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S1

Supporting Information for

Disclosing the complex structure of UiO-66 Metal OrganicFramework: a synergic combination of experiment and theory

Loredana Valenzano,1 Bartolomeo Civalleri,1 Sachin Chavan,1 Silvia Bordiga,1 Merete H. Nilsen,2 SrenJakobsen,2 Karl Petter Lillerud,2* Carlo Lamberti1

1 Department of Inorganic, Physical and Material Chemistry, NIS Centre of Excellence, and INSTM reference center,University of Turin, Via P. Giuria 7, I-10125 Torino, Italy2 inGAP centre of Research-based Innovation, Department of Chemistry, University of Oslo, Sem Saerlandsvei 26, N-0315 Oslo, Norway

S1. Adsorption isotherm.

The adsorption of nitrogen was measured volumetrically with a BELSORP-mini II instrument and

the specific surface area was obtained by the BET method. The sample was heated to 250 C andkept at this temperature under continuous evacuation for 6 hours prior to adsorption measurement.The adsorption of nitrogen follows a type I isotherm with no hysteresis (figure S16), and with aBET surface area of 1069 m2/g.

0.0 0.2 0.4 0.6 0.8 1.0

0

100

200

300

400

V/cm

3(S

TP)/g

P/P0

Figure S1: BET nitrogen adsorption (filled squares) and desorption (open squares) isotherms of Zr-BDC(UiO-66) at 77 K.

Corresponding authors: C. Lamberti Tel: +39011-6707841 Fax: +39011-6707855; E-mail: carlo.lamberti@unito.itK.-P Lillerud: Tel: +4722855457; E-mail: k.p.lillerud@kjemi.uio.no

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S2

S2. Remarkable structure stability upon interaction with solvents and chemicals.

The XRPD studies, reported in Figure S2 indicate that UiO-66 framework is stable in water,benzene, acetone, ethanol, and, obviously, DMF. As some reactions run at pH values significantlydifferent from neutrality, we also checked the stability in presence of a strong acid (HCl) and astrong base (NaOH). The patterns reported in Figure S2 indicate that UiO-66 is well stable in HCl

solution and that it still maintains an appreciable degree of crystallinity in NaOH solution.

10 15 20 25 30 35 4010 15 20 25 30 35 40

(b)

2

C2H5OH

HCl

H2O

NaOH

Acetone

2

As-synthesized

Water

Benzene

DMF

Si(111)(a)

Figure S2: Part (a):XRPD pattern of desolvated UiO-66 treated with various solvents at room temperature for 24 h instirred suspension. Part (b): XRPD pattern of desolvated UiO-66 after interaction at room temperature for 2 hours instirred suspension with, from top to bottom: ethanol, HCl, H 2O and NaOH. The arrow in part (a) indicates the Si(111)reflection at 2 = 28.4 used for calibration. = 1.5406 .

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S3

S3. Failure of XRPD in determining the local distortion of Zr6-clusters upon

dehydroxylation.

Figure S3a shows superimposed images of 7-coordinated Zr6-clusters oriented along differentdirections. The effect of this random orientation in the Rietveld refinement, made in a cubic spacegroup, is the systematic average of Zr and O atomic coordinates. This effect is evidenced in Figure

S3b, where the cluster in the middle is obtained by averaging two Zr6O6 clusters oriented along twoperpendicular directions. The Zr atoms are drawn with 0.3 spheres, the maximum deviation in Zrpositions is approximately 0.15 . The change in the zirconium coordination is not visible in theXRPD refinement, where only a change in the occupancy of the 3-oxygen from 1 to 0.75 and anincrease in the thermal parameters of all atoms are observed (see Figure 4a in the main text). Thechanges are however clearly illustrated by the EXAFS data presented in Figure 4c in the main text.

Figure S3. Part (a): superimposed images of 7-coordinated Zr6-clusters oriented along different directions simulatingthe statistically disorder undergone by the structure in dehydroxylation process. Part (b): top and bottom show twoZr6O6 clusters oriented along two different directions; their superimposition is reported in the middle, describing the

average situation observed by XRPD. Note that the averaging process restores the cubic symmetry lost in thedehydroxylation process.

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S4

S4. CRYSTAL input file: UiO-66 hydroxylated.

UiO-66 hydroxylated optimized structure - space group F-43m

CRYSTAL

0 0 0

216

20.97926200

9

40 1.203516233031E-01 -2.720175999485E-20 1.033412917069E-20

8 1.707235919326E-01 2.623530208754E-03 9.457583772936E-02

8 4.940721495497E-02 -4.940721495497E-02 -4.940721495497E-02

8 6.727434149412E-02 -6.727434149412E-02 6.727434149412E-02

6 1.523362250288E-01 -4.103997003988E-03 -1.523362250288E-01

6 2.028617545057E-01 6.226543937829E-03 2.028617545057E-01

6 2.674340184647E-01 6.592416200391E-03 1.856733104512E-01

1 9.377332139943E-02 -9.377332139943E-02 9.377332139943E-02

1 1.355515445794E-01 -2.800045798523E-01 -6.493727004219E-03

ENDG

40 8

0 0 9 2. 1.3450660.8 0.000034

467601.94 0.000322

92314.514 0.0021

21992.52 0.0112

6082.9917 0.0475

1915.2715 0.157

676.43927 0.3524

263.00267 0.4238

106.89395 0.1593

0 1 7 8. 1.

7730.9357 -0.000356 0.000918

1743.6542 -0.00657 0.00895

515.55964 -0.0586 0.0557

176.18824 -0.1469 0.219

67.946738 0.2212 0.4536

29.173149 0.6893 0.397

13.001228 0.2629 0.1064

0 1 6 8. 1.

177.67018 0.00399 -0.0124

59.986876 -0.0365 -0.0757

24.185965 -0.3385 0.0838

9.9783433 0.1865 0.9961

4.3099261 0.9971 1.2441

1.7492066 0.2468 0.308

0 1 3 8. 1.

3.8653 -1.595 -0.1149

1.739 -0.364 0.514

0.7875 4.9455 1.3848

0 3 6 10. 1.297.855 0.00597

87.4716 0.0474

31.5134 0.1925

12.3703 0.4114

4.9738 0.4381

1.957 0.1588

0 1 1 2. 1.

0.33848 1.0 1.0

0 3 2 2. 1.

2.6978 0.08308

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S5

0.9959 0.34899

0 3 1 0. 1.

0.413544 1.0

8 5

0 0 8 2. 1.

8020. 0.00108

1338. 0.00804

255.4 0.05324

69.22 0.1681

23.90 0.3581

9.264 0.3855

3.851 0.1468

1.212 0.0728

0 1 4 6. 1.

49.43 -0.00883 0.00958

10.47 -0.0915 0.0696

3.235 -0.0402 0.2065

1.217 0.379 0.347

0 1 1 0. 1.

0.476 1. 1.

0 1 1 0. 1.

0.202 1. 1.

0 3 1 0. 1.0.8 1.

1 3

0 0 3 1. 1.

0.1873113696D+02 0.3349460434D-01

0.2825394365D+01 0.2347269535D+00

0.6401216923D+00 0.8137573261D+00

0 0 1 0. 1.

0.1612777588D+00 0.1000000000D+01

0 2 1 0. 1.

0.1100000000D+01 0.1000000000D+01

6 4

0 0 6 2. 1.

0.3047524880D+04 0.1834737132D-02

0.4573695180D+03 0.1403732281D-010.1039486850D+03 0.6884262226D-01

0.2921015530D+02 0.2321844432D+00

0.9286662960D+01 0.4679413484D+00

0.3163926960D+01 0.3623119853D+00

0 1 3 4. 1.

0.7868272350D+01 -0.1193324198D+00 0.6899906659D-01

0.1881288540D+01 -0.1608541517D+00 0.3164239610D+00

0.5442492580D+00 0.1143456438D+01 0.7443082909D+00

0 1 1 0. 1.

0.1687144782D+00 0.1000000000D+01 0.1000000000D+01

0 3 1 0. 1.

0.8000000000D+00 0.1000000000D+01

99 0

ENDB

DFT

B3LYP

XLGRID

END

SCFDIR

BIPOSIZE

10000000

EXCHSIZE

20000000

SHRINK

2 2

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S6

TOLINTEG

7 7 7 7 16

FMIXING

90

BROYDEN

0.05 50 5

TOLDEE

8

ENDSCF

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S7

S5. CRYSTAL input file: UiO-66 dehydroxylated.UiO-66 dehydroxylated optimized structure - space group R-3

CRYSTAL

0 1 0

148

14.60005074 61.681471

1840 -1.280400453054E-01 1.200164917979E-01 1.234180397334E-01

8 -8.212898412323E-02 2.629728242440E-01 8.510834545953E-02

8 -2.432326350631E-01 4.968501528894E-02 -8.155579867320E-02

8 2.659074187348E-01 -7.663578265205E-02 -2.680307890997E-01

8 8.336473104159E-02 -2.743573842983E-01 2.586396595413E-01

8 -1.611707424856E-01 4.265294400011E-02 4.600921444731E-02

6 -3.026784322048E-01 -3.309231435712E-03 3.105628851130E-01

6 7.072953251050E-04 -2.953142950102E-01 -1.377748307962E-02

6 -3.928461995927E-04 4.014381843035E-01 6.123556286575E-03

6 4.043980156713E-01 1.858860687277E-03 -4.088330398747E-01

6 -9.015925803755E-02 4.629002514035E-01 7.267267573596E-02

6 -4.389887072846E-01 6.652316525391E-02 -8.984634038571E-02

6 4.569944865604E-01 -8.643911412216E-02 -4.500695462617E-01

6 8.828075199337E-02 -4.591699744298E-01 4.478562166367E-01

1 -4.101673587868E-01 4.225195131906E-01 -1.527632244318E-01

1 -4.262817023178E-01 4.063107079701E-01 1.559374195623E-01

1 1.285012235489E-01 -1.593351841741E-01 4.327738207815E-01

1 1.170627981461E-01 -1.589184182843E-01 -3.903185529063E-01

END

40 8

0 0 9 2. 1.

3450660.8 0.000034

467601.94 0.000322

92314.514 0.0021

21992.52 0.0112

6082.9917 0.0475

1915.2715 0.157

676.43927 0.3524

263.00267 0.4238106.89395 0.1593

0 1 7 8. 1.

7730.9357 -0.000356 0.000918

1743.6542 -0.00657 0.00895

515.55964 -0.0586 0.0557

176.18824 -0.1469 0.219

67.946738 0.2212 0.4536

29.173149 0.6893 0.397

13.001228 0.2629 0.1064

0 1 6 8. 1.

177.67018 0.00399 -0.0124

59.986876 -0.0365 -0.0757

24.185965 -0.3385 0.0838

9.9783433 0.1865 0.99614.3099261 0.9971 1.2441

1.7492066 0.2468 0.308

0 1 3 8. 1.

3.8653 -1.595 -0.1149

1.739 -0.364 0.514

0.7875 4.9455 1.3848

0 3 6 10. 1.

297.855 0.00597

87.4716 0.0474

31.5134 0.1925

12.3703 0.4114

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S8

4.9738 0.4381

1.957 0.1588

0 1 1 2. 1.

0.33848 1.0 1.0

0 3 2 2. 1.

2.6978 0.08308

0.9959 0.34899

0 3 1 0. 1.

0.413544 1.0

8 5

0 0 8 2. 1.

8020. 0.00108

1338. 0.00804

255.4 0.05324

69.22 0.1681

23.90 0.3581

9.264 0.3855

3.851 0.1468

1.212 0.0728

0 1 4 6. 1.

49.43 -0.00883 0.00958

10.47 -0.0915 0.0696

3.235 -0.0402 0.20651.217 0.379 0.347

0 1 1 0. 1.

0.476 1. 1.

0 1 1 0. 1.

0.202 1. 1.

0 3 1 0. 1.

0.8 1.

1 3

0 0 3 1. 1.

0.1873113696D+02 0.3349460434D-01

0.2825394365D+01 0.2347269535D+00

0.6401216923D+00 0.8137573261D+00

0 0 1 0. 1.

0.1612777588D+00 0.1000000000D+010 2 1 0. 1.

0.1100000000D+01 0.1000000000D+01

6 4

0 0 6 2. 1.

0.3047524880D+04 0.1834737132D-02

0.4573695180D+03 0.1403732281D-01

0.1039486850D+03 0.6884262226D-01

0.2921015530D+02 0.2321844432D+00

0.9286662960D+01 0.4679413484D+00

0.3163926960D+01 0.3623119853D+00

0 1 3 4. 1.

0.7868272350D+01 -0.1193324198D+00 0.6899906659D-01

0.1881288540D+01 -0.1608541517D+00 0.3164239610D+00

0.5442492580D+00 0.1143456438D+01 0.7443082909D+00

0 1 1 0. 1.

0.1687144782D+00 0.1000000000D+01 0.1000000000D+01

0 3 1 0. 1.

0.8000000000D+00 0.1000000000D+01

99 0

ENDB

DFT

B3LYP

XLGRID

END

SCFDIR

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S9

BIPOSIZE

10000000

EXCHSIZE

20000000

SHRINK

2 2

TOLINTEG

7 7 7 7 16

FMIXING

90

BROYDEN

0.05 50 5

TOLDEE

8

ENDSCF

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S10

S6. Adopted Zirconium Basis-Set.

Zr_all_electron_dovesi_unpub40 8

0 0 9 2. 1.3450660.8 0.000034

467601.94 0.000322

92314.514 0.0021

21992.52 0.0112

6082.9917 0.0475

1915.2715 0.157

676.43927 0.3524

263.00267 0.4238

106.89395 0.1593

0 1 7 8. 1.

7730.9357 -0.000356 0.000918

1743.6542 -0.00657 0.00895

515.55964 -0.0586 0.0557

176.18824 -0.1469 0.219

67.946738 0.2212 0.4536

29.173149 0.6893 0.397

13.001228 0.2629 0.1064

0 1 6 8. 1.

177.67018 0.00399 -0.0124

59.986876 -0.0365 -0.0757

24.185965 -0.3385 0.0838

9.9783433 0.1865 0.9961

4.3099261 0.9971 1.2441

1.7492066 0.2468 0.308

0 1 3 8. 1.

3.8653 -1.595 -0.1149

1.739 -0.364 0.514

0.7875 4.9455 1.3848

0 3 6 10. 1.297.855 0.00597

87.4716 0.0474

31.5134 0.1925

12.3703 0.4114

4.9738 0.4381

1.957 0.1588

0 1 1 2. 1.

0.33848 1.0 1.0

0 3 2 2. 1.

2.6978 0.08308

0.9959 0.34899

0 3 1 0. 1.

0.413544 1.0