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1 Electronic Supplementary Information Non-Enzymatic Hydrogen Peroxide Electrochemical Sensor Based on Three-Dimensional MnO 2 Nanosheets/Carbon Foam Composite Shuijian He, a, b Boya Zhang, a Minmin Liu a, b and Wei Chen a, * a State Key Laboratory of Electroanalytical Chemistry, Changchun institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, Jilin, China, and b University of Chinese Academy of Sciences, Beijing 100039, China Corresponding author: [email protected] , Tel. +86-431-85262061 Electronic Supplementary Material (ESI) for RSC Advances. This journal is © The Royal Society of Chemistry 2014

Non-Enzymatic Hydrogen Peroxide Electrochemical … · /CF1 MnO 2 /CF2 MnO 2 /CF3 MnO 2 /CF5 001 111 100 020 B CD A 02 46 Mn C O Mn Binding Energy (keV) 700 600 500 400 300 200 C

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Page 1: Non-Enzymatic Hydrogen Peroxide Electrochemical … · /CF1 MnO 2 /CF2 MnO 2 /CF3 MnO 2 /CF5 001 111 100 020 B CD A 02 46 Mn C O Mn Binding Energy (keV) 700 600 500 400 300 200 C

1

Electronic Supplementary Information

Non-Enzymatic Hydrogen Peroxide Electrochemical Sensor Based

on Three-Dimensional MnO2 Nanosheets/Carbon Foam Composite

Shuijian He, a, b Boya Zhang, a Minmin Liu a, b and Wei Chen a, *

aState Key Laboratory of Electroanalytical Chemistry, Changchun institute of Applied

Chemistry, Chinese Academy of Sciences, Changchun 130022, Jilin, China, and

bUniversity of Chinese Academy of Sciences, Beijing 100039, China

Corresponding author: [email protected], Tel. +86-431-85262061

Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2014

Page 2: Non-Enzymatic Hydrogen Peroxide Electrochemical … · /CF1 MnO 2 /CF2 MnO 2 /CF3 MnO 2 /CF5 001 111 100 020 B CD A 02 46 Mn C O Mn Binding Energy (keV) 700 600 500 400 300 200 C

2

F

1 μm

1 m

A

1 μm

E

B

1 m

C

1 m

D

1 m

Fig. S1 Cross section view SEM images of the as-prepared 3D porous nanomaterials, carbon foam

(CF, A), MnO2/CF0.5 (B), MnO2/CF1 (C), MnO2/CF2 (D), MnO2/CF3 (E) and MnO2/CF5 (F).

Page 3: Non-Enzymatic Hydrogen Peroxide Electrochemical … · /CF1 MnO 2 /CF2 MnO 2 /CF3 MnO 2 /CF5 001 111 100 020 B CD A 02 46 Mn C O Mn Binding Energy (keV) 700 600 500 400 300 200 C

3

Fig. S2 (A) EDS spectrum of MnO2/CF0.5. (B) XRD patterns of the carbon foam (CF) and the

MnO2/CF composites. (C, D) XPS survey spectra of MnO2/CF0.5 (C) and the core-level XPS

signals of Mn 2p (D).

660 655 650 645 640 635

11.7 eV

Mn 2p3/2

Mn 2p1/2

Inte

nsit

y (a

.u.)

2 (degree)

20 40 60 80

C foam

MnO2

Inte

nsity

(a.

u.)

2 (degree)

JCPDS 42-1317 CF MnO

2/CF0.5

MnO2/CF1

MnO2/CF2

MnO2/CF3

MnO2/CF5

001

002

111

100020

B

C D

A

0 2 4 6

Mn

C

O

K MnMn

Binding Energy (keV)

700 600 500 400 300 200

C 1

sO 1

s

Mn

2p

Binding Energy (eV)

Inte

nsit

y (a

.u.)

Page 4: Non-Enzymatic Hydrogen Peroxide Electrochemical … · /CF1 MnO 2 /CF2 MnO 2 /CF3 MnO 2 /CF5 001 111 100 020 B CD A 02 46 Mn C O Mn Binding Energy (keV) 700 600 500 400 300 200 C

4

Fig. S3 Thermogravimetric (TG) plots of CF and MnO2/CF composites.

0 150 300 450 6000

20

40

60

80

100

Wei

ght p

erce

nt (

%)

Temperature (oC)

MnO2/CF0.5

MnO2/CF1

MnO2/CF2

MnO2/CF3

MnO2/CF5

Page 5: Non-Enzymatic Hydrogen Peroxide Electrochemical … · /CF1 MnO 2 /CF2 MnO 2 /CF3 MnO 2 /CF5 001 111 100 020 B CD A 02 46 Mn C O Mn Binding Energy (keV) 700 600 500 400 300 200 C

5

-0.6 -0.3 0.0 0.3

-1.8

-1.2

-0.6

0.0

0 mM 1 mM 2 mM 3 mM 4 mM 5 mM

Cur

rent

(10

-4 A

)

Potential (V)-0.6 -0.3 0.0 0.3

-9

-6

-3

0

3

0 mM 1 mM 2 mM 3 mM 4 mM 5 mM

Cur

rent

(10

-4 A

)

Potential (V)

-0.9 -0.6 -0.3 0.0 0.3-9

-6

-3

0

3

Cur

rent

(10

-4 A

)

Potential (V)

0 mM 1 mM 2 mM 3 mM 4 mM 5 mM

-0.9 -0.6 -0.3 0.0 0.3

-1.5

-1.0

-0.5

0.0

Cur

rent

(10

-4 A

)

Potential (V)

0 mM 1 mM 2 mM 3 mM 4 mM 5 mM

A B

C D

Fig. S4 CVs of MnO2/CF0.5 (A), MnO2/CF1 (B), MnO2/CF3 (C) and MnO2/CF5 (D) in 0.1 M

PBS solution (pH=7.4) with the absence and presence of H2O2 at the scan rate of 0.02 V/s.

Page 6: Non-Enzymatic Hydrogen Peroxide Electrochemical … · /CF1 MnO 2 /CF2 MnO 2 /CF3 MnO 2 /CF5 001 111 100 020 B CD A 02 46 Mn C O Mn Binding Energy (keV) 700 600 500 400 300 200 C

6

-0.6 -0.3 0.0 0.3

-9

-6

-3

0

3

MnO2/CF2, 0 mM H

2O

2

MnO2/CF3, 0 mM H

2O

2

MnO2/CF2, 3 mM H

2O

2

MnO2/CF3, 3 mM H

2O

2

Cur

rent

(1

03 A/g

)

Potential (V)

Fig. S5 CVs of MnO2/CF2 and MnO2/CF3 electrodes in 0.1 M PBS solution (pH=7.4) with

absence and presence of 3 mM H2O2. Potential scan rate 0.02 V/s. The currents are normalized to

the mass loading of MnO2.

Page 7: Non-Enzymatic Hydrogen Peroxide Electrochemical … · /CF1 MnO 2 /CF2 MnO 2 /CF3 MnO 2 /CF5 001 111 100 020 B CD A 02 46 Mn C O Mn Binding Energy (keV) 700 600 500 400 300 200 C

7

0 300 600 900 1200 1500

-1.2

-0.9

-0.6

-0.3

0.0

200 300 400 500 600

-1.2

-1.0

-0.8

-0.6

Cur

rent

(10

- 4 A

)

Time (s)

a cb d ef

Cur

rent

(10-

5 A)

Time (s)

0 500 1000 1500-2.0

-1.5

-1.0

-0.5

0.0

200 300 400 500 600-4.6

-4.5

-4.4

-4.3

-4.2

Cur

rent

(10

- 4 A

)

Time (s)

a b c d ef

Cur

rent

(10-5

A)

Time (s)

0 300 600 900 1200

-0.6

-0.5

-0.4

-0.3

-0.2

200 300 400 500 600-2.8

-2.7

-2.6

-2.5

Cur

rent

(10

- 4 A

)

Time (s)

a b c de

f

Cur

rent

(10-5

A)

Time (s)

0 1 2 3 4 5-8

-6

-4

-2

Cur

rent

(10-

5 A)

Concentration of H2O

2 (mM)

0 2 4 6 8

-16

-12

-8

-4

Cur

rent

(10-

4 A)

Concentration of H2O

2 (mM)

0 1 2 3 4

-5.6

-4.8

-4.0

-3.2

-2.4

Cur

rent

(10-

5 A)

Concentration of H2O

2 (mM)

E

A B

C D

F

Fig. S6 The amperometric responses of the electrode to H2O2, MnO2/CF0.5 (A), MnO2/CF1 (C),

MnO2/CF3 (E), with 10 μL 7.5 mM, 15 mM, 60 mM, 0.15 M, 0.6 M and 1.5 M H2O2 added into

the PBS solution at a, b, c, d, e, f, respectively. Insets are the corresponding amperometric

responses to low H2O2 concentrations at the MnO2/CF electrodes. (B, D, F) The corresponding

plots of the response current vs. the H2O2 concentration obtained from the MnO2/CF0.5,

MnO2/CF1, and MnO2/CF3 electrodes, respectively.

Page 8: Non-Enzymatic Hydrogen Peroxide Electrochemical … · /CF1 MnO 2 /CF2 MnO 2 /CF3 MnO 2 /CF5 001 111 100 020 B CD A 02 46 Mn C O Mn Binding Energy (keV) 700 600 500 400 300 200 C

8

0 20 40 60 80 1000

15

30

45

60

Z' ()

-Z" (

)

MnO2/CF0.5

MnO2/CF1

MnO2/CF2

MnO2/CF3

MnO2/CF5

0 400 800 1200 16000

400

800

1200

1600 MnO

2/CF0.5

MnO2/CF1

MnO2/CF2

MnO2/CF3

MnO2/CF5

-Z" (

)

Z' ()

A B

Fig. S7 (A) Nyquist electrochemical impedance spectra of the sensors based on the MnO2/CF

composites (B) the enlarge view of Nyquist plots at high frequency region in (A).