Supporting Information

 Wiley-VCH 2014
69451 Weinheim, Germany

A Polyphenylene Support for Pd Catalysts with Exceptional Catalytic

Activity**
Feng Wang, Jerrik Mielby, Felix Herrmann Richter, Guanghui Wang, Gonzalo Prieto,
Takeshi Kasama, Claudia Weidenthaler, Hans-Josef Bongard, Søren Kegnæs, Alois Frstner, and
Ferdi Schth*

anie_201404912_sm_miscellaneous_information.pdf
anie_201404912_sm_movie_s1.mov
Contents

1. Experimental methods.

2. Supporting Figures.

Figs. S1-S10

3. Supporting Tables.

Table S1-S3

4. Supporting Movie

Movie S1

5. Supporting References.

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1. Experimental methods.

Synthesis of Pd/PPhen composites. To obtain 2.7wt% Pd/PPhen, 1,2,4,5-tetrabromobenzene

(0.765 g, 1.94 mmol) and benzene-1,4-diboronic acid (0.645 g, 3.89 mmol) were added into 60

mL dimethylformamide. The mixture was degassed through three freeze-pump-thaw cycles.

K2CO3 (2.0 M, 7.5 mL) and Pd(PPh3)4 (0.225 g, 0.19 mmol) were then added with subsequent

three freeze-pump-thaw cycles. The mixture was then purged with Ar and heated to 150 °C for

20 h under stirring. The product precipitated in water, and was washed by water, dichloromethane

and methanol. Approximately 600 mg of grey product was obtained in each batch. The synthesis

has also been carried out in air, similar structure is obtained. To synthesize Pd-free PPhen, the

reaction temperature was reduced to 100 °C, maintaining the other reaction conditions. The

amount of Pd(PPh3)4 was increased to 450 mg to obtain 5.9wt% Pd/PPhen. PVP (Mw = 55,000,

100 mg) was added into the synthesis to make the catalysts dispersible in water.

Synthesis of Pd/C, Pd/PDVB and Pd/TiO2 catalysts. To obtain 2.7wt% Pd/C or Pd/PDVB,

Pd(PPh3)4 (30 mg) was dissolved in 1 mL CH2Cl2. The solution was added dropwise to Pd-free

PPhen (100 mg), with subsequently calcination in 20% H2/Ar at 250 °C for 3 h. 5wt% Pd/TiO2

was prepared by impregnation of TiO2 (Degussa P25) according to a reported method[1].

Pd(NO3)22H2O (25 mg) was dissolved in 2 mL H2O. The solution was added dropwise into 200

mg TiO2. The mixture was first dried at 80 °C for 16 h, with subsequent calcination in air at

400 °C for 3 h.

Suzuki coupling reactions. Typically, phenylboronic acid (91.5 mg, 0.75 mmol), sodium

methoxide (81.0 mg, 1.5 mmol), 2.7wt% Pd/PPhen (15.7 mg, 4 µmol) and PVP (Mw = 55,000,

0.5 mg) were added into 5 mL water. The solution was treated with ultrasound for 0.5 h, and 4-

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chlorotoluene (63.3 mg, 0.50 mmol) and dodecane (35.0 mg, 0.21 mmol) were added. Dodecane

acted as the internal standard. The mixture was degassed through three freeze-pump-thaw cycles,

purged with Ar, and stirred at 80 °C for 3h. Toluene was added into the solution to extract the

products. The products were analyzed by gas chromatography (GC) equipped with flame

ionization detector (FID) for quantification. For other Suzuki coupling reactions, the same molar

amounts of aryl chloride or arylboronic acid were added instead of 4-chlorotoluene or

phenylboronic acid. For Suzuki coupling reactions with other catalysts, the same molar amount of

palladium were added instead of Pd/PPhen. The molar ratio between palladium and substrates

was kept constant. In the catalyst recycling experiments, after the reaction was concluded, the

catalysts were separated by filtration, washed with ethanol, dried and weighed. In all cases, for

the subsequent reaction cycle the weight ratio of substrates to catalyst was adjusted to the same

value as in the first reaction.

Solvent-free benzyl selective alcohol oxidation in batch. Typically, benzyl alcohol (10.4g,

0.096 mol) and Pd/PPhen (10 mg, 2.5 µmol) or Pd/C was added into a glass inset inside a

stainless steel autoclave reactor. The reactor was purged with O2 and kept under 5 bar O2. The

reactor was then heated to 100 °C and stirred at 1500 rpm. The product was analyzed by GC-FID

using dodecane as standard.

Benzyl alcohol selective oxidation in a gas-phase, plug-flow reactor. 2.7wt%Pd/PPhen (20 mg)

or commercial 5wt%Pd/C (4 mg) or 5wt%Pd/TiO2 (11 mg) was mixed with quartz sand (200 mg),

and packed into a tubular reactor (6mm  160 mm). An evaporator for benzyl alcohol was

connected to the inlet of the reactor. The temperatures of evaporator and reactor were controlled

by individual ovens. Benzyl alcohol (0.1 mLh1) was injected through a syringe pump into the

evaporator and carried by O2 (50 mLmin1) into the reactor. The partial pressure of benzyl

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alcohol was controlled to be lower than its vapor pressure. The products were collected in a dry

ice cooled-tetrahydrofuran solution with a gas outlet open to atmosphere. The solutions were

periodically analyzed by GC-FID with dodecane as standard.

Characterization. HAADF-STEM imaging was carried out on an FEI Titan 80-300ST field-

emission-gun (FEG) TEM operated at 300 kV. Electron tomography was performed by collecting

tilt-series of HAADF-STEM images over a tilt range of 70° to + 75° with a tilt increment of 2°.

Alignment of the tilt series was performed using a collection of palladium nanocrystals (2-3.5

nm), indigenous to the Pd/PPhen composite, as fiducial markers. Tomogram reconstruction was

carried out using a weighted back-projection algorithm in IMOD[2]. Segmentation and 3D

visualization of the different phases in the reconstructed volume was performed in Avizo (FEI).

SEM imaging was performed on a Hitachi S-5500 FEG SEM. XRD measurement was performed

on a Stoe STADI P Bragg-Brentano diffractometer with Cu Kα1,2 radiation, using a secondary

graphite monochromator. Solid densities were determined in a Micromeritics Accupyc 1330 gas

pycnometer. N2 adsorption isotherms were measured on Micromeritics ASAP 2010 adsorption

analyzer at 77 k after activation in vacuum at 250 °C for 24 h. XPS analyses were performed on a

Kratos HSi spectrometer with a hemispherical analyzer. The monochromatized Al K X-ray

source (E=1486.6 eV) was operated at 15 kV and 15 mA. An analyzer pass energy of 40 eV was

applied for the narrow scans. The hybrid mode was used as lens mode. The base pressure during

the experiment in the analysis chamber was 45×10-7 Pa. All spectra were charge corrected

referred to the C1s photopeak at 284.5 eV. TG measurements were performed on a Netzsch STA

449C thermal analyzer with a heating rate of 10 °C min-1. The solid-state NMR spectra were

recorded on a Bruker Avance 500WB spectrometer using a double-bearing standard MAS probe

(DVT BL4) at resonance frequencies of 125.8 MHz and 202.5 MHz for 13C and 31P,

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respectively. High-power proton decoupling (CW) and spinning rates between 10 and 12 kHz

were applied for all spectra.

2. Supporting Figures.

Figure S1. Reaction conditions of palladium precipitation by decomposition of Pd(PPh3)4 and

representative bright-field TEM micrograph of the resulting palladium nanoparticles. The
decomposition of Pd(PPh3)4 in DMF occurs at temperature above 110 °C.

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Figure S2. X-ray diffraction patterns of Pd/PPhen composites with different Pd loading (see
legend) as well as the Pd-free PPhen support material obtained via sequential leaching treatments
of the 2.7 wt% Pd/PPhen composite in aqueous H2O2 and HCl solutions. The indicated
reflections correspond to metallic palladium.

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Figure S3. a) TEM image of 5.9 wt% Pd/PPhen. To obtain 5.9 wt% Pd/PPhen, the molar ratio of
Pd(PPh3)4 to C-C coupling substrates was twice the normal ratio. b) Size distribution.

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Figure S4. Bright-field TEM micrographs of the metal-free polyphenylene polymer obtained by
Suzuki C-C coupling reaction of 1,2,4,5-tetrabromobenzene and benzene-1,4-diboronic acid at
100 °C. Pd(PPh3)4 in DMF does not decompose at this temperature, resulting in the Pd-free
PPhen. a) TEM image at low magnification. b) TEM image at high magnification.

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Figure S5. a) HAADF-STEM image of Pd/PPhen. b) Single dot EDX spectrum of the particle
indicated as green cross in a).

Figure S6. Bright-field TEM micrographs of the Pd-free polyphenylene polymer after palladium
leaching by HCl and H2O2 treatments. H2O2 oxidizes palladium in to PdCl2, resulting in the Pd-
free PPhen. a) TEM image at low magnification. b) TEM image at high magnification.

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Figure S7. X-ray photoemission spectrum of 2.7wt%Pd/PPhen composite showing the
characteristic 3d signals of metallic palladium. No indication of Pd (II) was found for these
materials.

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Figure S8. Bright-field TEM micrograph a) and corresponding palladium particle size histogram
b) of a commercial Pd/C catalyst (Sigma-Aldrich). The size of palladium particles is in the range
of 1.5-5 nm.

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Figure S9. HAADF-STEM micrographs of a,b) 2.7wt% Pd/C and d,e) 2.7wt% Pd/PDVB
catalysts prepared via impregnation of Pd(PPh3)4 on the supports followed by thermal
decomposition/reduction in flow of 20%H2/Ar. Palladium particle size distribution of c) 2.7wt%
Pd/C and f) 2.7wt% Pd/PDVB.

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Figure S10. a) HAADF-STEM image of 2.7wt%Pd/PPhen catalyst after 4 consecutive recycles
in the Suzuki coupling reaction of 4-chlorotoluene and phenylboronic acid. b) size distribution.

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3. Supporting Tables.

Table S1. Wetting and dispersion of Pd/PPhen in different solvents.

Solvent Dispersion
Benzene Yes
Toluene Yes
CH2Cl2 Yes
CH3OH Yes
C2H5OH Yes
Benzene alcohol Yes
acetone Yes
THF Yes
Diglyme Yes
DMF Yes
H2O No
H2O (PVP)1 Yes
1
10wt% of PVP is added in order to disperse Pd/PPhen in water.

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Table S2. Recycling of the Pd/PPhen catalyst for Suzuki coupling reaction.

Reaction cycle Product yield (%)

Initial run 82
1 79
2 82
3 84
4 78

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4. Supporting Movie.

Movie S1. Representative aligned HAADF HR-STEM tilt series.

The video shows a representative aligned HAADF HR-STEM tilt series. Palladium nanoclusters
and nanocrystals in the size range of 0.5-4 nm are observed. They are evenly distributed
throughout the polymer host.

Video Composites File type/size

Movie S1 2.7wt% Pd/PPhen QuickTime/17 MB

5. Supporting Reference.

[1] J. K. Edwards, B. E. Solsona, P. Landon, A. F. Carley, A. Herzing, C. J. Kiely, G. J.

Hutchings, J. Cata. 2005, 236, 69-79.
[2] J. R. Kremer, D. N. Mastronard, J. R. McIntosh, J. Struct. Biol. 1996, 116, 71-76.

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