Supplementary Material
Large Scale Computational Screening of Metal-Organic Frameworks for
CH4/H2 Separation
Dong Wu, Cuicui Wang
State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical
Technology, Beijing 100029, China
Bei Liu
State Key Laboratory of Heavy Oil Processing, China University of Petroleum,
Beijing 102249, China
Dahuan Liu, Qingyuan Yang and Chongli Zhong
State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical
Technology, Beijing 100029, China
I. Structural properties of the 105 MOFs studied in this work
Table S1. Structural Properties of the 105 MOFs Studied in This Work
cell angle a
Sacc b
Vfree b
φb
pore size a
(degree)
(m2/g)
(cm3/g)
(%)
(nm)
a = b = c = 2.58320
α = β = γ = 90
3519.78
1.34
79.94
1.09/1.43
IRMOF-21
a = b = c = 2.57718
α = β = γ = 90
2851.50
0.99
77.76
1.64
03
IRMOF-31
a = b = c = 2.57465
α = β = γ = 90
3252.15
1.23
78.58
1.86
04
IRMOF-61
a = b = c = 2.58421
α = β = γ = 90
3023.30
1.18
77.23
0.91/1.45
05
IRMOF-71
a = b = c = 2.58280
α = β = γ = 90
3230.46
1.06
75.17
1.01
06
IRMOF-81
a = b = c = 3.00915
α = β = γ = 90
4315.03
1.86
83.82
1.25/1.71
07
IRMOF-91
α = β = γ = 90
3254.59
1.14
74.78
08
IRMOF-101
a = b = c = 3.42807
α = β = γ = 90
4926.13
2.66
87.60
09
IRMOF-111
a = b = 2.48217,
α = β = 90,
c = 5.67340
γ = 120
2716.52
0.91
69.74
10
IRMOF-121
a = b = c = 3.42807
α = β = γ = 90
5240.43
2.23
84.98
11
IRMOF-131
a = b = 2.48217,
α = β = 90,
c = 5.67340
γ = 120
2689.88
0.94
71.38
12
IRMOF-141
a = b = c = 3.43810
α = β = γ = 90
4812.17
2.30
86.00
MOF
name of MOF
unit cell (nm) a
01
IRMOF-11
02
ID
a =1.71470, b =
2.33222, c = 2.52552
S1
0.45/0.63/0.81/
1.07
1.67/2.02
0.35/0.38/0.47/
0.61/0.73/1.11
1.41/1.79
0.42/0.47/0.61/
0.70/1.14
1.47/2.01
13
IRMOF-151
a = b = c = 2.14594
α = β = γ = 90
5985.91
2.00
82.77
0.80
14
IRMOF-161
a = b = c = 2.14903
α = β = γ = 90
5974.01
4.46
91.48
2.33
15
IRMOF-182
a = b = c = 2.56135
α = β = γ = 90
2237.86
0.96
71.51
0.81/1.33
16
IRMOF-203
a = b = c = 2.91840
α = β = γ = 90
4482.21
1.91
83.87
1.40/1.73
17
PCN-64
a = b = 3.29680,
α = β = 90,
c = 8.07830
γ = 120
3862.26
1.39
77.84
0.50/0.92
18
PCN-6’5
a = b = c = 4.66360
α = β = γ = 90
5106.98
3.17
88.82
19
PCN-96
a = b = c = 2.54387
α = β = γ = 90
846.680
0.76
65.93
0.67/1.40
20
PCN-107
a = b = 1.88140,
α = β = 90,
c = 3.05800
γ = 120
2814.81
0.95
73.49
0.81
21
PCN-117
a = b = 1.87950,
α = β = 90,
c = 3.12800
γ = 120
2888.57
0.98
73.91
0.81
22
PCN-138
a = b = c = 2.87900
α = β = γ = 90
1002.83
0.46
54.79
0.35
23
PCN-149
a = b = 1.84530,
α = β = 90,
c = 7.69760
γ = 120
2106.62
0.81
67.73
1.845
24
PCN-6010
a = b = c = 4.28434
α = β = γ = 90
3663.47
1.40
78.97
25
PCN-6110
a = b = c = 4.27958
α = β = γ = 90
3687.69
1.41
79.03
26
PCN-6610
a = b = c = 4.9112
α = β = γ = 90
4891.40
1.99
81.96
27
PCN-6811
a = b = c = 5.91530
α = β = γ = 90
5705.24
3.04
87.86
28
MOP-1412
a = b = c = 2.96630
α = β = γ = 90
1701.53
0.76
72.12
0.50/1.38
29
MOP-1512
α = β = γ = 90
3667.32
1.18
76.79
1.38
30
MOP-1712
α = β = γ = 90
1437.45
0.65
62.52
1.38
31
MOP-2312
α = β = γ = 90
2899.44
1.08
73.95
1.88
32
MOP-2412
4665.09
2.02
83.72
33
UMCM-113
4583.29
2.30
85.39
34
UMCM-214
4579.08
2.22
85.27
35
MIL-47(V)15
α = β = γ = 90
1489.92
0.61
61.95
1.05
36
MIL-53(Cr) 16
α = β = γ = 90
1361.78
0.57
59.32
0.85
37
MIL-53(Al) 17
α = β = γ = 90
1408.92
0.60
58.86
0.85
38
MIL-10218
341.930
0.24
41.17
0.44
a = b = 3.12356,
c = 3.06170
a =4.06540, b =
3.99400, c = 2.89350
a =4.42890, b =
3.94900, c = 3.71760
a = b =3.83867,
α= γ =90,
c = 14.1831
β =120
a = b = 4.15262,
α = β =90,
c=1.74916
γ =120
a = b = 4.21589,
α = β =90,
c=5.25682
γ =120
a = 0.68180, b =
1.61430, c = 1.39390
a =1.6733, b = 1.3038,
c = 0.6812
a = 0.66085,
b=1.66750, c = 1.2813
a = b =1.26320,
α = β = 90,
c = 0.962200
γ =120
S2
1.52/2.14/
3.03
1.30/1.50/
1.70
1.30/1.50/
1.70
1.3/1.6/2.6
1.20/1.48/
2.32
0.60/0.92/
1.88
1.40/2.40
1.40/1.60/
2.40
39
CUK-119
40
CUK-219
41
Cu-BTC20
42
Cu-BDT21
43
Bio-MOF-1122
44
mesoMOF-123
45
MOF-HTB’5
46
MOF-224
47
a =1.81020, b =
α = γ =90,
1.27694, c = 1.09701
β =103.4
757.640
0.36
52.74
1.11
α = β = γ =90
165.950
0.30
47.24
0.88
α = β = γ =90
2006.26
0.81
71.94
0.50/0.90
α = β = γ =90
1875.87
0.80
69.27
1.36×2.23
α = β = γ =90
787.270
0.43
53.60
0.58
a = b = c = 4.96188
α = β = γ =90
5435.54
3.56
89.95
2.25×2.61
a = b = c = 5.29930
α = β = γ =90
5473.57
4.09
91.21
1.00/1.91
a = 0.67180, b =
α = γ =90,
1.54880, c =1.24300
β =102.83
980.460
0.47
57.89
0.50
MOF-425
a = b = c = 1.47280
α = β = γ =90
3160.27
1.12
78.82
1.40
48
MOF-1426
a = b = c = 2.69190
α = β = γ =90
2654.26
0.96
69.96
1.64
49
MOF-7427
a = b = 2.59322,
α = β =90,
c = 0.683650
γ =120
1205.35
0.53
65.51
0.55×1.03
50
MOF-11412
a =2.22410, b =
α = γ =90,
1.27030, c = 1.76540
β =126.36
696.870
0.43
53.00
0.52c
51
MOF-11612
a =1.37180, b =
α = γ =90,
2.03880, c = 0.939100
β =93.44
272.840
0.55
56.51
1.52
52
MOF-11712
a =1.00680, b =
α = γ =90,
1.84490, c = 1.45670
β =104.79
2533.12
0.78
66.18
0.52c
53
MOF-11812
α = β = γ =90
3640.44
1.23
75.51
1.51
54
MOF-11912
α = β = γ =90
1694.18
0.72
64.42
1.70
55
MOF-17728
4669.61
1.95
83.53
1.08/1.18
56
MOF-22212
α = β = γ = 90
1726.36
0.66
60.39
0.62c
57
MOF-50029
a = b = c = 3.55091
α = β = γ = 90
3213.03
1.55
79.87
58
MOF-50530
a = b =1.84826,
α = β =90,
c = 2.47130
γ =120
2216.31
0.73
68.59
0.83/1.01
59
MOF-60112
a = b =4.40047,
α= γ =90,
c = 1.22617
β =120
4553.14
1.54
79.24
1.52
60
MOF-60212
a = b =4.63352,
α = β =90,
c = 1.04693
γ =120
4203.55
1.59
78.51
1.52
61
MOF-60312
a =3.01790, b =
α = γ =90,
3.94020, c = 2.65080
β =120.93
2393.55
0.94
77.58
0.87
62
MOF-60412
a =2.41640, b =
α = γ =90,
1.76710, c = 1.01070
β =113.97
861.350
0.44
51.13
0.48c
63
ZIF-131
a =0.97405, b =
α = γ =90,
285.950
0.46
55.75
0.694
a =1.11223, b =
1.35606, c = 1.21518
a = b = c =2.63430
a =2.22490, b =
0.705280, c = 1.35747
a = b = 1.54355,
c = 2.27750
a =2.44260, b =
1.78490, c = 1.51400
a =1.00480, b =
1.82410, c = 2.68950
a = b =3.70720,
α = β =90,
c = 3.00333
γ =120
a = b =1.53277,
c = 2.43220
S3
0.52/1.04/1.30
/1.80
1.52660, c = 1.49360
a =0.967900, b =
64
ZIF-232
65
ZIF-332
66
ZIF-631
67
ZIF-831
68
ZIF-1032
69
ZIF-1131
70
ZIF-6032
71
ZIF-6732
72
ZIF-6832
73
ZIF-6932
74
ZIF-7032
75
ZIF-7132
76
ZIF-7833
77
ZIF-7933
78
ZIF-8033
79
ZIF-8133
80
Ni(bpy)[Ni(CN)4]34
81
Ni2(dhbdc)35
82
Zn7O2(pda)536
83
MOF-20537
84
38
β =98.62
α = β = γ =90
1760.97
0.70
65.64
0.69
α = β = γ =90
1909.83
0.77
67.84
0.600
a = b = c = 1.85150
α = β = γ = 90
2650.41
0.94
71.45
0.88
a = b = c = 1.69910
α = β = γ = 90
667.85
0.69
62.53
1.16
α = β = γ =90
2433.58
1.04
72.64
1.21
α = β = γ = 90
531.14
0.59
58.78
1.46
α = β = γ = 90
2186.99
0.99
70.82
0.94/0.72
a = b = c = 1.69589
α = β = γ = 90
686.94
0.70
62.27
1.16
a = b = 2.66407,
α = β =90,
c = 1.84882
γ = 120
1117.74
0.58
60.69
1.03/0.75
a = b = 2.60840,
α = β =90,
c = 1.94082
γ = 120
1083.41
0.57
57.41
0.780/0.44
a = b = 2.70111,
α = β =90,
c = 1.80208
γ = 120
2127.76
0.97
72.09
1.59/1.31
a = b = c =2.85539
α = β = γ =90
986.30
0.57
63.21
1.65
a = b = 2.61174,
α = β = 90,
c = 1.94910
γ = 120
887.660
0.54
55.38
0.71/0.38
a = b = 2.59263,
α = β = 90,
c = 1.96532
γ = 120
1028.64
0.54
56.87
0.75/0.40
a = b = 2.63070,
α = β =90,
c = 1.93610
γ = 120
1186.17
0.59
63.70
0.98/1.32
a = b = 2.59929,
α = β = 90,
c = 1.96997
γ = 120
916.210
0.49
56.65
0.740/0.39
1377.83
0.54
57.48
0.50
1219.56
0.54
64.60
1.10
α = β = γ = 90
4093.04
2.04
83.83
1.73
α = β = γ = 90
4627.67
2.23
85.46
2.25c
α = β = γ = 90
1953.27
0.75
67.96
0.58/0.73c
α = β = γ = 90
2670.49
0.95
70.01
0.58/0.81c
1022.81
0.46
52.13
2.41140, c = 2.44500
a = b = 1.89701,
c = 1.67400
a = b = 2.70608,
c = 1.94060
a = b = c = 2.87595
a = b =2.72448,
c = 1.92254
a = b = 0.730000,
c = 1.12000
α = β = γ = 90
a = b = 2.57856,
α = β = 90,
c = 0.677010
γ = 120
a = b = 3.46957,
c = 4.10328
a = b = c = 3.0353
a = 2.16546,
Zn(L10)2
b = 3.09010, c =
0.929450
a = 2.16546,
85
38
Zn(L9)2
b = 3.09010, c =
0.929450
a = 1.40080,
86
Zn(L3)(L9)2
39
b = 1.15210, c =
1.57010
α = γ = 90,
β = 96.6790
S4
0.48/0.53/
0.58c
a = 1.12038,
87
Zn(L3)(L10)239
b = 1.39750, c =
α = β = γ = 90
3104.50
1.11
74.45
α = β = γ = 90
1343.82
0.56
55.82
3288.02
1.33
77.64
1.24c
α = β = γ = 90
1510.62
0.64
59.92
0.50/0.88c
α = β = γ = 90
4048.45
1.59
78.08
1.09c
3574.99
1.45
78.90
1.27c
1800.08
0.68
60.49
722.010
0.41
50.71
1.03×0.60
446.71
0.32
45.5
0.82×0.60
α = β = γ = 90
745.12
0.32
55.80
0.73/1.22
α = β = γ = 90
284.63
0.35
48.82
0.70
683.20
0.42
47.36
1.00
1924.36
0.68
62.19
1.37
896.03
0.50
54.30
0.50/1.06
1984.11
0.77
68.17
0.69c
α = β = γ = 90
4003.27
1.45
79.04
0.951
α = β = γ = 90
3832.14
1.41
67.41
0.80
2127.68
0.74
63.53
0.715/1.083
296.42
0.48
59.29
1.00
1.11c
1.58480
a = 1.56540,
88
Zn(L4)(L9)239
b = 1.59467, c =
1.16268
a = 1.17110,
89
39
Zn(L4)(L10)2
b = 1.56181, c =
1.60362
α = γ = 90,
β = 90.2050
0.46/0.55/
0.70c
a = 1.56740,
90
39
Zn(L5)(L9)2
b = 1.81180, c =
1.15857
a = 1.01617,
91
39
Zn(L6)(L10)2
b = 1.64510, c =
2.23130
92
Zn(L5)(L10)239
93
Zn(L6)(L9)239
94
CPL-540
95
CPL-240
96
FMOF-141
97
Ni(pyz)[Ni(CN)4]34
98
Ni(cyclam)(bpydc)42
99
Ni(dpac)[Ni(CN)4]34
100
Zn3(bpdc)3(bpy) 43
101
Zn3(BDT)3
b = 1.5648, c = 1.8163
β = 93.202
b = 1.5668, c = 2.2389
a =0.471100, b =
α= γ =90,
β =96.01
a =0.4702,
α = γ = 90,
b = 2.7933, c = 1.1023
β = 96.34
c = 3.9175
a = b =0.7150
c = 0.7000
a = b =2.6019
α = β = 90,
c = 1.13009
γ = 120
a = b =0.7300
c = 1.3700
α = γ = 90,
b = 1.8041, c = 2.4803
β = 90.005
b = 1.1736, c = 1.3619
44
103
Zn2(tmbdc)2(bpy) 45
104
44
Co3(D2-Htcppda)2
α = β = γ = 90
a =1.4608,
a =1.15713
17
α = β = γ = 90
3.18580, c = 1.10020
a = b =1.34273
Zn4O(D2-tcppda)1.5
105
α = γ = 90,
a = 2.2898,
102
UiO-6646
a =1.16151,
a = b = c = 3.83364
a = b =1.08773
c = 1.3964
a =1.3703
b = 1.4120, c = 1.5810
a = b = c = 2.07004
0.53/0.56/0.6/
0.62c
α =92.869，
β =114.443，
γ = 107.988
α = 105.069，
β =103.395，
γ = 109.052
α = β = γ = 90
S5
a
Obtained from the XRD crystal data.1-46
b
The accessible surface area (Sacc) and the total free volume (Vfree) of each MOF material were estimated using the
“Atoms Volume & Surfaces” calculation within the Materials Studio package,47 The porosity was obtained from
the ratio of free volume Vfree to the total volume per unit cell. The accessible surface area (Sacc) was calculated by
a probe molecule with diameter equal to the kinetic diameter of N2 (0.368 nm), while a probe size of 0.0 nm was
applied to determine the absolute amount of volume not occupied by the framework atoms.
c
The pore sizes of these MOFs were calculated in this work using the method of Bhattacharya and Gubbins.48
II. Force field parameters
Table S2. Force Field Parameters for the MOFs and Adsorbates
Atoms
a
H2_H
CH4
C
O
H
N
F
Cl
S
I
Br
σ (nm)
0.272
0.373
0.347
0.303
0.285
0.326
0.3090
0.3520
0.3590
0.370
0.352
/kB (K)
10.00
148.0
47.86
48.16
7.650
38.95
36.48
142.6
173.1
256.7
186.2
Atoms
Al
Fe
Zn
Cua
Coa
Nia
Va
Cra
Aga
Zra
σ (nm)
0.391
0.404
0.404
0.311
0.256
0.252
0.280
0.269
0.281
0.278
/kB (K)
156.00
27.680
27.68
2.516
7.045
7.549
8.050
7.549
18.12
34.72
Taken from the UFF force field49 (they are missed in the Dreiding force field).
Literature Cited
1
Eddaoudi M, Kim J, Rosi N, Vodak D, Wachter J, O’Keeffe M, Yaghi OM. Systematic design of pore size
and functionality in isoreticular MOFs and their application in methane storage. Science. 2002; 295: 469-472.
2
Rowsell JL, Millward AR, Park KS, Yaghi OM. Hydrogen sorption in functionalized metal-organic
frameworks. J Am Chem Soc. 2004; 126: 5666-5667.
3
Rowsell JL, Yaghi OM. Effects of functionalization, catenation, and variation of the metal oxide and organic
linking units on the low-pressure hydrogen adsorption properties of metal-organic frameworks. J Am Chem
Soc. 2006; 128: 1304-1315.
4
Sun DF, Ma SQ, Ke YX, Collins DJ, Zhou HC. An interweaving MOF with high hydrogen uptake. J Am
Chem Soc. 2006; 128: 3896-3897.
5
Ma SQ, Sun DF, Ambrogio M, Fillinger JA, Parkin S, Zhou HC. Framework-catenation isomerism in
metal-organic frameworks and its impact on hydrogen uptake. J Am Chem Soc. 2007; 129: 1858-1859.
6
Ma SQ, Zhou HC. A metal-organic framework with entatic metal centers exhibiting high gas adsorption
affinity. J Am Chem Soc. 2006; 128: 11734-11735.
S6
7
Wang XS, Ma SQ, Rauch K, Simmons JM, Yuan DQ, Wang XP, Yildirim T, Cole WC, López JJ, Meijere AD,
Zhou HC. Metal-Organic frameworks based on double-bond-coupled di-isophthalate linkers with high
hydrogen and methane uptakes. Chem Mater. 2008; 20: 3145-3152.
8
Ma SQ, Wang XS, Collier CD, Manis ES, Zhou HC. Ultramicroporous metal-organic framework based on
9,10-anthracenedicarboxylate for selective gas adsorption. Inorg Chem. 2007; 46: 8499-8501.
9
Ma SQ, Sun DF, Simmons JM, Collier CD, Yuan DQ, Zhou HC. Metal-organic framework from an
anthracene derivative containing nanoscopic cages exhibiting high methane uptake. J Am Chem Soc. 2008;
130: 1012-1016.
10 Zhao D,Yuan DQ, Sun DF, Zhou HC. Stabilization of metal-organic frameworks with high surface areas by
the incorporation of mesocavities with microwindows. J Am Chem Soc. 2009; 131: 9186-9188.
11 Yuan DQ, Zhao D, Sun DF, Zhou HC. An isoreticular series of metal-organic frameworks with dendritic
hexacarboxylate ligands and exceptionally high gas-uptake capacity. Angew Chem Int Ed. 2010; 49:
5357-5361.
12 Furukawa H, Kim J, Ockwig NW, O’Keeffe M, Yaghi OM. Control of vertex geometry, structure
dimensionality, functionality, and pore metrics in the reticular synthesis of crystalline metal-organic
frameworks and polyhedra. J Am Chem Soc. 2008; 130: 11650-11661.
13
Koh K, Wong-Foy AG, Matzger AJ. A crystalline mesoporous coordination copolymer with high
microporosity. Angew Chem Int Ed. 2008; 47: 677-680.
14
Koh K, Wong-Foy AG, Matzger AJ. A Porous coordination copolymer with over 5000 m2/g BET surface
area. J Am Chem Soc. 2009; 131: 4184-4185.
15 Barthelet K, Marrot J, Riou D, Férey G. A breathing hybrid organic- inorganic solid with very large pores and
high magnetic vharacteristics. Angew Chem Int Ed. 2002; 41: 281-284.
16 Serre C, Millange F, Thouvenot C, Noguès M, Marsolier G, Louër D, Férey G. Very large breathing effect in
the first nanoporous chromium(III)-based solids: MIL-53 or
CrIII (OH) ·{O2C-C6H4-CO2}·{HO2C-C6H4-CO2H}x ·H2Oy. J Am Chem Soc. 2002; 124: 13519-13526.
17 Loiseau T, Serre C, Huguenard C, Fink G, Taulelle F, Henry M, Bataille T, Férey G. A rationale for the large
breathing of the porous aluminum terephthalate (MIL-53) upon hydration. Chem Eur J. 2004; 10: 1373
-1382.
18 Surblé S, Millange F, Serre C, Düren T, Latroche M, Bourrelly S, Llewellyn PL, Férey G. Synthesis of
MIL-102, a chromium carboxylate metal-organic framework, with gas sorption analysis. J Am Chem Soc.
S7
2006; 128: 14889-14896.
19 Humphrey SM, Chang JS, Jhung SH, Yoon JW, Wood PT. Porous cobalt(II)-organic frameworks with
corrugated walls: structurally robust gas-sorption materials. Angew Chem Int Ed. 2007; 46: 272-275.
20 Chui SS, Lo SM, Charmant JP, Orpen AG, Williams ID. A chemically functionalizable nanoporous material
[Cu3(TMA)2(H2O)3]n . Science. 1999; 283: 1148-1150.
21 Dincǎ M, Yu AF, Long JR. Microporous metal-organic frameworks incorporating1,4-benzeneditetrazolate:
syntheses, structures, and hydrogen storage properties. J Am Chem Soc. 2006; 128: 8904-8913.
22 An J, Geib SJ, Rosi NL. High and selective CO2 uptake in a cobalt adeninate metal-organic framework
exhibiting pyrimidine- and amino-decorated pores. J Am Chem Soc. 2010; 132: 38-39.
23 Wang XS, Ma SQ, Sun DF, Parkin S, Zhou HC. A mesoporous metal-organic framework with permanent
porosity. J Am Chem Soc. 2006; 128: 16474-16475.
24 Li HL, Eddaoudi M, Groy TL,Yaghi OM. Establishing microporosity in open metal-organic frameworks: gas
sorption isotherms for Zn(BDC) (BDC = 1,4-Benzenedicarboxylate). J Am Chem Soc. 1998; 120: 8571-8572.
25 Yaghi OM, Davis CE, Li GM, Li HL. Selective guest binding by tailored channels in a 3-D porous
zinc(II)-benzenetricarboxylate network. J Am Chem Soc. 1997; 119: 2861-2868.
26 Chen BL, Eddaoudi M, Hyde ST, O’Keeffe M, Yaghi OM. Interwoven metal-organic framework on a
periodic minimal surface with extra-large pores. Science. 2001; 291: 1021-1023.
27 Rosi NL, Kim J, Eddaoudi M, Chen BL, O’Keeffe M, Yaghi OM. Rod packings and metal-Organic
frameworks constructed from rod-shaped secondary building units. J Am Chem Soc. 2005; 127: 1504-1518.
28 Chae HK, Siberio-Pérez DY, Kim J, Go Y, Eddaoudi M, Matzger AJ, O’Keeffe M, Yaghi OM. A route to high
surface area, porosity and inclusion of large molecules in crystals. Nature. 2004; 427: 523-527.
29 Sudik AC, Côté AP, Wong-Foy AG, O’Keeffe M, Yaghi OM. A metal-organic framework with a hierarchical
system of pores and tetrahedral building blocks. Angew Chem Int Ed. 2006; 45: 2528-2533.
30 Chen BL, Ockwig NW, Millward AR, Contreras DS, Yaghi OM. High H2 adsorption in a microporous metal
–organic framework with open metal sites. Angew Chem Int Ed. 2005; 44: 4745-4749.
31 Park KS, Ni Z, Côté AP, Choi JY, Huang R, Uribe-Romo FJ, Chae HK, O’Keeffe M, Yaghi OM. Exceptional
chemical and thermal stability of zeolitic imidazolate frameworks. Proc Natl Acad Sci. USA, 2006; 103:
10186-10191.
32 Banerjee R, Phan A, Wang B, Knobler C, Furukawa H, O’Keeffe M, Yaghi OM. High-throughput synthesis
of zeolitic imidazolate frameworks and application to CO2 capture. Science. 2008; 319: 939-943.
S8
33 Banerjee R, Furukawa H, Britt D, Knobler C, O’Keeffe M, Yaghi OM. Control of pore size and functionality
in isoreticular zeolitic imidazolate frameworks and their carbon dioxide selective capture properties. J Am
Chem Soc. 2009; 131: 3875-3877.
34 Culp JT, Natesakhawat S, Smith MR, Bittner E, Matranga C, Bockrath B. Hydrogen storage properties of
rigid three-dimensional hofmann clathrate derivatives:the effects of pore size. J Phys Chem C. 2008; 112:
7079-7083.
35 Dietzel PD, Panella B, Hirscher M, Blom R, Fjellvåg H. Hydrogen adsorption in a nickel based coordination
polymer with open metal sites in the cylindrical cavities of the desolvated framework. Chem Commun. 2006;
959-961.
36 Fang QR, Zhu GS, Xue M, Zhang QL, Sun JY, Guo XD, Qiu SL, Xu ST, Wang P, Wang DJ, Wei Y.
Microporous metal–organic framework constructed from heptanuclear zinc carboxylate secondary building
units. Chem Eur J. 2006; 12: 3754-3758.
37 Furukawa H, Ko N, Go YB, Aratani N, Choi SB, Choi E, Yazaydin AÖ, Snurr RQ, O’Keeffe M, Kim J,
Yaghi OM. Ultrahigh porosity in metal-organic frameworks. Science. 2010; 329: 424-428.
38 Farha OK, Hupp JT. Rational design, synthesis, purification, and activation of metal-organic framework
materials. Acc Chem Res. 2010; 43: 1166-1175.
39 Farha OK, Malliakas CD, Kanatzidis MG, Hupp JT. Control over catenation in metal-organic frameworks via
rational design of the organic building block. J Am Chem Soc. 2010; 132: 950-952.
40 Kondo M, Okubo T, Asami A, Noro S, Yoshitomi T, Kitagawa S, Ishii T, Matsuzaka H, Seki K. Rational
synthesis of stable channel-like cavities with methane gas adsorption properties: [{Cu2(pzdc)2(L)}n] (pzdc =
pyrazine-2,3-dicarboxylate; L= a pillar ligand). Angew Chem Int Ed. 1999; 38: 140-143.
41 Yang C, Wang XP, Omary MA. Fluorous metal-organic frameworks for high-density gas adsorption. J Am
Chem Soc. 2007; 129: 15454-15455.
42 Lee EY, Suh MP. A robust porous material constructed of linear coordination polymer chains: reversible
single-crystal to single-crystal transformations upon dehydration and rehydration. Angew Chem Int Ed. 2004;
43: 2798-2801.
43 Lee JY, Pan L, Kelly SP, Jagiello J, Emge TJ, Li J. Achieving high density of adsorbed hydrogen in
microporous metal organic frameworks. Adv Mater. 2005; 17: 2703-2706.
44 Sun DF, Collins DJ, Ke YX, Zuo JL, Zhou HC. Construction of open metal-organic frameworks based on
predesigned carboxylate isomers: from achiral to chiral nets. Chem Eur J. 2006; 12: 3768 -3776.
S9
45 Chun H, Dybtsev DN, Kim H, Kim K. Synthesis, X-ray crystal structures, and gas sorption properties of
pillared square grid nets based on paddle-wheel motifs: implications for hydrogen storage in porous materials.
Chem Eur J. 2005; 11: 3521-3529.
46 Cavka JH, Jakobsen S, Olsbye U, Guillou N, Lamberti C, Bordiga S, Lillerud KP. A new zirconium inorganic
building brick forming metal organic frameworks with exceptional stability. J Am Chem Soc. 2008; 130:
13850-13851.
47 Accelrys, Inc., Materials Studio, 3.0 V; Accelrys Inc: San Diego, CA, 2003.
48 Bhattacharya S, Gubbins KE. Fast method for computing pore size distributions of model materials.
Langmuir. 2006; 22: 7726-7731.
49 Rappé AK, Casewit CJ, Colwell KS, Goddard III WA, Skiff WM. UFF, a full periodic table force field for
molecular mechanics and molecular dynamics simulations. J Am Chem Soc. 1992; 114: 10024-10035.
S10