Supporting Information for

Disclosing the complex structure of UiO-66 Metal Organic

Framework: a synergic combination of experiment and theory
Loredana Valenzano,1 Bartolomeo Civalleri,1 Sachin Chavan,1 Silvia Bordiga,1 Merete H. Nilsen,2 Sren
Jakobsen,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, Italy
2
inGAP centre of Research-based Innovation, Department of Chemistry, University of Oslo, Sem Saerlandsvei 26, N0315 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 and
kept 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 a
BET surface area of 1069 m2/g.

400

200

V/cm (STP)/g

300

100

0
0.0

0.2

0.4

0.6

0.8

1.0

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.it

K.-P Lillerud: Tel: +4722855457; E-mail: k.p.lillerud@kjemi.uio.no

S1

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 significantly
different from neutrality, we also checked the stability in presence of a strong acid (HCl) and a
strong 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.

Si(111)

(a)

(b)

DMF
C2H5OH

Benzene
Acetone

HCl
Water
H2O

As-synthesized
10

15

20

25

30

35

NaOH
40

10

15

20

25

30

35

40

Figure S2: Part (a): XRPD pattern of desolvated UiO-66 treated with various solvents at room temperature for 24 h in
stirred suspension. Part (b): XRPD pattern of desolvated UiO-66 after interaction at room temperature for 2 hours in
stirred suspension with, from top to bottom: ethanol, HCl, H2O and NaOH. The arrow in part (a) indicates the Si(111)
reflection at 2 = 28.4 used for calibration. = 1.5406 .

S2

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 different
directions. The effect of this random orientation in the Rietveld refinement, made in a cubic space
group, 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 two
perpendicular directions. The Zr atoms are drawn with 0.3 spheres, the maximum deviation in Zr
positions is approximately 0.15 . The change in the zirconium coordination is not visible in the
XRPD refinement, where only a change in the occupancy of the 3-oxygen from 1 to 0.75 and an
increase in the thermal parameters of all atoms are observed (see Figure 4a in the main text). The
changes 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 simulating
the statistically disorder undergone by the structure in dehydroxylation process. Part (b): top and bottom show two
Zr6O6 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 the
dehydroxylation process.

S3

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

S4

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-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
0.1881288540D+01 -0.1608541517D+00
0.5442492580D+00 0.1143456438D+01
0 1 1 0. 1.
0.1687144782D+00 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

0.6899906659D-01
0.3164239610D+00
0.7443082909D+00
0.1000000000D+01

S5

TOLINTEG
7 7 7 7 16
FMIXING
90
BROYDEN
0.05 50 5
TOLDEE
8
ENDSCF

S6

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
18
40
-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
0.4238
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

S7

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 0.2065
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-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
0.1881288540D+01 -0.1608541517D+00
0.5442492580D+00 0.1143456438D+01
0 1 1 0. 1.
0.1687144782D+00 0.1000000000D+01
0 3 1 0. 1.
0.8000000000D+00 0.1000000000D+01
99 0
ENDB
DFT
B3LYP
XLGRID
END
SCFDIR

0.6899906659D-01
0.3164239610D+00
0.7443082909D+00
0.1000000000D+01

S8

BIPOSIZE
10000000
EXCHSIZE
20000000
SHRINK
2 2
TOLINTEG
7 7 7 7 16
FMIXING
90
BROYDEN
0.05 50 5
TOLDEE
8
ENDSCF

S9

S6. Adopted Zirconium Basis-Set.

Zr_all_electron_dovesi_unpub
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
1743.6542
-0.00657
515.55964
-0.0586
176.18824
-0.1469
67.946738
0.2212
29.173149
0.6893
13.001228
0.2629
0 1 6 8. 1.
177.67018
0.00399
59.986876
-0.0365
24.185965
-0.3385
9.9783433
0.1865
4.3099261
0.9971
1.7492066
0.2468
0 1 3 8. 1.
3.8653
-1.595
1.739
-0.364
0.7875
4.9455
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

0.000918
0.00895
0.0557
0.219
0.4536
0.397
0.1064
-0.0124
-0.0757
0.0838
0.9961
1.2441
0.308
-0.1149
0.514
1.3848

S10