Supporting Information

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1 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 , China b School of Materials Science and Engineering, Zhejiang University, Hangzhou , China c Department of Chemistry and Materials Technology, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto , Japan s: jfan@zju.edu.cn S-1

2 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 b Pd/TiO 2 Benzyl alcohol Ref b Au-Pd/TiO 2 Benzyl alcohol a Nanoporous Au Benzyl alcohol a Au/EP-FDU-12 Benzyl alcohol b Au/SiO 2 Benzyl alcohol a NiO Benzyl alcohol b Au/MgCuCr 2 O 4 ethanol a Nanoporous Au Methanol a Au/EP-FDU-12 Cyclohexanol b Au@PION-1 Cyclohexanol a Au/SiO 2 1-propanol b Pt/HT 1-octanol b Ru/Al 2 O 3 1-phenylethanol a, gas-phase reaction; b, liquid-phase reaction; c, space time yield (STY) of benzyl aldehyde (BAD). S-2

3 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 ev ev Å Au 30 Ni ev ev Å S-3

4 Figure S2. TEM images and particle size distribution of a-c) AuNP and d) PdNP seeds. S-4

5 Figure S3. HAADF STEM picture of Au 1 Ni o C NP. S-5

6 Figure S4. HAADF STEM mappings of row A) Au 3 Ni o C, B) Au 2 Ni o C, C) Au 1 Ni o C and D) Au 1 Ni o C. S-6

7 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

8 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 Au 5.1 ± Au 3 Ni ± Au 2 Ni ± Au 1 Ni ± Au 1 Ni ± Au 1 Ni ± Au 1 Ni ± S-8

9 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 Ni Au 5.1 ± Au 3 Ni ± Au 2 Ni ± Au 1 Ni ± Au 1 Ni ± Au 1 Ni ± Au 1 Ni ± S-9

10 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

11 Figure S8. Gas-phase BA oxidation kinetics over Au 3 Ni o C, Au 2 Ni o C, Au 1 Ni o C and Au 1 Ni o C (5.1 ± 0.2 nm AuNPs as seeds). S-11

12 Figure S9. Conversion of benzyl alcohol over Au 1 Ni 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

13 Figure S10. Catalytic selectivity over Au-500 o C and Au 1 Ni 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

14 Figure S11. Time-on-stream catalytic performance (conversion and space time yield (STY) of benzyl aldehyde) over Au 1 Ni 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

15 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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