Microwave Synthesis and Gas Sorption of Calcium … Supplementary information Microwave Synthesis and Gas Sorption of Calcium and Strontium Frameworks Chun-Ting Yeh,a Wei-Cheng Lin,

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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 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

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10 20 30 40 50

500oC

450oC

400oC

300oC

200oC

30oC Cal.

2 theta



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


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


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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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


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.


S-5

10 20 30 40 50

500oC

450oC

400oC

300oC

250oC

200oC

150oC

100oC

30oC Cal.

2 theta



S-6

10 20 30 40 50

450 oC400 oC350 oC300 oC250 oC200 oC150 oC100 oC

50 oC

Arb

. Un

it


30 oC

5 10 15 20 25 30 35 40 45 50 55 60

50

100

150

200

250

300

350

400

450


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


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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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


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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(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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(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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(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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(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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(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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(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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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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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.


Documents

Microwave Synthesis and Gas Sorption of Calcium … Supplementary information Microwave Synthesis and Gas Sorption of Calcium and Strontium Frameworks Chun-Ting Yeh,a Wei-Cheng Lin,