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Electronic Supplementary Information (ESI)

From covalent organic framework to hierarchically porous B-doped

carbons: A molten-salt approach

Yuan-Biao Huang, Pradip Pachfule, Jian-Ke Sun, Qiang Xu*

National Institute of Advanced Industrial Science and Technology (AIST) Ikeda, Osaka

563-8577, Japan. E-mail: q.xu@aist.go.jp; Fax: +81-72-751-9628

Fig. S1 PXRD patterns of simulated COF-5 (black), as-synthesized COF-5 (red),

ZnCl2@COF-5 (blue) and ZnCl2 (green).

Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.This journal is © The Royal Society of Chemistry 2016

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0.0 0.2 0.4 0.6 0.8 1.0

0

100

200

300

400

500

600

700

Relative Pressure (P/P0)

N2

up

take

(cm

3 g1 , S

TP)

B D

Fig. S2 N2 sorption isotherms of as-synthesized COF-5.

1 2 3 30 40 50 60

0

5

10

15

20

25

30

dVp /

d lo

gdp

Pore size / nm

Fig. S3 Pore size distribution of as-synthesized COF-5 by NLDFT method.

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Fig. S4 SEM image of the as-synthesized COF-5.

Fig. S5 TGA curves of COF-5, BC-700 before and after washing, BC-MS-700-21 after

washing.

4

10 20 30 40 50 60

0.0

5.0x105

1.0x106

Inte

nsit

y

2 theta / degree

BC-1200 before washing BC-1100 before washing BC-900 before washing BC-700 before washing

Fig. S6 PXRD of the as-prepared BC-700, BC-900, BC-1100, BC-1200 before washing

with water.

10 20 30 40 50 60 70 80

0.00

1.50x105

3.00x105

4.50x105

10 20 30 40 50 60 70 80

2 Theta / degree

BC-900 as prepared

Inte

nsity

(a.

u.) - B

2O

3 PDF#06-0297

Fig. S7 PXRD of the as-prepared BC-900 before washing, and B2O3 (PDF#06-0297,

blue).

5

5 10 15 20 25 30 35 40 45 50 55 60

0.0

2.0x105

4.0x105

6.0x105

8.0x105

1.0x106

1.2x106

Inte

nsit

y

2 theta / degree

BC-900 washed BC-900 before washing BC-700-washed BC-700 before washing

Fig. S8 PXRD of BC-700 and BC-900 before and after washing with hot water.

0.0 0.2 0.4 0.6 0.8 1.00

50

100

150

200

250

N2 u

pta

ke (

cm3 g

-1, S

TP)

Relative Pressure P/P0

BC-700 BC-900 BC-1100 BC-1200

Fig. S9 N2 sorption isotherms of BC-700, BC-900, BC-1100 and BC-1200 (closed

symbols, adsorption; open symbols, desorption).

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Fig. S10 SEM images of (a) BC-700 and (b) BC-MS-700-14

1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0

0.0

0.2

0.4

0.6

0.8

1.0

1.2

dVp /

d lo

gdp

Pore width / nm

Fig. S11 Pore size distribution of BC-700 by NLDFT method.

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0.0 0.2 0.4 0.6 0.8 1.00

100

200

300

400

500

N2 u

pta

ke (

cm3 g

-1, S

TP)

Relative Pressure (P/P0)

BC-MS-700-3 BC-MS-900-3 BC-MS-1100-3

Fig. S12 N2 sorption isotherms of BC-MS-700-3, BC-MS-900-3, and BC-MS-1100-3

(closed symbols, adsorption; open symbols, desorption).

5 10 15 20 25 30 35 40 45 50 55

0.0

2.0x105

4.0x105

6.0x105

Inte

nsi

ty

2 theta / degree

BC-MS-700-3 BC-MS-700-7 BC-MS-700-14 BC-MS-700-21 BC-700

Fig. S13 PXRD of the carbons BC-700, BC-MS-700-3, BC-MS-700-7, BC-MS-700-14

and BC-MS-700-21 after washing.

Table S1. Summary of the surface areas and pore volume distributions for the carbons

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Sample BET Specific

surface area[a]

(m2 g-1)

Total pore

volume[b]

(cm3 g-1)

Meso-Macropore

volume[c]

(cm3 g-1)

Micropore

volume[d]

(cm3 g-1)

COF-5 1828 0.963 0.1366 0.8264

BC-700 449 0.2626 0.0835 0.1791

BC-MS-700-3 965 0.8057 0.5240 0.2817

BC-MS-700-7 1293 1.5318 1.2540 0.2778

BC-MS-700-14 1460 1.7678 1.3398 0.4280

BC-MS-700-21 1329 1.8598 1.6067 0.2531

[a] Calculated from the BET surface area analysis.

[b] Calculated by a single point method at P/P0 = 0.99.

[c] Calculated by subtracting the total pore volume with the micropore volumes.

[d] Calculated using a t-plot method.

Fig. S14 Raman spectra of (a) COF-5 and (b) BC-MS-700-14.

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Fig. S15 XPS spectra of B1s for: (a) COF-5, BC-700 (b) before and (c) after washing.

0.0 0.2 0.4 0.6 0.8 1.00

100

200

300

400

500

N2 u

pta

ke (

cm3 g

-1, S

TP

)

Relative Pressure P/P0

BC-MS-700-3 BC-S2 BC-S1 BC-700

Fig. S16 N2 sorption isotherms of the carbons BC-700, BC-S1, BC-S2 and

BC-MS-700-3 at 77 K.

10

0 10 20 30 40 50-2

0

2

4

6

8

10

12

14

dVp /

d lo

gdp

Pore size / nm

Fig. S17 The NLDFT pore size distribution of BC-S1.

0 10 20 30 40 50 60 70 80 90 100

0

1

2

3

4

5

6

7

dVp /

d lo

gdp

Pore size / nm

Fig. S18 The NLDFT pore size distribution of BC-S2.

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0.0 0.2 0.4 0.6 0.8 1.00

20

40

60

80

100

H2 u

pta

ke (

cm3 g

-1)

Relative Pressure P/P0

BC-700 BC-900 BC-1100 BC-1200

Fig. S19 H2 adsorption uptakes of the carbons BC-700, BC-900, BC-1100 and BC-1200

at 77 K

-0.4 -0.2 0.0 0.2 0.4

-80

-40

0

40

80

120

160

200

Spec

ific

Cap

acit

ance

(F

g-1)

Cell Voltage (V)

10 mV S-1

20 mV S-1

50 mV S-1

100 mV S-1

150 mV S-1

300 mV S-1

400 mV S-1

Fig. S20 Cyclic voltammograms of BC-700 at different sweep rates.

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-0.6 -0.4 -0.2 0.0 0.2 0.4 0.6

-150

-100

-50

0

50

100

150

Spec

ific

Cap

acit

ance

(F

g-1)

Cell Voltage (V)

10 mV S-1

20 mV S-1

50 mV S-1

100 mV S-1

200 mV S-1

300 mV S-1

400 mV S-1

Fig. S21 Cyclic voltammograms of BC-MS-700-3 at different sweep rates.

-0.6 -0.4 -0.2 0.0 0.2 0.4 0.6

-200

-150

-100

-50

0

50

100

150

200

B

A

10 mV S-1

20 mV S-1

50 mV S-1

100 mV S-1

200 mV S-1

300 mV S-1

400 mV S-1

Fig. S22 Cyclic voltammograms of BC-MS-700-7 at different sweep rates.

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-0.4 -0.2 0.0 0.2 0.4-200

-150

-100

-50

0

50

100

150

Spec

ific

Cap

acit

ance

(F

g-1)

Cell Voltage (V)

10 mV S-1

20 mV S-1

50 mV S-1

100 mV S-1

200 mV S-1

300 mV S-1

400 mV S-1

Fig. S23 Cyclic voltammograms of BC-MS-700-14 at different sweep rates.

-0.4 -0.2 0.0 0.2 0.4

-150

-100

-50

0

50

100

150

Spec

ific

Cap

acit

ance

(F

g-1)

Cell Voltage (V)

10 mV S-1

20 mV S-1

50 mV S-1

100 mV S-1

200 mV S-1

300 mV S-1

400 mV S-1

Fig. S24 Cyclic voltammograms of BC-MS-700-21 at different sweep rates.

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Fig. S25 Nyquist plots of the carbons BC-700, BC-MS-700-3, BC-MS-700-7,

BC-MS-700-14 and BC-MS-700-21 in a frequency range of 10−3 to 106 Hz.