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Electronic Supplementary Material

Composition-tuned oxidation levels of Pt–Re bimetallic nanoparticles for the etherification of allylic alcohols

Yuhao Wang1, Lindong Li1, Ke Wu1, Rui Si2, Lingdong Sun1 (), and Chunhua Yan1 ()

1 Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications,

PKU-HKU Joint Laboratory in Rare Earth Materials and Bioinorganic Chemistry, College of Chemistry and Molecular Engineering,Peking University, Beijing 100871, China

2 Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204, China

Supporting information to https://doi.org/10.1007/s12274-018-2102-0

Supplementary figures and tables

Figure S1 TEM images of the NPs synthesized under the same condition as Pt-Re bimetallic NPs: (a) Only Pt(acac)2 as precursor, (b) Only NH4ReO4 as precursor. The size was 1.80.2 nm with diameters of 200 Re NPs collected.

Figure S2 (a) STEM image and (b) line scan EDS of PR-4.

Address correspondence to Chunhua Yan, yan@pku.edu.cn; Lingdong Sun, sun@pku.edu.cn

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Figure S3 (a) TEM image and (b) size distribution of Pt NPs synthesized via a solvothermal method. The size was 3.40.4 nm with diameters of 200 Pt NPs collected.

Figure S4 Fitting in k space of EXAFS spectra for Re L3-edge for PR-1, PR-2, PR-3, PR-4, PR-5 and Re NPs from bottom to up, respectively. The normalization range was limited to 700 eV post-edge to avoid overlap with Pt L3-edge absorption. The spectra presented were plotted using k-weights of 3. The related Δk parameters during fitting were set 3.8−12.1 Å−1.

Table S1 Data fitting of Re L3-edge EXAFS spectra of Pt-Re bimetallic and Re NPs: coordination number and interatomic distance in Re‒O and Re‒M shells

sample shell CN R (Å) ΔE0 (eV) σ2 (Å2)

Re‒M 6.0±2.8 2.687±0.027 3.4±4.7 0.004±0.004 PR-1

Re‒O 1.7±0.7 1.720±0.024 18.8±5.4 -0.001±0.003

Re‒M 5.0±2.2 2.703±0.024 6.2±4.0 0.006±0.004 PR-2

Re‒O 1.9±0.4 1.724±0.012 20.6±2.8 -0.001±0.002

PR-3 Re‒O 3.6±0.9 1.728±0.014 20.8±3.2 0.001±0.002

PR-4 Re‒O 3.5±0.5 1.722±0.009 19.4±2.0 0.0006±0.0015

PR-5 Re‒O 2.9±0.4 1.714±0.010 18.0±2.0 -0.0002±0.0015

Re NPs Re‒O 1.6±0.6 1.714±0.017 18.4±5.2 -0.002±0.003

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Table S2 Fitting data of Pt 4f XPS

Pt(0) Pt(II) Sample

B. E. / eV a Ratio / % B. E. / eV Ratio / % av B. E. (eV) b

Pt NPs 70.9 65.4 71.8 34.6 71.2

PR-1 71.4 72.0 72.6 28.0 71.7

PR-2 71.5 66.0 72.5 34.0 71.8

PR-3 71.5 64.2 72.5 35.8 71.9

PR-4 71.5 53.1 72.5 46.9 72.0

PR-5 71.6 44.9 72.3 55.1 72.0 a B. E. = binding energy. b Weighted average binding energy.

Figure S5 (a) Pt 4f XPS of Pt NPs and (b) Re 4f XPS of Re NPs. Red lines for Pt(0) or Re(II) fitting, violet lines for Re(IV) fitting and olive lines for Pt(II) or Re(VII) fitting.

Table S3 Fitting data of Re 4f XPS

Re(0) to Re(II) Re(IV) to Re(VI) Re(VII) Sample

B. E. / eV a Ratio / % B. E. / eV Ratio / % B. E. / eV Ratio / % av B. E. (eV) b

PR-1 40.8 65.4 - 0 45.5 34.6 42.4

PR-2 41.0 25.3 43.1 16.4 45.5 58.3 44.0

PR-3 41.0 6.0 43.7 4.6 45.8 89.4 45.4

PR-4 41.4 3.9 43.8 6.5 45.8 89.6 45.5

PR-5 41.4 2.9 45.1 19.8 46.1 77.3 45.8

Re NPs 41.6 22.5 43.7 5.9 45.5 71.6 44.5

a B. E. = binding energy. b Weighted average binding energy.

Figure S6 XRD pattern of Re NPs.

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Table S4 Mass activities and specific activities of Pt, Re and Pt-Re bimetallic NPs

Sample Mass activitiesa (10-5 mol∙g-1∙s-1) Specific activitiesb (10-7 mol∙m-2∙s-1)

Pt NPs 0.01030.0008 0.01050.0008

PR-1 0.0370.006 0.0420.007

PR-2 0.310.02 0.350.02

PR-3 3.40.8 3.80.9

PR-4 7.10.8 7.30.9

PR-5 131 131

Re NPs 4.70.2 3.00.1 a Normalized by the total mass of metal. b Mass activities divided by specific surface area. The specific surface areas were calculated

based on the diameters of NPs.

Figure S7 (a) TEM image of PR-5 after the catalysis. (b) Catalytic cycles of PR-5.

Scheme S1 Reaction between DPO and 2-butyne-1-ol catalyzed by PR-5

The allylic alcohol DPO (21.2 mg, 0.1 mmol) was added to 1 mL 2-butyn-1-ol and stirred for 5 minutes,

followed by the injection of PR-5 catalyst (3 μmol Pt and Re in total). Then the reaction tube was immersed into

a 60 °C oil bath. After 24 h, the started material disappeared indicated by TLC. The reaction solution was

cooled down and concentrated, followed by the purification through flash column chromatography on silica

gel to afford the final product (Rf = 0.6, hexane/ethyl acetate = 5:1). After the removal of solvents, 24.1 mg of

colorless oil was obtained (92% yield). 1H NMR (400 MHz, CDCl3) δ 7.44–7.19 (m, 10H), 6.64 (d, J = 15.9 Hz, 1H),

6.30 (dd, J = 15.9, 7.1 Hz, 1H), 5.16 (d, J = 7.1 Hz, 1H), 4.13 (qq, J = 15.2, 2.2 Hz, 2H), 1.87 (t, J = 2.3 Hz, 3H). 13C

NMR (101 MHz, CDCl3) δ 140.5, 136.6, 132.0, 129.6, 128.6, 128.6, 127.9, 127.8, 127.2, 126.7, 82.5, 80.9, 75.2, 56.0,

3.8. HRMS (ESI) calcd for C19H18O (M+Na): 285.1250. Found: 285.1248.

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Figure S8 O 1s XPS of the bimetallic Pt-Re NPs and Re NPs. Red lines for metal oxide species (M=O or M–O–M) fitting and olive lines for metal hydroxide species (M–OH) fitting.

Table S5 Fitting data of O 1s XPS

M=O or M–O–M M–OH Sample

B. E. / eV a Ratio / % B. E. / eV Ratio / %

PR-1 531.0 68.0 532.2 32.0

PR-2 530.8 66.1 532.0 33.9

PR-3 530.9 62.0 532.0 38.0

PR-4 531.0 57.9 532.0 42.1

PR-5 531.1 47.8 532.0 52.2

Re NPs 531.0 65.0 532.0 35.0 a B. E. = binding energy.

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NMR data