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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
2
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.
3
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).
6
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.
7
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
8
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.
9
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.
11
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.
12
-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.
13
-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.
14
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.
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