Supporting Information
Enhancement in CO2 Adsorption Capacity and Selectivity in the Chalcogenide Aerogel CuSb2S4 by Post-synthetic Modification with LiCl
Ejaz Ahmed and Alexander Rothenberger*
Physical Sciences and Engineering Division, King Abdullah University of Science and Technology Thuwal, Kingdom of Saudi Arabia
Supplementary Figures:
Figure S1Powder XRD patterns; a) ternary phase KSbS2, b) predominantly amorphous nature of the unmodified gel with4wt % LiCl-doped gel, c) 7.5wt % LiCl-doped gel with simulated pattern of LiCl.
Figure S2 EDS results of the CuSb2S4aerogel with SEM image in the inset.
Table S1:ICP-OES results for 1LiCl@CuSb2S4 aerogel.
Units
|
Cu
|
Sb
|
S
|
Li
|
PPM
|
135413
|
275680
|
499294
|
39814
|
%
|
13.54
|
27.57
|
49.93
|
3.98
|
Figure S3 EDS results of 1LiCl@CuSb2S4 aerogel.
Table S2: ICP-OES results for 2LiCl@CuSb2S4 aerogel.
Units
|
Cu
|
Sb
|
S
|
Li
|
PPM
|
131252
|
262136
|
501217
|
74930
|
%
|
13.13
|
26.21
|
50.12
|
7.49
|
Figure S4 EDS results of 2LiCl@CuSb2S4 aerogel.
Figure S5 TGA results of the aerogels, a) CuSb2S4 and b) 2LiCl@CuSb2S4.
Figure S6: Solid-state UV-Vis optical absorption spectra for CuSb2S4 aerogel.
Table S3 Properties of the aerogels with respect to their surface area, porosity, skeletal density and CO2 capture capacity.
Adsorbent
|
BET
(m2/g)
|
Average Pore Size
(nm)
|
Pore Volume
(cm3/g)
|
Density
(g/cm3)
|
CO2 capacity
(mmol/g)
|
CuSb2S4
|
412
|
16.07
|
1.655
|
1.34
|
0.63
|
4wt%LiCl@CuSb2S4
|
371
|
13.48
|
1.252
|
1.89
|
1.51
|
7.5wt%LiCl@CuSb2S4
|
303
|
9.74
|
0.737
|
2.26
|
2.31
|
8wt%LiCl@CuSb2S4
|
274
|
8.44
|
0.563
|
2.71
|
1.93
|
Figure S7 TEM images of the aerogels, a) CuSb2S4, b) 1LiCl@CuSb2S4, and c) 2LiCl@CuSb2S4.
Figure S8a) N2adsorption-desorption isotherm of the aerogels, b)Pore-size (V-D) distribution plot calculated from the adsorption isotherm by the BJH method, c) Adsorption isotherms of CO2 at 273 K in CuSb2S4 and LiCl-loaded aerogels.
Figure S9 Adsorption isotherms of CO2, CH4 and H2 observed at 263 K in unmodified and LiCl-loadedaerogels.
Figure S10 Heat of adsorption in unmodified and LiCl-loaded aerogels, a) H2 and, b) CH4.
Figure S11 Fitting of Henry’s constant for CO2, CH4 and H2 in 2LiCl@CuSb2S4 aerogel.
Table S4. Empirical parameters from fitting of virial equation in 2LiCl@CuSb2S4aerogel.
Constant
|
CO2
|
CH4
|
H2
|
Quantity absorbed (mmol/g)
|
2.244
|
0.1771
|
0.0363
|
Pressure (mmHg)
|
760
|
760
|
760
|
K (mmol/g/mmHg)
|
0.00705
|
6.40776x10-5
|
2.76048x10-5
|
Figure S12 Statistics of Fitting of Henry’s constant for CO2, CH4 and H2 in 2LiCl@CuSb2S4 aerogel.
Table S5. Empirical parameters from fitting of virial equation in CuSb2S4 aerogel.
Constant
|
CO2
|
CH4
|
H2
|
Quantity absorbed (mmol/g)
|
0.5863
|
0.0563
|
0.0227
|
Pressure (mmHg)
|
760
|
760
|
760
|
K (mmol/g/mmHg)
|
3.12188x10-4
|
4.15002x10-5
|
7.78002x10-6
|
Figure S13. Fitting of Henry’s constant for CO2, CH4 and H2 in CuSb2S4 aerogel.
Figure S14 Statistics of Fitting of Henry’s constant for CO2, CH4 and H2 in CuSb2S4 aerogel.
Table S6. Comparison of CO2/H2 and CO2/CH4 selectivity in different porous materials.
Adsorbent
Surface Area
m2/g
Temperature
K
Selectivity
CO2/H2, CO2/CH4
Ref
FAU-type zeolite
3213
298
18, NA
1
Cu-BTC
1600
298
60, 10
2
MOF-5 (IRMOF-1)
2304
296
25, 3
2
SIFSIX-2-Cu-i
735
298
33, 240
3
SIFSIX-3-Zn
250
298
>1800, 231
3
Mg2(dobdc)
1800
313
800, NA
4
Chalcogel (Co, Ni-MoS4)
340
273
16, NA
5
Chalcogel-Pt-1 (PtGeS)
323
273
6, NA
6
Chalcogel-PtSb-1 (PtSbGeSe)
226
273
12, NA
6
Chalcogel (CoMo3S13)
570
273
120, NA
7
KFeSbS3
636
273
217, 60
8
NaFeAsS3
505
273
188, 100
8
CuSb2S4
412
273
67, 22
This work
2LiCl@CuSb2S4
303
273
235, 105
This work
X-ray photoelectron spectroscopy (XPS)
The XPS studies of the powder samples were carried out in a Kratos Axis Ultra DLD spectrometer equipped with a monochromatic Al-Kα x-ray source (hν = 1486.6 eV) operating at 150 W, a multichannel plate and delay line detector under a vacuum of ~10−9 mbar. Measurements were performed in hybrid mode using electrostatic and magnetic lenses, and the take-off angle (angle between the sample surface normal and the electron optical axis of the spectrometer) was 0°. All spectra were recorded using an aperture slot of 300 μm×700 μm. The survey and high-resolution spectra were collected at fixed analyzer pass energies of 160 eV and 20 eV respectively. Samples were mounted in floating mode in order to avoid differential charging. Charge neutralization was required for all samples. Binding energies were referenced to the sp3 hybridized (C-C,C-H) carbon for the C1s set at 285.0 eV.
XPS analysis of the Cu 2p shows lines at 934.4 eV and 954.4 eV which can be assigned to Cu 2p3/2 and Cu 2p1/2 respectively, indicates the presence of Cu(II) species, similarly Sb 3d lines appear at 539.2 eV and 529.3 eV correspond to Sb 3d3/2 and Sb 3d 5/2 respectively. The spectral line for S 2p doublet were observed at 161.4 eV and 162.6 eV that can be assigned to 2p1/2 and 2p3/2 (Figure S15).9-12
Figure S15: High-resolution XPS spectrum of Cu 2p, Sb 3d and S 2p core levels in CuSb2S4.
Figure S16 Adsorption-desorption isotherms of H2 observed at 273 K in unmodified aerogel; a) CuSb2S4 and LiCl-loaded aerogels; b) 1LiCl@CuSb2S4, c) 2LiCl@CuSb2S4.
References:
-
C. Ducrot-Boisgontier, J. Parmentier, A. Faour, J. Patarin, G. D. Pirngruber, Energy Fuels. 24 (2010) 3595.
-
(a) Q. Yang and C. Zhong, J. Phys. Chem. B. 110 (2006) 17776. (b) Z. Zhao, Z. Li, Y. S. Lin, Ind. Eng. Chem. Res. 48(2009) 10015.
-
P. Nugent, Y. Belmabkhout, S. D. Burd, A. J. Cairns, R. Luebke, K. Forrest, T. Pham, S. Ma, B. Space, L. Wojtas, M. Eddaoudi, M. J. Zaworotko, Nature 495 (2013) 80.
-
Z. R. Herm, J. A. Swisher, B. Smit, R. Krishna and J. R. Long, J. Am. Chem. Soc. 133 (2011) 5664.
-
S. Bag, A. F. Gaudette, M. E. Bussell, M. G. Kanatzidis, Nat. Chem. 1 (2009) 217-224.
-
S. Bag and M. G. Kanatzidis, J. Am. Chem. Soc.132 (2010) 14951.
-
M. Shafaei-Fallah, A. Rothenberger, A. P. Katsoulidis, J. Q. He, C. D. Malliakas, M. G. Kanatzidis, Adv. Mater. 23 (2011) 4857.
-
E. Ahmed, J. Khanderi, D. H. Anjum, A. Rothenberger, Chem. Mater. 26 (2014) 6454.
-
B. Xie, C. C. Finstad, A. J. Muscat, Chem. Mater. 17 (2005) 1753.
-
K. Uemura, M. Ebihara, Inorg. Chem. 52 (2013) 5535.
-
NIST Chemistry WebBook.
-
D. H. Kim, S. J. Lee, M. S. Park, J. K. Kang, J. H. Heo, S. H. Im, S. J. Sung, Nanoscale, 6 (2014) 14549-14554.
Dostları ilə paylaş: |