Supporting Information for

In situ Energy-Dispersive X-ray Diffraction for the

synthesis optimization and scale-up of the porous
zirconium terephthalate UiO-66
Florence Ragon,a, Patricia Horcajada,*,a Hubert Chevreau,a, Young Kyu Hwang,b U-Hwang

Lee,b Stuart Miller,a, Thomas Devic,a Jong-San Chang,b Christian Serre*,a

Institut Lavoisier, UMR CNRS 8180, Universit de Versailles Saint-Quentin-en-Yvelines, 45

avenue des tats-Unis, 78035 Versailles cedex, France.

b

Research Group for Nanocatalyst, Biorefinery Research Center, Korea Research Institute of

Chemical Technology (KRICT), P.O. Box 107, Yusung, Daejeon 305-600, Republic of Korea.

S1. Synthesis conditions ......................................................................................................... S3

S2. Bragg peaks integration................................................................................................... S4
S2.1 Bragg peak integration softwares ............................................................................................................. S5
S2.2 (200) Bragg peak integration .................................................................................................................... S6

S3. Comparison between both zirconium precursors with same addition of water ........ S9
S4. Comparison between induction and crystallization times (t0 and tf) ......................... S10
S5. Sharp-Hancock (SH) Plots ............................................................................................ S11
S6. Non-linear Gualtieri fits ................................................................................................ S14
S7. Arrhenius Plots ............................................................................................................... S20
S8. Particle size investigation, TGA and Yield calculations ............................................. S26
S9. Laboratory scale-up of the UiO-66(Zr) solid ............................................................... S27
S9.1 Influence of the zirconium concentration on the crystallinity and the porosity ...................................... S27
S9.2 Characterisations of the UiO-66(Zr) solid obtained from the scale-up synthesis at 1 L. ........................ S28

S1

S9.3 Characterisations of the UiO-66(Zr) solid obtained from the scale-up synthesis at 5 L. ........................ S32

References ............................................................................................................................. S33

S2

S1. Synthesis conditions

Solvothermal synthesis.

Note that the data 0 HCl and 0 H2O correspond to the same data in pure DMF.
Table S1. Synthesis conditions of the solvothermal reactions to form UiO-66(Zr) solid, using ZrCl4 or ZrOCl28
H2O, in presence of 0 to 10 equivalents of HCl (37 %) per Zr.
37 % HCl/Zr

DMF

DMF

37 % HCl

37 % HCl

(mL)

(mmol)

(mL)

(mmol)

2.000

25.9

0.000

0.0

1.967

25.5

0.033

0.4

1.933

25.1

0.067

0.8

1.900

24.6

0.100

1.2

1.833

23.8

0.167

2.0

7.5

1.750

22.7

0.250

3.0

10

1.667

21.6

0.333

4.0

(eq.)

2
3
5

H2BDC

ZrCl4

ZrOCl28H2O

66 mg

93 mg

129 mg

0.4 mmol

0.4 mmol

0.4mmol

Table S2. Synthesis conditions of the solvothermal reactions to form UiO-66(Zr) solid, using ZrCl4 or
ZrOCl28H20, in presence of the same amount of pure water that was present in the aqueous solution of HCl (x
eq. H2O/Zr = amount of H2O added upon addition of x eq. of HCl/Zr).
H2O/Zr

DMF

DMF

H2O

H2O

(mL)

(mmol)

(mL)

(mmol)

2.000

25.9

0.000

0.0

1.967

25.5

0.021

1.2

(eq.)

H2BDC

ZrCl4

ZrOCl28H2O

66 mg

93 mg

129 mg

1.933

24.6

0.063

3.5

0.4 mmol

0.4 mmol

0.4mmol

1.900

23.8

0.105

5.8

7.5

1.833

22.7

0.158

8.8

10

1.750

21.6

0.210

11.7

S3

S2. Bragg peaks integration

UiO-66(Zr) solid1 crystallizes in the cubic Fm-3m space group (n 225) with a unit cell of
20.7004(2) and a unit cell volume of 8870.3(2) 3.
Table S3 gives the position of the characteristics Bragg peaks of the phase, illustrated in
Figure S1.

Table S3. Characteristic reflections of the UiO-66(Zr) solid, 2Theta between 6 and 20 , with a Cu Kalpha1
radiation ( = 1.54056 ).
Bragg peak

Bragg peak position

(hkl)

2Theta ()

111

7.4

200

8.5

220

12.1

311

14.2

222

14.8

400

17.1

331

18.7

420

19.2

Figure S1. (a) Schematic view of the UiO-66(Zr) structure. (b) Tetrahedral cage. (c) Octahedral cage. Zirconium
polyhedra, carbon, oxygen and hydrogen atoms are respectively in green, black, red and light blue. (d) Simulated
X-ray powder diffraction (XRPD) pattern (Cu Kalpha1 radiation = 1.54056 ) of the UiO-66(Zr) solid using
MERCURY software.2

S4

S2.1 Bragg peak integration softwares

Bragg peaks integration was performed using different tools: i) calf3 (software offered and
available for free at beamline F3, private copy by A. Rothkirch/DESY) and ii) Peak
Analyser contained in the Origin software (OriginLab, Northampton, MA). Integration using
both softwares was not significantly different. The choice of the software depends on which
one give us the best integrated data at short times as it can be seen on Figure S2.

Figure S2. Comparison of extent of crystallization () obtained with different methods (a) data from 0 to 90
minutes; (b) zoom at shorter times when the crystallinity is poor. Square: calf3 tool; circle: calf3 tool with
background correction and triangle: Peak Analyser tool.

S5

S2.2 (200) Bragg peak integration

From Figure S3 to Figure S5, all (200) integrated data can be found and the kinetics
parameters are indicated from Table S4 to Table S7.

Study of the effect of HCl or H2O addition with ZrCl4 as metallic precursor.

Figure S3. Plots of extent of crystallization () against time obtained by integration of the (200) Bragg peak of
the phase UiO-66(Zr) synthesized at 423 K using ZrCl4 in presence of (a) 1 to 10 equivalents of HCl/Zr; (b) 1 to
10 equivalents of H2O/Zr.

Table S4. Crystallization time tf, induction time t0 and kinetics parameters (nSH and kSH) obtained by the SharpHancock (SH) method with the Avrami-Erofeev (AE) equation of the UiO-66(Zr) phase at 423 K using ZrCl4
with the addition of 1 to 10 equivalents of HCl or H2O per Zr. Values based on the integration of the (200) Bragg
peak.
Additive (eq./Zr)

tf (min)

t0 (min)

nSH

kSH (min-1)

1 HCl

80

0.82

0.057

3HCl

26

2.61

0.125

5 HCl

14

1.49

0.195

7.5 HCl

1.81

0.575

10 HCl

0.75

0.985

1 H2O

1.35

0.569

3 H2O

1.10

0.996

5 H2O

0.95

0.982

7.5 H2O

0.20

4428

10 H2O

0.85

4.170

S6

Study of the effect of HCl or H2O addition with ZrOCl28H2O as metallic precursor.
Hereafter, note that only data obtained in presence of 2 to 7.5 equivalents of HCl per
zirconium are shown due to the poor crystallinity at lower HCl concentration and H2O
conditions hampers the integration of the (200) Bragg peak.

Figure S4. Plots of extent of crystallization () against time obtained by integration of the (200) Bragg peak of
the UiO-66(Zr) synthesized at 423 K using ZrOCl28H2O in presence of 2 to 7.5 equivalents of HCl/Zr.

Table S5. Crystallization time tf, induction time t0 and kinetics parameters (nSH and kSH) obtained by the SharpHancock (SH) method with the Avrami-Erofeev (AE) equation of the UiO-66(Zr) phase at 423 K using
ZrOCl28H2O with the addition of 2 to 7.5 equivalents of HCl or H2O. Values based on the integration of the
(200) Bragg peak.
Additive (eq./Zr)

tf (min)

t0 (min)

nSH

kSH (min-1)

2 HCl

2.07

0.464

3HCl

3.25

0.382

5 HCl

5.29

0.598

7.5 HCl

1.14

0.650

S7

Study of the effect of the temperature.

(a)

1.0

(d)

0.8

-1

kSH (min )

0.6
0.4
0.2

0.6
0.4
0.2
0.0
340

350

360

370

T (K)

0.0
0

20

40
60
time (min)

80

100

(e)

(b)

(c)

(f)

1.0
0.8

kSH (min )

0.6
-1

0.4
0.2

0.3
0.2
0.1
0.0
-0.1

340 360 380 400 420

0.0

T (K)

40

80
time (min)

120

160

Figure S5. Plots of extent of crystallization () against time obtained by integration of the (200) Bragg peak of
the UiO-66(Zr) synthesized at four different temperatures and the corresponding SH analyses using the AE
nucleation-growth crystallization model: (a) and (d) from 343 to 373 K, using ZrCl4 with the addition of
7.5HCl/Zr; (b) and (e) from 343 to 423 K, using ZrOCl28H2O with the addition of 7.5 HCl/Zr; (c) and (f) from
343 to 413 K, using ZrOCl28H2O with the addition of 2 HCl/Zr.

S8

Table S6. Crystallization time tf, induction time t0 and kinetics parameters (nSH and kSH) obtained by the SH
method with the AE equation as well as calculated pre-exponential factors (A) and activation energies (Ea).

T (K)

tf

t0

(min)

kSH

nSH

(min)

-1

Ea
-1

(min )

(min )

(kJ.mol-1)

3 x 103

27(26)

104

20(1)

2 x 105

46(4)

ZrCl4 7.5 HCl

343

87

0.39

0.101

353

14

0.90

0.367

363

12

1.18

0.313

373

0.95

0.604

ZrOCl28H2O 7.5 HCl

343

55

14

0.83

0.081

353

26

1.18

0.152

363

20

2.05

0.169

423

0.88

0.359

ZrOCl28H2O 2HCl
343

149

1.02

0.018

373

38

0.83

0.092

393

23

1.15

0.141

413

1.90

0.289

Table S7. Kinetics parameters (a, b, kg and kn) obtained by the Gualtieri equation as well as calculated preexponential factors (Ag and An) and activation energies (Eag and Ean) for both nucleation and growth.

T (K)

a
(min)

b
(min)

kg

kn
-1

(min )

Ag

-1

(min )

Eag
-1

(kJ.mol )

An

Ean
(kJ.mol-1)

ZrCl4 7.5 HCl

353

2.4(2)

1.3(2)

0.091(5)

0.42(4)

363

3.59(4)

1.48(4)

0.5(2)

0.279(4)

373

1.22(9)

0.73(9)

0.159(7)

0.82(7)

1 x 10^5

37(47)

8 x 103

32(26)

33(8)

7 x 103

63(2)

56(5)

10(26)

ZrOCl28H2O 7.5 HCl

343

23(2)

9(2)

0.07(2)

0.043(5)

353

9.4(6)

3.9(5)

0.14(2)

0.106(8)

363

6.1(7)

2.2(4)

0.20(4)

0.16(3)

373

2.0(2)

1.3(2)

4.74

0.50(6)

3 x 108

ZrOCl28H2O 2 HCl
343

50.8(9)

12.5(3)

4(3)

0.0196(4)

373

29.4(9)

7.0(3)

4.2(5)

0.034(1)

393

0.056(3)

0.19(1)

0.07(4)

18(1)

413

6 x 106

S3. Comparison between both zirconium precursors with same addition of water
S9

Figure S6. Comparison of crystallization curves of the phase UiO-66(Zr) synthesized at 423 K using ZrCl4 in
presence of 7.5 equivalents of H2O/Zr (blue spheres) and ZrOCl28H2O with no addition (purple triangle) and in
the presence of 1 (black square) and 5 (green triangle) equivalents of H2O/Zr.

S4. Comparison between induction and crystallization times (t0 and tf)
S10

Study of the effect of the temperature.

Figure S7. Crystallization time tf and induction time t0 as a function of the temperature using ZrCl4 with HCl/Zr,
= 7.5 (blue triangle), ZrOCl28H2O with HCl/Zr = 7.5 (red circle) and ZrOCl28H2O with HCl/Zr = 2 (black
square).

Figure S8. Comparison of induction and crystallization time (t0 and tf) of UiO-66(Zr) phase synthesized using
ZrCl4 with HCl/Zr, = 7.5, ZrOCl28H2O with HCl/Zr = 7.5 and ZrOCl28H2O with HCl/Zr = 2 (from the bottom
to the top) at different temperatures.

S5. Sharp-Hancock (SH) Plots

S11

From Figure S9 to Figure S12, the SH analyses using the AE nucleation-growth

crystallization model can be found.

Study of the effect of HCl or H2O addition with ZrCl4 as metallic precursor.

Figure S9. SH analyses using the AE nucleation-growth crystallization model of the phase UiO-66(Zr) phase
synthesized at 423 K using ZrCl4 in presence of 1 to 10 equivalents of HCl/Zr.

Figure S10. SH analyses using the AE nucleation-growth crystallization model of the phase UiO-66(Zr) phase
synthesized at 423 K using ZrCl4 in presence of 1 to 10 equivalents of H2O/Zr.

S12

Study of the effect of HCl or H2O addition with ZrOCl28H2O as metallic precursor.

Figure S11. SH analyses using the AE nucleation-growth crystallization model of the phase UiO-66(Zr) phase
synthesized at 423 K using ZrOCl28H2O in presence of 1 to 10 equivalents of HCl/Zr.

Figure S12. SH analyses using the AE nucleation-growth crystallization model of the phase UiO-66(Zr) phase
synthesized at 423 K using ZrCl4 in presence of 0 to 7.5 equivalents of H2O/Zr.

S13

S6. Non-linear Gualtieri fits

From Figure S13 to Figure S18, the crystallization curves and corresponding non-linear leastsquares fits with the Gualtieri equation (dotted line) can be found as well as probability curves
of nucleation PN (solid line). In fact, the probability function for nucleation (PN vs. time) can
be calculated after the determination of the constants related to the nucleation (a and b) using
the following equation: PN = exp [(t-a)2 / (2*b)].3

Study of the effect of the temperature.

353 K

363 K

373 K

Figure S13. Extent of crystallization vs. time for the Bragg peak (111) of UiO-66(Zr) phase from ZrCl4 with 7.5
HCl/Zr and corresponding non-linear least-squares fits with the Gualtieri equation (dotted line) as well as
probability curves of nucleation PN (solid line).

S14

353 K

363 K

373 K

Figure S14. Extent of crystallization vs. time for the Bragg peak (200) of UiO-66(Zr) phase from ZrCl4 with 7.5
HCl/Zr and corresponding non-linear least-squares fits with the Gualtieri equation (dotted line) as well as
probability curves of nucleation PN (solid line).

S15

343 K

353 K

363 K

373 K

Figure S15. Extent of crystallization vs. time for the Bragg peak (111) of UiO-66(Zr) phase from ZrOCl28H2O
with 7.5 HCl/Zr and corresponding non-linear least-squares fits with the Gualtieri equation (dotted line) as well
as probability curves of nucleation PN (solid line).

S16

343 K

353 K

363 K

373 K

Figure S16. Extent of crystallization vs. time for the Bragg peak (200) of UiO-66(Zr) phase from ZrOCl28H2O
with 7.5 HCl/Zr and corresponding non-linear least-squares fits with the Gualtieri equation (dotted line) as well
as probability curves of nucleation PN (solid line).

S17

Figure S17. Extent of crystallization vs. time for the Bragg peak (111) of UiO-66(Zr) phase from ZrOCl28H2O
with 2 HCl/Zr and corresponding non-linear least-squares fits with the Gualtieri equation (dotted line) as well as
probability curves of nucleation PN (solid line).

S18

343 K

373 K

393 K

Figure S18. Extent of crystallization vs. time for the Bragg peak (200) of UiO-66(Zr) phase from ZrOCl2.8H2O
with 2 HCl/Zr and corresponding non-linear least-squares fits with the Gualtieri equation (dotted line) as well as
probability curves of nucleation PN (solid line).

S19

S7. Arrhenius Plots

For each precursor and HCl/Zr ratio, pre-exponential factors (A) and activation energies (Ea)
were extracted using the Arrhenius equation (k = A * exp (- Ea/RT) where k is the rate
constant of the chemical reaction on the temperature T and R is the universal gas constant).
The Arrhenius plots corresponding can be found from Figure S19 to Figure S30.

Figure S19. Arrhenius plots of the UiO-66(Zr) phase with ZrCl4 with 7.5 HCl/Zr for the Bragg peak (111) for
the temperature-dependant rate constants from the Avrami-Erofeev equation.

Figure S20. Arrhenius plots of the UiO-66(Zr) phase with ZrCl4 with 7.5 HCl/Zr for the Bragg peak (111) for
the temperature-dependant rate constants of nucleation (triangle) and growth (circle) from the Gualtieri model.

S20

Figure S21. Arrhenius plots of the UiO-66(Zr) phase with ZrCl4 with 7.5 HCl/Zr for the Bragg peak (200) for
the temperature-dependant rate constants from the Avrami-Erofeev equation.

Figure S22. Arrhenius plots of the UiO-66(Zr) phase with ZrCl4 with 7.5 HCl/Zr for the Bragg peak (200) for
the temperature-dependant rate constants of nucleation (triangle) and growth (circle) from the Gualtieri model.

S21

Figure S23. Arrhenius plots of the UiO-66(Zr) phase with ZrOCl28H2O with 7.5 HCl/Zr for the Bragg peak
(111) for the temperature-dependant rate constants from the Avrami-Erofeev equation.

Figure S24. Arrhenius plots of the UiO-66(Zr) phase with ZrOCl28H2O with 7.5 HCl/Zr for the Bragg peak
(111) for the temperature-dependant rate constants of nucleation (triangle) and growth (circle) from the Gualtieri
model.

S22

Figure S25. Arrhenius plots of the UiO-66(Zr) phase with ZrOCl28H2O with 7.5 HCl/Zr for the Bragg peak
(200) for the temperature-dependant rate constants from the Avrami-Erofeev equation.

Figure S26. Arrhenius plots of the UiO-66(Zr) phase with ZrOCl28H2O with 7.5 HCl/Zr for the Bragg peak
(200) for the temperature-dependant rate constants of nucleation (triangle) and growth (circle) from the Gualtieri
model.

S23

Figure S27. Arrhenius plots of the UiO-66(Zr) phase with ZrOCl28H2O with 2 HCl/Zr for the Bragg peak
(111) for the temperature-dependant rate constants from the Avrami-Erofeev equation.

Figure S28. Arrhenius plots of the UiO-66(Zr) phase with ZrOCl28H2O with 2 HCl/Zr for the Bragg peak (111)
for the temperature-dependant rate constants of nucleation (triangle) and growth (circle) from the Gualtieri
model.

S24

Figure S29. Arrhenius plots of the UiO-66(Zr) phase with ZrOCl28H2O with 2 HCl/Zr for the Bragg peak (200)
for the temperature-dependant rate constants from the Avrami-Erofeev equation.

Figure S30. Arrhenius plots of the UiO-66(Zr) phase with ZrOCl28H2O with 2 HCl/Zr for the Bragg peak (200)
for the temperature-dependant rate constants of nucleation (triangle) and growth (circle) from the Gualtieri
model.

S25

S8. Particle size investigation, TGA and Yield calculations

Figure S31. XRPD patterns (Cu Kalpha1 radiation = 1.54056 ) of the UiO-66(Zr) phase with both ZrCl4 and
ZrOCl28H2O precursors at two different ratios of HCl and H2O/Zr (1 and 7.5).

100

Weight (%)

90
80
70

1 HCl/Zr_ZrCl4
7.5 HCl/Zr_ZrCl4

60

1 H2O/Zr_ZrCl4
7.5 H2O/Zr_ZrCl4

50

1 HCl/Zr_ZrOCl2.8H2O
7.5 HCl/Zr_ZrOCl2.8H2O

40

1 H2O/Zr_ZrOCl2.8H2O
7.5 H2O/Zr_ZrOCl2.8H2O

30
0

100

200 300 400 500

Temperature (C)

600

Figure S32. TGA curves of the UiO-66(Zr) phase with both ZrCl4 and ZrOCl28H2O precursors at two different
ratios of HCl and H2O/Zr (1 and 7.5).

S26

Typically, TGA curves show two characteristic weight losses: the first, between 70 and 400

C, corresponds to the departure of the guest molecules (MeOH and/or H2O and/or DMF) and
the dehydroxylation of UiO-66(Zr) solid, and the second weight loss, between 400 and 520
C, corresponding to the combustion of the organic linker. Thus, after TG analysis, the
residual product was identified as ZrO2 by XRPD. For a better comparison regardless the
solvent amount, the ZrO2 wt% was calculated taking into account the dehydrated
dehydroxylated solid (considering the weight at 400C as the 100 wt% corresponding with the

formula Zr6O6(BDC)6).
Yield calculation.
The yield (Table 5, page 26 in the text) was determined using the following formula:
% yield = (experimental yield*(1-(%ZrO2/100)) / theoretical yield)
The experimental and theoretical yields have been both based on zirconium. The experimental yield
has been calculated from the molar mass of the dry activated UiO-66(Zr) obtained at the end of the
reaction and corrected to take into account the presence of ZrO2. The theoretical yield has been
calculated taking into account the initial molar mass of the zirconium precursor (ZrCl 4 or
ZrOCl2.8H2O) and the fact that 6 mol of Zr precursor are necessary to form 1 mol of UiO-66(Zr)
(Zr6O4(OH)4(BDC)6).

S9. Laboratory scale-up of the UiO-66(Zr) solid

S9.1 Influence of the zirconium concentration on the crystallinity and the porosity

Figure S33. X ray powder diffraction (XRPD) patterns (Cu Kalpha1 radiation = 1.54056 ) of UiO-66(Zr)
solid synthesized at different zirconium concentrations (0.2, 0.4 and 1 M).

S27

Figure S34. Nitrogen adsorption isotherm of UiO-66(Zr) solid synthesized at different zirconium concentrations
(0.2, 0.4 and 1 M) at T=77K (p0 = 1 atmosphere) as well as BET specific surface are (SBET) and microporous
volume (Vp).

S9.2 Characterisations of the UiO-66(Zr) solid obtained from the scale-up synthesis at
1 L.

X ray powder diffraction.

The addition of 2 equivalent of HCl/Zr seems to be the best comprise between fast reaction
kinetics and a good crystallinity.

S28

Figure S35. Comparison of XRD pattern of synthesis of UiO-66(Zr) with and without adding HCl.

Figure S36. Experimental X-ray powder diffraction (red) compared with the reported one (black).

S29

Fourier Transform Infra-Red spectroscopy.

Figure S37. IR curve of UiO-66(Zr) solid after activation.

Thermal behavior.
TGA and X-ray thermodiffractometry of the solid have been collected under air (Figure S39
and Erreur ! Source du renvoi introuvable.) :

Figure S38. TGA curve of UiO-66(Zr) phase after activation. Measurement performed between 20 and 600 C
with a rate of 2 C.min-1. (w% ZrO2: 45.4 (theoretical ZrO2 percentage for an ideal 12-connected Zr6 cluster) vs.
50 (calculated)).

S30

Figure S39. X-ray thermodiffractometry under air of the solid after activation. Co K radiation ( = 1.79).
Measurement performed between 20 and 400 C with a 10 C step.

The thermal stability of the UiO-66(Zr) solid according to the X-ray thermodiffractometry, is
around 400 C, which closely agrees with the TGA. Any significant difference was observed
between the solid synthesized from the ZrOCl28H2O precursor and that one prepared from
the ZrCl4 .1

N2 adsorption.

Figure S40. Nitrogen adsorption isotherm of UiO-66(Zr) at T=77K (p0 = 1 atmosphere).

S31

S9.3 Characterisations of the UiO-66(Zr) solid obtained from the scale-up synthesis at
5 L.

Intensity (a.u.)

X ray powder diffraction.

10

15

20

25

30

2 Theta ( )
Figure S41. XRD pattern of synthesis of UiO-66(Zr) solid obtained from the scale-up synthesis at 5 L.

Fourier Transform Infra-red spectroscopy.

80

40

20

3500

3000

2500

2000

1500

Transmittance (%)

60

1000

-1

Wavenumber (cm )
Figure S42. IR curve of UiO-66(Zr) obtained from the scale-up synthesis at 5 L.

S32

References
1
2

Cavka, J. H. et al. A New Zirconium Inorganic Building Brick Forming Metal Organic
Frameworks with Exceptional Stability. J. Am. Chem. Soc. 130, 13850-13851 (2008).
Macrae, C. F. et al. Mercury CSD 2.0 - new features for the visualization and investigation of
crystal structures. J. Appl. Crystallogr. 41, 466-470, doi:doi:10.1107/S0021889807067908
(2008).

S33