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then classified and discussed in terms of different Zr-based secondary building units and organic ligands.
DOI: 10.1039/c5cs00837a
Finally, applications of Zr-MOFs in catalysis, molecule adsorption and separation, drug delivery, and
fluorescence sensing, and as porous carriers are highlighted. Such a review based on a specific type of MOF
www.rsc.org/chemsocrev
is expected to provide guidance for the in-depth investigation of MOFs towards practical applications.
1. Introduction
As an emerging class of highly ordered crystalline porous materials,
metalorganic frameworks (MOFs) with various potential
Beijing Key Laboratory for Green Catalysis and Separation and Department of
Chemistry and Chemical Engineering, College of Environmental and Energy
Engineering, Beijing University of Technology, Beijing 100124, P. R. China.
E-mail: jrli@bjut.edu.cn
b
Department of Chemistry, Texas A&M University, College Station,
Texas 77842-3012, USA
Yan Bai
Yibo Dou
Review Article
uniform covalent bonds, MOFs are constructed by the coordination bonding of metal ions and organic ligands. The poor stability
of MOFs derived from the reversible nature of coordination bonds
is commonly regarded as the major drawback for their practical
applications in most research fields.610
Much eort has been devoted to constructing MOFs with
improved stability.1122 Among them, post-treatments or postsynthetic modifications have proven effective.2326 For example,
IRMOF-1 (MOF-5) showed enhanced stability against moisture
after thermal modification and formation of an amorphous
carbon coating on the MOF particle surfaces, or after coating
the MOF surface with a thin hydrophobic polydimethysiloxane
(PDMS) layer via the thermal vapor deposition technique.25,26
However, the improved stability of the MOFs after posttreatment is always at the price of reduction of their micropore
surface areas or functionality. In addition, most experimental
steps or physical techniques in post-treatments are labor and
Lin-Hua Xie
William Rutledge
Review Article
Modulated synthesis
Review Article
Table 1
Zr-MOF
UiO-66
UiO-67
UiO-68
NU-1000
NU-1100
NU-1101
NU-1102
NU-1103
NU-1104
MOF-801
MOF-802
MOF-804
MOF-805
MOF-806
MOF-808
MOF-812
MOF-841
MOF-525
MOF-535
MOF-545
MOF-867
PCN-56
PCN-57
PCN-58
PCN-59
PCN-94
PCN-221
PCN-222
PCN-223
PCN-224
PCN-225
PCN-228
PCN-229
PCN-230
PCN-521
PCN-700
PCN-777
DUT-51
DUT-52
DUT-84
DUT-67
DUT-68
DUT-69
BUT-10
BUT-11
BUT-30
MIL-140A
MIL-140B
MIL-140C
MIL-140D
MIL-153
MIL-154
MIL-163
CPM-99
UMCM-309a
Zr-TTMC
Zr-BTB
Zr-ABDC
PIZOF
BPV-MOF
mBPV-MOF
mPT-MOF
ZrBTBP
UPG-1
UiO-66(AN)
UiO-66-1,4-Naph
Zr-ADC
Zr-DTDC
Zr-TCPS
Zr-BTDC
Liganda
2
BDC
BPDC2
TPDC2
TBAPy4
PTBA4
Py-XP4
Por-PP4
Py-PTP4
Por-PTP4
FUM2
PZDC2
BDC-2OH2
NDC-2OH2
BPDC-2OH2
BTC3
MTB4
MTB4
TCPP4
XF4
TCPP4
BPYDC2
TPDC-2CH32
TPDC-4CH32
TPDC-2CH2N32
TPDC-4CH2N32
ETTC4
TCPP4
TCPP4
TCPP4
TCPP4
TCPP4
TCP-14
TCP-24
TCP-34
MTBC4
Me2BPDC2
TATB3
DTTDC2
2,6-NDC2
2,6-NDC2
TDC2
TDC2
TDC2
FDCA2
DTDAO2
EDDB2
BDC2
2,6-NDC2
BPDC2
Cl2ABDC2
pgal3
Hgal3, Hsal
TzGal6
TCBPP4
BTB3
TTMC2
BTB3
ABDC2
PEDC2
BPV2
BPHV2, BPV2
PT2, TPHN2
H3BTBP3
H4TTBMP2
AN2
1,4-NDC2
ADC2
DTDC2
TCPS4
BTDC2-
Zr cluster/core
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-OH)8
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)8
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr8(m4-O)6
Zr6(m3-OH)8
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-OH)8
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)6(m3-OH)2
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)8
Zr6(m3-O)6(m3-OH)2
Zr6(m3-O)6(m3-OH)2
Zr6(m3-O)4(m3-OH)42
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr(m3-O)3O4
Zr(m3-O)3O4
Zr(m3-O)3O4
Zr(m3-O)3O4
ZrO8
ZrO8
ZrO8
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
ZrO6
ZrO6
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Topology
fcu, 12-connected
fcu, 12-connected
fcu, 12-connected
csq, (4,8)-connected
ftw, (4,12)-connected
ftw, (4,12)-connected
ftw, (4,12)-connected
ftw, (4,12)-connected
ftw, (4,12)-connected
fcu, 12-connected
bct, 10-connected,
fcu, 12-connected
fcu, 12-connected
fcu, 12-connected
spn, (3,6)-connected
ith, (4,12)-connected
flu, (4,8)-connected
ftw, (4,12)-connected
ftw, (4,12)-connected
csq, (4,8)-connected
fcu, 12-connected
fcu, 12-connected
fcu, 12-connected
fcu, 12-connected
fcu, 12-connected
ftw, (4,12)-connected
ftw, (4,12)-connected
csq, (4,8)-connected
shp, (4,12)-connected
she, (4,6)-connected
sqc, (4,8)-connected
ftw, (4,12)-connected
ftw, (4,12)-connected
ftw, (4,12)-connected
flu, (4,8)-connected
bcu, 8-connected
spn, (3,6)-connected
reo, 8-connected
fcu, 12-connected
(4,4)IIb, 6-connected
reo, 8-connected
8-connected
bct, 10-connected
fcu, 12-connected
fcu, 12-connected
fcu, 12-connected
ftw, (4,12)-connected
kgd, (3,6)-connected
fcu, 12-connected
kgd, (3,6)-connectedc
fcu, 12-connected
fcu, 12-connected
fcu, 12-connected
fcu, 12-connected
fcu, 12-connected
fcu, 12-connected
fcu, 12-connected
fcu, 12-connected
fcu, 12-connected
flu, (4,8)-connected
fcu, 12-connected
1187
3000b
4170b
2320
4020
4422
4712
5646
5290
990
o20
1145
1230
2220
2060
2335
1390
2620
1120
2260
2646
3741
2572
2185
1279
3377
1936
2223
1600
2600
1902
4510
4619
4455
3411
1807
2008
2335
1399
637
1064
891
560
1848
1310
3940.6
415
460
670
701
90170
1030
810
705
613
3000
2080
373
1207
3834
o10
410
627
2776
1200
1039
2207
Ref.
27
27
27
121
83
63
63
63
63
155
155
155
155
155
155
155
155
159
159
159
282 and 154
97
97
97
97
163
135
144
143
146
145
65
65
65
34
89
147
49
149
149
50
50
50
205
205
214
139
139
139
139
141
141
142
161
51
54
157
72
73
100
100
100
136
137
150
148
151
152
36
153
Zr-MOF
Zr-BTBA
Zr-PTBA
MMPF-6
Zr-AP-1
Zr-AP-2
Zr-AP-3
Review Article
(continued)
Liganda
4
BTBA
PTBA4
TCPP4
AP-CH32
AP2
AP2
Zr cluster/core
Topology
Ref.
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)4(m3-OH)4
Zr6(m3-O)8
Zr6(m3-OH)8
Zr6(m3-OH)8
Zr6(m3-OH)8
ftw, (4,12)-connected
ftw, (4,12)-connected
csq, (4,8)-connected
bcu, 8-connected
dia, 4-connected
bcu, 8-connected
4342
4116
2100
162
162
160
156
156
156
a
Ligands (see their structures in Scheme 1) are abbreviated as: BDC2 = terephthalate; BPDC2 = biphenyl-4,4 0 -dicarboxylate; TPDC2 = [1,1 0 :4 0 ,100 terphenyl]-4,400 -dicarboxylate; TBAPy4 = 1,3,6,8-tetrakis(p-benzoate)pyrene; Py-XP4 = 4 0 ,4 0 0 0 ,4 0 0 0 0 0 ,4 0 0 0 0 0 0 0 -(pyrene-1,3,6,8-tetrayl) tetrakis(2 0 ,5 0 Por-PP4
=
meso-tetrakis-(4-carboxylatebiphenyl)-porphyrin;
PTBA4
=
4-[2-[3,6,8-tris[2-(4dimethyl-[1,1 0 -biphenyl]-4-carboxylate);
carboxylatephenyl)-ethynyl]-pyren-1-yl]ethynyl]-benzoate; Py-PTP4 = 4,4 0 ,400 ,4 0 0 0 -((pyrene-1,3,6,8-tetrayltetrakis(benzene-4,1-diyl))tetrakis(ethyne4
2
2
= meso-tetrakis-(4-((phenyl)ethynyl)benzoate)porphyrin; FUM
= fumarate; PZDC
= 1H-pyrazole-3,52,1-diyl))tetrabenzoate; Por-PTP
dicarboxylate; BTC3 = benzene-1,3,5-tricarboxylate; MTB4 = 4,4 0 ,400 ,4 0 0 0 -methanetetrayltetrabenzoate; TCPP4 = meso-tetrakis(4-carboxylatephenyl)porphyrin; XF4 = 4,4 0 -((1E,10 E)-(2,5-bis((4-carboxylatephenyl)ethynyl)-1,4-phenylene)bis(ethene-2,1-diyl))dibenzoate; BPYDC2 = 2,20 -bipyridine5,5 0 -dicarboxylate; ABDC2 = 4,4-azobenzenedicarboxylate; TCBPP4 = tetrakis(4-carboxylatebiphenyl)porphyrin; ETTC4 = 40 ,400 ,40 0 0 ,40 0 0 0 -(ethene-1,1,2,2tetrayl)tetrabiphenyl-4-carboxylate; TDC2 = 2,5-thiophenedicarboxylate; MTBC4 = 4 0 ,400 ,40 0 0 ,4 0 0 0 0 -methanetetrayltetrabiphenyl-4-carboxylate; TATB3 =
4,4 0 ,400 -s-triazine-2,4,6-triyl-tribenzoate; DTTDC2 = dithieno[3,2-b;2 0 ,30 -d]-thiophene-2,6-dicarboxylate; 2,6-NDC2 = naphthalene-2,6-dicarboxylate;
FDCA2 = 9-fluorenone-2,7-dicarboxylate; DTDAO2 = dibenzo[b,d]thiophene-3,7-dicarboxylate 5,5-dioxide; EDDB2 = 4,4 0 -(ethyne-1,2-diyl)dibenzoate;
H3pgal = pyrogallol; H4gal = gallic acid; H2sal = salicylic acid; H6TzGal = 5,5 0 -(1,2,4,5-tetrazine-3,6-diyl)bis(benzene-1,2,3-triol); BTB3 = 5 0 -(4carboxyphenyl)[1,1 0 :300 ,100 -terphenyl]-4,400 -dicarboxylate; TTMC2 = (2E,4E)-hexa-2,4-dienedioate; ABDC2 = azobenzenedicarboxylate; H6BTBP =
1,3,5-tris(4-phosphonophenyl)benzene; H6TTBMP = 2,4,6-tris(4-(phosphonomethyl)phenyl)-1,3,5-triazine; PEDC2 = 4,4 0 -(1,4-phenylenebis(ethyne-2,1-diyl))dibenzoate; BPV2 = 5,5 0 -bis(carboxylateethenyl)-2,2 0 -bipyridine; BPHV2 = 4,4 0 -bis(carboxylateethenyl)-1,1 0 -biphenyl; TPHN2 =
4,4 0 -bis(carboxylatephenyl)-2-nitro-1,1 0 -biphenyl; ADC2 = 9,10-anthacenyl bis(benzoate); DTDC2 = 3,4-dimethylthieno[2,3-b]thiophene-2,5dicarboxylate; TCPS4 = tetrakis(4-carboxyphenyl) silane; BTBA4 = 4,4 0 ,400 ,4 0 0 0 -(biphenyl-3,3 0 ,5,5 0 -tetrayltetrakis(ethyne-2,1-diyl))tetrabenzoate;
AP2 = 1,6-adipate. b Langmuir surface area. c The structure of Zr-BTB is constructed from two-dimensional (2D) - three-dimensional (3D)
interpenetration based on a 3,6-connected kgd net.
Review Article
Isoreticular expansion
Fig. 2 Schematic representation of the modulated synthesis of Zr6(m3O)4(m3-OH)4(TTMC)6 (right) starting from the precursor Zr6(m3-O)4(m3OH)4(OMc)12, in which the OMc ligands were replaced by TTMC2 (left).
Reprinted with permission from ref. 54. Copyright 2010 The Royal Society
of Chemistry.
through inserting a triple bond in the arms of original tetratopic ligands Py-XP4 and Por-PP4, respectively. The geometric
surface areas of NU-1101 to NU-1104 calculated by using a
rolling probe method independent of BET theory64 are 4422,
4712, 5646, and 5290 m2 g1, respectively. It is worth mentioning that NU-1103 with Py-PTP4 as the linker has a pore volume
of 2.91 cm3 g1 and a BET surface area of 6650 m2 g1, being
the highest value reported to date for Zr-MOFs. Such high
surface areas render them attractive for energy gas storage,
such as H2 and CH4. Similarly, Liu et al. inserted a benzene
ring, and one and two triple-bond spacers in the arms of the
ligand to synthesize a series of extended porphyrinic linkers,
H4TCP-1, H4TCP-2, and H4TCP-3.65 Using them, a series of
Zr6(m3-O)4(m3-OH)4(TCP)4 from PCN-228 to -230 were obtained,
which have BET surface areas of 4510, 4619, and 4455 m2 g1,
and pore sizes of 25, 28, and 38 , respectively.
Note that although the surface area of MOFs can be increased
with the extension of the ligand length, the framework stability is
usually inversely correlated. Some MOFs synthesized by isoreticular
expansion with increased surface areas became unstable.6670
For example, the Langmuir surface areas of UiO-66 and -67 are
1187 and 3000 m2 g1, respectively. However, the stability
became worse for UiO-67.29
Another phenomenon often encountered in isoreticular
expansion is network interpenetration, especially when using
a long ligand with small steric hindrance.71 Interpenetration of
networks always leads to a large reduction of surface area and
pore volume of the MOFs, which is not favorable for some
applications, such as gas storage, separation and catalysis
where large molecules are involved. For example, Peter Behrenss
group synthesized three Zr-MOFs with three dierent ligands in
length. Among them, Zr-FUM was isostructural to UiO-66 with a
BET surface area of 856 m2 g1.48 Due to the short length of the
FUM2 ligand, it is not surprising that the surface area is smaller
than that of UiO-66 (1069 m2 g1). Later, they reported another
isostructural Zr-MOF, Zr6(m3-O)4(m3-OH)4(ABDC)6 (Zr-ABDC), with
a high surface area of 3000 m2 g1 and a large pore volume of
1.41 cm3 g1.72 With an even more elongated triphenylethynyl
dicarboxylate ligand PEDC-2OMe2, Zr6(m3-O)4(m3-OH)4(PEDC2OMe)4 (PIZOF-2) with a 2-fold interpenetrated structure of
the same topology was obtained.73 As a result, PIZOF-2 showed
Review Article
Fig. 3 Tetratopic organic linkers of Py-XP4, Por-PP4, Py-PTP4, and Por-PTP4 used for constructing NU-11011104 (top). The increasing dimensions
of the organic linkers result in the isoreticular expansion of the MOF structures, with surface areas of 4422, 4712, 5646, and 5290 m2 g1, respectively
(bottom). Reprinted with permission from ref. 63. Copyright 2015 American Chemical Society.
Topology-guided design
Review Article
Postsynthetic functionalization
Similar to conventional linker pre-functionalization, the functional groups of organic linkers and metal clusters in Zr-MOFs
are also tailorable based on postsynthetic functionalization. It
has been proved that the postsynthetic method is a versatile
tool to prepare topologically identical Zr-MOFs with diverse
functionalities and uncompromised structural stability.90,91
Covalent modification is the most common route of postsynthetic functionalization that endows MOFs with tailor-made
internal surfaces to meet the requirements for specific applications.9296 Jiang et al. reported the preparation and covalent
modifications of a series of highly stable isoreticular Zr-MOFs,
Zr3O2(OH)2(TPDC-R)3 (PCN-56, R = 2CH3, PCN-57, R = 4CH3;
PCN-58, R = 2CH2N3, and PCN-59, R = 4CH2N3).97 In PCN-58
and -59 the accessible and reactive azide groups enable the
obtained MOFs to undergo a quantitative click reaction98 with
alkynes to form various triazole groups containing substituents
Fig. 6 Schematic representation of the click reaction for the pore surface
engineering of PCN-5859 with precise control over the composition,
density, and functionality by two steps. Reprinted with permission from
ref. 97. Copyright 2012 American Chemical Society.
on their pore surfaces (Fig. 6). It was revealed that the loading
of azide groups can be accurately tuned by varying the ratio of
ligands with and without azide groups during synthesis. Thus,
a variety of functional groups were anchored onto the pore
walls of obtained MOFs with precise control over loading,
density, and functionality. Therefore, the resulting materials
showed tunable CO2 selective adsorption ability over N2, being
potentially useful in CO2 capture.
Besides covalent modification, coordination modification of
ligands in postsynthetic metalation (PSM) was also adopted.
Toyao et al. reported the coordination modification in free
chelating sites of 2,2 0 -bipyridine in Zr6(m3-O)4(m3-OH)4(BPYDC)6
(Zr-MOF-BPYDC) with CuBr2.99 It was found that after loading
B3.3 wt% of CuBr2 to the MOF, 20.6% of BPYDC units could be
metalated with Cu(II). Another typical example was reported by
Manna et al. In their work, a series of bipyridyl- and phenanthrylbased Zr-MOFs, Zr6(m3-O)4(m3-OH)4(BPHV)6 (BPHV-MOF), Zr6(m3-O)4(m3-OH)4(BPHV)4(BPV)2 (mBPV-MOF), and Zr6(m3-O)4(m3-OH)4(TPHN)4(PT)2 (mPT-MOF), were prepared.100 Treatment of these
Zr-MOFs with dierent equivalences of [Ir(COD)(OMe)]2 in tetrahydrofuran (THF) aorded Ir-functionalized Zr-MOFs, BPV-MOF-Ir,
mBPV-MOF-Ir, and mPT-MOF-Ir. Inductively coupled plasma-mass
spectroscopy (ICP-MS) analyses of the Ir/Zr ratio revealed that the Ir
loadings could reach 65%, 16%, and 20% for the three MOFs,
respectively. Significantly, these Ir-functionalized Zr-MOFs showed
high catalytic activity for tandem hydrosilylation of aryl ketones and
aldehydes. Additionally, based on the postsynthetic metalation,
Manna et al. also treated Zr6(m3-O)4(m3-OH)4(BPYDC)6 (BPY-UiO)
with [Ir(COD)(OMe)]2 in THF to obtain BPY-UiO-Ir, and with
[Pd(CH3CN)4][BF4]2 in dimethyl sulfoxide (DMSO) to obtain BPYUiO-Pd, in which Zr/Ir in BPY-UiO-Ir and Zr/Pd ratios in BPYUiO-Pd reached 30 and 24%, respectively.101
Review Article
Review Article
after UiO-66 was treated with HfCl4. But, only about 20% of Hf(IV)
ions were introduced into UiO-66 even at an enhanced temperature.
On the other hand, substitution of coordinated guest molecules represents another method for the pore modification of
MOFs. Deria et al. used mesoporous Zr6(m3-OH)8(OH)8(TBAPy)2
(NU-1000) as the platform to prepare a series of functionalized
Zr-MOFs (Fig. 9). NU-1000 contains octahedral [Zr6(m3-OH)8(OH)8]8+
nodes, where eight of twelve octahedral edges are connected
with carboxylate groups of TBAPy4 ligands, while the remaining
coordination sites of Zr(IV) ions are occupied by eight terminal
OH groups. First, based on a solvent-assisted ligand incorporation (SALI) method, these OH groups were substituted by a
series of perfluoroalkyl carboxylate entities with varying chain
length by exposing a NU-1000 sample into a DMF solution of
respective fluoroalkyl carboxylic acids.118 It was found that about
3.44.0 perfluoroalkyl carboxylates per Zr6 node could be incorporated within NU-1000. As a result, these modified MOFs showed
enhanced CO2 capture capacities due to the presence of CF dipoles.
Then, they also incorporated other carboxylate-based alkyl and
aromatic functional groups into NU-1000 by a similar procedure.119
Chemical reactions such as click chemistry, imine condensation,
and pyridine quaternization were then performed for the further
modification of these materials.
Similarly, NU-1000 was modified by phenylphosphonate
(PPA) through the SALI method.120 It was found that the
phosphonate displaced OH/H2O ligands and meanwhile chelated
with Zr(IV) atoms of the MOF through phosphonate O atoms.
Moreover, they also demonstrated that the incorporation of
PPA rendered parent NU-1000 more renitent to hydroxide
attack and framework dissolution. Except for the above SALI
method, reactive incorporation of metal ions via atomic layer
deposition in MOFs (AIM) was proposed by the same group as
well.121 They exposed the NU-1000 microcrystalline sample into
diethylzinc (ZnEt2) or trimethylaluminum (AlMe3) vapors, and
Review Article
3. Structures
Zr-MOFs are constructed by interconnection of polyatomic
inorganic Zr-containing clusters and polytopic organic ligands.
The structural diversity of the two components and various
ways the two components connect contribute to the variety of
structures in Zr-MOFs. The structures of reported Zr-MOFs are
discussed in this section, in terms of assorted Zr-based clusters
generated and organic ligands utilized.
3.1
Zr-based cluster/core
Review Article
coordinated by twelve carboxylate groups, a Zr6(m3-O)4(m3-OH)4(CO2)12 SBU is generated with the Oh-symmetry, which is
observed in most of the reported Zr-MOFs (Fig. 12a). However,
in Zr6(m3-O)4(m3-OH)4(TCPP)3 (PCN-223) reported by Feng et al.,
an unprecedented 12-connected D6h symmetric Zr6 cluster
was found.143 For the D6h Zr6 cluster, each Zr(IV) located in
the equatorial plane of the Zr6 octahedron is coordinated by
eight O atoms, four O atoms from two m3-O and two m3-OH
groups, and four O atoms only supplied by three carboxylates.
So, only eight carboxylates are bridging two adjacent Zr atoms,
and the other four in the equatorial plane are chelating single
Zr atoms, respectively (Fig. 12b). The cluster was initially regarded
as a 12-connected Zr18 cluster in this MOF structure, but additional
experiments confirmed that it was a 12-connected Zr6 cluster
instead of Zr18. The Zr18 cluster was actually a crystallographic
disordered model where three Zr6 clusters oriented in dierent
directions.
The Oh symmetry includes many symmetry subgroups. From
a topological point of view, there is a large possibility for
construction of three-dimensional (3D) frameworks from the
highly symmetric Zr6(m3-O)4(m3-OH)4(CO2)12 SBU and organic
ligands by reducing the symmetry and/or connectivity. For
example, in DUT-69, only ten edges of the Zr6 octahedral cluster
are occupied by carboxylate groups while the remaining four
coordination sites in the equatorial plane are occupied by two
AcO and two water molecules, leading to the formation of a
10-connected [Zr6(m3-O)4(m3-OH)4(CO2)10]2+ (Fig. 12c).50
In addition, Feng et al. also reported Zr6(m3-OH)8(OH)8(TCPP)2
(PCN-222), in which only eight edges of the Zr6 octahedral
cluster are occupied by carboxylate groups while the remaining
eight coordination sites of Zr(IV) centers in the equatorial plane
are occupied by terminal OH groups.144 Consequently, the
SBU becomes 8-connected Zr6(m3-OH)8(OH)8(CO2)8 with the
symmetry being reduced from Oh to its subgroup D4h (Fig. 12d).
In addition to PCN-222, another 8-connected SBU was observed
in Zr6(m3-O)4(m3-OH)4(OH)4(H2O)4(TCPP)2 (PCN-225) reported
by Jiang et al.145 Interestingly, in this MOF six Zr atoms formed
an exact octahedron, while eight m3-O capped on the triangular
faces formed a highly distorted polyhedron instead of an ideal
one as observed in PCN-222. As a result, the cluster symmetry of
D4h in PCN-222 reduces to D2d in PCN-225, leading to lower
symmetry of the latter (Fig. 12e).
Furthermore, a 6-connected Zr6 octahedron SBU was observed
in Zr6(m3-O)4(m3-OH)4(OH)6(H2O)6(TCPP)1.5 (PCN-224).146 Only six
edges of the Zr6 octahedron are occupied by carboxylate groups in
the structure, leading to the formation of a hexagonal planar SBU
with the D3d symmetry (Fig. 12f). In addition, Feng et al. also
synthesized another Zr-MOF, Zr6(m3-O)4(m3-OH)4(OH)6(H2O)6(TATB)2
(PCN-777), in which another 6-connected trigonal prismatic
Zr6(m3-O)4(m3-OH)4(OH)6(H2O)6(CO2)6 SBU was observed (Fig. 12g).147
It was suggested that switching positions of carboxylate groups
and terminal OH/H2O groups in the Zr6 cluster could realize the
cluster interconversion between PCN-777 and PCN-224.
3.1.2 Zr8O6 cluster. The appearance of the Zr8(m4-O)6 cubic
cluster (Fig. 10b) in Zr8(m4-O)6(OH)8(TCPP)3 (PCN-221) reported by
Feng et al. further enriched the structural diversity of Zr-MOFs.135
Review Article
Fig. 12 The observed SBU based Zr6(m3-O)4(m3-OH)4 cluster in reported Zr-MOFs: (a) 12-connected Zr6(m3-O)4(m3-OH)4(CO2)12 in UiO-66; (b) 12-connected
Zr6(m3-O)4(m3-OH)4(CO2)12 in PCN-223; (c) 10-connected Zr6(m3-O)4(m3-OH)4(CO2)10(AcO)2 in DUT-69; (d) 8-connected Zr6(m3-OH)8(OH)4(CO2)8 in PCN-222;
(e) distorted 8-connected Zr6(m3-O)4(m3-OH)4(OH)4(H2O)4(CO2)8 in PCN-225; (f) 6-connected Zr6(m3-O)4(m3-OH)4(OH)6(H2O)6(CO2)6 in PCN-224; and
(g) 6-connected Zr6(m3-O)4(m3-OH)4(OH)6(H2O)6(CO2)6 in PCN-777. Atom color scheme: C, black; O, red; and Zr, blue.
Review Article
Fig. 13 (a) Structures of a series of MIL-140 viewed along the c axis and
(b) the chain SBU based on Zr(m3-O)3O4 cores in MIL-140. Reprinted with
permission from ref. 139. Copyright 2012 Wiley-VCH Verlag GmbH & Co.
KGaA, Weinheim.
Review Article
Scheme 1
ones with diameters of 15.6 and 18.8 , respectively. The cubooctahedral cage possesses six square and eight triangular windows
with the size of 9 and 4.2 , respectively. Each triangular
Review Article
Fig. 14 Structure of UiO-66: (a) tetrahedral cage; (b) octahedral cage; and
(c) packing of the two types of cages.27
Fig. 15 (a) One of the two frameworks of PIZOF-2 showing the arrangement of concave and convex tetrahedral cavities; (b) topological representation of the interpenetrated structure in PIZOF-2; (c) convex cavity;
(d) concave cavity; and (e) the whole structure of PIZOF-2. Reprinted with
permission from ref. 73. Copyright 2011 Wiley-VCH Verlag GmbH & Co.
KGaA, Weinheim.
Review Article
Fig. 18 (a) The SBU and framework connectivity in Zr6(m3-OH)8(OH)8(AP-CH3)4; (b) core architecture and framework structure of Zr6(m3OH)8(OH)4(SO4)4(AP)2; and (c) core architecture and framework structure
of Zr6(m3-OH)8(OH)2(Cr2O7)3(AP)4. Reprinted with permission from ref. 156.
Copyright 2015 The Royal Society of Chemistry.
Review Article
Zr-BTB crystallizes in the space group of I41/amd. In its structure, the Zr6 clusters as 6-connected nodes were connected
by BTB3 ligands as the 3-connected linkers to give rise to a
(3,6)-connected 2D network with the kgd topology. The 2D
framework possesses elliptical windows with the size of
7.16 12.61 . Moreover, the parallel 2D layers of one set
interpenetrate perpendicularly with another set to generate a
3D open framework with 1D square channels (14.37 14.37 ).
Zr-BTB thus represented the first Zr-MOF with a 2D - 3D
interpenetration structure.
3.2.3 Tetratopic carboxylic ligands. Compared with di- and
tricarboxylate ligands, tetracarboxylate ligands have more coordination sites and rich coordination patterns. More importantly,
tetracarboxylic ligands with large space steric hindrance could
eectively avoid framework interpenetration, being favorable for
constructing mesoporous Zr-MOFs. Among all tetracarboxylic
ligands for constructing reported Zr-MOFs, H4TCPP is quite
common. Some related studies can be found in a published
review on metal-metalloporphyrin frameworks reported by Gao
et al.158 The variation of its connecting number and symmetry
provides a large number of topological possibilities to form
various frameworks with dierent pore sizes and shapes. In
addition, most reported porphyrinic Zr-MOFs exhibited excellent
thermal and chemistry stability, providing good platforms for
exploring the applications of MOFs under harsh conditions.
Currently, eight Zr-MOFs constructed using H4TCPP have been
reported by Zhous group from PCN-221 to PCN-225,135,143146
Yaghis group for Zr6(m3-O)4(m3-OH)4(TCPP)3 (MOF-525) and
Zr6(m3-O)8(H2O)8(TCPP)2 (MOF-545),159 and Mas group for
Zr6(m3-O)8(H2O)8(CO2)8 (MMPF-6).160 In PCN-221, four peripheral
benzene rings of the ligand are perpendicular to the central
porphyrin ring.135 Each TCPP4 linker connects with four Zr8
clusters in a 4-connected mode, and each Zr8 cluster is linked
by twelve TCPP4 linkers in a 12-connected node, resulting in
a (4,12)-connected ftw topological network. In addition, the
structure features two types of polyhedral cages with distorted
octahedral and cubic shapes. The slightly distorted octahedral
cage, with a cavity diameter of B11 , involves two Zr8 clusters at
the vertices along the axial direction and four TCPP4 ligands in
the equatorial plane. The vertices and faces of the cubic cage
with the edge length of B20 are delimited by eight Zr8 clusters
and six TCPP4 ligands, respectively. For PCN-223, following the
same topological simplification way of PCN-221, each Zr6 cluster
can be regarded as a 12-connected node and the TCPP4 linker
can be simplified to a 4-connected node.143 The framework
represents the first (4,12)-connected MOF with the shp topology.
In addition, PCN-223 contains uniform triangular 1D channels
of 12 in diameter delimited by three SBUs and three ligands.
MOF-545 prepared by Morris et al. crystallizes in the hexagonal
space group P6/mmm.159 In its structure, eight edges of the Zr6
octahedral cluster are bridged by carboxylate groups and the
remaining positions are occupied by terminating water, leading
to the formation of a SBU with a formula of Zr6(m3-O)8(CO2)8(H2O)8.
Combination of these SBUs and the tetratopic linker TCPP4
resulted in a network with the csq topology. The structure of
MOF-545 features triangular and hexagonal 1D channels with
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Review Article
Fig. 23 Structure of MIL-163: (a) view of a single chain SBU showing the
Zr atoms coordinated by 1,2,3-trioxobenzene groups; and (b) view of the
structure along the [001] direction showing square-shaped channels.
Reprinted with permission from ref. 142. Copyright 2015 Wiley-VCH Verlag
GmbH & Co. KGaA, Weinheim.
Fig. 22 (a) The single layer of ZrBTBP along the c-axis; and (b) the
stacking of layers in ZrBTBP in an ABAB mode. Reprinted with permission
from ref. 136. Copyright 2014 The Royal Society of Chemistry.
Catalysis
Fig. 24 The schematic representation of Meerwein reduction of 4-tertbutylcyclohexanone catalyzed by UiO-66 with unsaturated metal sites.56
acid catalysis, oxidation catalysis, biomimetic catalysis, electrocatalysis, hydrogenation catalysis, and photocatalysis.
4.1.1 Lewis acid catalysis. Zr-MOFs with unsaturated metal
sites were mainly applied in Lewis acid catalysis reactions, in
which the open metal sites act as electron pair acceptors
capable of accelerating the reaction process. Vermoortele
et al. revealed that coordinatively unsaturated metal sites in
UiO-66 can be drastically increased by using specific modulators in the synthesis.56 Thus, the Lewis acid catalytic activity of
the MOF can be improved correspondingly. With UiO-66 as the
catalyst the Meerwein reduction of 4-tert-butylcyclohexanone
(TCH) with isopropanol (IPA) was studied, which requires
activating the alcohol and ketone simultaneously to facilitate
the transfer of hydride (Fig. 24). The results illustrated that the
non-modulated UiO-66 shows nearly no activity, while the
materials modulated with ten equivalents of TFA display
high catalytic activity, leading to appreciable yields of tertbutylcyclohexanol. Moreover, it was also demonstrated that
the space around the Zr cluster in UiO-66-NO2 increased when
HCl and TFA were used as modulators, which could facilitate
the simultaneous activation of reactants. As a result, 93%
conversion of tert-butylcyclohexanol was achieved.
Similarly, Wang et al. successfully removed coordinated water of
Zr6(m3-O)4(m3-OH)4(OH)6(H2O)6(CO2)6 SBUs in Zr-BTB (Fig. 25).157
Fig. 25 The single layer structure of Zr-BTB and its Lewis acid catalyzed
reaction of carbonyl compounds with cyanide.157
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Catalyst
Conversion (%)
Yield (%)
Selectivity (%)
Zr-MOF-BPYDC-CuBr2
BPYDC-CuBr2
Zr-MOF-BPYDC
No catalyst
88.5
28.5
23.0
13.4
84.3
21.2
20.1
8.5
95.3
74.4
87.3
63.2
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Fig. 28 (a) Structure of CPM-99; (b) cyclic voltammetry (CV) curves and (c) RDE polarization curves of CPM-99X/C and 20% Pt/C in 0.1 M KOH solution;
(d) RDE polarization curves of CPM-99Fe/C at dierent rotation rates. Inset: KL plot of J1 vs. o1 at different potentials; (e) RDE polarization curves of
CPM-99X/C and 20% Pt/C in 0.1 M HClO4 solution. Reprinted with permission from ref. 161. Copyright 2015 American Chemical Society.
Fig. 30 Schematic representation for constructing superacid MOF-8082.5SO4. Reprinted with permission from ref. 198. Copyright 2014 American
Chemical Society.
Review Article
Fig. 31 Structure model of the doped UiO-67 and the illustration of its
photocatalytic application in CO2 reduction and organic transformations.182
Review Article
Fig. 32 CO2 adsorption isotherms at 298 K and IAST-predicted selectivities toward CO2/N2 in BUT-11, BUT-10, and UiO-67. Reprinted with permission
from ref. 205. Copyright 2014 American Chemical Society.
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Drug delivery
Fluorescence sensing
Review Article
Fig. 35 (a) Free AL release profile from the dialysis bag at pH 7.4 (black) and the cumulative release profiles of AL from UiO-66 NPs in 5 mM PBS at pH
values of 5.5 (red) and 7.4 (green) at 37 1C; (b) the merged confocal image of HepG2 cells after their incubation with 100 mg mL1 of UiO-66-FMN for 4 h
at 37 1C; cell viabilities of (c) HepG2, (d) MCF-7 cells incubated with free AL and AL-UiO-66 at dierent concentrations for 24 and 48 h. Reprinted with
permission from ref. 227. Copyright 2014 The Royal Society of Chemistry.
increase of pH value led to only a slightly increase of fluorescence intensity. The reason for this unique pH-sensitive fluorescence in PCN-225 was that the protons in acidic solution
combined with pyridine-type N atoms of the porphyrin center,
destroying the p-electron conjugated double-bond system of
porphyrin, ultimately leading to significant fluorescence
quenching. However, when the pH was above 7, the fluorescence intensity increased significantly in close association with
the pH values, which might arise from the deprotonation of the
imino group of porphyrin. Based on these findings, PCN-225 was
regarded with potential applications in pH sensing, especially in
the pH range of 710.
Capitalizing on the intrinsic fluorescence of MOFs, researchers
explored extensive sensing applications.247259 For instance, high
levels of phosphates may lead to the pollution of water and
consequent massive death of creatures.260 As discussed above,
Zr-MOFs presented high affinity towards phosphoric groups due
to the formation of ZrOP bonds. Thus, Yang et al. exploited
Review Article
4.5
Fig. 36 (a) ETTC4 linker in PCN-94; (b) PCN-94 framework; (c) solidstate absorption (dashed lines) and emission spectra (solid lines) of PCN94 and H4ETTC at room temperature; (d) photos of PCN-94 and H4ETTC
are shown under ambient light and UV light. Reprinted with permission
from ref. 163. Copyright 2014 American Chemical Society.
explosives in aqueous media.265 Especially for 2,4,6-trinitrophenol (TNP) with concentrations as low as 2.6 mM, fast and
high fluorescence quenching was observed, illustrating low
detection limitation for UiO-67@N. In contrast, all of the other
nitro analytes had minor effects on the fluorescence intensity,
indicative of high selectivity towards TNP. Such unprecedented
selective fluorescence quenching can be attributed to the occurrence of both electron and energy transfer processes between the
MOF and TNP.
MOFs are also applicable in metal sensing, mainly involving
the detection of Eu(III), Fe(III), Tb(III), Cu(II), and Ag(I).247,252259 As
for Zr-MOFs, Carboni et al. prepared Zr6(m3-O)4(m3-OH)4(H2O)8(L1)4
(H2L1 = H2TPDC-NH2 derivative) with metal binding sites orthogonal to succinic acid, which possesses a broad emission band
at 390 nm upon excitation at 330 nm.266 The ligand H2L1 was
prepared by treating H2TPDC-NH2 with succinic acid in dry DMSO
at room temperature for 12 h. Thus, the chelation of amide
groups with transition metal cations leads to changes of the
fluorescence intensity. Interestingly, those transition metal ions
with unpaired d-electrons presented a significant quenching
effect even at low metal concentrations, especially for Mn(II).
An exceptionally high KSV value of (0.91 0.04) 106 m1, with
the detection limit of o0.5 ppb for Mn(II), was obtained on
Zr6O8(H2O)8(L1)4, which is three to four orders of magnitude
greater sensitivity than those of previously reported MOFs.
In addition to the fluorescence properties, scintillation is
also an important emissive phenomenon found in luminescent
materials. For example, luminescent organic crystals can work
as radiation scintillators for detecting low-energy b-rays and
neutrons.267,268 X-ray scintillating Zr-MOFs, Zr6(m3-O)4(m3-OH)4(ADC)6
with anthracene-based bridging ligands H2ADC as emitters, were
designed and prepared by Wang et al. (Fig. 39).151 The high
atomic number of Zr in the SBUs serves as the eective X-ray
antenna. Upon X-ray absorption, the outer-shell electrons
of the Zr(IV) ions are converted to fast electrons via the
Electrochemistry
Recently, there has been rapidly growing interest in electrochemistry applications of MOFs, such as in energy storage and
conversion (supercapacitors) or electrode materials, which have
been proven to be excellent candidates in this field.269273 It is
mainly because the chemical composition of MOFs can be tuned
at the molecular level. Moreover, the high porosity of MOFs
is favorable for fast mass transportation of related species. The
studies of Zr-MOFs in electrochemistry application mostly
involve three aspects: ionic and proton conduction, as well as
supercapacitors.
Ameloot et al. prepared LiOtBu-grafted UiO-66 upon
dehydration of Zr-based clusters followed by lithium alkoxide
grafting.122 The grafted tBuO anions shielded the negative
charge, leading to a higher mobility of Li(I) ions. As a result, the
ionic conductivity of the LiOtBu-grafted UiO-66 was promoted
to be 1.8 105 S cm1, which is on par with current solid
polymer electrolytes.274,275 The activation energies (Ea) declined
as low as 0.18 eV, which is in the range for superionic
conductors and even slightly lower than that of H+ conduction
in Nafion.276,277 Moreover, the impedance spectra obtained
from a setup prepared by placing a pellet of LiOtBu-grafted
UiO-66 in a Swagelok cell showed that no Li(I) blocking passivation layer was formed. Furthermore, this cell could be cycled
three times and the crystallinity of the MOF was intact after
contacting with the Li electrode for three days, indicating a
high electrode compatibility. With these properties, the solid
electrolytes based on this LiOtBu-grafted UiO-66 are potentially
usable in Li-based batteries.
On the other hand, ligand defects in MOFs have been demonstrated to have important eects on their pore sizes and surface
properties, which subsequently influence their performances,
such as in gas storage and catalysis. Interestingly, Taylor et al.
first showed that defect control could also enhance the proton
conductivity of Zr-MOFs.278 Dierent from common methods
for improving proton conductivity of MOFs by increasing overall acidity, they controlled the formation of ligand defects by
introducing stearic acid to change the proton mobility within
the UiO-66 framework.279281 The results demonstrated that the
ligand defects were favorable for improving proton mobility.
As a result, proton conductivity increased by nearly three orders
of magnitude to 6.93 103 S cm1.
In addition, supercapacitors represent an important class of
energy storage devices because of their high power density.270,283
Choi et al. recently prepared twenty-three dierent nanocrystals
of MOFs (nMOFs) with various structures, geometries and
functionalities, which were applied in the fabrication of MOF
thin films doped with graphene and then incorporated into
Review Article
Fig. 37 (a) Structure of PCN-225; (b) pH dependent fluorescence intensity of PCN-225 with pH ranging from 0 to 10.2 measured under excitation of
415 nm; (c) fluorescence emission of PCN-225 at dierent pH values matching the simulation fluorescence intensity; (d) protonation and deprotonation
processes of porphyrin involved in the PCN-225 framework in experimental acidic and basic media (pH = 010.2). Reprinted with permission from
ref. 145. Copyright 2013 American Chemical Society.
Fig. 38 A schematic illustration of the phosphate coordination induced fluorescence enhancement eect in MOFs of UiO-66-NH2 for the selective and
sensitive detection of phosphate with inorganic nodes as natural recognition sites and organic struts as the fluorescent reporter. Reprinted with
permission from ref. 261. Copyright 2015 The Royal Society of Chemistry.
Review Article
devices to serve as supercapacitors.282 Among them, Zr6(m3-O)4(m3-OH)4(BPYDC)6 (nMOF-867) exhibited the highest capacitance
(Fig. 40). The max stack capacitance (0.644 F cmstack3) and max
areal capacitance (5.085 mF cmareal2) were over six and ten
times those of activated carbon and graphene, respectively. The
gravimetric capacitance, maximum energy, and power densities
of nMOF-867 were estimated to be 726 F gnMOF-867/electrode,
6.04 104 Wh cmstack3, and 1.097 W cmstack3, respectively.
It is worth noting that at the power density of 0.386 W cmstack3,
the energy density (2.86 104 Wh cmstack3) of nMOF-867 was
over three times that of activated carbon. Moreover, nMOF-867
based on this supercapacitor could consistently preserve its excellent performances for at least 10 000 cycles under the conditions of
exposing to the maximum voltage (02.7 V).
4.6
Porous carrier
Zr-MOFs are excellent candidates as carriers for various applications because of their porosity and high chemical and thermal
stability. The integration of Zr-MOFs with encapsulated functional entities leads to the formation of new multifunctional
composites, which could exhibit unique properties superior to
the individual components.284,285 Moreover, the multifunctional
nature and the remarkable properties of such composites will
enrich functional applications of MOFs, typically in catalysis,
molecule adsorption, as well as drug delivery.
As a mesoporous Zr-MOF, PCN-777 has high chemical and
thermal stability with the highest pore volume of 2.8 cm3 g1.147
Moreover, in this MOF each Zr6 cluster is coordinated by six
carboxylates, leaving rich terminal OH groups pointing into the
mesoporous cages, which renders PCN-777 a suitable candidate
as a carrier. Feng et al. used 4-tert-butylbenzolate (tBu) and
4-carboxy-1-methylpyridinium iodide (MePy) to modify the internal surface of PCN-777. After that, the originally hydrophilic
properties of the internal surface changed into highly hydrophobic.
Three functionalized guest molecules, mesotetra(4-sulfonatophenyl)porphyrin (TSPP), tris(2,20 -bipyridine)-dichlororuthenium(II)
([Ru(bpy)3]Cl2), and tetra-amido macrocyclic ligand catalytic
Review Article
Fig. 40 (a) Construction for nMOF supercapacitors; (b) the stack capacitance of nMOF-867 and comparison to activated carbon and graphene.
Reprinted with permission from ref. 282. Copyright 2014 American Chemical Society.
Fig. 41 Schematic representation of the synergistic photocatalytic hydrogen evolution process via the photoinjection of electrons from the light harvesting
MOF frameworks into the Pt NPs (a) and POMs (c); (b) time-dependent hydrogen evolution curves of Pt@1 (green), Pt@2 (red), and homogeneous control
[Ir(ppy)2(bpy)]Cl/K2PtCl4 (blue and black for dierent Pt/Ir ratios) under optimized conditions; (d) time-dependent HER TONs of POM@UiO with methanol as
the sacrificial electron donor. Reprinted with permission from ref. 286 and 287. Copyright 2012 and 2015 American Chemical Society.
the catalytic activity was twofold compared with the nonfunctionalized Pt C nUiO-66. For Pt C nUiO-66-N, while the
selectivity for C6-cyclic products decreased to o50%, the
acyclic isomer selectivity increased to 38.6%. Interestingly, for
Review Article
Acknowledgements
We thank the financial support of the Natural Science Foundation of China (No. 21322601, 21271015, and 21576006) and
the Program for New Century Excellent Talents in University
(No. NCET-13-0647).
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