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The chemistry of titanium-based

metal–organic frameworks
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Cite this: New J. Chem., 2017,

41, 14030
Ha L. Nguyen

Received 23rd August 2017,
Accepted 4th October 2017
DOI: 10.1039/c7nj03153j
rsc.li/njc
Due to the many potential applications of metal–organic frameworks (MOFs), research focusing on the
design, syntheses, and surface modifications of the new generation of crystalline-based MOF materials
has recently received much attention. Among these materials, MOFs based on Ti–oxo clusters are
potential candidates for practical applications such as photocatalysis, CO2 reduction, and pollutant
degradation because of their high optical responsitivities and photoredox properties. The capabilities of
Ti-MOFs in a wide range of applications are inspiring their use as a replacement for TiO2, which has
recently been classified as a potential carcinogen. However, the number of tianium–organic framework
structures is very limited compared to the many structures of other MOFs. In order to emphasize
the importance of discovering new Ti-MOF materials and their related features, this work aims to
describe the chemistry of titanium-based MOFs, including their synthetic methods, crystal structures,
and topological analysis, as well as further key novel applications, which are desirable for extension to
many industrial fields.

Introduction
Metal–organic frameworks (MOFs) are constructed by the
combination of rigid covalent bonds of organic linkers and
inorganic metal ion or clusters acting as nodes, designated as
secondary building units (SBUs).1 The organic linkers are also
termed as SBUs from a geometrical standpoint and are used for
topological analysis. Recently, almost 70 000 structures of
MOFs have been reported and studied, showing the tremendous
development of these crystalline porous materials.2 Considered
as a new class of microporous material possessing promising
properties of high porosity, well-defined crystallinity, increased
number of active sites, catalytic activity, etc., MOFs have been
studied to address many issues, such as environmental
problems,3–5 sustainable energy,6 and catalytic transformation.7,8
However, the low stability of MOFs under working conditions
of high temperature and humidity as well as in fluid solvents
reduces the practical applications of this material. In order to
overcome this challenge, MOFs based on high valence metals
and carboxylate linking units have been the subject of increasing
studies. Zr(IV)- and Ti(IV)-based MOFs are candidates that not only
contain strong metal–carboxylate bonds and rigid frameworks,
but also demonstrate good photocatalytic properties.9–11 It should
be noted that the number of these materials is still limited
compared to MOFs based on di- and tri-valence metal clusters
Center for Innovative Materials and Architectures (INOMAR), Vietnam National
University-Ho Chi Minh (VNU-HCM), Ho Chi Minh City 721337, Vietnam.
E-mail: nlha@inomar.edu.vn, hanguyen@manar.edu.vn
due to the high reactivity of the metal(IV) ions and carboxylate
linkers, which leads to poorly crystalline or amorphous powders.11
TiO2 is known as a commercial reagent that is useful as a
white pigment and in other industrial fields, such as paints,
plastics, paper, foods, cosmetics, and medicines, because of its
UV blocking features. However, very recently, the European
Chemicals Agency (ECHA) has proposed the classification of
P25-TiO2 as a potential carcinogen.12 Titanium–oxo cluster-
based MOFs are promising materials that may replace TiO2 in
many industrial applications due to their extreme stability
against harsh working conditions of high temperature and
humidity and/or chemical environments.13,14 In this contribution,
we seek to review the chemistry of MOFs based on titanium–oxo
clusters; their synthetic methods, crystal structures, topological
networks and potential applications will be described and
discussed in detail.
Synthetic methods, crystal structures,
and topological analysis
The syntheses of MOFs were carefully presented in early
published literature reports,15 in which the formation of MOFs
was described through solvothermal, hydrothermal, electro-
chemical, mechanochemical, and microwave-assisted synthesis
methods. In some cases, slow evaporation was used to obtain
large crystals that were utilized for structural elucidation by
single crystal X-ray diffraction analysis.16,17 In the process of
Ti-MOFs formulation, the strong interaction between highly

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reactive titanium sources and organic carboxylate linkers leads
to difficult association and dissociation of Ti–carboxylate
bonds, which results in the production of poorly crystalline
products such as sols, gels or amorphous powders.11 Hence,
highly crystalline Ti-MOFs can only be achieved by choosing
suitable synthetic conditions, including the organic solvent,
ratio of the reacted solution mixture, pH environment, and
temperature. Very recently, Serre and co-workers demonstrated
the Pourbaix diagrams of titanium calculated for [Ti4+] =
103 mol L1 at 25 1C using Hydra and Medusa software.18
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This calculation can guide the synthesis of Ti-MOFs based on
consideration of the pH factor.
It should be noted that materials containing Ti-based clusters,
Ti(BuOH) and MIL-91, produced by reaction of 1,4-butanediol
(Bu(OH)2) and N,N 0 -piperazinebismethylenephosphonate, respec-
tively, with a titanium source, were reported as early as 2006.
Although Ti(BuOH) dissolves in most organic solvents, which is
unusual in MOFs chemistry, its crystal structure reveals the first
3-dimensional (3-D) view of an extended titanium coordination
complex.19 In the case of MIL-91, this material is the first titanium
diphosphonate with well-defined porosity, showing an internal
surface area of 550 m2 g1 based on the Langmuir method.20 In
this context, we focus the discussion on the details of the
structural properties and applications of Ti-MOFs based on
organic carboxylate linker building units.
Direct synthesis
The first Ti-MOF constructed from a 1,4-benzenedicarboxylate
(BDC) linker and a Ti–oxo cluster, termed MIL-125, was reported
by Serre and Sanchez and co-workers in 2009.21 MIL-125 was
solvothermally synthesized using a solvent mixture of N,N-
dimethylformamide (DMF)/methanol that dissolved the starting
reagents, BDC and titanium(IV) isopropoxide; the mixture was
heated to 140 1C in a solvothermal oven to yield a crystalline
powder. Undoubtedly, MIL-125 is an exemplary material, possessing
the first octameric Ti–oxo cluster and ditopic linker; it inspired other
studies, including novel Ti-MOF synthesis efforts, structural
modifications, and promising applications (Fig. 1).22,23
The crystalline powder of MIL-125 was obtained by solvothermal
synthesis, and its crystal structure was determined by powder
Fig. 1 Stages of Ti-based MOFs. Details of the synthetic methods and the observed titanium–oxo clusters are provided along with the materials that
have been synthesized and reported.
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X-ray diffraction (PXRD) analysis. Indeed, the ab initio method
was applied to elucidate the structure via direct methods using
EXPO software. The refinement was performed through Rietveld
refinement executed by Fullprof. The 3-D structure of MIL-125
revealed that MIL-125 crystallized in a body-centered tetragonal
lattice with the I4/mmm space group (No. 139). The refined
lattice parameters were convergent with a = b = 18.6453(10) Å
and c = 18.1444(10) Å. Eight (8) oxo atoms were divided by two
parallel planes, in which each plane contained four (4) oxo
atoms. Ti8(OH)4 was located in the middle and parallel with two
planes holding oxo atoms. The 8-member ring Ti8O8(OH)4(CO2)12
was built by the connection of 4 carboxylates on the top,
4 carboxylates on the bottom and 4 carboxylates in the middle
plane, which divided the cluster into two parts (Fig. 2). BDC
moieties acted as 2-connected (2-c) to link 12-connected (12-c)
distorted cuboctahedra clusters to each other, resulting in a 3-D
view of a crystal structure which contains triangular faces and
belongs to the fcu topology. It is noteworthy that the fcu network
of MIL-125, which is identical to the UiO-66 system,24 was not
mentioned in the published literature. The transitivity, defined
by [p q r s] (where p is the number of vertices, q is the number of
edges, r is the number of faces, and s is the type of tile),25 and the
natural tiling for MIL-125 were found to be [1 1 1 2] and 2[34] +
[38], respectively (Table 1). The linking of these triangular faces
leads to the creation of two types of pores in MIL-125. The
Fig. 2 Crystal structure of MIL-125 showing a 3-D view with two kinds of
pores, octahedral and tetrahedral, which are represented by yellow and
orange balls, respectively. 12-c of the 8-member ring of Ti8O8(OH)4(CO2)12
is also displayed on the right side. Color code: O, red; C, black; Ti, blue.
H atoms are omitted for clarity.
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Table 1 Summary of the topological features of Ti-MOFs

Material Net Node Transitivitya Natural tiling

b
MIL-91 sql 4-c [1 1 1 1] [44]
Ti-BuOHb bct 10-c [1 2 2 1] [34.42]
MIL-125b fcu 12-c [1 1 1 2] 2[34] + [38]
ZTOF-1b bcu 6-c [1 1 1 1] [44]
MIL-125-NH2b fcu 12-c [1 1 1 2] 2[34] + [38]
NTU-9b hcb 3-c [1 1 1 1] [63]
COK-69b acs 3-c [1 1 2 2] [43] + [4362]
Ti-CAT-5b srs 3-c [1 1 1 1] [103]
MIL-167b srsb 3-c [1 1 1 1] [103]
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MOF-901b hxl 6-c [1 1 1 1] [36]

MOF-902b hxl 6-c [1 1 1 1] [36]
Cd–Ti-MOF-1c,d ctmb 4,6-c [2 3 5 3] [462] + [6282]
Cd–Ti-Silan-1c rtl 3,6-c [2 2 3 2] [462] + [6282]
ZTOF-2c she 6,8-c [2 1 2 2] 3[4482] + [41286]
PCN-22d,e kimb 4,4,7-c [5(10)96] 2[63] + 2[6282] + [4284] + [64122] + [4464122]
MIL-101(Ti) f mtn-e 6,6,6,6-c [4 7 9 5] 17[34] + 2[320512] + [32851264]
a
Transitivity is defined by [p q r s] (where p is the number of vertices, q is the number of edges, r is the number of faces, and s is the type of tile).
b
The structural topology is uninodal. c The structural topology is binodal. d These MOFs were found to have new topologies which were not
named and/or acknowledged by the authors in their publications. e The structural topology is trinodal. f The structural topology is tetranodal.

internal diameters of the octahedral and tetrahedral cages were

found to be ca. 12.55 and 6.13 Å, respectively (Fig. 2).22
Based on an organic linker containing carboxylate and hydroxyl
bifunctionality, 2,5-dihydroxyterephthalic acid (H4DOBDC), which
is the same link used to synthesize the MOF-74 series, Zhang and
co-workers reported the structure of NTU-9 in 2014.26 NTU-9 was
solvothermally produced by the reaction of H4DOBDC and
titanium isopropoxide [Ti(i-OPr)4] in acetic acid. The acidic
medium created by acetic acid prevented seed crystals from
forming too quickly, which increased the possibility of yielding
larger crystals. NTU-9 was obtained as large red crystals after 5 d
of reaction in a Teflon-lined stainless-steel autoclave at 120 1C.
The structure of NTU-9 is a 2-D layer that contains a single
pure Ti atom, in which the connection of 3 carboxylates and
3 hydoxyl groups yields a single octahedral Ti cluster. Each
single cluster is bound by 3 DOBDC linking units, and the
combination of these 3-c points creates an hcb network con-
taining one type of hexagonal face with the signature of [63]
tiling (Table 1). In NTU-9, the layer structure is stacked together
along the c axis, constructing an 11  11 Å 1-D channel. The
distance between the first layer and second layer, calculated
from the crystal structure, is around 6 Å (Fig. 3).
Fig. 3 Single Ti atom cluster formation (a) that is the fundamental unit
In order to reduce the high reactivity and hydrolysis of titanium
used to build the NTU-9 structure (b). The layer distance is also presented
isopropoxide, a Ti-based complex precursor was considered for use on the right side of (a). Color code: O, red; C, black; Ti, blue; second layer,
as a reagent in the synthesis of MOFs. A hydrolytically organo- orange. H atoms are omitted for clarity. Yellow balls are placed in the
metallic Ti precursor, dicyclopentadienyl titanium(IV) dichloride cages to show the pores.
([Cp2TiIVCl2]), was explored to react with a flexible linker,
trans-1,4-cyclohexanedicarboxylic acid (H2CDC), to generate
a breathing Ti-MOF, termed COK-69.27 The microcrystalline material represents the first flexible Ti-based MOF, in which the
powder of COK-69 was solvothermally produced by the reaction linker trans-1,4-cyclohexanedicarboxylate (CDC) can transform its
of [Cp2TiIVCl2] precursor and H2CDC in DMF solvent in the conformation to adopt either the equatorial e,e 0 or the axial a,a 0
presence of acetic acid at 110 1C for 48 h. position. In the as-synthesized sample, COK-69 contains DMF
COK-69 represents a triangular geometrical cluster similar guest molecules inside the pores; the ratio of the a,a 0 /e,e 0 con-
to the exemplary Fe–oxo clusters found in MIL-100, PCN-332, formation was found to be 1/1. Moreover, 100% a,a conformation
and PCN-333.28 In particular, trinuclear Ti(IV)3(mO)O2(CO2)6 is of the CDC linking units, proven by 13C NMR spectroscopy, was
an unprecedented Ti(IV)-based cluster in Ti-MOF chemistry. In observed after the activation step to evacuate the trapped solvents
addition, the crystal structure of COK-69 clearly reveals that this (DMF). The open-pore size was calculated to be 4.9 Å, which is

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Fig. 4 Crystal structure and topological deconstruction of COK-69.
(a) The triangular Ti(IV)3(mO)O2(CO2)6 and CDC linking units are simplified
as 6- and 2-c, respectively. This combination results in the 3-D COK-69
structure (b) corresponding to the acs topology. Color code: O, red; C,
black; Ti, blue polyhedral. H atoms are omitted for clarity. Yellow balls are
placed in the cages to show the pores.
larger than the closed-pore size of 2.7 Å. The underlying net of
COK-69 was identified after structural simplification, in which
the presence of triangular clusters and ditopic organic linkers
were simply reduced to 6-c and 2-c, respectively. The combination
of 2-c and 6-c nodes formed an acs topology in the COK-69
structure (Fig. 4), which adopts [1 1 2 2] transitivity and two types
of tiling abbreviated as [43] + [4362] (Table 1).
At the same time, Long and co-workers reported the first
Ti-MOF based on a Ti(III)–oxo cluster29 whose structure is
an analogue of MIL-101.30 The synthesis of MIL-101(Ti) was
rigorously maintained under inert conditions using a glovebox
and vacuum Schlenk line system. Indeed, the mixture of
anhydrous DMF/ethanol was transferred to a Schlenk flask that
had been charged with TiCl3 salt and 1,4-benzenedicarboxylic
acid (H2BDC) executed in the glovebox. The reaction solution
was then heated at 120 1C under positive N2 pressure with
stirring for 18 h to yield MIL-101(Ti) as a dark purple powder.
Although it shows clusters with triangular geometry, similar
to COK-69, MIL-101(Ti) is the only recent example of an MOF
constructed from a Ti(III)–oxo cluster and a tritopic linking
block (BTC) with high porosity (2970 m2 g1 based on the
BET method).29 The conformation of the Ti(III) cluster in
MIL-101(Ti) is presented in Fig. 5, in which all Ti(III) atoms
are directly capped with solvent molecules (ethanol). After
solvent exchange and activation under vacuum and at high
temperature (150 1C), one guest solvent molecule was evaporated,
leaving an unsaturated Ti(III) atom. Due to the strong interaction
of O2 with Ti(III) atom, titanium(IV) superoxo and peroxo species
were generated by reaction of oxygen molecules and titanium(III)
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Fig. 5 Structural conformation of the triangular Ti(III) cluster containing
Ti–OEt and Ti–solvent linkages (a). A Ti–solvent bond was evacuated after
the activation step conducted under vacuum at 150 1C (b). The Ti(IV)
superoxide (c) and Ti(IV) peroxide (d) formed by the reaction of O2 and
the unsaturated Ti(III) cluster. Color code: O, red; C, black; Ti, blue. Modified
with permission from ref. 29. Copyright 2016 American Chemical Society.
complexes.31 This observation was proven by O2 adsorption
measurements, in which at 25 1C, MIL-101(Ti) exhibited very
steep isotherms at low pressures and reached a capacity of
0.85 mmol g1 (2.6 wt%) at 0.9 mbar. This phenomenon is due
to a chemisorption process inside the structure of MIL-101(Ti).
The presence of Ti(III) atoms in the structure was proven by
electron paramagnetic resonance (EPR) studies, which clearly
showed coincidence between the relevant g values for oxidized
MIL-101(Ti) and literature values.29
Crystalline 3D frameworks of metal-catecholates (M-CAT) are
porous materials constructed from metal ions and catecholate-
based organic units as a type of linker, similar to MOFs.32 In
2015, Nguyen et al. determined the synthetic conditions to afford
the first 3-D Me-CAT (Me = V, Ti, or Fe).33 In this study, Ti-CAT-5 was
constructed from H6THO [THO6 = triphenylene-2,3,6,7,10,11-
hexakis(olate)] and a single titanium atom. In particular, Ti-CAT-5
was prepared by heating a solution mixture of DMF/water/
methanol, dissolved titanium isopropoxide, H6THO, tetrabutyl-
ammonium nitrate, and amylamine to 180 1C for 48 h.
The 3-D crystal structure of Ti-CAT-5 was solved by PXRD
and electron density map (EDM) generation through the
Charge Flipping method.34 In particular, Rietveld refinement
provided the convergence residual factor with Rp = 5.66%, Rwp =
8.05%. Ti-CAT-5 crystallizes in a primitive cubic lattice with a
cell parameter of a = 17.996 Å and the P213 space group, as
extracted from the indexing results. The SBU of Ti-CAT-5 was
built by the connection of 3 catachol fragments, abbreviated as
Ti(C2O2)3, which were linked to each other through THO building
units. It is noted that the combination of the 3-connected nodes
of the Ti(C2O2)3 cluster and THO in Ti-CAT-5 produces a 2-fold
interpenetrated srs network due to the relatively large pore
space (Fig. 6). The pore space of this structure, which covered
two dimethylammonium (DMA) counter ions, was created by
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Fig. 6 Synthetic scheme demonstrating the formation of 3-D Ti-CAT-5.
The combination of a single Ti building block and THO unit forms the
2-fold interpenetrated framework of Ti-CAT-5. Color code: O, red; C,
black; Ti, blue; second framework, grey. The yellow ball indicates the free
space in the cage. H atoms and DMA anions are omitted for clarity.
interlocking two frameworks in which the center-to-center
distance between two THO linkers of the framework was found
to be 6.6 Å. The discovery of Ti-CAT-5 contributed greatly to our
understanding of the architectures and physical and chemical
properties of MOFs as well as the promise of accessing new
properties in the scope of Ti-MOFs.
Very recently, Assi et al. presented a study that utilized the
synthetic scheme of reacting 2,5-dihydroxyterephthalic acid
(H4DOBDC) with titanium(IV) precursors to successfully synthe-
size three new Ti-based MOFs, namely MIL-167, MIL-168, and
MIL-169.35 MIL-167 was solvothermally synthesized by reacting
a solvent mixture of N,N-diethylformamide (DEF)/methanol at
180 1C for 24 h. An alternative procedure was slightly modified
to use glacial acetic acid and diethylamine in DEF solvent. The
temperature was reduced to 150 1C, and the reaction time was
5 d. No explanation was provided for the presence of acetic acid
and diethylamine in the alternative synthetic technique for
MIL-167. A similar procedure was applied to produce MIL-168,
which used catechol as the starting modulator. Moreover, MIL-169
was obtained at 150 1C in 72 h by the reaction of oxalalatotitanate
precursor, H4DOBDC, and catechol in distilled water.
In terms of crystallography, MIL-168 and MIL-169 can be
classified as 1-D and 2-D, respectively.35 In particular, MIL-168
was built from a connection of zig-zag chains containing
Ti(IV)(CO3)2(cat) (cat = catechol) building units. In the case of
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Fig. 7 The 3-c bulding unit of MIL-167 (a) was found to be identical to the
NTU-9 building block. The linkage of Ti(CO3)3 SBUs via DOBDC building
units forms the 3-D structure of MIL-167, whose topology belongs to the
single frame srs network (b). Color code: O, red; C, black; Ti, blue. H atoms
are omitted for clarity.
MIL-169, two Ti(IV)(CO3)2 SBUs directly share the m2-O atom,
which also acts as the edge that combines two layer chains of
the structure. In contrast, MIL-167 exhibited a 3-D structure in
which the building unit is Ti(CO3)3 (Fig. 7). This SBU is similar to
the SBU of NTU-9. However, the rotated direction of the DOBDC
linking units is different from the structural geometry of NTU-9,
resulting in a single frame srs topology which contains the
transitivity signature of [1 1 1 1] and a natural tiling of [103].
Heterometallic approach
Direct synthesis, which involves the reaction of various titanium
salts and organic linkers, is the typical method used to produce
Ti-MOFs. However, the high reactivity of the titanium precursor
leads to an increase in the reaction speed and a decrease in the
possibility of obtaining large crystals. In order to form single
crystals of Ti-based MOFs by solvothermal reaction, Cui and
co-workers proposed the bimetalic synthetic strategy, in which a
titanium-based metallosalan organic linking unit was initially
synthesized and used as a starting reagent which was then
combined with biphenyl-4,4 0 -dicarboxylic acid (H2BPDC) and
Cd salt to form a 3-D Cd–Ti–oxo cluster-based MOF. This
material was the first single crystal Ti-MOF based on a carbox-
ylate linker and chiral salen linking unit (Fig. 8).36
Interestingly, the linker H2L first linked to Ti(OBu)4 to
generate the titanium-based salan linking unit, which is a
6-connected point of extension. The combination of the

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Fig. 8 Synthetic scheme for the production of bimetalic Cd–Ti-MOF-1.
metallosalan-based building block and hexameric Cd–oxo cluster
via pyridine bonds extended the structure to a 2-D framework.
Finally, BPDC acted as a pillar to connect these layers to each
other, resulting in a 3-D structure. The hexameric Cd-based
building units stacked to create a 0.5 nm  1.5 nm 1-D channel
(Fig. 9). The topological analysis for Cd–Ti-MOF was found to be a
new net, which had not been published before and does not exist
in the RCSR or TOPOS databases.37,38 For future reference, we
will refer to this net as the ctm topology. The connection of the
4,6-c points of extension in ctm leads to a binodal network that
possesses 2 different vertices, 3 different edges, 5 different faces,
and 3 different tiles. The signature for natural tiling is [462] + [62
82]. The metallosalan-based approach for Ti-MOF single crystal
preparation was successfully applied to synthesize Me–Ti-Silan-1
(where Me equals Cd or Zn).39 Indeed, the chiral Ti–salan
complex based on carboxylate and a pyridine terminal was
obtained by the designed synthesis. The solvothermal reactions
of Ti-metalloligand and TiL(OBu)2 with CdBr24H2O and
Zn(OAc)22H2O afforded Cd–Ti-Silan-1 and Zn–Ti-Silan-1,
respectively.
Using heterometallic MOFs that contain metal(II) ion and
metal(IV) ion within the SBUs can reduce the complications of
Fig. 9 Crystal structure of Cd–Ti-MOF-1 (a) and its topological network
(b), which is unknown in the RCSR and TOPOS databases. Color code: O,
red; C, black; N, green, Ti, blue; Cd, orange. H atoms are omitted for clarity.
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the MOF formulation process, such as insoluble metal oxides,
which disrupt crystalline growth in Me(IV)-based MOFs.40,41
The synthetic approach that exploits the presence of
bi-functionalized carboxylate and hydroxyl within the integral
organic building blocks to simultaneously bond to Zn2+– and
Ti4+–oxo clusters was first reported by Chun and co-workers in
2013. Taking advantage of the two metal–oxo clusters, which
are stoichiometrically included in the crystal structures of
ZTOF-1 and ZTOF-2, these frameworks were stabilized and
crystalized in large crystals. In particular, heterometallic MOFs
based on 2-hydroxyterephthalic acid (H3OBDC) and Zn6Ti2
clusters were obtained as orange crystals.40 A similar procedure
was used to synthesize ZTOF-2 by a combination of an analogue
linker of H3OBDC, 3-hydroxy-2,7-naphthalenedicarboxylic acid
(H3ONDC), and the bimetallic–oxo cluster Zn6Ti2 in the
presence of 1,4-diazabicyclo-[2.2.2]octane (DABCO), which
acted as the linking pillar of the 3-D framework (Scheme 1).41
Indeed, the SBUs of ZTOF-1 was composed of Zn6Ti2 with
6 Zn atoms linked to each other through m3-oxo linkages.
Moreover, 2 tetrahedral Zn atoms in the center of the Zn6Ti2
SBU share the edge via O–O bonds from carboxylate, while the
octahedral Ti atom is located at the head and terminal of the
Zn6–oxo block (Fig. 10a). Simplification of the heterometallic
SBUs in ZTOF-1 afforded a uninodal structure constructed by
the connection of 6-connected nodes through ditopic linking
units, resulting in the bcu topology (Fig. 10b). In the case of
ZTOF-2, the pillar created by DABCO links the Zn3 clusters to
each other and contributes to the generation of 2 tetrahedral Zn
building blocks, which contain 3 Zn–O bonds and one Zn–N
linkage. The last octahedral Zn atom was located in the center
of the homometallic SBU. In addition, the heterometallic SBU
in ZTOF-2 was formulated from 3 tetrahedral Zn atoms located
in the middle of the Zn3Ti2 SBU and 2 octahedral Ti atoms,
where each single Ti atom acted as a 3-connected node
(Fig. 10a). In terms of topology, the Zn3Ti2 SBU was simplified
as one node possessing a 6-connected point of extension. This
point directly linked to the 8-c node of the pinwheel Zn3
clusters, generating an seh network (Fig. 10b). The connection
of Ti atoms in the Zn3Ti2 SBU with the central Zn atoms from
the pinwheel Zn3 clusters generated a 12-faced polyhedron,
termed a trapezo-rhombic dodecahedron, covering the pore,
which was found to be ca. 16 Å in internal diameter. It should
Scheme 1 Representations of the syntheses of ZTOF-1 and ZTOF-2,
which possess heterometalic Zn/Ti–oxo clusters.
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Fig. 10 Representative structures of ZTOF-1 and ZTOF-2, which exhibit
heterometalic SBUs, (a) and response topological network (b). Color code:
O, red; C, black; N, green, Ti, blue; Cd, orange. H atoms are omitted for
clarity.
be noted that the surface areas of ZTOF-1 and ZTOF-2 calculated
by the BET method were 1045 and 1878 m2 g1, respectively.
These values are comparable with those of other highly porous
Ti-MOF materials, such as MIL-125, MIL-125-NH2, and PCN-22,42
which will be discussed in the next section. The success of
heterometallic-based MOFs was further investigated by Chun
and co-workers. He combined Co(II)Ti(IV) with terephthalic acid
(BDC), forming CTOF-1, or 2-hydroxyterephthalic acid, producing
CTOF-2, an isoreticular structure of CTOF-1.43 Both materials
were formed from triangular building blocks, Co2TiO(CO2)6
SBUs, and linear building units to generate an open acs frame-
work with intriguing dynamic properties.
Reticular chemistry method
A reversible bond association/dissociation process in Ti-MOF
synthesis is extremely difficult due to the strong Ti–O bond, which
is a challenge to achieving crystalline Ti-MOFs. The building block
synthesis method uses the metal cluster as a starting reagent to
link to the organic linker. This methodology is also known as
reticular chemistry,44 meaning that the designed structures were
precisely predicted by topological principles.38,44
The linking of terminal ligands to metal–oxo clusters was
subsequently replaced by linking of ditopic organic units to form
MOF structures. This synthetic method was reported by Guillerm
et al., who synthesized UiO-66-type analogues from zirconium
methacrylate–oxo cluster and the corresponding organic linkers
(trans,trans-muconic acid for Zr-muconate and H2BDC for
UiO-66).11 The building block approach was also applied to synthe-
size MIL-125 from Ti8O8(OOCC(CH3)3)16 clusters and H2BDC,22 as
reported by Hendon et al. in 2013. Recently, Yuan et al. reported a
similar technique using a hexameric tianium–oxo cluster,
Ti6O6(AB)6(i-OPr)6 (AB = 4-aminobenzoate); this building block
reagent was reacted with tetrakis((4-carboxyphenyl)porphyrin)
(TCPP) to generate a Ti-MOF, PCN-22, based on the porphyrin unit.
Interestingly, after formation of the MOF, the titanium–oxo cluster
was found to be rearranged, yielding an unprecedented heptameric
Ti7O6 cluster (Fig. 11).42
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Fig. 11 Crystal strcuture of PCN-22 viewed from the a direction (top) and
b direction (bottom), comprising a TCPP linking unit and an unprecedented
Ti7O6 cluster. Color code: O, red; C, black; Ti, blue. The yellow ball indicates
the free space in the cage. H atoms are omitted for clarity.
The topological analysis of PCN-22 was conducted using the
TOPOS pro package,38 in which the crystal structure was
initially simplified to yield a simple net through the edges
and nodes. Particularly, the Ti7O6 SBU can be divided into two
parts that are symmetric to each other by the octahedral Ti
central atom acting as the intersection point of the C2 axis and
Ti6O6 plane. In order to simplify the net, the octahedral Ti
central atom was assigned as the edge linking two Ti3O3 SBUs,
which were then reduced to two 7-c nodes. The TCPP linking
units are clearly 4-connected nodes that combine the 7-c nodes
of the Ti–oxo SBUs to generate a binodal 4,4,7-c network,
showing a new topology (Fig. 12). We will refer to this net as
the kim network in future discussions. It is noteworthy that the
PCN-22 structure can be alternatively simplified by the connection
of 4-c TCPP linking units and 12-c of the Ti7O6 cluster, forming a
4,4,12-c trinodal network with (4-c)2(4-c)(12-c) stoichiometry.
Interestingly, depending on how the augment node is analyzed,
4-c of the point of extension of TCPP could be assigned as the
connection of 3 3-c nodes. In this case, the topological network
was found to be a 3,3,12-c net, corresponding to (3-c)8(3-c)4(12-c)
stoichiometry.
In situ cluster generation
Only MIL-125 and PCN-22 were successfully obtained by the
building block synthetic approach; finding a new synthetic
technique to produce Ti-MOFs remains a challenge. Using
robust synthetic conditions, which avoid cluster decomposition
during MOF growth, in situ cluster generation was described in
the synthesis of MOF-90145 and MOF-90246 reported by Nguyen
et al. In particular, 4-aminobenzoic acid was first reacted with

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Fig. 12 Topological deconstruction of PCN-22. (a) Ti7O6 cluster simpli-
fied by two SBUs of 7-c nodes, linking to 4-c of the TCPP linker to form the
unprecedented kim network (b).
Scheme 2 Synthetic strategy combining MOF and COF chemistry via
in situ cluster generation and an imine condensation reaction. Color code:
O, red; C, black, N, green, Ti, blue.
titanium isopropoxide to generate in situ Ti6O6(AB)6(OMe)6
clusters, which were then linked to each other through an
imine condensation reaction by the combination of the amino
functionality and aldehyde moiety. MOF-902, possessing longer
imine linking units, is an isoreticular structure of MOF-901.
These are the first two examples exploiting robust synthetic
conditions to synthesize porous materials based on a combination
of MOF and COF chemistry (Scheme 2).
In particular, MOF-901 is based on the hexameric Ti6O6-
(AB)6(OMe)6 cluster, which possesses 6 4-aminobenzoate term-
inal chelates binding to a Ti6O6 triangular prism to form 6-c
points of extension. It is clear that the AB chelates are co-planar
and are then linked to each other through the imine condensation
reaction of the amino terminal and aldehyde functionality to
yield the 2-D crystal structure. The reaction of AB and 4,4 0 -
biphenyldicarboxaldehyde (BPDA) linking units formed the
imine linker with a distance of 24.10 Å, which is longer than
the 19.97 Å-imine linking blocks in the MOF-901 structure
(Fig. 13). The staggered frameworks in MOF-901 and MOF-902
generated hexagonal cages, whose pore sizes were found to be
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Fig. 13 Synthetic strategy combining in situ Ti6O6(AB)6(OMe)6 clusters
and aldehyde fuctionalities (a) to produce MOF-901 and isoreticular MOF-
902, which are presented as space filling models of their crystal structures
(b). Color code: O, red; C, black; N, green; H, pink; Ti, blue; second
framework, orange. Capping methoxide moieties have been removed for
clarity. Reprinted with permission from ref. 46. Copyright 2016 American
Chemical Society.
14 and 16 Å, respectively. The 2-D layer hxl topology adopting 36
faces was identified for both MOF-901 and MOF-902.
Post synthesis modification
The concept of post synthesis modification (PSM) in MOF
materials was first reported by Cohen and Wang,47 who anchored
an amide functional group into the framework of IR-MOF-3
through a condensation reaction. The PSM technique is useful
for the synthesis of MOFs containing bulky functionalities, which
cannot be obtained through direct synthesis because the geo-
metrical hindrance of organic linkers disrupts the MOF structure.
In addition, metal ion exchange by PSM results in more new
materials that include bimetal–oxo clusters, which cannot be
synthesized directly due to the highly reactive properties of metal
salts (Ti sources or Cr salts), resulting in new attractive properties
compared to the host materials.48,49
The manufacturing of Ti-based MOFs via PSM has been
demonstrated by many research groups.50–52 Ti atoms were
exchanged at the positions of host metal atoms in the metal
cluster by immersing the parent MOFs in organic solvent
containing titanium salts such as TiCl3 or TiX4 (X = Br or Cl).
A UiO-66(Zr/Ti)-type structure was reported by Kim et al.,
showing successful exchange by an increase of the percentage
of Ti atom from 53% to 94% (Fig. 14).53 MOF-5(Zn/Ti) was also
synthesized by partial PSM metal exchange of Ti(III) and Zn(II).
Although the percentage of Ti(III) in MOF-5(Zn/Ti) was only
found to be 2%,54 this synthetic scheme provided powerful
evidence that engineering the structural functionality can
afford new materials (Fig. 15).
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Fig. 14 The synthesis procedure of UiO-66(Zn/Ti) obtained by a PSM
method. In this strategy, UiO-66(Zr) was initially synthesized by a sol-
vothermal method, and the host material was then immersed in a solution
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containing the TiX4 source, resulting in UiO-66(Zn/Ti).
Fig. 15 The PSM strategy to produce MOF-5(Zn/Me) (where Me = Ti, V,
Cr, Mn or Fe). Reprinted with permission from ref. 54. Copyright 2016
American Chemical Society.
Very recently, Zhou and co-workers published a versatile
synthetic route for Ti-based MOFs preparation that used the
high valence metathesis and oxidation (HVMO) approach to
synthesize a series of porous photoactive titanium MOFs, PCN-
333(Sc)-Ti, MIL-100(Sc)-Ti, MOF-74(Zn)-Ti and MOF-74(Mg)-Ti
(Fig. 16).55 Indeed, these materials were initially acquired
through Sc(III) to Ti(III) or Zn(II)/Mg(II) to Ti(III) metathesis.
Subsequently, the metathesized materials underwent an oxidation
step, leading to the oxidization of Ti(III) to Ti(IV). The Ti atomic
Fig. 16 Synthetic scheme of the stepwise HVMO procedure using the
template MOFs (a) MIL-100(Sc) and PCN-333(Sc) to exchange with Ti(III) via
metal metathesis. The oxidation reaction was then followed by metal node
oxidation in air (it should be noted that PCN-333(Sc) and MIL-100(Sc) have
the same topology but different structures). (b) A similar process was
conducted to obtain MOF-74(Zn) and MOF-74(Mg).55 Reprinted with
permission from ref. 55. Copyright 2015 The Royal Society of Chemistry.
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percentages in PCN-333(Sc/Ti), MIL-100(Sc/Ti), MOF-74(Zn/Ti) and
MOF-74(Mg/Ti) were proven by ICP-MS, which displayed that high
concentrations of Ti replaced Sc, Zn, and Mg atoms, respectively
[88.8%, 48.8%, 94.7%, and 37.9% Ti for PCN-333(Sc/Ti), MIL-
100(Sc/Ti), MOF-74(Zn/Ti) and MOF-74(Mg/Ti), respectively].
Clearly, the success of utilizing the HVMO approach to synthesize
various Ti-based MOFs from MOF platforms not only introduced
an effective methodology for the synthesis of Ti-MOFs, but also
opened a pathway to explore the promising features of Ti-based
MOF materials, such as photoresponsive properties, which are
related to photocatalytic applications, and redox activity.
Applications of Ti-MOFs
Photocatalytic applications
Semiconductor photocatalysis provides an environmentally
friendly technology that exploits solar energy to convert carbon
dioxide and water to hydrocarbons and oxygen. The first
photocatalytic study of water splitting was demonstrated by
Fujishima and Honda in 1972, in which titanium dioxide (TiO2)
generated hydrogen and oxygen under UV irradiation.56 The
discovery of the photocatalytic properties of TiO2 inspired the
research field of photocatalysts based on TiO2 and related
materials. However, the large bandgap energy (3.2 eV) of TiO2
not only limits57 its activity in the UV region, which represents
only 5% of the solar spectrum, but also makes it unsuitable for
some photoreactions that require high energy of the catalyst to
activate the initial reagent. The first study of the photocatalytic
properties of a MOFs material demonstrated the degradation
of phenol by MOF-558 in aqueous solution. Although the
structural transformation of MOFs based on Zn–oxo carboxylates
was later confirmed by Hausdorf and co-workers,59 the photo-
activities of MOFs generated more interest in the research fields
of phototransformation and renewable energy.60
MOFs based on Ti–oxo clusters are materials whose redox
and photocatalytic activities may be exploited in future to explore
studies of their photoreactions and photocatalytic applications.
As discussed in the previous section, the exemplary MIL-125
contains 8-member ring Ti–oxo clusters. These clusters are linked
to each other through BDC building units. The photoresponsive
properties of MIL-125 were demonstrated by the light absorption
spectrum, which exhibited broad and intense bands in the visible
light region (400 to 800 nm), as indicated by two maxima located
at 250 and 300 nm.21,22 The band gap energy of MIL-125 was
predicted based on the HSE06-calculated VB and CB energy,
which was found to be 3.60 eV,22,61 which is in good agreement
with the experimental estimation. Interestingly, under UV
irradiation, benzyl alcohol adsorbed inside the MIL-125 frame-
work under inert gas (nitrogen) clearly changed color from
white to purple-gray-blue within a few seconds (Fig. 17).
The phenomenon of the fast photochromic effect was
further explained by intervalence electron transfer hopping in
the bivalence-based cluster of MIL-125, which simultaneously
contained Ti(III) and Ti(IV); this was observed and proven by EPR
spectra. The transition valence of MIL-125 was helpful for the

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Fig. 17 The photochromic effect observed when benzyl alcohol was
loaded in MIL-125 after UV light irradiation (a). The proposed mechanism
for the reduction of MIL-125 under irradiation (b). Modified with permission
from ref. 21. Copyright 2015 American Chemical Society.
photo-oxidation reaction of alcohols to aldehydes under UV
light excitation. This observation, which demonstrates the
photoredox activity of Ti-based MOFs, additionally suggests
them to be promising candidates as potential photoactive
catalysts in practical applications. The alcohol oxidation reaction
of ethanol was similarly conducted using COK-69 under a UV-A
(l = 315–400 nm) light source, affording a color change from
white to blue, which indicated the transfer of Ti(IV) to Ti(III).27
Although it possesses a triangular Ti(IV)–oxo cluster, COK-69
also exhibited an identical bivalence transfer phenomenon to
MIL-125.
By incorporating the porphyrin-based linking unit into a
highly ordered porous material, the resulting MOF, based
on the high efficiency of the porphyrin antenna framework,
displayed high visible light photo-responsiveness compared to
MIL-125 and its derivatives. This desirable PCN-2242 structure
results in a low band gap energy of 1.93 eV, which is lower than
the values of 3.60 and 2.60 eV for MIL-125 and MIL-125-NH2,
respectively, and corresponds to a broad range of absorption
(200–640 nm) of visible light. The red-shifted visible light
absorption of PCN-22 indicates that this material is an active
photocatalyst that can promote the transformation of photo
reactions. In particular, the oxidation of phenyl alcohol to
benzaldehyde was demonstrated under a PCN-22/TEMPO catalyst
system (where TEMPO = 2,2,6,6-tetramethylpiperidinyloxyl) and
various catalysts such as TiO2, TCPP, a mechanical mixture of
TiO2 and TCPP, and PCN-224 (a Zr-porphyrin-based MOF). The
experimental results clearly showed that PCN-22 outperformed
other candidates, as indicated by the observation of a twofold
higher conversion of benzaldehyde over 2 h of reaction time.
Taking advantage of its good photoresponsive properties,
NTU-9 exhibited excellent properties of a p-type semiconductor
in promoting the degradation of organic dyes. Indeed, the
photocatalytic activity of NTU-90 was studied for the degradation
of rhodamine B (RB) and methylene blue (MB) in aqueous solution
under visible light irradiation (l 4 420 nm). The photocatalytic
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experiments showed that RB and MB were degraded completely
after 80 min and 20 min, respectively.26 In addition, the photo-
catalytic properties and the crystallinity of NTU-9 were retained
after 6 h of experimental testing, as proven by consecutive
recycling results and PXRD analysis, respectively.
Currently, photocatalytic hydrogen production from water
splitting is an important topic that is receiving much consideration
from the chemical research community. Semiconductor-type photo-
catalysts are being developed to conduct this process. However, the
challenge of current photocatalysts is that these materials are only
activated under UV irradiation, similar to MIL-125, COK-169 or
MIL-167, which accounts for only 2% to 3% of natural solar
energy.62 In order to overcome these problems, photocatalysts
are being modified to achieve a high optical response that can
transform light absorption to the red-shifted region, resulting in
low band gap energy materials. In this context, the PSM method
was used to prepare materials possessing highly conjugated
systems (p–p interaction liking units, using more electron-
donating functional groups in the framework),9,46,63 resulting
in a high photoresponse, which is attributed to ligand-to-metal
charge transfer (LMCT).64 The optical engineering approach for
reducing the band gap energy of MIL-125 was introduced by
Hendon et al. by exploiting the amino functional groups in the
framework.65 The resulting material, MIL-125-NH2, is an iso-
reticular structure with MIL-125; however, it possesses a lower
band gap energy compared to the host material (2.60 eV for
MIL-125-NH2, compared to 3.60 eV for MIL-125). In addition,
the introduction of various functional BDC-X linking units
(X = CH3, Cl, OH) into MIL-125 was reported.
In 2012, Masuoka and co-workers utilized the photocatalytic
activity of MIL-125-NH2 for the photocatalytic hydrogen production
reaction.66 The LMCT (linker-to-cluster charge transfer (LCCT) was
used in that work) mechanism was illustrated by the results of
in situ ESR experiments. After 3 h of visible light irradiation, the
sample was applied to measure ESR at 77 K. It is noted that the
characteristic behaviour of paramagnetic Ti3+ atoms in a distorted
rhombic oxygen ligand field (gx = 1.980, gy = 1.953, and gz = 1.889)
was clearly observed. In contrast, no Ti3+ signal was observed on
conducting an identical experiment under the same conditions
using MIL-125 catalyst. This result confirmed that LMCT in MIL-
125-NH2 occurred following the hydrogen production reaction,
which transferred an electron from the excited BDC-NH2
functionality to the titanium–oxo cluster, resulting in the
presence of Ti3+ (Fig. 18).
Taking advantage of the capabilities of a well-defined structure,
the surfaces as well as the frameworks of MOFs can be easily
modified through PSM to encapsulate more active molecules.67
Recently, using MIL-125-NH2 as a MOF platform to load active
metal complexes for further applications of hydrogen production
led to enhanced photocatalytic properties of the resulting material
compared to the parent MIL-125-NH2.68,69 In particular, MIL-125-
NH2 exhibited high chemical stability, suitable pore size for large
molecule encapsulation, and fast light-harvesting properties,
which is very important due to the necessity of charge separation
and electron transport inside the material during the reaction
process. In order to achieve an efficient photocatalyst for hydrogen
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Fig. 18 The photocatalytic hydrogen production reaction over Pt-supported
MIL-125-NH2 based on the LMCT mechanism, demonstrating electron
transfer from the excited BDC-NH2 linker to the titanium–oxo cluster,
generating Ti3+. Reprinted with permission from ref. 66. Copyright 2012
American Chemical Society.
production, van der Vlugt and Gascon and co-workers published a
study that combined the phototocatalytic features of MIL-125-NH2
and cobaloxime activity to produce Co@MIL-125-NH2, which
was prepared by a stepwise PSM approach (ship-in-a-bottle
technique).68 Indeed, the ligand was initially loaded into the
pores of MIL-125-NH2, followed by reaction of the Co2+ source
with the ligand@MIL-125-NH2 processed inside the pores to
create the targeted material. The hydrogen production reaction
was then conducted in Co@MIL-125-NH2 and the host material
MIL-125-NH2. Interestingly, the catalytically active site of the
Co complex loaded into MIL-125-NH2 exhibited a 20-fold
enhancement in the H2 production reaction compared to the
pristine MIL-125-NH2.
Very recently, Jiang and co-workers introduced the encapsulation
of a Co(II) complex, [CoII(TPA)Cl][Cl] (TPA = tris(2-pyridylmethyl)-
amine), acting as a molecular photocatalytic site, into MIL-125-NH2
to prepare a new photocatalyst with efficient spatial separation of
electrons and holes (Fig. 19).69 The catalytic tests conducted under
visible light showed that the 1.97% Co(II) complex encapsulated into
the pores of MIL-125 was able to generate H2 evolution with the
highest H2 production rate (553 mmol g1 h1) compared to
17 mmol g1 h1 for pristine MIL-125-NH2.
Fig. 19 The ‘‘ship-in-a-bottle’’ synthetic pathway to produce Co(II)@MIL-
125-NH2 photocatalyst. Reprinted with permission from ref. 69. Copyright
2016 American Chemical Society.
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It is accepted that capturing and efficient use of CO2 are
currently important issues due to the issue of global warming.
Using MOF photocatalysts to convert CO2 into valuable organic
products has received much attention in both academic and
industrial research. In 2012, Li and co-workers reported for the
first time the use of MIL-125-NH2 for CO2 reduction under
visible light irradiation.70 Acetonitrile (MeCN) and triethanol-
amine (TEOA) were utilized as organic solvent and sacrificial
agent, respectively, to conduct the CO2 reduction experiments.
Under visible light irradiation and the presence of MIL-125-NH2
catalyst, the formation of formate anion (HCOO) in the liquid
phase was detected, which reached 8.14 mmol after 10 h of
reaction time. This study not only opened an avenue for the
application of CO2 reduction using photoresponsive catalysts
such as MOFs and related porous materials, but also demon-
strated the power of crystal structure modification technique in
crystalline engineering for further applications;71,72 just recently,
Uribe-Romo and co-workers explored the photocatalytic activity
of an isoreticular series of titanium-based MIL-125.71 N-Alkyl
substituted MIL-125-NHR (where R = methyl, ethyl, isopropyl,
n-butyl, cyclopentyl, cyclohexyl, or n-heptyl) was synthesized and
fully characterized; it was also applied for CO2 reduction under
blue light. The CO2 conversion using MIL-125-NHR catalyst
reached a higher yield compared to pristine MIL-125-NH2, as
indicated by the increased excited-state lifetime.
The framework engineering technique was further studied
by Gascon and co-workers, who demonstrated the uses of PSM
to extend the visible light absorption region of MIL-125-NH2 and
methyl red MIL-125 (MR-MIL-125) via anchoring of antenna-like
moieties.73 Very recently, the photocatalytic performance of MIL-125
and analogue MIL-125-NH2 was evaluated with increasing amounts
of amino functionality. Mellot-Draznieks and co-workers reported
the synthesis and characterization of MIL-125-NH2 with various
percentages of BDC-NH2 in the structure (0%, 20%, 46%, 70%, and
100%).62 Although 100% BDC-NH2 was able to transform visible
absorption to the red-shifted region, corresponding to decreased
band gap energy, it did not achieve the best results for the benzyl
alcohol oxidation reaction. The maximum photocatalytic properties
of MIL-125 with mixed BDC and BDC-NH2 in the structure were
found at B50% BDC-NH2. This finding provides an important
insight to further guide linker exchange and crystal structure
engineering for photocatalytic activity enhancement within MOFs.
Engineering the crystal structure of Ti-based MOFs undoubtedly
leads to targeted structures possessing suitable band gap energies as
well as active sites, which enhances the photoactive properties of the
materials. Taking advantage of the well-defined topological net-
works and stability of the Ti-MOFs, the active sites were decorated
either into the pores of the MOFs through interaction between the
post modification motifs and the MOF framework or on the linking
units via chemical reactions. Another method for post synthesis
modification was reported by Yuan and co-workers, who success-
fully modified and synthesized graphitic carbon nitride as a support
of MIL-1254 to prepare new photocatalytic systems exhibiting high
photocatalytic activity for Cr(VI) reduction and dye mineralization in
wastewater under visible light irradiation. Recently, Wang et al.
reported the technique for in situ synthesis of In2S3@MIL-125

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core–shell microparticles. This material acted as an integrated
photocatalytic adsorbent, demonstrating high efficiency for the
removal of antibiotics (i.e., tetracycline) in wastewater.61
Highlighted potential applications
Based on their high photoresponsitivities, MIL-125 and MIL-
125-NH2 have been utilized in a wide range of photocatalytic
applications. However, the biological activity of Ti-based MOF
had not been reported and studied. Very recently, Silva and
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co-workers successfully modified fabrics, including viscose, linen,
and 100% cotton, with 3-glycidyloxypropyltrimethoxysilane,
followed by coating with MIL-125-NH2.74 The coated material
was characterized by PXRD, UV-vis spectroscopy, FT-IR and
scanning electron microscopy (SEM) with energy-dispersive
X-ray spectroscopy, which demonstrated the uniform coating
of the coated fabrics. Interestingly, the modified fabrics
exhibited antimosquito properties, both attracting and killing
mosquitoes. The proposed mosquito killing mechanism of
MIL-125-NH2 is that mosquitoes can easily find a person by
sensing temperature and carbon dioxide, which was produced
by the photodegradation of dimethylol dihydroxyethylene urea
under the MIL-125-NH2 photocatalyst. Hence, mosquitoes were
attracted to the modified fabrics. This study provides new
insight into the use of MOFs materials for novel applications
such as biological activity to address public health problems.
Recently, MIL-125-NH2 has been modified to achieve high
crystallinity using various Ti(IV) sources such as Ti(i-PrO)4 and
Ti(BuO)4 under reflux or solvothermal synthetic methods.
MIL-125-NH2 synthesized from Ti(BuO)4 salt by the solvo-
thermal method not only showed the highest internal surface
area (1553 m2 g1) compared to the other published MIL-125-
NH2 material, but also exhibited an ideal S-shaped isotherm for
water uptake measurement, with a steep increase at 0.2P/P0 of
relative pressure at 35 1C. The water uptake capacities of
Ti(BuO)4-derivative-MIL-125-NH2 were found to be 0.550 and
0.670 g g1 at P/P0 = 0.30 and 0.92, respectively. This result
outperformed comparable materials such as A520, MIL-100(Fe),
MIL-100(Cr), MIL-101(Cr), and MIL-101-NH2(Cr).75
One of the most important applications in industrial fields
is polymer chemistry. In particular, the global polymethyl
methacrylate (polyMMA) market is anticipated to reach USD
8.16 billion by 2025.76 Hence, developing a strategy based on a
new catalyst for uniform and high molecular weight polyMMA
preparation is necessary. In this view, Nguyen et al. developed
two new Ti-based MOFs materials, MOF-901 and MOF-902,
possessing high optical response and low band gap energies
(2.65 and 2.50 eV for MOF-901 and MOF-902, respectively).45,46
PolyMMA, which was prepared using MOF-901 photocatalyst
under visible light irradiation, reached 26 850 g mol1 and a
polydispersity index (PDI) of 1.60. MOF-902 was found to be
more active than that of MOF-901, TiO2, and other related
Ti-based MOFs. MOF-902 could promote the reaction of poly-
MMA under identical conditions used for MOF-901; however, it
accounted for a molecular weight of 31 465 g mol1 and a PDI
value of 1.11.
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Conclusions and outlook
Although the discovery of Ti-MOFs faces challenges due to the
high reactivity of the starting titanium sources, the study of the
architectural design and new strategies for the preparation of
new Ti-MOFs are still dramatically developing. In this review,
we have summarized the progress of Ti-based metal–organic
frameworks developed in just one decade, including their
synthetic methodologies, crystal structures and topological
descriptions, and highlighted their applications. Particularly,
we would like to conclude that the synthetic conditions are an
important factor that contributes to determining robust synthesis
methodologies for the preparation of new MOFs. Moreover,
structural features and topological networks were selectively
evaluated to provide the chemistry of molecular design, topology,
and the power of reticular chemistry. These factors are irreplace-
able for most structural analyses, opening pathways to synthesize
crystalline materials. This study contributes to the overall road-
map for further research based on the crystallographic design of
novel Ti-MOF chemistry as well as post synthetic engineering for
novel applications. It is fair to note that most Ti-MOF studies
focus on photocatalytic applications for H2 production, CO2
conversion, organic dye degradation, and alcohol oxidation due
to the structural properties of Ti-MOFs, which are correlated to
their photoactivities. This may lead to the development of a new
Ti-based MOF that is not only stable in harsh conditions and
provides sufficient power for water oxidation, but can also reduce
the gap between academic research and practical applications.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
H. L. N. would like to pay final respects to his father who just
passed away. H. L. N. acknowledges Prof. Davide M. Proserpio
(University of Milan) for advanced discussion on topological
analysis and Mr Bao N. Truong (KITECH, Korea) for positive
suggestions and recommendations. H. L. N. also acknowledges the
funding from VNU-HCM under grant number VNUB-2017-50-01.
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