Supplementary information - images.nature.com€¦ · a ) STEM image of OMC-PtBi-1.5 nm (annular...

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Supplementary informationdoi: 10.1038/nchem.553

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Supplementary Information

Nucleated Growth of Nanocrystalline Intermetallics in Ordered Mesoporous Carbon:

Direct Formic Acid Fuel Cell Anodes

Xiulei Ji a, Kyu Tae Lee a, Reanne Holden a, Lei Zhang b, Jiujun Zhang b

Gianluigi Bottonc, Martin Couillardc and Linda F. Nazar a,*

a University of Waterloo, Department of Chemistry, Waterloo, Ontario, Canada N2L 3G1

b Institute for Fuel Cell Innovation, National Research Council Canada, Vancouver, BC, Canada

V6T 1W5

c McMaster University, Department of Materials Science and Engineering, Hamilton, Ontario,

Canada L8S 4L8

* to whom correspondence should be addressed: [email protected]




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Figure S1. XRD patterns of OMC, sulphur functionalized OMC, and OMC

supported Pt and intermetallic PtBi samples. a, Low angle XRD patterns of (i) OMC;

(ii) OMC-S; (iii) OMC-Pt-1nm. b, Wide angle XRD pattern of CMK-3/Pt (24 wt% Pt)

prepared by conventional methods via deposition from acetone solution as described in

the experimental. c, Wide angle XRD patterns of (i) OMC; (ii) OMC-PtBi-1nm; (iii)

OMC-PtBi-3nm. In b, the red markers indicate the PtBi phase. Note that the broad

carbon contribution from the OMC does not interfere with the PtBi pattern.

iii

ii

i

: Pt : PtBi

a b

c




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Figure S2. TGA and DSC curves recorded in air with a heating rate of 20 ºC/min of a,

H2PtCl6 impregnated OMC-S. b, OMC-Pt-1nm before evacuation at 300ºC. c, OMC-Pt-

1nm after evacuation at 300 ºC for 12 hrs.

a b

c




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Figure S3. Representative HRTEM images (bright field; FEI Titan™ S/TEM), obtained

of OMC-Pt treated at a, 600 °C; b, 800 °C as discussed in the text.

a

b

2 nm

2 nm




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Figure S4. Wide angle XRD patterns of a, OMC-Bi. b, i) Bi(NO3)3·5H2O and ii) OMC-S

impregnated with Bi(NO3)3·5H2O.

b

a

iii




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Figure S5. a ) STEM image of OMC-PtBi-1.5 nm (annular dark-field).

b) representative TEM image of a nanocrystallite in OMC-PtBi-3nm (bright field).

Material Reflection 1 Reflection 2 Difference reflection distance

Pt 1.98Å (002) 2.29Å (111) 0.31ÅPtBi 2.15Å (012) 2.21Å (110) 0.05ÅObserved 2.16Å 2.21Å 0.06Å

20 nm




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Fig. S6 a) EDX spectra obtained on the FEI Titan™ 80-300 Cubed for additional (ie,

different set of) individual PtBi nanoparticles in OMC-PtBi-3nm. The inset shows the

high-angle annular dark-field STEM image with the labeling for the corresponding

analysed nanoparticles; b) Additional EDX spectra, including those showing absence of

Pt-Bi signal in regions devoid of PtBi nanocrystallites.

a)

5 nm

b)




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Figure S7. CA curve of the OMC-PtBi-3nm with the working electrode rotated at 200

rpm at a potential of 0.3 V vs. RHE. a, for an hour; b, for 20 hours.

a

b




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Figure S8. a, SEM image of OMC-Rh. b, Image expansion corresponding to the area

outlined by the red square in a. c, Corresponding Rh EDX elemental map. d, TEM image

(1100KX, dark field).

c

a

d

20 nm

b




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Figure S9. a, SEM image of OMC-Ru. b, Image expansion corresponding to the area

outlined by the red square in a. c, Corresponding Ru EDX elemental map, d, TEM image

(1100KX, dark field).

b

c

a

d

20 nm

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