2S4 by Post-synthetic Modification with LiCl

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Supporting Information
Enhancement in CO₂ Adsorption Capacity and Selectivity in the Chalcogenide Aerogel CuSb₂S₄by 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.
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Figure S2 EDS results of the CuSb₂S₄aerogel with SEM image in the inset.
Table S1:ICP-OES results for 1LiCl@CuSb₂S₄aerogel.

Units	Cu	Sb	S	Li
PPM	135413	275680	499294	39814
%	13.54	27.57	49.93	3.98

Figure S3 EDS results of 1LiCl@CuSb₂S₄aerogel.
Table S2: ICP-OES results for 2LiCl@CuSb₂S₄aerogel.

Units	Cu	Sb	S	Li
PPM	131252	262136	501217	74930
%	13.13	26.21	50.12	7.49

Figure S4 EDS results of 2LiCl@CuSb₂S₄aerogel.

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Figure S5 TGA results of the aerogels, a) CuSb₂S₄ and b) 2LiCl@CuSb₂S₄.

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Figure S6: Solid-state UV-Vis optical absorption spectra for CuSb₂S₄aerogel.

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.

$c:\users\ahmede\desktop\picture1.tif$ 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

Cu-BTC

1600

298

60, 10

MOF-5 (IRMOF-1)

2304

296

25, 3

SIFSIX-2-Cu-i

735

298

33, 240

SIFSIX-3-Zn

250

298

>1800, 231

Mg₂(dobdc)

1800

313

800, NA

Chalcogel (Co, Ni-MoS₄)

340

273

16, NA

Chalcogel-Pt-1 (PtGeS)

323

273

6, NA

Chalcogel-PtSb-1 (PtSbGeSe)

226

273

12, NA

Chalcogel (CoMo₃S₁₃)

570

273

120, NA

KFeSbS₃

636

273

217, 60

NaFeAsS₃

505

273

188, 100

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

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Figure S15: High-resolution XPS spectrum of Cu 2p, Sb 3d and S 2p core levels in CuSb₂S₄.

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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.
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