S-1
Supplementary information
Microwave Synthesis and Gas Sorption of Calcium
and Strontium Frameworks
Chun-Ting Yeh,a Wei-Cheng Lin, a Sheng-Han Lo,a Ching-Che Kao,a Chia-Her Lin,*a and
Chun-Chuen Yangb
aDepartment of Chemistry, Chung-Yuan Christian University, Chungli 32023, Taiwan. Fax:
+886-3-2653399; Tel: +886-3-2653315; E-mail: [email protected] bDepartment of Physics, Chung-Yuan Christian University, Chungli 32023, Taiwan.
Figure S1. Powder X-ray diffraction patterns with varied temperatures for CYCU-1.
Figure S2. Powder X-ray diffraction patterns under vacuum and varied temperatures for CYCU-1.
Figure S3. Observed and fitted X-ray powder diffraction patterns for CYCU-1.
Figure S4. Powder X-ray diffraction patterns with varied temperatures for CYCU-2.
Figure S5. Powder X-ray diffraction patterns under vacuum and varied temperatures for CYCU-2.
Figure S6. Observed and fitted X-ray powder diffraction patterns for CYCU-2.
Figure S7. FT-IR spectra.
Figure S8. UV-vis absorption spectra.
Figure S9. Photoluminescence emission spectra.
Figure S10. Powder X-ray diffraction patterns after N2 sorption.
Figure S11. The pore size distributions.
Figure S12. The CO2 adsorption isotherms at 195 K and 273 K for CYCU-1.
Figure S13. Isosteric heat of adsorption for CO2 in CYCU-1
Table S1. Selected bond lengths.
Electronic Supplementary Material (ESI) for CrystEngCommThis journal is © The Royal Society of Chemistry 2012
S-2
10 20 30 40 50
500oC
450oC
400oC
300oC
200oC
30oC Cal.
2 theta
Figure S1. Powder X-ray diffraction patterns with varied temperatures for CYCU-1.
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S-3
10 20 30 40 50 60 700
1
2
3
4
5
6
7
450 oC
400 oC
350 oC
300 oC
250 oC
200 oC
150 oC
100 oC
50 oC
10
2 co
un
ts/s
ec
Scattering angle 2 ( deg. )
25 oC
10 20 30 40 50 60 70
50
100
150
200
250
300
350
400
450
Scattering angle 2 ( deg. )
T (
oC
)
0.000
56.00
112.0
168.0
224.0
280.0
10 15 20 25 30 35
50
100
150
200
250
300
350
400
450
Scattering angle 2 ( deg. )
T (
oC
)
10.00
20.00
30.00
40.00
50.00
60.00
70.00
80.00
Figure S2. Powder X-ray diffraction patterns under vacuum (1x10-4 torr) and varied
temperatures for CYCU-1.
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S-4
10 20 30 40 50 60 70-2.5
0.0
2.5
5.0
7.5
10.0
12.5 = Cu K
monoclinic P 1 21 /n 1
a = 11.727(5) Ab = 5.5460(24) Ac = 22.786(10) A
10
3 co
un
t/se
c
Scattering angle 2 ( deg. )
Figure S3. Observed (crosses) and fitted (solid lines) X-ray powder diffraction patterns for
CYCU-1, assuming a monoclinic symmetry of space group P21/n. The difference between the
calculated and observed is plotted at the bottom. The solid vertical lines mark the calculated
positions of Bragg reflections for the proposed crystalline structure. The bottom plots are
electron density from X-ray powder diffraction pattern and structure from single crystal X-ray
diffraction.
Electronic Supplementary Material (ESI) for CrystEngCommThis journal is © The Royal Society of Chemistry 2012
S-5
10 20 30 40 50
500oC
450oC
400oC
300oC
250oC
200oC
150oC
100oC
30oC Cal.
2 theta
Figure S4. Powder X-ray diffraction patterns with varied temperatures for CYCU-2.
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S-6
10 20 30 40 50
450 oC400 oC350 oC300 oC250 oC200 oC150 oC100 oC
50 oC
Arb
. Un
it
Scattering angle 2 ( deg. )
30 oC
5 10 15 20 25 30 35 40 45 50 55 60
50
100
150
200
250
300
350
400
450
Scattering angle 2 ( deg. )
T (
oC
)
0.00025.0050.0075.00100.0125.0150.0175.0200.0
10 15 20 25 30 35
50
100
150
200
250
300
350
400
450
Scattering angle 2 ( deg. )
T (
oC
)
0.00025.0050.0075.00100.0125.0150.0175.0200.0
Figure S5. Powder X-ray diffraction patterns under vacuum (1x10-4 torr) and varied
temperatures for CYCU-2.
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S-7
10 20 30 40 50 60-1
0
1
2
3
4
5
6
7
8
= Cu K
monoclinic P 1 21 /n 1
a = 12.1817(28) Ab = 5.7431(10) Ac = 22.937(5) A
102
co
un
t/se
c
Scattering angle 2 ( deg. )
Figure S6. Observed (crosses) and fitted (solid lines) X-ray powder diffraction patterns for
CYCU-2, assuming a monoclinic symmetry of space group P21/n. The difference between the
calculated and observed is plotted at the bottom. The solid vertical lines mark the calculated
positions of Bragg reflections for the proposed crystalline structure. The bottom plots are
electron density from X-ray powder diffraction pattern and structure from single crystal X-ray
diffraction.
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S-8
(a) CYCU-1as
4000 3500 3000 2500 2000 1500 1000 5000
20
40
60
80
100
Wavelentgh (cm-1)
T (
%)
(b) CYCU-2as
4000 3500 3000 2500 2000 1500 1000 50030
40
50
60
70
80
90
100
T (
%)
Wavelentgh (cm-1)
Figure S7. FT-IR spectra.
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S-9
(a) CYCU-1as
200 300 400 500 600 700 800
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
A
bso
rban
ce (
a.u
.)
Wavelentgh (nm)
(b) CYCU-2as
200 300 400 500 600 700 800
0.2
0.3
0.4
0.5
0.6
0.7
Ab
sorb
ance
(a.
u.)
Wavelength (nm)
Figure S8. UV-vis absorption spectrua.
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S-10
(a) CYCU-1as
200 300 400 500 6000
100
200
300
400
500
600
excitation emission
Inte
nsi
ty (
a.u
.)
Wavelength (nm)
(b) CYCU-2as
200 300 400 500 6000
300
600
900
1200
excitation emission
Inte
nsi
ty (
a.u
.)
Wavelength (nm)
Figure S9. Photoluminescence emission spectra.
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S-11
(a) CYCU-1
10 20 30 40 502 theta
(a) CYCU-2
10 20 30 40 502 theta
Figure S10. Powder X-ray diffraction patterns after N2 sorption.
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S-12
(a) CYCU-1
5 10 15 20 25
0.00
0.01
0.02
0.03
0.04
0.05
Pore Width(Å)
dV/d
w (
cm3/g
Å)
(a) CYCU-2
5 10 15 20 25
0.0
0.1
0.2
0.3
0.4
0.5
0.6
Pore Width(Å)
dV/d
w (
cm3/g
Å)
Figure S11. The pore size distributions obtained by the Horvath-Kawazoe (HK) method.
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S-13
(a)
0 100 200 300 400 500 600 700 800
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0 absorption desorption
Up
take
(m
mo
l/g
)
Pressure/torr
(b)
0 100 200 300 400 500 600 700 800
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8 absorption desorption
Up
take
(m
mo
le/g
)
Pressure/torr
Figure S12. The CO2 adsorption isotherms at (a) 195 K and (b) 273 K for CYCU-1.
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S-14
The isosteric heat of adsorption for hydrogen and carbon dioxide adsorption on
CYCU-1.
The differential heat of adsorption was calculated from the measured carbon dioxide
adsorption at 298 K and 273 K by applying the Clausius-Clapeyron equation: 1
∆
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.40
5
10
15
20
25
30
Qst
(kJ
/mm
ol)
CO2 Uptake (mmol/g)
Figure S13. Isosteric heat of adsorption for CO2 in CYCU-1.1
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S-15
Table S1. Selected bond lengths (Å).
CYCU-1as Ca(1)-O(3) 2.2977(15) Ca(1)-O(1)#1 2.4367(15) Ca(1)-O(4) 2.3010(16) Ca(1)-O(5) 2.4555(14) Ca(1)-O(2) 2.3604(15) Ca(1)-O(2)#2 2.8850(17) Ca(1)-O(1) 2.3772(16)
CYCU-1 Ca(1)-O(3)#1 2.2868(17) Ca(1)-O(1)#4 2.4324(17) Ca(1)-O(4)#1 2.2873(18) Ca(1)-O(5) 2.4475(17) Ca(1)-O(2)#2 2.3439(16) Ca(1)-O(2)#4 2.8870(18) Ca(1)-O(1)#3 2.3678(17)
CYCU-2as Sr(1)-O(2) 2.4323(19) Sr(1)-O(4)#1 2.5725(17) Sr(1)-O(1) 2.4368(18) Sr(1)-O(5) 2.5882(17) Sr(1)-O(4) 2.4926(17) Sr(1)-O(3)#2 2.9326(18) Sr(1)-O(3) 2.5164(17)
CYCU-2
Sr(1)-O(2) 2.431(2) Sr(1)-O(4)#1 2.573(2)
Sr(1)-O(1) 2.435(2) Sr(1)-O(5) 2.589(2)
Sr(1)-O(4) 2.491(2) Sr(1)-O(3)#2 2.937(2)
Sr(1)-O(3) 2.513(2)
Symmetry transformations used to generate equivalent atoms: for CYCU-1as, #1
-x+1/2,y+1/2,-z+1/2, #2 -x+1/2,y-1/2,-z+1/2; for CYCU-1, #1 -x-1/2,y-1/2,-z+1/2, #2
-x,-y+2,-z, #3 -x,-y+1,-z, #4 x+1/2,-y+3/2,z+1/2; for CYCU-2as and CYCU-2, #1
-x+1/2,y-1/2,-z+3/2, #2 -x+1/2,y+1/2,-z+3/2.
References
S1. P. A. Webb, C. Orr, Analytical Methods in Fine Particle Technology; Micromeritics
Instrument Corp.: Norcross, USA, 1997; pp 230-231.
Electronic Supplementary Material (ESI) for CrystEngCommThis journal is © The Royal Society of Chemistry 2012