Copyright WILEY-VCH Verlag GmbH & Co. KGaA, 69469 Weinheim, Germany, 2016.

Supporting Information

for Adv. Funct. Mater., DOI: 10.1002/adfm.201601904

A New Approach to Tuning Carbon Ultramicropore Size at

Sub-Angstrom Level for Maximizing Specific Capacitance
and CO2 Uptake

Jin Zhou, Zhaohui Li, Wei Xing,* Honglong Shen, Xu Bi,

Tingting Zhu, Zhipeng Qiu, and Shuping Zhuo*
A new approach to tuning carbon ultra-micropore size at sub-angstrom level for
maximizing specific capacitance and CO2 uptake

Jin Zhou, Zhaohui Li, Wei Xing,* Honglong Shen, Xu Bi, Tingting Zhu, Zhipeng Qiu,
Shuping Zhuo*

Contents:

1. Analysis of the narrow microporosity by Dubinin−Radushkevich equation

2. Calculation of Gibbs free energies change (ΔG)

3. Calculation of heats of adsorption

Captains of figures and tables:

Figure S1. SEM images of cesium phenolic resin carboxylate xerogel

Figure S2. Optical image of parent resin xerogel of CsAC

Figure S3. EDS image of alkali phenolic resin carboxylate xerogels (a, b) Na, (c, d) K,

(e, f) Cs

Figure S4. TG-MS analysis of PR-COOM: (a) TG curves, MS responses of (b) H2O,

(c) CO2, and (d) CO

Figure S5. Detection of CO32-

Figure S6. Atomic and ionic diameter of alkaline metals

Figure S7. TEM images (a, b) LiAC, (c, d) NaAC, (e, f) KAC, (g, h) RbAC, (i, j)

CsAC

Figure S8. D-R plots for CO2 sorption on LiAC

Figure S9. (a) XRD patterns and (b) Raman spectraof MAC materials

Figure S10. XPS spectra of MAC materials

Figure S11. High-resolution XPS spectra of MAC materials (a-e) C1s and (f-j) O1s of
LiAC, NaAC, KAC, RbAC and CsAC, respectively

Figure S12. Galvanostatic charge/discharge measurements (a) MAC in KOH

electrolyte at 0.2 A g-1; (b) CsAC in KOH electrolyte; (c) MAC in IL at 0.2 A g-1; (d)

CsAC in IL

Figure S13. (a) Cyclic voltammetry curves of CsAC in KOH electroyte; (b) Ragone

plots in KOH; (c) Ragone plots in IL; (d) cycling stability test of CsAC in KOH

Figure S14. (a) Initial slope calculation for CO2 and N2 isotherms collected at 25 °C,

(b) Regeneration of CsAC for CO2 sorption.

Table S1 Gibbs free energy change (ΔG) for the proposed reaction between the

carbon and M2O at 900 °C

Table S2 Specific capacitance of CsAC in comparison to reported porous carbons

Table S3 CO2 sorption capacities of MAC samples

Table S4 CO2 uptake of MAC in comparison to reported carbons at 25 °C and 1.0 bar

Table S5 CO2 uptake of MAC in comparison to reported carbons at 25 °C and 20 bar

1. Analysis of the narrow microporosity by Dubinin−Radushkevich equation

Dubinin-Radushkevitch (D-R) equation (Equation 1), which was originally proposed

as an empirical adaptation of the Polanyi adsorption potential theory, has been the

fundamental equation to quantitatively describe the adsorption of gases and vapors by

microporous sorbents. This equation, based on the postulate that the mechanism for

adsorption in micropores is that of pore-filling rather than layer-by-layer surface

coverage, generally applies well to adsorption systems involving only van der Waals

forces and is especially useful to describe adsorption on activated carbon. The D-R

equation has been used to calculate micropore volumes and to estimate the mean pore

size widths (L) from both N2 and CO2 adsorption on different samples. The mean pore

width could been estimated using the equation of Stoeckli et al. (Equation 2) when the

characteristic energy is between 42 and 20 kJ mol-1, where L is the mean pore width,

and E0 is the characteristic energy (kJ mol-1). Its validity has been tested by direct

determination of the distribution in the range 0.35-1.3 nm. It is also proved that CO2

could be a more efficient adsorptive than N2 to characterize narrow micropores. Thus,

in this work, we used D-R method for the analysis of the CO2 adsorption isotherms at

0 °C.

The CO2 adsorption data obtained at 0°C were used to analyze the narrow

microporosity by means of the Dubinin−Radushkevich (D−R) equation[S1]:

k RT /  ) 2 [2.303lg( P0 / P )]2 }
V  V0 exp{（ (1)

where V (cm3 g-1) is the volume filled at a temperature T and a relative pressure (P/P0),

V0 (cm3 g-1) is the micropore volume, and k and β are constants about the pore
structure and the affinity coefficient (β = 0.35 for CO2), respectively. The average

micropore width, L (nm), was calculated by means of the empirical correlation

proposed by Stoeckli et al.[S2]:

L  10.8 /( E0  11.4) (2)

where E0 is the characteristic energy.

2. Calculation of Gibbs free energies change (ΔG)

Gibbs free energies change (ΔG) were calculated by Van't Hoff equation (3) and

Gibbs relation (4):

pCO
G  G  RT ln (3)
p

G   H   T  S  (4)

where ΔG° (kJ mol-1), ΔH°(kJ mol-1) and ΔS°(kJ mol-1) are standard change of Gibbs

free energy, enthalpy and entropy of reaction, respectively. The relative pressure of

CO (pCO/p°) is assumed to 10-3.

3. Calculation of heats of adsorption

The isosteric heats of adsorption (Qst) were calculated according to

Clausius-Clapeyron equation:

p  T T
ln  1   Qst  2 1 (5)
 p2  R  T1  T2

where Qst is the isosteric heats of adsorption, Ti represents a temperature at which an

isotherm i is measured, pi represents a pressure at which a specific equilibrium

adsorption amount is reached at Ti, R is the gas constant (8.314 J K-1 mol-1).
 Figure S1. SEM images of cesium phenolic resin carboxylate xerogels

Figure S2. Optical image of parent resin xerogel of CsAC

Figure S3. EDS mapping of alkali phenolic resin carboxylate xerogels (a) Na, (b) K,

(c) Cs
Figure S4. TG-MS analyses of PR-COOM: (a) TG curves, MS responses of (b) H2O,

(c) CO2, and (d) CO

Figure S5. Detection of CO32- after heating PR-COOK at different temperatures

 0.6
atom
ion

Diameter (nm)
0.4

0.2

0.0
Li Na K Rb Cs

Figure S6. Atomic and ionic diameter of alkaline metals

Figure S7. TEM images (a, b) LiAC, (c, d) NaAC, (e, f) KAC, (g, h) RbAC, (i, j)

CsAC
 1.2
2
R =0.9900 LiAC
L(II)=1.17 nm

0.6

logV
2
R =0.9960
L(I)=0.60 nm
0.0

0 5 10 15
2
log (P0/P)

Figure S8. D-R plots for CO2 sorption on LiAC

Figure S9. (a) XRD patterns and (b) Raman spectraof MAC materials
 Figure S10. XPS spectra of MAC materials

Figure S11. High-resolution XPS spectra of MAC materials (a-e) C1s and (f-j) O1s of

LiAC, NaAC, KAC, RbAC and CsAC, respectively

 Figure S12. Galvanostatic charge/discharge measurements (a) MAC in KOH

electrolyte at 0.2 A g-1; (b) CsAC in KOH electrolyte; (c) MAC in IL at 0.2 A g-1; (d)

CsAC in IL
Figure S13. (a) Cyclic voltammetry curves of CsAC in KOH electroyte; (b) Ragone

plots in KOH; (c) Ragone plots in IL; (d) cycling stability test of CsAC in KOH

Figure S14. (a) Initial slope calculation for CO2 and N2 isotherms collected at 25 °C,

(b) Regeneration of CsAC for CO2 sorption.

Table S1 Gibbs free energy change (ΔG) for the proposed reaction between the

carbon and M2O at 900 °C

M2O+C→2M+CO(g)

MAC sample ΔG (kJ mol-1)

LiAC 231.93

NaAC -46.38

KAC -128.58

RbAC -154.49

CsAC -143.94
Table S2 Specific capacitance of CsAC in comparison to reported porous carbons
Capacitance (F
Carbon materials Ionic liquid Ref.
g-1)
1-ethyl-3-methylimidazolium This
CsAC 223
tetrafluoroborate study
1-ethyl-3-methylimidazolium
carbide-derived carbon 203 [S3]
tetrafluoroborate
1-ethyl-3-methylimidazolium
a-P-CNF 180 [S4]
tetrafluoroborate
1-ethyl-3-methylimidizolium
Carbon derived
108 ± 9 bis(trifluoromethylsulfonyl) [S5]
from bovine bone
imide
1-ethyl-3-methylimidizolium
Activated carbon nanofiber 161 bis(trifluoromethylsulfonyl) [S6]
imide
1-ethyl-3-methylimidazolium
Graphene ~154 [S7]
tetrafluoroborate
1-ethyl-3-methylimidazolium
d-glucose derived carbon 158 [S8]
tetrafluoroborate
Carbon nanotube spaced 1-ethyl-3-methylimidazolium
183 [S9]
graphene aerogels tetrafluoroborate
1-ethyl-3-methylimidazolium
GO-doped ion gel ~135 [S10]
tetrafluoroborate
Buckypaper
~63 EMIBF4+ 0.5 wt% SWCNTs [S11]
carbon
nanofibers 1,3-ethylmethylimidizaolium
derived from ~120 bis(trifluoromethanesulfonyl) [S12]
electrospun PIM-1 imide
Tetrafluoroborate
GAC ~94 [S13]
1-ethyl-3-methylimidazolium
N-butyl-N-methylpyrrolidinium
pMeT ~100 bis (trifluoromethanesulfonyl) [S14]
imide
1-butyl-3-methylimidazolium
RGO ~158 [S15]
hexafluorophosphate
N-butyl-N-methylpyrrolidinium
microporous
~60 bis (trifluoromethanesulfonyl) [S16]
activated carbon
imide
1-ethyl-3-methyl-imidazolium
ACT carbon ~100 bis (trifluoromethanesulfonyl) [S17]
imide
Table S3 CO2 sorption capacities of MAC samples

CO2 sorption capacity (mmol g-1)

Sample 0 °C, 1 bar 25 °C, 1 bar 25 °C, 0.15 bar 25 °C, 20 bar

LiAC 0.87 0.63 0.21 2.77

NaAC 2.78 2.06 0.68 4.05

KAC 5.16 3.55 1.12 7.03

RbAC 6.00 4.10 1.20 9.63

CsAC 6.77 5.20 1.52 9.18

Table S4 CO2 uptake of MAC in comparison to reported carbons at 25 °C and 1.0 bar

Materials SBET Vtotal CO2 uptake Ref.

2 -1 3 -1 -1
(m g ) (cm g ) (mmol g )
CsAC 1312 0.67 5.20 This
work
N-Doped Porous Carbon Spheres 1458 0.65 4.54 [S18]
NC-650-3 1535 0.60 4.80 [S19]
SU-MAC-500 941 0.35 4.5 [S20]
HCM-DCH-1 670 0.46 2.6 [S21]
PCN-71 610 0.31 2.88 [S22]
CS-6 530 0.23 3.8 [S23]
CS3-6A 1184 0.37 4.1 [S24]
N-doped ZTCs 3360 1.71 4.38 [S25]
PAF-1/C-900 1174 N.A. 4.1 [S26]
ACFK-3 2180 1.00 5.7 [S27]
CS-8 669 0.29 3.0 [S28]
KOH-activated OMC 1820 0.95 3.4 [S29]
activated graphite nanofibers 567 0.71 1.35 [S30]
CP-2-600 1700 0.88 3.9 [S31]
N-doped porous carbon monoliths 464 0.23 3.13 [S32]
NAC 2546 1.47 3.75 [S33]
porous carbon nitride spheres 550 0.90 2.90 [S34]
IBN9-NC1-A 1181 0.73 4.50 [S35]
PC-1 1600 0.72 3.5 [S36]
MFB-600 490 0.91 2.25 [S37]
AS-2-600 1260 0.62 4.8 [S38]
SK-0.3-700 1060 0.52 4.24 [S39]
AC-750-0.5 1060 0.52 4.30 [S40]
Table S5 CO2 uptakes of MACs in comparison to reported carbons at 25 °C and 20

bar
Materials SBET Vtotal a CO2 uptake b Ref.
2 -1 3 -1 -1
(m g ) (cm g ) (mmol g )
CsAC 1312 0.67 (0.63) 9.18 (5.20) This
work
RbAC 1243 0.70 (0.55) 9.63 (4.10) This
work
ACCA4800 3537 1.85 (1.21) 21.1 (2.8) [S41]
LAC4800 3235 1.77 (0.93) 17.0 (2.8) [S41]
CN4700 3202 2.14 (0.50) 20.0 (2.7) [S41]
AX21 3191 1.80 (0.89) 22.5 (2.6) [S41]
SU-AC-400 4196 2.26 (1.56) 28.3 (30 bar) [S42]
A3-48 1586 N.A. (0.77) ~7.90 [S43]
M3M 2610 N.A. (0.93) ~9.50 [S43]
CKHP900-2 2104 1.11 (0.81) 12.7 (3.0) [S44]
A-NCF-4 2309 1.03 (0.95) 15.98 (3.75) [S45]
HPC5b2-1100 2734 5.23 (N.A.) 20.5 (~3.0) [S46]
ACB-5 3537 2.56 (1.03) 20.8 (18bar) [S47]
a-GDC-2 3240 2.23 (N.A.) 21.1 [S48]
KH-AC-93 2643 1.39 (0.53) ~15.0 [S49]
AC-1 3120 N.A.(1.25) ~20.5 [S50]
a)
The values in parentheses refer to micropore volume determined by N2 sorption
measurement; b) CO2 uptake at 25 °C and 1.0 bar.

References:

[S1] M. Dubinin, Carbon 1989, 27, 457; A. Wahby, J. M. Ramos-Fernandez, M.

Martinez-Escandell, A. Sepulveda-Escribano, J. Silvestre-Albero, F.

Rodriguez-Reinoso, ChemSusChem 2010, 3, 974.

[S2] F. Stoeckli, L. Ballerini, Fuel 1991, 70, 557.

[S3] K. Pinkert, M. Oschatz, L. Borchardt, M. Klose, M. Zier, W. Nickel, L. Giebeler,

S. Oswald, S. Kaskel, J. r. Eckert, ACS applied materials & interfaces 2014, 6,

2922.
[S4] C. Tran, D. Lawrence, F. W. Richey, C. Dillard, Y. A. Elabd, V. Kalra, Chemical

Communications 2015, 51, 13760.

[S5] P. A. Goodman, H. Li, Y. Gao, Y. Lu, J. Stenger-Smith, J. Redepenning, Carbon

2013, 55, 291.

[S6] C. H. Kim, J.-H. Wee, Y. A. Kim, K. seung Yang, C.-M. Yang, Journal of

Materials Chemistry A 2016, 6, 4763.

[S7] C. Liu, Z. Yu, D. Neff, A. Zhamu, B. Z. Jang, Nano letters 2010, 10, 4863.

[S8] T. Tooming, T. Thomberg, H. Kurig, A. Jänes, E. Lust, Journal of Power Sources

2015, 280, 667.

[S9] Q. Shao, J. Tang, Y. Lin, J. Li, F. Qin, J. Yuan, L.-C. Qin, Journal of Power

Sources 2015, 278, 751.

[S10] X. Yang, F. Zhang, L. Zhang, T. Zhang, Y. Huang, Y. Chen, Advanced

Functional Materials 2013, 23, 3353.

[S11] C. Kong, W. Qian, C. Zheng, Y. Yu, C. Cui, F. Wei, Chemical

Communications 2013, 49, 10727.

[S12] J. S. Bonso, G. D. Kalaw, J. P. Ferraris, Journal of Materials Chemistry A

2014, 2, 418.

[S13] Y. Chen, X. Zhang, H. Zhang, X. Sun, D. Zhang, Y. Ma, RSC Advances 2012,

2, 7747.

[S14] A. Balducci, W. A. Henderson, M. Mastragostino, S. Passerini, P. Simon, F.

Soavi, Electrochimica Acta 2005, 50, 2233.

[S15] Y. Chen, X. Zhang, D. Zhang, P. Yu, Y. Ma, Carbon 2011, 49, 573.
[S16] A. Balducci, R. Dugas, P.-L. Taberna, P. Simon, D. Plee, M. Mastragostino, S.

Passerini, Journal of Power Sources 2007, 165, 922.

[S17] C. Arbizzani, M. Biso, D. Cericola, M. Lazzari, F. Soavi, M. Mastragostino,

Journal of Power Sources 2008, 185, 1575.

[S18] H. S. Kim, M. S. Kang, W. C. Yoo, The Journal of Physical Chemistry C

2015, 119, 28512.

[S19] J. Chen, J. Yang, G. Hu, X. Hu, Z. Li, S. Shen, M. Radosz, M. Fan, ACS

Sustainable Chemistry & Engineering 2016, 4, 1439.

[S20] J. W. F. To, J. He, J. Mei, R. Haghpanah, Z. Chen, T. Kurosawa, S. Chen,

W.-G. Bae, L. Pan, J. B. H. Tok, J. Wilcox, Z. Bao, Journal of the American

Chemical Society 2016, 138, 1001.

[S21] G. P. Hao, W. C. Li, D. Qian, G. H. Wang, W. P. Zhang, T. Zhang, A. Q.

Wang, F. Schuth, H. J. Bongard, A. H. Lu, Journal of the American Chemical

Society 2011, 133, 11378.

[S22] G.-P. Hao, Z.-Y. Jin, Q. Sun, X.-Q. Zhang, J.-T. Zhang, A.-H. Lu, Energy &

Environmental Science 2013, 6, 3740.

[S23] N. P. Wickramaratne, M. Jaroniec, Journal of Materials Chemistry A 2013, 1,

112.

[S24] N. P. Wickramaratne, J. Xu, M. Wang, L. Zhu, L. Dai, M. Jaroniec,

Chemistry of Materials 2014, 26, 2820.

[S25] Y. Xia, R. Mokaya, G. S. Walker, Y. Zhu, Advanced Energy Materials 2011, 1,

678.
[S26] Y. Zhang, B. Li, K. Williams, W. Y. Gao, S. Ma, Chemical communications

2013, 49, 10269.

[S27] S. Y. Lee, S. J. Park, J Colloid Interface Sci 2013, 389, 230.

[S28] N. P. Wickramaratne, M. Jaroniec, ACS applied materials & interfaces 2013,

5, 1849.

[S29] M. Sevilla, A. B. Fuertes, Journal of Colloid Interface Science 2012, 366,

147.

[S30] L. Y. Meng, S. J. Park, Journal of Colloid Interface Science 2010, 352, 498.

[S31] M. Sevilla, P. Valle-Vigón, A. B. Fuertes, Advanced Functional Materials

2011, 21, 2781.

[S32] G. P. Hao, W. C. Li, D. Qian, A. H. Lu, Advanced materials 2010, 22, 853.

[S33] Z. Zhang, M. Xu, H. Wang, Z. Li, Chemical Engineering Journal 2010, 160,

571.

[S34] Q. Li, J. Yang, D. Feng, Z. Wu, Q. Wu, S. S. Park, C.-S. Ha, D. Zhao, Nano

Research 2010, 3, 632.

[S35] Y. Zhao, L. Zhao, K. X. Yao, Y. Yang, Q. Zhang, Y. Han, Journal of

Materials Chemistry 2012, 22, 19726.

[S36] J. Wang, A. Heerwig, M. R. Lohe, M. Oschatz, L. Borchardt, S. Kaskel,

Journal of Materials Chemistry 2012, 22, 13911.

[S37] C. Pevida, T. C. Drage, C. E. Snape, Carbon 2008, 46, 1464.

[S38] M. Sevilla, A. B. Fuertes, Energy & Environmental Science 2011, 4, 1765.

[S39] W. Xing, C. Liu, Z. Zhou, L. Zhang, J. Zhou, S. Zhuo, Z. Yan, H. Gao, G.

 Wang, S. Z. Qiao, Energy & Environmental Science 2012, 5, 7323.

[S40] Z. Zhang, J. Zhou, W. Xing, Q. Xue, Z. Yan, S. Zhuo, S. Qiao, Physical

Chemistry Chemical Physics 2013, 15, 2523.

[S41] H. M. Coromina, D. A. Walsh, R. Mokaya, Journal of Materials Chemistry A

2016, 4, 280.

[S42] J. He, J. W. To, P. C. Psarras, H. Yan, T. Atkinson, R. T. Holmes, D. Nordlund,

Z. Bao, J. Wilcox, Advanced Energy Materials 10.1002/aenm.201502491.

[S43] J. Marco-Lozar, M. Kunowsky, F. Suárez-García, J. Carruthers, A.

Linares-Solano, Energy & Environmental Science 2012, 5, 9833.

[S44] B. Adeniran, E. Masika, R. Mokaya, Journal of Materials Chemistry A 2014,

2, 14696.

[S45] Y. Li, M. Cao, Chemistry–An Asian Journal 2015, 10, 1496.

[S46] G. Srinivas, V. Krungleviciute, Z.-X. Guo, T. Yildirim, Energy &

Environmental Science 2014, 7, 335.

[S47] X. Shao, Z. Feng, R. Xue, C. Ma, W. Wang, X. Peng, D. Cao, AIChE Journal

2011, 57, 3042.

[S48] A. Ganesan, M. M. Shaijumon, Microporous and Mesoporous Materials

2016, 220, 21.

[S49] A. M. Rashidi, D. Kazemi, N. Izadi, M. Pourkhalil, A. Jorsaraei, E. Ganji, R.

Lotfi, Korean Journal of Chemical Engineering 2016, 33, 616.

[S50] J. P. Marco-Lozar, J. Juan-Juan, F. Suárez-García, D. Cazorla-Amorós, A.

Linares-Solano, International Journal of Hydrogen Energy 2012, 37, 2370.