Electronic Supplementary Material (ESI) for CrystEngComm.

This journal is The Royal Society of Chemistry 2014

Electronic Supporting Information

Tuning pore size in a zirconium-tricarboxylate metal-organic framework

Weibin Liang,a Hubert Chevreau,b Florence Ragon,a Peter D. Southon,a Vanessa K. Peterson,b
Deanna M. DAlessandroa*
aSchool

of Chemistry, The University of Sydney, New South Wales 2006, Australia

Nuclear Science and Technology Organisation, Kirrawee DC, New South Wales 2232,
Australia

bAustralian

Table of Contents
Contents

Page
number

S1. Materials

S2

S2. Syntheses

S2

S3. Laboratory powder X-ray diffraction (PXRD)

S2

S4. Nuclear magnetic resonance (NMR)

S6

S5. Diffuse reflectance infrared spectra (DRIFTS)

S11

S6. Thermogravimetric analysis (TGA)

S11

S7. Elemental Analyses

S12

S8. Synchrotron X-ray powder diffraction

S13

S9. Schematic of the cage system of Zr6O4(OH)(bdc)6

S13

S10. Gas Sorption

S14

S11. Attempts at using benzoic acid (B) and isobutyric acid for (isoB)
Zr6O4(OH)4(X)6(btc)2 synthesis

S18

S12. References

S18

S1

S1. Materials.
All chemicals and solvents were purchased from commercial sources and were used as received without
further purification.

S2. Syntheses.
All attempted synthesis conditions for Zr6O4(OH)4(A)6(btc)2 are summarised in Table 1.
Zr6O4(OH)4(A)6(btc)2 was synthesised using a conventional solvothermal heating method. A 21-mL glass
vial was charged with 116.5 mg (0.50 mmol) of ZrCl4 (> 99.5%, Sigma-Aldrich) and 35.3 mg (0.168 mmol) of
1,3,5-benzenetricarboxylic acid (> 99%, Sigma-Aldrich). Thereafter, 2.8 mL (49 mmol) of acetic acid (> 99.7%,
Ajax) and 5 mL of N,N-dimethylformamide (DMF, > 95%, Ajax) were introduced. The mixture was sonicated
for an additional 20 minutes before being sealed and heated at 135 oC for a period of 24 h. The mixture was
subsequently cooled to room temperature in the oven before the precipitate was isolated by vacuum filtration and
washed with DMF (2 x 30 mL), acetone (2 x 30 mL) and methanol (3 x 30 mL). The resulting powder was dried
in air.

Table S1. Attempted synthesis conditions for Zr6O4(OH)4(A)6(btc)2 using conventional solvothermal heating
method.

a1,3,5-benzentricarboxylic

acid.

S2

S3. Laboratory powder X-ray diffraction (PXRD).

PXRD. PXRD measurements for all Zr6O4(OH)4(X)6(btc)2 (X = formate (F), acetate (A), or propionate (P))
were carried out on a PANalytical Xpert Pro diffractometer fitted with a solid-state PIXcel detector (40 kV, 30
mA, 1o divergence and anti-scatter slits, and 0.3 mm receiver and detector slits) using Cu-K ( = 1.5406 )
radiation. Le Bail analysis was performed on these data using Topas2, and yielded space group Fd 3 m. Powder
measurements were also carried out on Zr6O4(OH)4(A)6(btc)2 activated at different temperatures.

220 C
o

Intensity [-]

180 C

140 C
o

100 C

10

20

30

40

50

2[ ]

Figure S1. PXRD patterns of Zr6O4(OH)4(X)6(btc)2 after activation overnight at different temperatures (100
(black), 140 (red), 180 (blue) and 220 oC (purple)) under dynamic vacuum (~ 10-6 bar).

10

15

20

25

2 ()

30

35

40

45

50

Figure S2. Le Bail profile fitting for Zr6O4(OH)4(F)6(btc)2 using Laboratory PXRD data. Experimental data is
shown as empty red circles, the calculation in black, difference in green, and Bragg reflection markers in blue.

S3

10

15

20

25

2 ()

30

35

40

45

50

Figure S3. Le Bail profile fitting for Zr6O4(OH)4(A)6(btc)2 using Laboratory PXRD data. Experimental data is
shown as empty red circles, the calculation in black, difference in green, and Bragg reflection markers in blue.

10

15

20

25

2 ()

30

35

40

45

50

Figure S4. Le Bail profile fitting for Zr6O4(OH)4(P)6(btc)2 using Laboratory PXRD data. Experimental data is
shown as empty red circles, the calculation in black, difference in green, and Bragg reflection markers in blue.
Table S2. Space group and cell parameter and volume for the compounds Zr6O4(OH)4(X)6(btc)2 where X = F, A,
and P, obtained from the Le Bail analysis.
Compound

35.3734(16)

35.3062(15)

35.3851(18)

Volume
(3)

44261.9(62)

44010.2(57)

44306.0(66)

Rwp (%)

3.50

2.49

3.63

GOF

1.10

1.31

1.14

Cell parameter

()

S4

Variable temperature PXRD (VT-PXRD). VT-PXRD analysis of all Zr6O4(OH)4(X)6(btc)2 was carried out
using an Anton-Parr XRK900 vacuum furnace interfaced with a PANalytical Xpert Pro diffractometer using CuK radiation ( = 1.5406 ). Measurements were performed between 50 and 450 oC with a 20 oC step and a ramp
rate of 5 oC.min-1.

450 oC

Intensity [-]

350 oC

250 oC

150 oC

50 oC
10

20

30

40

50

2 [ ]

Figure S5. VTPXRD patterns of Zr6O4(OH)4(A)6(btc)2 in air taken every 20 oC from 50 - 450 oC.

450 oC

Intensity [-]

350 oC

250 C

150 oC

50 oC
10

20

30

40

50

2 [ ]

Figure S6. VTPXRD patterns of Zr6O4(OH)4(F)6(btc)2 in air taken every 20 oC from 50 - 450 oC.

S5

450 C

Intensity [-]

350 oC

250 oC

150 C

50 C
10

20

30

40

50

2 [ ]

Figure S7. VTPXRD patterns of Zr6O4(OH)4(P)6(btc)2 in air taken every 20 oC from 50 - 450 oC.

S4. Nuclear magnetic resonance (NMR).

NMR. 1H NMR spectra were recorded for all Zr6O4(OH)4(X)6(btc)2 as well as the btc, F, A, and P ligands,
from a KOH/D2O solution using a Bruker AVANCE200 NMR spectrometer.

Figure S8. 1H NMR spectrum of 1,3,5-benzenetricarboxylic acid (H3btc) in KOH/D2O.

S6

Figure S9. 1H NMR spectrum of acetic acid (AH) in KOH/D2O.

Figure S10. 1H NMR spectrum of formic acid (FA, HCOOH) in KOH/D2O.

Figure S11. 1H NMR spectrum of propionic acid (PA, CH3CH2COOH) in KOH/D2O.

S7

Figure S12. 1H NMR spectrum of Zr6O4(OH)4(A)6(btc)2 activated at 100 oC under ~10-6 bar vacuum after
digestion in KOH/D2O solution. The calculated btc : A is 1 : 2.7.

Figure S13. 1H NMR spectrum of Zr6O4(OH)4(A)6(btc)2 activated at 140 oC under ~10-6 bar vacuum after
digestion in KOH/D2O solution. The calculated btc : A is 1 : 2.
S8

Figure S14. 1H NMR spectrum of Zr6O4(OH)4(A)6(btc)2 activated at 180 oC under ~10-6 bar vacuum after
digestion in KOH/D2O solution. The calculated btc : A is 1 : 1.3.

Figure S15. 1H NMR spectrum of Zr6O4(OH)4(A)6(btc)2 activated at 220 oC under ~10-6 bar vacuum after
digestion in KOH/D2O solution. The calculated btc : A is 1 : 1.3.

S9

Figure S16. 1H NMR spectrum of solvent-exchanged Zr6O4(OH)4(F)6(btc)2 after digestion in KOH/D2O solution.
The signal for btc and F overlap at ~ 8.1 ppm and thus the ratio between them cannot be obtained.

Figure S17. 1H NMR spectrum of Zr6O4(OH)4(P)6(btc)2 activated at 220 oC under ~10-6 bar vacuum after
digestion in KOH/D2O solution. The calculated btc : A is ~1 : 2.8.

S10

S5. Diffuse reflectance infrared spectra (DRIFTS).

DRIFTS. DRIFTS were recorded for Zr6O4(OH)4(A)6(btc)2 after methanol washing and activated at different
temperatures, on a Bruker Tensor 27 FTIR spectrometer using KBr as the background reference.

Figure S18. DRIFTS of HA, H3btc, and Zr6O4(OH)4(A)6(btc)2 after methanol washing and after activation at 100,
140, 180, and 220 oC under dynamic vacuum (~ 10-6 bar). * indicates coordinated acetate groups (1660 cm-1) and
# free acetic acid (1710 cm-1).
S6. Thermogravimetric analysis (TGA).
TGA. TGA measurements were performed for [Zr6O4(OH)4(X)6(btc)2].xH2O, X = A, F, and P, on a TA
Instruments Hi-Res TGA 2950 Thermogravimetric Analyser. Approximately 5 mg of sample was placed on a
platinum pan which was heated under a flow of N2 at a rate of 1 oC.min-1 up to 800 oC. The water content for X =
A was found to be [Zr6O4(OH)4(A)6(btc)2].32H2O.

Figure S19. TGA weight loss (a) and differential weight loss (b) profiles for Zr6O4(OH)4(A)6(btc)2.
S11

Figure S20. TGA weight loss profile for Zr6O4(OH)4(F)6(btc)2 (Activation condition: 100 oC and ~ 10-6 bar
dynamic vacuum overnight after solvent exchanged).

Figure S21. TGA weight loss profile for Zr6O4(OH)4(P)6(btc)2 (Activation condition: 100 oC and ~ 10-6 bar
dynamic vacuum overnight after solvent exchanged).

S7. Elemental Analyses.

Elemental Analyses Elemental analyses were performed at the Chemical Analysis Facility, Macquarie
University, Sydney, Australia. Elemental analysis (%): Calculated: C = 17.8, H = 4.5, N = 0. Found: C = 17.2, H
= 4.45, N = 0.2.

S12

S8. Synchrotron X-ray powder diffraction.

High-resolution powder X-ray diffraction data were recorded for Zr6O4(OH)4(A)6(btc)2 using beamline 17BM at the APS synchrotron, Chicago, US, using a 0.7 mm diameter glass capillary. The incident X-ray
wavelength was =0. 0.728080 and data were collected over the angular range 1.2 - 23 2 with a step 0.005 at
room temperature.
The data were indexed to Fd 3 m with lattice parameter ~ 35.2922 using Topas.1 Structure determination was
performed using the EXPO package, with EXTRA for extracting integrated intensities.2 Only the unique
independent Zr atom could be located and the simulation tool was used to construct the initial structure containing
Zr polyoxo clusters and ligands with the simulated pattern from this model reasonably describing the
Zr6O4(OH)4(A)6(btc)2 data. Rietveld refinement of the starting model was performed using Topas,2 with pore
solvent atoms located using Fourier difference methods. Soft distance and angle constraints were applied to the
asymmetric unit during the refinement, important for stability of the btc ligand. The refinement converged with
Rexp= 2.321%, Rp= 3.85%, and Rwp=5.75%. The refined cell parameter was found to be a = 35.26748 .

Figure S22. Rietveld plot for Zr6O4(OH)4(A)6(btc)2 using synchrotron X-ray powder diffraction data.
Experimental data are shown as red circles, the calculated pattern in black, difference line in green, and Bragg
reflection markers in blue.

S13

S9. Schematic of the cage system of Zr6O4(OH)(bdc)6.3

Figure S23. View of the supertetrahedra (a) and central octahedral cage in Zr6O4(OH)(bdc)6. Zr are shown in
green, O in red, C in grey. H atoms are omitted for clarity.

S10. Gas Sorption.

Gas Sorption. N2 sorption isotherms were measured on an Accelerated Surface Area & Porosimetry System,
(ASAP) 2020 (Micromeritics Instruments Inc.). Prior to analysis, the materials were washed with DMF, acetone
and methanol (vide supra). Approximately 100 mg of the powdered solid was placed in a glass analysis tube and
out-gassed for 12 h under vacuum at 100 oC. N2 adsorption and desorption isotherms were measured at 77 K and
the data was analysed using the Brunauer-Emmett-Teller (BET) and Langmuir analytical model to determine the
surface area. The general BET equation can be expressed as equation 1:4
/0
= 1/0 1

(1 )
0
+

(1)

In this equation, Q is the excess amount of N2 adsorbed under a given equilibrium pressure P at 77 K, P/P0 is the
relative pressure (where P0 = 1 atm and P is the saturation vapor pressure of N2 at 77 K), Qm is the monolayer
adsorbed N2 amount and c is the BET constant. The BET surface areas of Zr6O4(OH)4(X)6(btc)2 were calculated
with two consistency criteria suggested by Rouquerol and Snurr:4, 5 (i) within the pressure range chosen for the
SBET calculation, Q(1-P/P0) should always increase with increasing P/P0; (ii) the straight line fitted to the BET
plot must have a positive intercept to yield a meaningful value for the c parameter (c > 0). The so-obtained value
of Qm is used to calculate the surface area from equation 2.
0
=

(2)

where Na is Avogadros number and S0 is the cross section area (16.2 2) of one nitrogen molecule at liquid state.4
VSTP is the molar volume of N2 at standard temperature and pressure (273 K, 1 atm), its value being 2.24 x 104
cm3.mol-1. The general Langmuir equation can be expressed as equation 3:6, 7

=1+

(3)

In this equation, Q is the quantity of N2 adsorbed at a given equilibrium pressure P at 77K, Qm is the quantity of
N2 gas molecules adsorbed when the entire surface is covered with a monolayer, and b is an empirical constant. If
the model applies then a plot of P/Q vs. P gives a straight line from which b and Qm can be determined from the
slope and Y intercept. The Langmuir surface area (SLangmuir) is then calculated from equation 4:
0
=

(4)
S14

where Na is Avogadros number and S0 is the cross section area (16.2 2) of one nitrogen molecule at liquid state.4
VSTP is the molar volume of N2 at standard temperature and pressure (273 K, 1 atm), its value being 2.24 x 104
cm3.mol-1, and m is the mass of the adsorbing sample.

-1

N2 Absorption @ 77K [mmol.g ]

20
100 oC, Des.
o
100 C, Abs.
o
140 C, Des.
o
140 C, Abs.
180 oC, Des.

15

10

o
180 C, Abs.
o
220 C, Des.
o
220 C, Abs.

0
0.00 0.05 0.10 0.15 0.20 0.25 0.30
P/P0

Figure S24. N2 adsorption and desorption isotherms of Zr6O4(OH)4(A)6(btc)2 activated at 100 (red), 140 (blue),
180 (purple) and 220 oC (green) under high vacuum (~10-6 bar).

6
2

-1

P/Q [mbar.g.mmol ]

-1

SLangmuir = 1864.4(5) m .g
b = 0.1189
Qm = 19.1077

5
4

R2 = 0.9999

3
2
1
0
0

20

40

60

80

100

Pressure [mbar]

Figure S25. Consistency plot (a) and the BET (b) and Langmuir fitting (c) for Zr6O4(OH)4(A)6(btc)2.
S15

-1

P/Q [mbar.g.mmol ]

2
2

-1

SLangmuir = 2770.4(4) m .g
b = 0.0368
Qm = 28.3929

R = 0.9996
0
0

20

40

60

80

100

Pressure [mbar]

Figure S26. Consistency plot (a) and the BET (b) and Langmuir-fitting (c) for Zr6O4(OH)4(F)6(btc)2.

S16

-1

P/Q [mbar.g.mmol ]

-1

SLangmuir = 1633.2(2) m .g
b = 0.1296
Qm = 16.7383

6
5

R = 0.9999

4
3
2
1
0
0

20

40

60

80

100

Pressure [mbar]

Figure S27. Consistency plot (a) and the BET-fitting for Zr6O4(OH)4(P)6(btc)2.

S17

S11. Attempts at using benzoic acid (B) and isobutyric acid for (isoB) Zr6O4(OH)4(X)6(btc)2 synthesis.

Table S3. Attempted synthesis conditions for Zr6O4(OH)4(X)6(btc)2 X = B and isoB using conventional
solvothermal heating.

S12. References

1.
2.
3.
4.
5.
6.
7.

TOPAS V4.2 Bruker A X S General Profile and Structure Analysis Software for Powder Diffraction Data.
A. Altomare, M. C. Burla, M. Camalli, B. Carrozzini, G. L. Cascarano, C. Giacovazzo, A. Guagliardi, A.
G. G. Moliterni, G. Polidori and R. Rizzi, J. Appl. Crystallogr., 1999, 32, 339-340.
J. H. Cavka, S. Jakobsen, U. Olsbye, N. Guillou, C. Lamberti, S. Bordiga and K. P. Lillerud, J. Am. Chem.
Soc., 2008, 130, 13850-13851.
Y.-S. Bae, A. O. Yazaydin and R. Q. Snurr, Langmuir, 2010, 26, 5475-5483.
J. Rouquerol, P. Llewellyn and F. Rouquerol, Stud. Surf. Sci. Catal., 2007, 160, 49-56.
I. Langmuir, J. Am. Chem. Soc., 1916, 38, 2221-2295.
I. Langmuir, J. Am. Chem. Soc., 1918, 40, 1361-1403.

S18