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Supplementary Information Growth and Deposition of Au Nanoclusters on Polymer-wrapped Graphene and Their Oxygen Reduction Activity Tsuyohiko Fujigaya* 1,2 , ChaeRin Kim 1 , Yuki Hamasaki 2 , , and Naotoshi Nakashima* 1,2,3 1 International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University, 744 Motooka Nishi-ku, Fukuoka 819-0395, Japan 2 Department of Applied Chemistry, Graduate School of Engineering, Kyushu University, 744 Motooka Nishi-ku, Fukuoka 819-0395, Japan E-mail: [email protected], nakashima- [email protected] 3 JST-CREST, 5 Sanbancho, Chiyoda-ku, Tokyo, 102-0075, Japan 1

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Supplementary Information

Growth and Deposition of Au Nanoclusters on Polymer-wrapped Graphene and Their Oxygen Reduction Activity

Tsuyohiko Fujigaya*1,2, ChaeRin Kim1, Yuki Hamasaki2, , and Naotoshi Nakashima*1,2,3

1International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University, 744 Motooka Nishi-ku, Fukuoka 819-0395, Japan

2 Department of Applied Chemistry, Graduate School of Engineering, Kyushu University, 744 Motooka Nishi-ku, Fukuoka 819-0395, Japan E-mail: [email protected], [email protected]

3 JST-CREST, 5 Sanbancho, Chiyoda-ku, Tokyo, 102-0075, Japan

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Table S1 | XRD analysis. Crystal sizes of s-Graphene/PyPBI/Au calculated by Scherrer’s equation using the XRD patterns.

s-Graphene/PyPBI/Aux

FCC Assignment

X= 1.6 X= 3.3 X= 4.5

(111) 4.4 6.1 11.2

(200) 4.3 3.8 6.4

(220) 3.1 4.6 7.4

(311) 4.7 5.5 8.1

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Table S2 | XPS analysis. Au composition ratio of s-Graphene/PyPBI/Au determined from XPS narrow scans shown in Figure 7b.

Au(0) Au(I) Au(III)

s-Graphene/PyPBI/Au1.6 67.28 20.75 11.97

s-Graphene/PyPBI/Au3.3 75.74 16.99 7.27

s-Graphene/PyPBI/Au4.5 81.89 11.10 7.01

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Table S3 | Electrochemical analysis. Calculated number of electrons (n) transferred during ORR for the Au-NP.

s-Graphene/PyPBI/AuxX= 6. 6 3.3 1.6

number of electrontransfer (n) 1.7 2.4 2.3

a b c

Figure S1 | Low magnification TEM images. Low magnification of TEM images for

(a) s-Graphene/PyPBI/Au4.5, (b) s-Graphene/PyPBI/Au3.3 and (c)

s-Graphene/PyPBI/Au1.6.

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a b c

1.00 μm 1.00 μm1.00 μm

500 nm500 nm500 nm

Figure S2 | Comparison of the electron microscope images. STEM (a) bright-field

and (b) dark-field images and (c) SEM image of s-Graphene/PyPBI/Au3.3 at (upper)

lower and (lower) high magnifications.

a b

Figure S3 | Effect of PyPBI layer. (a, b) STEM images of Au-NPs directly grown on

s-Graphene using 0.14 mM of HAuCl4.

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a b

-3

-2

-1

0

-0.8 -0.6 -0.4 -0.2 0 0.2

400 rpm600 rpm800 rpm1200 rpm1600 rpm2400 rpm

Potential / V vs. Ag/AgCl

Cur

rent

den

sity

/ m

A c

m-2

-3

-2

-1

0

-0.8 -0.6 -0.4 -0.2 0 0.2

400 rpm600 rpm800 rpm1200 rpm1600 rpm2400 rpm

Potential / V vs. Ag/AgCl

Cur

rent

den

sity

/ m

A c

m-2

Figure S3 | Electrochemical analysis. LSV curves of (a) s-Graphene/PyPBI/Au4.5

and (b) s-Graphene/PyPBI/Au3.3 on the ORR at the specified rotation rates.

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