SI_In Situ Energy Dispersive Xray Diffraction ..Ragon2014 (Info TGA y Rendimiento)

7/25/2019 SI_In Situ Energy Dispersive Xray Diffraction ..Ragon2014 (Info TGA y Rendimiento)

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S1

Supporting Information for

I n situ Energy-Dispersive X-ray Diff raction for the

synthesis optimization and scale-up of the porous

zirconium terephthalate UiO-66

Florence Ragon,a,Patricia Horcajada,*,aHubert Chevreau,a,Young Kyu Hwang,bU-Hwang

Lee,bStuart Miller,a,

Thomas Devic,aJong-San Chang,bChristian Serre*,a

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

avenue des tats-Unis, 78035 Versailles cedex, France.bResearch 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 (t0and 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


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S2

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

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


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S3

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 ZrCl4or ZrOCl28

H2O, in presence of 0 to 10 equivalents of HCl (37 %) per Zr.

37 % HCl/Zr

(eq.)H2BDC ZrCl4 ZrOCl28H2O

DMF

(mL)

DMF

(mmol)

37 % HCl

(mL)

37 % HCl

(mmol)

0

66 mg

0.4 mmol

93 mg

0.4 mmol

129 mg

0.4mmol

2.000 25.9 0.000 0.0

1 1.967 25.5 0.033 0.42 1.933 25.1 0.067 0.8

3 1.900 24.6 0.100 1.2

5 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

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 (xeq. H2O/Zr = amount of H2O added upon addition of x eq. of HCl/Zr).

H2O/Zr

(eq.)H2BDC ZrCl4 ZrOCl28H2O

DMF

(mL)

DMF

(mmol)

H2O

(mL)

H2O

(mmol)

0

66 mg

0.4 mmol

93 mg

0.4 mmol

129 mg

0.4mmol

2.000 25.9 0.000 0.0

1 1.967 25.5 0.021 1.2

3 1.933 24.6 0.063 3.5

5 1.900 23.8 0.105 5.8

7.5 1.833 22.7 0.158 8.810 1.750 21.6 0.210 11.7


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S4

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

(hkl)

Bragg peak position

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


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S5

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 onFigure 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: calf3tool; circle: calf3tool withbackground correction and triangle: Peak Analysertool.


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S2.2 (200) Bragg peak integration

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

Study of the effect of HCl or H2O addition with ZrCl4as 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 ZrCl4in presence of (a) 1 to 10 equivalents of HCl/Zr; (b) 1 to

10 equivalents of H2O/Zr.

Table S4. Crystallization timetf, induction time t0and kinetics parameters (nSHandkSH) obtained by the Sharp-

Hancock (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 7 0.82 0.0573HCl 26 1 2.61 0.125

5 HCl 14 1 1.49 0.195

7.5 HCl 7 1 1.81 0.575

10 HCl 5 1 0.75 0.985

1 H2O 5 0 1.35 0.569

3 H2O 4 0 1.10 0.996

5 H2O 3 0 0.95 0.982

7.5 H2O 2 0 0.20 4428

10 H2O 1 0 0.85 4.170


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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 t0and kinetics parameters (nSHand kSH) obtained by the Sharp-

Hancock (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 5 0 2.07 0.464

3HCl 5 1 3.25 0.382

5 HCl 3 1 5.29 0.598

7.5 HCl 2 0 1.14 0.650


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Study of the effect of the temperature.

(a) (d)

(b) (e)

(c) (f)

0 20 40 60 80 100

0.0

0.2

0.4

0.6

0.8

1.0

340 350 360 3700.0

0.2

0.4

0.6

kSH

(min-1 )

T (K)

time (min)

0 40 80 120 160

0.0

0.2

0.4

0.6

0.8

1.0

340 360 380 400 420-0.1

0.0

0.1

0.2

0.3

kSH

(min-1

)

T (K)

time (min)

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 ZrCl 4 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.


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Table S6.Crystallization time tf, induction time t0and 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

(min)

t0

(min)nSH

kSH

(min-1

)

A

(min-1

)

Ea

(kJ.mol-1

)

ZrCl47.5 HCl

343 87 4 0.39 0.101

3 x 103 27(26)353 14 2 0.90 0.367

363 12 1 1.18 0.313

373 9 1 0.95 0.604

ZrOCl28H2O 7.5 HCl

343 55 14 0.83 0.081

104 20(1)353 26 5 1.18 0.152

363 20 2 2.05 0.169423 9 0 0.88 0.359

ZrOCl28H2O 2HCl

343 149 8 1.02 0.018

2 x 105 46(4)373 38 4 0.83 0.092

393 23 1 1.15 0.141

413 8 0 1.90 0.289

Table S7.Kinetics parameters (a, b, kg and kn) obtained by the Gualtieri equation as well as calculated pre-

exponential factors (AgandAn) and activation energies (EagandEan) for both nucleation and growth.

T (K)a

(min)

b

(min)

kg

(min-1

)

kn

(min-1

)Ag

Eag

(kJ.mol-1

)An

Ean

(kJ.mol-1

)

ZrCl47.5 HCl

353 2.4(2) 1.3(2) 0.091(5) 0.42(4)

1 x 10^5 37(47) 8 x 103 32(26)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)

ZrOCl28H2O 7.5 HCl

343 23(2) 9(2) 0.07(2) 0.043(5)

3 x 108 33(8) 7 x 103 63(2)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)

ZrOCl28H2O 2 HCl

343 50.8(9) 12.5(3) 4(3) 0.0196(4)

6 x 106 56(5) 3 10(26)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 - - - -

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


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Figure S6. Comparison of crystallization curves of the phase UiO-66(Zr) synthesized at 423 K using ZrCl 4 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 (t0and tf)


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Figure S7. Crystallization timetfand induction time t0as 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 (t0and 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 bottomto the top) at different temperatures.

S5. Sharp-Hancock (SH) Plots


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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 ZrCl4as 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 ZrCl4in presence of 1 to 10 equivalents of HCl/Zr.


synthesized at 423 K using ZrCl4in presence of 1 to 10 equivalents of H2O/Zr.


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


synthesized at 423 K using ZrOCl28H2O in presence of 1 to 10 equivalents of HCl/Zr.


synthesized at 423 K using ZrCl4in presence of 0 to 7.5 equivalents of H2O/Zr.


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S6. Non-linear Gualtieri fits

FromFigure S13 toFigure S18,the crystallization curves and corresponding non-linear least-

squares 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 (PNvs.time) can

be calculated after the determination of the constants related to the nucleation (aand b) using

the following equation: PN= exp [(t-a)2/ (2*b)].3


Figure S13.Extent of crystallization vs.time for the Bragg peak (111) of UiO-66(Zr) phase from ZrCl4with 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).

353 K 363 K

373 K


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Figure S14.Extent of crystallization vs.time for the Bragg peak (200) of UiO-66(Zr) phase from ZrCl4with 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).

353 K 363 K

373 K


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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 wellas probability curves of nucleation PN(solid line).

343 K 353 K

363 K 373 K


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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).

343 K 353 K

363 K 373 K


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S18

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 asprobability curves of nucleation PN(solid line).


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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 asprobability curves of nucleation PN(solid line).

343 K 373 K

393 K


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S20

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 fromFigure S19 toFigure S30.

Figure S19.Arrhenius plots of the UiO-66(Zr) phase with ZrCl4with 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 ZrCl4with 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.


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Figure S21.Arrhenius plots of the UiO-66(Zr) phase with ZrCl4with 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 ZrCl4with 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.


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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.


(111) for the temperature-dependant rate constants of nucleation (triangle) and growth (circle) from the Gualtieri

model.


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(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.


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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.


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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-Erofeevequation.

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.


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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 ZrCl 4and

ZrOCl28H2O precursors at two different ratios of HCl and H2O/Zr (1 and 7.5).

0 100 200 300 400 500 600

30

4050

60

70

80

90

100

Weight(%)

Temperature (C)

1 HCl/Zr_ZrCl4

7.5 HCl/Zr_ZrCl4

1 H2O/Zr_ZrCl

4

7.5 H2O/Zr_ZrCl

4

1 HCl/Zr_ZrOCl2.8H2O7.5 HCl/Zr_ZrOCl

2.8H

2O

1 H2O/Zr_ZrOCl

2.8H

2O

7.5 H2O/Zr_ZrOCl

2.8H

2O

Figure S32.TGA curves of the UiO-66(Zr) phase with both ZrCl4and ZrOCl28H2O precursors at two different

ratios of HCl and H2O/Zr (1 and 7.5).


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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 (ZrCl4 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).


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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 (S BET) 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.


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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).


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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 ZrO2percentage for an ideal 12-connected Zr6cluster) vs.

50 (calculated)).


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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

N2adsorption.

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


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

5 L.

X ray powder diffraction.

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.

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

5 10 15 20 25 30

2 Theta (O)

Intens

ity

(a.u.)

3500 3000 2500 2000 1500 1000

20

40

60

80

Transmittance(%)

Wavenumber (cm-1

)


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References

1 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).

2 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).

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SI_In Situ Energy Dispersive Xray Diffraction ..Ragon2014 (Info TGA y Rendimiento)