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Page 1: mesoporous silica nanoparticles as Nafion fillers on the ... · Effect of pore-directing agents and silanol groups in mesoporous silica nanoparticles as Nafion fillers on the performance

Effect of pore-directing agents and silanol groups in

mesoporous silica nanoparticles as Nafion fillers on the

performance of DMFCs

Ciao-Wei Yanga, Kuei-Hsien Chenb, and Soofin Chenga, *

aDepartment of Chemistry, National Taiwan University, Taipei 10617, Taiwan

bInstitute of Atomic & Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan

Supporting information

Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2016

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Table S1 The average thicknesses (μm) from five points of various membranes after drying at room temperature overnight.Membrane Ave Thickness (μm) Membrane Ave Thickness (μm)

N117 198±2 recasting 201±10

1%-Ex-SBA-15n 200±7 1%-S-SBA-15n 188±5

2.5%-Ex-SBA-15n 201±5 2.5%-S-SBA-15n 199±2

5%-Ex-SBA-15n 211±6 5%-S-SBA-15n 213±9

10%-Ex-SBA-15n 212±7 10%-S-SBA-15n 223±7

15%-Ex-SBA-15n 228±11 15%-S-SBA-15n 224±6

20%-Ex-SBA-15n 236±12 20%-S-SBA-15n 231±5

1%-Ex-MSN 177±4 1%-S-MSN 186±42.5%-Ex-MSN 199±6 2.5%-S-MSN 197±95%-Ex-MSN 195±14 5%-S-MSN 210±810%-Ex-MSN 210±4 10%-S-MSN 216±4

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0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0-2

-1

0

1

2

3

4

5

-Z'' (

Ohm

)

Z' (Ohm)

N117 recasting 1%-Ex-SBA-15n 2.5%-Ex-SBA-15n 5%-Ex-SBA-15n 10%-Ex-SBA-15n 15%-Ex-SBA-15n 20%-Ex-SBA-15n

(A)

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0-2

-1

0

1

2

3

4

5

-Z'' (

Ohm

)

Z' (Ohm)

N117 recasting 1%-S-SBA-15n 2.5%-S-SBA-15n 5%-S-SBA-15n 10%-S-SBA-15n 15%-S-SBA-15n 20%-S-SBA-15n

(B)

Fig. S1 Nyquist plot of (A) x%-Ex-SBA-15n and (B) x%-S-SBA-15 with different loadings in

comparison to those with Nafion®117 and recasting Nafion membranes at 60 oC and 90% percentage

humidity.

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0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0-2

-1

0

1

2

3

4

5

-Z'' (

Ohm

)

Z' (Ohm)

N117 recasting 1%-Ex-MSN 2.5%-Ex-MSN 5%-Ex-MSN 10%-Ex-MSN

(A)

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0-2

-1

0

1

2

3

4

5

-Z'' (

Ohm

)

Z' (Ohm)

N117 recasting 1%-S-MSN 2.5%-S-MSN 5%-S-MSN 10%-S-MSN

(B)

Fig. S2 Nyquist plot of (A) x%-Ex-MSN and (B) x%-S-MSN with different loadings in comparison to

those with Nafion®117 and recasting Nafion membranes at 60 oC and 90% percentage humidity.

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Fig. S3 Mapping photographs of silicon in the cross-sections of composite membranes with different

loadings of Ex-SBA-15n (a) 1%, (b) 2.5%, (c) 5%, (d) 10%, (e) 15% and (f) 20%.

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Fig. S4 Mapping photographs of silicon in the cross-sections of composite membranes with different

loadings of S-SBA-15n (a)1%, (b) 2.5%, (c) 5%, (d) 10%, (e) 15% and (f) 20%.

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Fig. S5 Mapping photographs of silicon in the cross-sections of composite membranes with different

loadings of Ex-MSN (a) 1%, (b) 2.5%, (c) 5% and (d) 10%

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Fig. S6 Mapping photographs of silicon in the cross-sections of composite membranes with different

loadings of S-MSN (a) 1%, (b) 2.5%, (c) 5% and (d) 10%.

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0 10 20 30 40 50 60 70 80 90 10002468

1012141618

(A)

Stre

ss (M

Pa)

Strain (%)

N117 recasting 1%-Ex-SBA-15n 5%-Ex-SBA-15n 10%-Ex-SBA-15n 15%-Ex-SBA-15n 20%-Ex-SBA-15n

0 10 20 30 40 50 60 70 80 90 10002468

1012141618

Stre

ss (M

Pa)

Strain (%)

N117 recasting 1%-S-SBA-15n 5%-S-SBA-15n 10%-S-SBA-15n 15%-S-SBA-15n 20%-S-SBA-15n

(B)

0 10 20 30 40 50 60 70 80 90 1000

2

4

6

8

10

12(C)

Stre

ss (M

Pa)

Strain (%)

N117 recasting 1%-Ex-MSN 2.5%-Ex-MSN 5%-Ex-MSN 10%-Ex-MSN

0 10 20 30 40 50 60 70 80 90 1000

2

4

6

8

10

12(D)

Stre

ss (M

Pa)

Strain (%)

N117 recasting 1%-S-MSN 2-5%-S-MSN 5%-S-MSN 10%-S-MSN

Fig. S7 Stress–strain curves of Nafion membranes with different loadings of (A) Ex-SBA-15n, (B) S-

SBA-15n, (C) Ex-MSN and (D) S-MSN in comparison to those of Nafion® 117 and recast Nafion

membranes.

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200 400 600 8000

20

40

60

80

100

Weig

ht %

Temperature (oC)

N117 recasting 1%-Ex-SBA-15n 2.5%-Ex-SBA-15n 5%-Ex-SBA-15n 10%-Ex-SBA-15n

(A)

200 400 600 8000

20

40

60

80

100

N117 recasting 1%-S-SBA-15n 2.5%-S-SBA-15n 5%-S-SBA-15n 10%-S-SBA-15n

Weig

ht %

Temperature (oC)

(B)

200 400 600 800

0

20

40

60

80

100

N117 recasting 1%-Ex-MSN 2.5%-Ex-MSN 5%-Ex-MSN 10%-Ex-MSN

Weig

ht %

Temperature (oC)

(C)

200 400 600 8000

20

40

60

80

100

N117 recasting 1%-S-MSN 2.5%-S-MSN 5%-S-MSN 10%-S-MSN

Weig

ht %

Temperature (oC)

(D)

Fig. S8 TGA curves of Nafion membranes with different loadings of (A) Ex-SBA-15n, (B) S-SBA-

15n, (C) Ex-MSN and (D) S-MSN in comparison to those of Nafion® 117 and recast Nafion

membranes.

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2.70 2.85 3.00 3.15-4.2

-4.0

-3.8

-3.6

-3.4

-3.2

lnσ

1/T(103 K-1)

Fig. S9 Temperature dependence of the proton conductivities for Nafion 117 (), recasting Nafion

membrane (), 5%-Ex-SBA-15n (◇), 5%-S-SBA-15n (◆), 5%-Ex-MSN () and 5%-S-MSN (▲)

composite membranes.