.88 506 Au 1 Ni 1 7.8 ± 0.5 0.83 479 S-9
Figure. S7 a) Au 4f and b) Ni 2p XPS patterns of samples with different Ni/Au feeding ratio after annealing at 500 o C (5.1 ± 0.2 nm AuNPs as seeds). S-10
Figure S8. Gas-phase BA oxidation kinetics over Au 3 Ni 1-500 o C, Au 2 Ni 1-500 o C, Au 1 Ni 1-500 o C and Au 1 Ni 2-500 o C (5.1 ± 0.2 nm AuNPs as seeds). S-11
Figure S9. Conversion of benzyl alcohol over Au 1 Ni 1-500 o C of different size. Reaction conditions: 10 mg catalyst, 500 mg quartz, 1.8 ml/h BA liquid, 30 ml/min O 2, 240 o C. S-12
Figure S10. Catalytic selectivity over Au-500 o C and Au 1 Ni 1-500 o C (5.1 ± 0.2 nm AuNPs as seeds) in oxidations of a variety of alcohols (Reaction conditions: 10 mg catalyst, 500 mg quartz, 1.8 ml h -1 alcohol liquid, 30 ml min -1 O 2, 240 o C). S-13
Figure S11. Time-on-stream catalytic performance (conversion and space time yield (STY) of benzyl aldehyde) over Au 1 Ni 1-500 o C (5.1 ± 0.2 nm AuNPs as seeds). Reaction conditions: 10 mg catalyst, 500 mg quartz, 0.9 ml/h BA liquid, 30 ml/min O 2, 240 o C. S-14
Figure S12. XRD patterns of as obtained samples by using 5.1 ± 0.2 nm AuNP seeds or 4.8 ± 0.3 PdNP seeds and using nitrate as precursor of second metal. S-15
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