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Covalent organic frameworks (COFs): from design

Cite this: Chem. Soc. Rev., 2013,
to applications
42, 548
San-Yuan Ding and Wei Wang*

Covalent organic frameworks (COFs) represent an exciting new type of porous organic materials, which
are ingeniously constructed with organic building units via strong covalent bonds. The well-defined
crystalline porous structures together with tailored functionalities have offered the COF materials
superior potential in diverse applications, such as gas storage, adsorption, optoelectricity, and catalysis.
Since the seminal work of Yaghi and co-workers in 2005, the rapid development in this research area
Received 12th March 2012 has attracted intensive interest from researchers with diverse expertise. This critical review describes the
DOI: 10.1039/c2cs35072f state-of-the-art development in the design, synthesis, characterisation, and application of the crystalline
porous COF materials. Our own opinions on further development of the COF materials are also
www.rsc.org/csr presented for discussion (155 references).

1. Introduction made great progress1–13 in constructing numerous chemical

architectures with discrete (zero-dimensional, 0D) to extended
Inspired by nature’s ability to create complex systems with (1D, 2D, and 3D) structures by assembling the diverse building
advanced functions from atomic-level assembly, scientists have units in different ways. Fig. 1 depicts some representative
examples ranging from 0D discrete14–16 to 3D10 extended
State Key Laboratory of Applied Organic Chemistry, College of Chemistry and
structures, from inorganic17,18 to pure organic9 components,
Chemical Engineering, Lanzhou University, Lanzhou, Gansu 730000, China. from disordered19 to regular17 arrangements, and from non-
E-mail: [email protected] porous19,20 to porous21 nature. The elegant assembly of building

San-Yuan Ding was born in 1986 Wei Wang was born in 1972 in
in Jiangxi, P. R. China. He Xinjiang, P. R. China. He
received his BSc degree in 2008 received his PhD in physical
from Gannan Normal University. organic chemistry from Lanzhou
Then, he joined the research University in 1998. After his
group of Professor Wei Wang at postdoctoral research at
the State Key Laboratory of University of Stuttgart
Applied Organic Chemistry (2000–2001) and at University of
(SKLAOC) in Lanzhou Southern California (2001–2002),
University. Currently, he is he worked at the Institute of
completing his PhD in the Chemical Technology, University
design, synthesis, and of Stuttgart until 2006. He then
San-Yuan Ding application of functional Wei Wang moved back to Lanzhou
covalent organic frameworks University and was appointed as
(COFs). the Cheung Kong Professor from the Ministry of Education of
China. Currently he serves as the Deputy Director of the State Key
Laboratory of Applied Organic Chemistry (SKLAOC). The research
in his laboratory focuses on homogeneous and heterogeneous
organocatalysis, organic porous materials, and solid-state
NMR spectroscopy.

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Fig. 1 Selected examples for diverse assembly of building units to construct inorganic/hybrid/organic chemical architectures, ranging from the discrete
0D/non-porous/amorphous structures to the extended 3D/porous/crystalline structures. For clarity, many related systems, such as active carbons, mesoporous silicas,42
periodic mesoporous organosilicas,43 mesoporous carbons,44 and supermolecules,5,45,46 are not included herein.

units to these architectures has been achieved via different recently is the construction of (nano)porous organic polymers
connecting strategies based on weak1,4,22–25 (such as p–p stack- (Fig. 1), such as hypercrosslinked polymers (HCPs),31,32 polymers
ing) to strong interactions7–9,26,27 (such as covalent bonding). of intrinsic microporosity (PIMs),33,34 conjugated microporous
For example, the crystalline porous coordination polymers, i.e., polymers (CMPs),27,35 and so on.36 In these cases, construction
the hybrid metal–organic frameworks (MOFs),25,28 could be of persistent porous structures via covalent bonds becomes the
obtained via the coordinative assembly between metal ions main concern for advanced applications. The key strategy for
and organic ligands as the building units, the discovery of this purpose is the use of rigid building units with multi-
which represents an exciting breakthrough in coordination connectivities.37 This new field has found dramatic progress in
chemistry and materials science.10 the last decade, and excellent reviews on the synthesis and
On the other hand, the convergent strategies for assembling applications of these porous organic polymers have appeared
building units via covalent bonds have long been applied in the recently.8,21,27,34,37–40 However, the amorphous networks
total synthesis of natural products and pharmaceuticals (discrete together with wide pore-size-distribution may restrict, to some
0D structure).7 One of the most brilliant examples is Robinson’s extent, their further applications. In this context, the most
total synthesis of tropinone (Fig. 1) from succindialdehyde, prominent discovery appeared in 20059 when Yaghi and
methylamine, and acetone in one step in 1917.29 Chronologi- co-workers developed the crystalline porous organic polymers,
cally, the unprecedented application of organic synthetic strate- i.e., the so-called covalent organic frameworks (COFs). In their
gies in constructing the 1D disordered macromolecules (Fig. 1) seminal work,9 the first two 2D COF materials were ingeniously
resulted in the blossom of polymer science since 1920s.19,30 constructed via the dehydration reactions of 1,4-benzenedi-
Obtained via the covalent polymerisation of small building units boronic acid itself (COF-1) or together with hexahydroxytri-
(e.g., alkenes, amines, and acids), the synthetic organic poly- phenylene (COF-5, Fig. 1), respectively. The first synthesis of
mers, such as polyethylene, nylon, and polystyrene, have found 3D COF materials (one of them is COF-102, Fig. 1) appeared in
wide applications in daily life. An important development made 2007, which was also pioneered by Yaghi and co-workers.41

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Besides the basic concerns of the building units and syn- on the synthetic organic reactions and the building units which
thetic strategies as for the construction of amorphous porous have been successfully applied in the COF synthesis.
polymers, the designed synthesis of COF materials should In principle, all the synthetic methodologies for the
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simultaneously meet the demands for crystallinity and porosity.9 covalent-bond formation developed in organic synthesis are
In this regard, the design principles and synthetic experiences of potential interest for the construction of organic polymers.
for other crystalline porous materials (such as inorganic zeo- However, in order to construct the polymeric structure with
lites and hybrid MOFs, Fig. 1) may, therefore, provide insightful both structural regularity and porosity, many limitations still
information. In comparison with these crystalline porous exist, as in the case of COF materials. While the assembly of
solids, the COF materials possess the advantages of low density, building units in MOF systems could well be self-adjusted
large surface area, tunable pore size and structure, facilely- via the coordination bonds, the structural regularity of COF
tailored functionality, versatile covalent-combination of materials is much difficult to control via the strong covalent
building units, and so on. These advantages provide the COF bonds. It is by far believed that only the reversible reactions13
materials with high potentials in further applications for gas are applicable for the possible construction of crystalline COF
storage, adsorption, optoelectricity, catalysis, and as functional structures. Fig. 2 summarises the synthetic reactions success-
devices. The rapid development in this area has, therefore, fully applied for the COF synthesis. The reaction A is based
attracted increasing interest from scientific researchers on the reversible formation of boronate anhydride from the
working in the fields of materials, organic synthesis, and dehydration of boronic acid. Via this reaction, Yaghi and
diverse applications. co-workers synthesized the first COF material, COF-1.9 An
Several recent reviews8,21,37,38 on porous organic polymers analogous dehydration reaction (reaction B) between boronic
have included some of the COF issues, but no comprehensive acid and (acetonide-protected) catechol results in the reversible
review is available so far to focus specifically on this fascinating formation of boronate esters,9,48 by which a series of boron-
area. Accordingly, this review will give an overview on the containing COFs have been successfully obtained. Similarly,
current research in this area, which covers the design, syn- the dehydration reaction of boronic acid and silanol results in
thesis, characterisation, and applications of the COF materials. the formation of borosilicate (reaction C). The reaction D
We start with the survey of the synthetic reactions and the represents a unique method to synthesize the covalent
building units which have been applied for the COF synthesis triazine-based frameworks (CTFs) via the nitrile cyclotrimerisa-
(Section 2). It is then followed by the description of the design tion. The reactions E and F are based on the reversible formation
principles in terms of porosity, crystallinity, and functionality of imine bonds (–CQN–), by which several COFs have been
(Section 3). The different synthetic methods developed for the
COF synthesis are presented in Section 4. The classification of
the synthesized COFs and the survey of their structural pro-
perties are given in Section 5. Section 6 focuses on the char-
acterisation of COF materials, while Section 7 summarises the
applications of COF materials in gas storage, photoelectricity,
and catalysis. In Section 8, our own opinions on the further
development in this area are presented for discussion.

2. Basic concern: covalent bond formation of

building units
As discovered by Yaghi and co-workers in 2005,9 COFs are
crystalline porous materials with pure organic groups con-
nected via robust covalent bonds, which could be considered
as ‘‘organic zeolites’’. Besides the lower density, COF materials
possess many unique advantages in comparison with inorganic
zeolites. The crystalline zeolite structures are based on three-
dimensional frameworks via the multiple formation of Si–O–Si
and Si–O–Al bonds. The basic building units of zeolites are, in
most cases, limited as the silica and alumina tetrahedral. In
contrast, COF materials could be constructed from a variety of
rigid organic building units with different structural configura-
tions. The formation of strong covalent bonds through diverse
synthetic organic reactions between the building units provides Fig. 2 Reversible reactions that have been successfully developed for the
the COF materials with well-defined and predictable 2D or 3D construction of COF materials. The covalent bonds formed through these
crystalline structures. This section will, therefore, give a survey synthetic routes are highlighted in red.

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synthesized with the new networks. The dehydration of aldehyde demonstrated that the pore sizes of the synthesized 2D COFs
and amine gives rise to the Schiff-base type linkage (reaction E), could be tailored from 1.1 to 1.8 nm.49 Dichtel and co-workers
while that of aldehyde and hydrazide affords the hydrazone also found that the synthesized 2D square COFs possess the
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formation (reaction F). Although the synthetic reactions applied diagonal pore sizes varied from 2.7 to 4.4 nm, when diboronic
for the COF synthesis are still limited, it is expected that new and acids with different molecular lengths (3, 11, 12 and 13) were
diverse strategies will appear in the future to largely expand the applied.50 In this regard, if certain functional moieties are
synthetic scope of the COF materials. introduced into the building units, functional COFs could
Based on the synthetic reactions mentioned above, a further be obtained. For example, a semiconducting p-conjugated
variety of designed building units have found success in COF, TP-COF, has been synthesized by Jiang and co-workers via
constructing the COF materials. Fig. 3 summarises the building introducing the pyrene groups into the diboronic building
units being used, the general features of which are the unit.51 Furthermore, the structural topology of COFs could also
rigidity in structure and the symmetric multi-connectivities so be tuned via varying the shape of the building units. For
as to meet the requirement for constructing the regular pores of example, based on the same synthetic reaction B, the 2D
the COF materials. Most of these building blocks are boronic or 3D COFs could be synthesized with linear-shaped (1) or
acids and (acetonide-protected) catechols designed for the tetrahedral-structured (26) building units, respectively.9,41
construction of boron-containing COFs via the reactions These examples have clearly demonstrated that various possi-
A and B. bilities exist in the construction of COFs with varied building
In the zeolite cases, the building units are limited as silica units based on certain synthetic reaction. Detailed discussion
and alumina tetrahedral, and the structural topology is governed on this issue is available in Section 3.
by the templates and the hydrothermal conditions. In contrast, Though many building units and several synthetic reactions
the porous structure and functionality of COFs could be facilely have been developed, it is still not an easy issue for constructing
tuned with the building units, even based on the same syn- COFs with both porosity and crystallinity. Generally speaking,
thetic reaction. For instance, by employing the building units the crystallinity mainly requires the reversible formation of
(14a to 14d) with R in different lengths, Lavigne and co-workers covalent bonds13 in the COF synthesis, while the porosity

Fig. 3 Building units that have been successfully utilised for the synthesis of COFs.

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requires at least the rigid building units. The design principles of rigid building units and the careful selection of synthetic
for the COF synthesis will be discussed in the next section. reactions. It is highly likely that the reversible formation of
covalent bonds13 is of great importance in synthesizing the
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3. Design principles crystalline COFs, as it is in zeolite synthesis.17,26 However, even

these prerequisites have been well met, synthesis of COFs with
Similar to the case of MOFs, the COF materials to be syn- structural regularity is still not a guaranteed outcome. This
thesized could be designed through the principles of reticular issue has been demonstrated by Thomas and co-workers.56
chemistry.22,23,52–54 In both cases of MOFs and COFs, the basic When rigid but contorted nitrile building units were employed
concerns for design should focus on the porosity and the in the reversible cyclotrimerisation reaction, amorphous porous
structural regularity. In this regard, much experience has been materials were, however, obtained. This result implies that
obtained for the MOF systems, which should be applicable to the match of both shapes and angles of the building units
the COF synthesis as well. However, self-assembly of building should be taken into account for the reversible formation of
units to construct crystalline MOFs via the coordination bonds covalent bonds.
is much easier than that to construct crystalline COFs via As an example, we discuss herein the simplest cases in
the covalent bonds. Accordingly, the design principles for which one of the building units applied is linear. When this
inorganic zeolites might also provide additional insight into linear building unit is subject to reaction with another linear
the designed synthesis of COFs. Moreover, additional concerns building unit, the constructed material should be linear as well
for constructing functional COFs for certain applications (Fig. 4).60 When it reacts to those with the angle of 1201 or 901,
should also be invoked. the hexagon9 (Fig. 5) or tetragonal48 (Fig. 6) 2D COF structures
would be, respectively, assumed to obtain. Accordingly, when it
3.1 Porosity reacts with a tetrahedrally-structured monomer, a predicted 3D
The first concern for constructing COF materials, as for other COF structure would be afforded (Fig. 7).57 In this context, the
porous organic polymers, is the issue of porosity. In this regard, design principles in crystal engineering, which have well been
the design strategies applied to other covalently-bonded porous established for the formation of crystalline structures via
solids could be adapted to the COF synthesis. For example, the relatively weak interactions (e.g. hydrogen bonding or metal
templating method for synthesizing microporous zeolites and coordination bonding) may also be applicable for those of
mesoporous (organo)silicas employs the structural-directing crystalline COF materials.2,45,61
agents to assemble the building blocks.17,43,55 The template
extraction from the as-synthesized materials would provide the
porous structures. Another strategy is to use the rigid building
units to create the porous structures. For example, a series of
conjugated porous polymers have been successfully synthesized
from the rigid monomers via coupling reactions.27,33–36 To
date, most of the synthesis of porous COF materials applies
Fig. 4 Assembly of linear materials from linear building units.60
the latter strategy by designing the rigid building units to create
the extended porous structures. The molecular length of the
building units will, accordingly, govern the pore size of COFs,
while the shape of the building units will determine the
topology of the porous structure. In most cases, the linking groups
formed are boroxines,9 triazines,56 imines,57 or hydrazones,58
which are all rigid with a planar geometry. For the efficient
construction of porous structure, building units (Fig. 3)
with rigid aromatic moieties are preferable, as found in
most of the MOF structures23 and amorphous porous organic
materials.38

3.2 Structural regularity

Obviously, porosity concerns do not necessarily guarantee the
crystalline formation in the COF synthesis. Indeed, as mostly
found in porous organic polymers, the formation of strong
covalent bonds tends to produce the disordered materials.38,59
Therefore, in difference from that of amorphous organic poly-
mers, the control of structural regularity becomes the key issue
for the designed synthesis of COFs.
As addressed in Section 2, the prerequisites for possible Fig. 5 Assembly of 2D hexagonal COFs (COF-5 as an example) from linear and
construction of regular pore structures are the rational design trigonal building units.9

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for this purpose, which is similar to those applied for con-

structing other functional materials.43,62–64
The one most used is the post-synthesis strategy (route A
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in Fig. 8), which introduces the functional moieties into the

given COF networks via the subsequent modification, such as
coordinative incorporation or chemical transformation.63,64 As a
nice example shown in Fig. 9, the functionalised COF materials
have been successfully synthesized by Jiang and co-workers via
this strategy.65 First of all, the co-condensation reaction of
building units 1, 5 and 21 results in the azide-appended
N3-COF-5 as the parent material (Fig. 9). A series of triazole-
functionalised COFs could then be obtained via the Cu(I)-
catalysed ‘‘click’’ reaction of N3-COF-5 with various alkynes.
Though the pendent functional moieties might be inhomo-
Fig. 6 Assembly of 2D tetragonal COFs (Pc-PBBA COF as an example) from linear
geneously distributed and the crystalline COF structure could
and tetragonal building units.48
be disturbed, the post-synthesis strategy provides a versatile
access to the designed synthesis of functional COFs with
tunable properties for further applications. We also synthesized
the Pd(II)-coordinated COF-LZU1 material via a simple post-
treatment of COF-LZU1 with Pd(OAc)2 at room temperature.66
The obtained Pd/COF-LZU1 proves to be a highly efficient catalyst
in the Suzuki–Miyaura coupling reaction (see Section 7.3).
A straightforward but more difficult strategy for constructing
functional COFs is the bottom-up approach (route B in Fig. 8).
In this case, the functional moieties have to be directly included
in the designed building units prior to the COF synthesis. The
obvious advantage is that the homogeneous distribution of the
functional moieties can be reached and the hydrothermal or
chemical stability of the synthesized COFs may further be
improved. For this purpose, the design principles for the
periodicity and porosity should meet simultaneously the
demand for functionality. It therefore brings more trouble both
Fig. 7 Assembly of 3D COFs (COF-300 as an example) from linear and in the synthesis of functional building units and in the main-
tetrahedrally-structured building units.57 tenance of structural regularity of the functional COFs. Never-
theless, the bottom-up strategy has found great success in
constructing functional COFs for gas (ammonia) storage67
3.3 Functionality and for photoelectric applications (see Section 7).51 In this
The basic principles mentioned above focus on the periodicity regard, further development of the facile bottom-up strategy
and porosity towards the designed synthesis of crystalline is highly desired towards the diversity-oriented synthesis of
porous COF materials. In order to construct the functional functional COFs. To achieve this goal, the rigidity, shape, and
COFs for certain applications, however, further concerns on functionality of the building units have to be overall consid-
how to introduce the functional moieties into the COF net- ered, together with the synthetic reactions and optimal condi-
works should be invoked. Fig. 8 depicts the general strategies tions for the construction of crystalline COFs.

4. Synthetic methods of COFs

Given that the building units and synthetic routes can be
carefully selected based on the design principles discussed
above, finding suitable synthetic conditions for the COF syn-
thesis is by no means a trivial issue. Since Yaghi and co-workers
exploited the solvothermal method to achieve the first success
in the COF synthesis,9 many research groups have attempted to
expand the synthetic possibility in different ways. Herein, we
summarise the solvothermal,9 ionothermal,56 and microwave68
Fig. 8 General strategies for the designed synthesis of functional COF materials. methods applied for the COF synthesis. Methods for growing
The red ovals represent the functional moieties. COFs onto crystalline metal surfaces via the sublimation of

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Fig. 9 Post-modification of the pore surface of N3-COF-5 via the ‘‘click’’ reaction to construct the functionalised COFs.65 The percentage (x%) of the building unit 5 in
the original mixture could range from 5% to 100%. R represents the functional organic groups.

building units have been developed,69 which will be described

in this section as well. Our recent progress in synthesizing the
imine-based COFs at room temperature will also be briefly
mentioned.70

4.1 Solvothermal synthesis

Most of the synthesized COFs are obtained via the solvothermal
synthesis method. Similar to those for synthesizing inorganic
zeolites in autoclaves,17 the solvothermal synthesis of COF
materials often takes 2 to 9 days and requires heating (80–120 1C)
within a sealed vessel. The pressure inside the sealed vessel is
of importance, which may affect the reaction yields signifi- Fig. 10 PXRD patterns for the COF materials synthesized from the reaction of 30b
cantly. Yaghi and co-workers found that 150 mTorr is the and 14a in mixed solvents of mesitylene and dioxane. (Reproduced from ref. 72.)

optimal pressure in the vacuum line before the vessel is sealed

with a given volume (ca. 10 cm3).9 Noteworthily, Lavigne and
co-workers developed a reflux procedure under ambient Mechanistic studies further revealed that the self-dehydration
pressure to synthesize COF materials.71 This method is easy of boronic acids to boroxines and the formation of aryl boronic
to control, by which the COF-18Å material could be obtained in acid–BF3 complex would strongly influence the formation rate
3 days under ambient pressure without the use of sealed of boronate esters during the synthetic procedure.73
vessels. Moreover, the solvent chosen for the condensation Solvothermal methods often produce the COF materials as
reactions is crucial, as it governs the solubility of reactants. powders, which may limit their applications under certain
Also, the reaction rate determined by various synthetic para- circumstance, such as, for the interfaced incorporation into
meters is the key to obtaining the COF materials with structural devices. Dichtel and co-workers have recently developed a
regularity. As an example, the influence of solvents on the solvothermal method for producing 2D COF materials as thin
crystallinity of COFs has been demonstrated.72 Co-condensation films on single-layer graphene (SLG) (Fig. 11).74 As demon-
of zinc(II) 5,10,15,20-tetrakis(4-(dihydroxyboryl)phenyl) porphyrin strated by synchrotron X-ray diffraction analysis, the obtained
30b and 1,2,4,5-tetra-hydroxybenzene 14a in a mixture of COF materials exhibit improved crystallinity in comparison
mesitylene and dioxane with v/v = 1/1 resulted in amorphous with the powder samples. Scanning electron microscopy
solids as indicated by the PXRD measurement (Fig. 10, black). (SEM) was further applied to determine the thickness of the
In contrast, when the ratio of mesitylene and dioxane was COF films. Continuous layers of COF-5 film grown on SLG/Cu
changed to v/v = 19/1 or 9/1, COF materials with high crystal- could be obtained in 30 minutes with the thickness of 195 
linity could be obtained (Fig. 10, red and green). 20 nm (Fig. 12a) and with the area as large as 100 mm2
Recently, Spitler and Dichtel synthesized the boron-contain- (Fig. 12b). Some other 2D COF films could also be synthesized
ing COFs via the solvothermal procedure assisted with a Lewis via this method and exhibit unique properties.50 For example,
acid.48 This process employs acetonide-protected catechol as films of NiPc-PBBA COF on transparent SLG/SiO2 show strong
the reactant which could be deprotected in the presence of a absorption capacities of visible light. This elegant method not
Lewis acid catalyst (BF3
OEt2). This approach avoids the use of only achieves for the first time the assembly of functional COFs
unstable and insoluble polyfunctional catechols, and thus, into a large planar form, but also broadens the applications of
broadens the scope of the building units for the COF synthesis. COFs, especially for the potential use in optoelectronic devices.

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building units (e.g. 1,4-dicyanobenzene 7) in molten ZnCl2 at

400 1C affords the covalent triazine-based frameworks (CTFs)
with high crystallinity together with excellent chemical and
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thermal stabilities. The molten ZnCl2 salt plays important roles

in the CTF synthesis, not only as the solvent but also as the
catalyst for the reversible cyclotrimerisation reaction. In com-
parison with those COF materials obtained via the solvo-
thermal method, the CTF polymers have the disadvantage in
crystallinity control because the reversible cyclotrimerisation
reaction takes place under harsh reaction conditions. Also, the
requirement of high reaction temperature narrows the scope of
building units82 and thus, the ionothermal synthesis finds
limited applications so far. To date, only two building units
(7 and 8) have been successfully utilised to synthesize the
crystalline CTFs.56,83
Fig. 11 Solvothermal synthesis of 21 (HHTP) and 1 (PBBA) on a single-layer
4.3 Microwave synthesis
graphene surface, affording COF-5 as the film on the graphene surface and as the
powder precipitated around the bottom of the tube. (Reprinted with permission Microwave heating has been widely used as a means to accel-
from ref. 74. Copyright 2011 AAAS.) erate the chemical reactions.84,85 It has been found that crystal-
line MOF materials could be synthesized using microwaves.86,87
Accordingly, a rapid microwave-assisted method has recently been
developed by Cooper and co-workers for the COF synthesis.68,88
2D COF-5 and 3D COF-102 could be obtained via the microwave
heating in 20 minutes, which is more than 200 times faster than
the reaction time of 72 h required in the solvothermal synthesis.9
Moreover, the BET surface area of COF-5 (2019 m2 g 1) obtained
via microwave synthesis is slightly higher than that solvo-
Fig. 12 Cross-sectional (a) and top-down (b) SEM images of the COF-5 film on single- thermally synthesized in a sealed vessel (1590 m2 g 1). Com-
layer graphene/Cu. (Adapted with permission from ref. 74. Copyright 2011 AAAS.) pared with the solvothermal methods, microwave heating
allows the synthetic process to be completed in a faster and
cleaner manner, providing new possibility for further applica-
tions in large scales.

4.4 Room-temperature synthesis

Recently, we found that imine-based COFs could be facilely
synthesized at room temperature and ambient atmosphere.70
By avoiding both the use of sealed vessels and the difficulty in
controlling different synthetic parameters, this method makes
bulk production of the COF materials possible. The generality
Fig. 13 The STM image of the near-complete monolayer of SCOF-1 film of this approach is being under investigation.
synthesized from the deposition of 1 on Ag (111). The inset shows the proposed
chemical structure for SCOF-1. (Reprinted with permission from ref. 69. Copyright
2008 American Chemical Society.) 5. Types of synthesized COFs
Based on the design principles described above, COF materials
Methods for synthesizing the COF submonolayers on certain have been successfully synthesized so far with the diverse
crystalline metal surface have also been developed.69,75–81 For combination of the building units under optimal reaction
example, through the sublimation of monomer 1 under ultra- conditions. Table 1 summarises the structural properties of the
high vacuum, surface covalent organic frameworks (SCOFs-1) with reported COFs, which can be classified into three categories:
near-complete monolayer has successfully been obtained on Ag boron-containing, triazine-based, and imine-based COFs.
(111) (Fig. 13).69 The formation of molecular layers of SCOFs could
5.1 Boron-containing COFs
be directly monitored by scanning tunneling microscopy (STM).
Since the ingenious construction of the first COF materials
(COF-1 and COF-5) by Yaghi and co-workers,9 diverse synthesis
4.2 Ionothermal synthesis of boron-containing COFs through the formation of boronate
Thomas and co-workers exploited the ionothermal synthesis method ester or boronate anhydride has attracted intensive research interest.
to produce crystalline porous COFs.56 Cyclotrimerisation of nitrile Indeed, the most synthesized COFs so far are boron-containing

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Table 1 Structural information of the synthesized COFs

Pore sizec BET surface

Type Material Building unit(s)a Synthetic reactionb Space group (Å) area (m2 g 1) Ref.
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Boron-containing COF-1 1 A P63/mmc 7 711 9

COF-102 26 A I4% 3d 12 3472 41
COF-103 27 A I4% 3d 12 4210 41
PPy-COF 3 A P6/mmm 17 923 89
COF-102-C12 25a + 26 A I4% 3d — >2000 91
COF-102-allyl 25b + 26 A I4% 3d — — 91
COF-5 1 + 21/22 B P6/mmm 27 1590 9
COF-105 26 + 21 B I4% 3d 21 — 41
COF-108 27 + 21 B P4% 3m 19, 31 — 41
COF-6 17 + 21 B P6/mmm 9 750 92
COF-8 19 + 21 B P6/mmm 16 1350 92
COF-10 4 + 21/22 B P6/mmm 32 1760 92
COF-11Å 17 + 14d B P6/mmm 11 105 49
COF-14Å 17 + 14c B P6/mmm 14 805 49
COF-16Å 17 + 14b B P6/mmm 16 753 49
COF-18Å 17 + 14a B P6/mmm 18 1263 49
TP-COF 3 + 21 B P6/mmm 32 868 51
Pc-PBBA COF 1 + 29a B P4/mmm 20 450 48
NiPc-PBBA COF 1 + 28a/29b B P4/mmm 23 776 73 and 74
2D-NiPc-BTDA COF 2 + 28a B P4 22 877 93
NiPc COF 1 + 28a B P4/mmm 19 624 94
BTP-COF 19 + 15b B P6/mmm 40 2000 95
HHTP-DPB COF 11 + 21 B P6/mmm 47 930 90
x%N3-COF-5 5 + 21 B P6/m 18–29d 1421–2160 65
(x = 5, 25, 50, 75, 100)
100%N3-NiPc-COF 5 + 28a B P4/mmm 18d 675 65
COF-66 30a + 15a B P4/mmm 23 360 96
ZnPc-Py COF 3 + 28b B P4/mmm 27 420 50
ZnPc-DPB COF 11 + 28b B P4/mmm 34 485 50
ZnPc-NDI COF 13 + 28b B P4/mmm 40 490 50
ZnPc-PPE COF 12 + 28b B P4/mmm 44 440 50
CTC-COF 1 + 24 B P3m1 23 1710 97
H2P-COF 30a + 14a B P1 25 1894 149
ZnP-COF 30b + 14a B P1 25 1713 72 and 149
CuP-COF 30c + 14a B P1 25 1724 149
COF-202 16 + 26 C I4% 3d 11 2690 98
Triazine-based CTF-1 7 D P6/mmm 12 791 56
CTF-2 8 D P63/mmc 20 90 83
Imine-based COF-300 23 + 6 E I41/a 8 1360 57
COF-LZU1 9 + 18 E P6/m 18 410 66
COF-366 31 + 6 E P4/m 20 735 96
COF-42 10 + 18 F P6/m 28 710 58
COF-43 10 + 20 F P6/m 35 620 58
a b
See Fig. 3. See Fig. 2. c Calculated values based on the ideal periodic structures, unless otherwise noted. d
Experimental values.

materials which can be sorted into two categories according to

the synthetic strategies.
One category of boron-containing COFs is those constructed
via the self-condensation of single building units. For example,
the 2D COF-1 was synthesized through the self-condensation
reaction of 1,4-benzenediboronic acid 1.9 As shown in the
reaction A in Fig. 2, the condensation of boronic acid groups
produces boronate anhydrides with planar six-membered B3O3 Fig. 14 Self-condensation of monomer 1 (a) to synthesize 2D COF-1 with the
rings. As a result, the synthesized COF-1 material exhibits a proposed crystalline structure (b). (Adapted with permission from ref. 9.
layered staggered structure (Fig. 14b) with a BET surface area of Copyright 2005 AAAS.)
711 m2 g 1 and an average pore size of 0.7 nm. Moreover, 3D
boron-containing COFs have also been successfully synthesized
via the self-condensation of tetrahedrally-structured building 1590 m2 g 1 for COF-5). So far, monomers 1,9 3,89 26,41 and 2741
units, which exhibit much higher surface areas. For example, have been successfully applied to synthesize the boron-containing
3D COF-103 synthesized from the monomer 27 (Fig. 15) pos- COFs via the self-condensation strategy.
sesses a BET surface area of 4210 m2 g 1,41 which is much Another large category of boron-containing COFs is
higher than those of 2D COFs (e.g. 711 m2 g 1 for COF-1 and those constructed via the co-condensation of two or more

556 Chem. Soc. Rev., 2013, 42, 548--568 This journal is c The Royal Society of Chemistry 2013
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–B(OH)2 react individually with different triols. Similarly, the

dodecyl- and allyl-functionalised COF-102 materials could be
successfully synthesized via the co-condensation of 26 with 25a
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and 25b, respectively (Fig. 18).91 It is worth mentioning that the

percentage of the incorporated monomer 25 can be further
determined by 1H NMR spectroscopic analysis on the digested
COF materials.
Fig. 15 Self-condensation of monomer 27 (a) to synthesize 3D COF-103 with the In general, the boron-containing COFs possess the advantages
proposed crystalline structure (b). (Adapted with permission from ref. 41. of low densities and high BET surface areas. Specifically, the 3D
Copyright 2007 AAAS.) boron-containing COFs have the lowest densities among the
porous materials reported. Moreover, as revealed by the
thermogravimetric analysis, the boron-containing COFs often
building units.9,41,48–51,65,71,72,90–98 The dehydration reaction of
have excellent thermal stabilities (up to 450–600 1C). Based on
boronic acid and diol would lead to the formation of five-
the great success in constructing boron-containing COFs with
membered C2O2B rings (boronate ester, reaction B in Fig. 2). By
diverse synthetic strategies, synthesis and further practical
this means, the layered eclipsed structures are often formed in
applications of functional boron-containing COFs are highly
the cases of 2D COFs wherein the 2D adjacent layers are vertically
expected. However, it should be noted that most of the syn-
stacked. If tetrahedrally-structured building units are used, 3D
thesized boron-containing COFs are not stable in moist air99 or
COFs with complicated structures could be obtained. The obvious
in water.100 Although COF-202 could maintain both porosity
advantage of this co-condensation strategy is the diverse combi-
and crystallinity after exposure to air for 24 h,98 the hydrolysis
nation of boronic acids and diols as building units, by which a
experiments on COF-5, COF-18Å, and COF-14Å indicate the
series of COFs could be constructed with different properties and
severe loss of structural regularity (Fig. 19).100 This might, to
functionalities. For example, via the co-condensation of mono-
some extent, limit the practical applications of boron-containing
mers 11 and 21, a 2D COF material (HHTP-DPB COF) has been
COFs in future.
successfully obtained (Fig. 16), which possesses the largest pore
size (4.7 nm) among the reported COFs.90 Moreover, the func- 5.2 Triazine-based COFs (CTFs)
tionality of COF materials could be tailored through this
Another type of COFs is the covalent triazine-based frameworks
co-condensation strategy. For instance, via the co-condensation
(CTFs) which were developed by Thomas and co-workers.56 The
of tert-butylsilane triol [tBuSi(OH)3] and tetra(4-dihydroxyboryl-
covalent construction of CTFs is based on the cyclotrimerisa-
phenyl)methane 26 (Fig. 17), 3D COF-202 with butyl functional
tion of nitrile building units in the presence of ZnCl2 at 400 1C
groups was synthesized due to the borosilicate formation
(reaction D in Fig. 2). For example, cyclotrimerisation of
(reaction C in Fig. 2).98 Different from the dehydration reaction
1,4-dicyanobenzene (DCB) 7 affords the CTF-1 material with a
of boronic acids with diols by which five-membered C2O2B
BET surface area of 791 m2 g 1 and a pore size of 1.2 nm
rings are formed, in this case, the two hydroxyl groups of one
(Fig. 20). Analysis of the PXRD pattern suggested that CTF-1
possesses a hexagonal 2D structure as found in COF-1. Inter-
estingly, the higher ratio of ZnCl2 to monomer 7 (10 : 1) would
lead to an amorphous polymer but with a higher surface area
(1123 m2 g 1). 2,6-Dicyanonaphthaline 8 was also successfully
applied to synthesize the highly crystalline CTF-2 material but
with a BET surface area of 90 m2 g 1 only.83 The low surface
area of CTF-2 may be attributed to the partially-staggered
arrangement of the material layers. Similarly, the surface area
of CTF-2 was increased with the increased ratio of ZnCl2 to 8
and with the increased reaction temperature.
In comparison with boron-containing COFs, the triazine-
based COFs (CTFs) are often of lower crystallinity but with
excellent thermal and chemical stability. The high amount of
nitrogen atoms may render CTFs with potential applications as
catalyst supports.101–103 However, no application example is
available for the crystalline CTF materials yet.

5.3 Imine-based COFs

The third class is the imine-based COFs which were initially
Fig. 16 Co-condensation of monomers 11 and 21 to synthesize 2D HHTP-DPB
developed by Yaghi and co-workers.57 The imine-based COFs
COF and the proposed crystalline structure. (Adapted with permission from synthesized so far can be divided into two categories according to
ref. 90. Copyright 2011 American Chemical Society.) the covalent formation of distinct –CQN– bonds. One category is

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Fig. 17 Co-condensation of monomers 16 and 26 to synthesize 3D COF-202 and the proposed crystalline structure. (Adapted with permission from ref. 98. Copyright
2008 American Chemical Society.)

Fig. 18 Co-condensation of monomers 26 and 25 to synthesize 3D dodecyl- and allyl-functionalised COF-102 materials, with the proposed crystalline structure shown
in the right side (Reprinted with permission from ref. 91. Copyright 2012 Wiley-VCH.)

Fig. 20 Synthesis of CTF-1 and the extended crystalline structures. (Adapted with
permission from ref. 56. Copyright 2008 Wiley-VCH.)

Fig. 19 Top: the initial COF material (a) experiences partial hydrolysis and release Unlike COF-300, COF-LZU1 possesses a 2D eclipsed structure
of monomers into solution (b), and eventually, is subject to the complete
with the layer distance of 3.7 Å, which makes incorporation
hydrolysis (c) upon submersion in water. Bottom: PXRD patterns of COF-14Å,
COF-18Å, and COF-5 before (blue) and after (red) hydrolysis in water. (Reprinted
of metal ions feasible. Very recently, porphyrin-containing
with permission from ref. 100. Copyright 2011 American Chemical Society.) COF-366 has also been synthesized and further exploited for
the optoelectronic applications (see Section 7.2).96
Another type of imine-based COFs are hydrazone-linked, the
the ‘‘Schiff base’’ type formed via the co-condensation of synthesis of which was pioneered by Yaghi and co-workers via
aldehydes and amines (reaction E in Fig. 2). In 2009, Yaghi the co-condensation reaction of aldehydes and hydrazides
and co-workers successfully constructed the first imine-based (reaction F in Fig. 2). By employing hydrazide 10 and aldehyde
COF, COF-300,57 via the dehydration reaction of aldehyde 6 and 18 or 20 as the building units, COF-42 and COF-43 were
amine 23 (Fig. 7). COF-300 possesses a 3D diamond-like structure successfully synthesized via the solvothermal method
with a BET surface area of 1360 m2 g 1 and an average pore size of (Fig. 21).58 Both COF-42 and COF-43 are determined as the
7.8 Å. In 2011, for the purpose of catalytic applications, we syn- 2D eclipsed layered structures with the BET surface areas of
thesized the COF-LZU1 material via the co-condensation of 1,3,5- 710 and 620 m2 g 1, respectively. The existence of abundant
triformylbenzene 18 and 1,4-diaminobenzene 9 (see Section 7.3).66 hydrogen bonds within the hydrazone units is beneficial to the

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Fig. 22 Powder X-ray diffraction analysis of COF-42 using MS programs with the
observed pattern (red), the refined profile (black), the calculated PXRD pattern
(purple), and the difference plot (blue). (Reprinted with permission from ref. 58.
Fig. 21 Building units and the extended structures of COF-42 and COF-43. Copyright 2011 American Chemical Society.)
(Adapted with permission from ref. 58. Copyright 2011 American Chemical
Society.)
determination from the obtained PXRD patterns is quite
troublesome and has to be assisted with computational simula-
formation of the eclipsed structures. Moreover, these hydrazone- tion using certain software, e.g. Material Studio (MS) programs
linked COFs proved to display excellent chemical and thermal (Fig. 22).58 In general, the Pawley method is applied to refine
stability. the observed PXRD patterns so as to produce the unit-cell
Superior to the triazine-based COFs (CTFs) in terms of lattice in a most possible manner. It should be noted that the
structural regularity, the imine-based COFs are found to have Rietveld method, which has well been utilised in determining
comparable crystallinity with those of boron-containing COFs. precisely the framework topology of zeolites, is unfortunately
Moreover, the imine-based COFs are stable in most organic not applicable for the COF systems due to the low resolution of
solvents and insensitive to water. Also, the nitrogen atoms PXRD patterns. In this regard, the average pore size derived
within the framework may be coordinated with a series of from the gas absorption isotherm data can provide further
metal ions. These advantages provide the imine-based COFs evidence for the preferable COF structures.58 Additionally,
with high potential in further development, especially for comparison of measured density with the calculated value
diverse applications. Noteworthily, although very limited examples can help to suggest the preferable 3D COF structures.57
are available for the construction of imine-based COFs, amor- Besides the issue of structural regularity, atomic connectivity
phous porous polymers based on the ‘‘Schiff base’’ type have been in the COF materials, especially for the formation of new
reported recently.104,105 For instance, Nguyen and coworkers105 covalent bonds, is an important criterion for characterisation.
synthesized several amorphous polymers via the co-condensation In this regard, solid-state NMR spectroscopy is undoubtedly the
of 1,3,5-triformylbenzene 18 and diamine monomers. The reaction most powerful technique which has also well been applied in
was, however, conducted under different conditions as for the characterising other solid materials,106 such as zeolites, organic
synthesis of imine-based COFs. This not only underlines the polymers, and MOFs. Many atoms in the COF frameworks, e.g.
1
importance of optimising reaction parameters for the COF H, 13C, 11B, 15N, 29Si, and 17O, possess the nuclear spin I, which
synthesis, but also provides useful information for the designed renders them NMR active. For those with nuclear spin I = 1/2,
synthesis of new imine-based COFs. such as 13C, 15N, and 29Si, sufficient line-narrowing can be
reached by the conventional magic-angle spinning (MAS) NMR
6. Characterisation of COFs technique together with cross-polarisation (CP) or high-power
proton decoupling (HPDEC). Due to the low natural abundance
Characterisation of COF materials is essentially similar to that of the 15N isotope, using 15N-enriched building units for COF
of crystalline MOFs but with more complexity. The main synthesis is normally necessary for the 15N MAS NMR measure-
concerns for characterising COFs include the structural regu- ments. Although 1H possesses the nuclear spin I = 1/2 as well,
1
larity, atomic connectivity, porosity, and morphology. In the H MAS NMR spectra are less informative because of the strong
case of MOF materials, suitable single crystals could often be homonuclear dipole–dipole interactions. On the other hand,
obtained and directly subjected to the structural identification isotopes with the nuclear spin I > 1/2, such as 11B, 14N, and 17O,
by single crystal X-ray diffraction. Unfortunately, no single crystal are involved in quadrupolar interactions which cause severe
of COF materials has been obtained so far, ruling out the line-broadening of their NMR signals. Therefore, sophisticated
possibility of using this powerful technique. The left choice for solid-state NMR techniques operated at higher magnetic fields,
the structural analysis on the COF samples is the powder X-ray such as the multiple-quantum MAS (MQMAS) NMR method, are
diffraction (PXRD). The crystalline quality of COF samples can be often necessary. A large category of COFs synthesized so far are
roughly assessed by the signal intensity. However, the structural boron-containing ones. Fortunately, the quadrupolar coupling

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the adjacent layers of 2D planar HHTP-DPB COF are horizon-

tally offset by 1.7–1.8 Å.90
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7. Applications of COFs
Based on the design principles described in Section 3, a
diversity of functional COF materials with tailored function-
alities could be obtained. With tunable chemical and physical
properties, these COF materials are new candidates for further
applications, such as in gas storage, photoelectricity, and
Fig. 23 11B MAS NMR spectra of COF-1 (top), model compound (middle), and the catalysis. This section summarises the application progress of
building unit 1 (bottom). (Reprinted with permission from ref. 9. Copyright
functional COF materials.
2005 AAAS.)

7.1 Gas storage

constants of 11B in these materials are normally not too large, 7.1.1 Hydrogen storage. The need for the reduction of air
which makes the conventional 11B MAS NMR measurement still pollution and the increasing demands for energy have led to
possible (Fig. 23). Due to the low natural abundance and large the search of new and clean energy sources. Due to its clean
quadrupolar interactions of the 17O isotope, solid-state 17O combustion and high chemical energy density, hydrogen has
MAS NMR investigation on the COF materials has not been been pursued as an ideal substitute for traditional fossil fuels,
achieved. Meanwhile, other characterisation methods, such as especially in the automotive applications.129,130 For commercial
IR and UV-Vis spectroscopies are also applicable, providing use of hydrogen as a power source, efficient and safe storage of
complementary information on the COF materials. hydrogen is one of the main bottlenecks. Accordingly, a large
The porosity and surface areas of COF materials are normally number of studies have focused on the hydrogen storage with
assessed by gas (nitrogen or argon) adsorption–desorption measure- porous materials.130–132 The possibility of applying COF materials
ments. Scanning electron microscopy (SEM) is utilised to observe for hydrogen storage has also been pursued recently.
the morphology of COF materials. X-ray photoelectron spectroscopy Table 2 (column 4) summarises the capabilities of hydrogen
(XPS) is helpful to investigate the state of metal ions incorporated storage reported for the COF materials.97,99,133 In general, COFs
into the COF materials.66 with larger surface areas possess higher hydrogen uptake
Based on the classical molecular modelling method, com- capacities when measured under the same conditions. For
putational modelling of the COF materials has attracted intense example, COF-18Å with a BET surface area of 1263 m2 g 1
interest recently.107 Most of the theoretical studies focus on the shows the highest hydrogen uptake (1.55 wt% at 1 bar, 77 K)
structural modelling of the COF materials,108–116 some of which among similar 2D COFs with different alkyl chain lengths.49
deal further with the property prediction,117–120 such as the In contrast, COF-11Å with the surface area of 105 m2 g 1 shows
capability of COFs for hydrogen storage.107,121–128 The theore- the hydrogen uptake of 1.22 wt% at 1 bar and 77 K. In this
tical investigations have provided important information for context, 3D COFs may have superior potential for hydrogen
characterisation and application of COF materials in a predic- storage due to the higher surface areas and lower densities.
tive way. For example, using molecular dynamics and density Indeed, many studies have focused on the predicted and
functional theory (DFT) calculations, Dichtel and co-workers measured hydrogen uptakes of 3D COFs.123,134 For example,
demonstrated that, in difference from the entirely eclipsed structure, 3D COF-102 material shows the highest hydrogen uptake of

Table 2 Hydrogen, methane, and carbon dioxide uptakes of COFs

BET surface area Pore volume H2 uptakea CH4 uptakec CO2 uptaked
Material (m2 g 1) (Vp, cm3 g 1) (wt%) (mg g 1) (mg g 1) Ref.
b
COF-1 750 0.30 1.48 40 230 133
COF-5 1670 1.07 3.58b 89 870 133
COF-6 750 0.32 2.26b 65 310 133
COF-8 1350 0.69 3.50b 87 630 133
COF-10 1760 1.44 3.92b 80 1010 133
COF-102 3620 1.55 7.24b 187 1200 133
COF-103 3530 1.54 7.05b 175 1190 133
COF-1 628 0.36 1.28 (1 bar) — — 99
COF-11Å 105 0.05 1.22 (1 bar) — — 49
COF-14Å 805 0.41 1.23 (1 bar) — — 49
COF-16Å 753 0.39 1.40 (1 bar) — — 49
COF-18Å 1263 0.69 1.55 (1 bar) — — 49
CTC-COF 1710 1.03 1.12 (1.05 bar) — — 97
a b
H2 uptake measured at 77 K. H2 uptake at saturation. c CH4 uptake at 35 bar and 298 K. d
CO2 uptake at 55 bar and 298 K.

560 Chem. Soc. Rev., 2013, 42, 548--568 This journal is c The Royal Society of Chemistry 2013
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7.24 wt% at saturation (B35 bar, 77 K) which is slightly higher silicas, and MOFs.139–141 The use of COF materials as the
than that of amorphous PAF-1 (7.0 wt%).135 Noteworthily, storage media has also been attempted. The reported CO2
the amorphous PAF-1 possesses the highest BET surface area uptakes for COFs are summarised in Table 2 (column 6),
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(5600 m2 g 1) among all porous organic polymers,36 while the showing a maximum value of 1200 mg g 1 for COF-102 at
crystalline 3D COF-102 has a BET surface area of 3620 m2 g 1.133 55 bar and 298 K.133 As demonstrated in other porous materials
On the other hand, a recent report by Zheng and co-workers such as ZIFs,142,143 incorporation of functional moieties into
suggests that the capacity of hydrogen storage can be enhanced COFs might become a preferable choice to enhance their
by incorporating undulated macrocyclic cyclotricatechylene capacity of CO2 storage.
into 2D COFs. The obtained CTC-COF shows higher hydrogen 7.1.4 Ammonia storage. Ammonia is widely used in
uptake (1.12 wt%) at low pressure (1.05 bar) than those of 2D industrial applications, such as in the production of nitrogen
COFs with similar structures. The value of hydrogen uptake fertilisers. For commercial transportation and application,
under this condition for CTC-COF is even close to those of 3D compressed liquid ammonia is often needed. However, the
COF materials.97 liquid ammonia is difficult to handle due to its toxicity and
The US Department of Energy (DOE) has set a target for corrosiveness. Efficient and scalable storage of ammonia in
hydrogen storage of 5.5 wt% at an operating temperature of adsorbents is, therefore, a practical way to solve this problem.
40 to 60 1C under a maximum pressure of 100 atm until 2017. Recently, Yaghi and co-workers reported that a boron-
However, most of the hydrogen uptakes reported for porous containing COF, COF-10, has exceptionally high ammonia
materials were measured at 77 K, far away from the ideal uptake in comparison with other porous materials.67 The total
temperature range required for the practical applications. Never- ammonia uptake capacity of COF-10 is 15 mol kg 1 at 298 K
theless, theoretical studies on the COF systems indicate that the and 1 bar, which is the highest among the porous materials
hydrogen storage at a temperature range of 273 to 298 K is reported, such as Amberlyst 15 (11 mol kg 1), zeolite 13X
practically possible,107 particularly for the metal-doped COFs. (9 mol kg 1), and MCM-41 (7.9 mol kg 1) (Fig. 24). Moreover,
For example, it has been theoretically predicted that lithium- the ammonia uptake of COF-10 can be released and re-adsorbed
doped COFs should possess improved capacity of hydrogen in a reversible manner with a slight reduction (4.5%) in the total
storage, which is attributed to the proposed formation of a uptake capacity. The layered morphology of COF-10 was found
dative bond between the H2 and the Li atom.123 The calculated disrupted during the adsorption cycles, but the atomic connec-
hydrogen uptakes for Li-doped COF-105 and COF-108 (6.84 and tivity and periodicity are well maintained. The exceptionally high
6.73 wt%, respectively, at 298 K and 100 bar) are superior to uptake of ammonia in COF-10 was explained by the formation of
those for MOF materials and non-doped COFs. Although the a classical ammonia–borane coordination bond (Scheme 1). This
experimental and theoretical results have shed light on employing research represents a nice example of applying COF materials in
COFs as the ideal candidates for hydrogen storage, the practical functional applications.
use of COF materials toward this goal is still far away.
7.1.2 Methane storage. As the main component of natural
gas, methane is abundant and inexpensive in comparison with
conventional fossil fuels. The current US DOE target for
methane storage is 180 (v/v) at 35 bar and 298 K. In order to
put methane into driving automobiles in a practical manner,
effective and safe storage systems need to be developed.136
Accordingly, the capability of methane storage in certain COF
materials has been examined (Table 2, column 5).133 Analogous
to the cases of hydrogen storage, the capacities of methane
storage in 3D COFs are higher than those of 2D COFs. For
example, the gravimetric uptakes of methane at 35 bar and
298 K in 3D COF-102 (187 mg g 1) and COF-103 (175 mg g 1) Fig. 24 Ammonia uptakes in COF-10 and in other porous materials.
(Adapted with permission from ref. 67. Copyright 2010 Nat. Chem.,
are higher than that of 2D COF-5 (89 mg g 1), but slightly lower
Macmillan Publishers Ltd.)
than that of 3D MOF PCN-14 (253 mg g 1 at 290 K).137 Although
the capacities of methane storage in these COF materials more
or less reach the DOE target, decreasing the costs and efforts in
synthesizing the COF materials still remains a big challenge
towards the practical applications.
7.1.3 Carbon dioxide storage. Nowadays, carbon dioxide
emitting from the combustion of fossil fuels is thought to be a
major contribution to the global warming. Therefore, how to
efficiently capture and store carbon dioxide is an urgent issue
for research.138 The storage of CO2 has been extensively studied Scheme 1 The proposed ammonia–boron interaction upon the adsorption of
using a wide range of porous materials, such as porous carbons, ammonia on COF-10.67

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7.2 Photoelectric applications

With certain photoelectric moieties embedded into the well-
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defined framework, functional COF materials could possess

unique optical and electrical properties. Jiang and co-workers
pioneered the research by synthesizing the pyrene-functionalised
COFs for further photoelectric applications. PPy-COF was
obtained via the self-condensation of pyrene-2,7-diboronic
acid (PDBA, 21),51 while the TP-COF was obtained via the
co-condensation of 2,3,6,7,10,11-hexahydroxytriphenylene
(HHTP, 3) and PDBA 21 (Fig. 25).89 Both PPy-COF and TP-COF
possess 2D eclipsed structures with the BET surface areas of
868 m2 g 1 and 932 m2 g 1, respectively. Remarkably, TP-COF is
highly luminescent with a capacity of harvesting photons from
ultraviolet to visible regions. Moreover, TP-COF exhibits the
p-type semiconductive characters due to the eclipsed arrange-
ment of triphenylene and pyrene units. Similarly, with the
eclipsed alignment of polypyrene in the framework, PPy-
COF shows a fluorescence shift comparable to the PDBA
solids (Fig. 26). PPy-COF is electrically conductive, revealing
photoconductivity with a quick response to light irradiation
(Fig. 27).
Fig. 27 (a) I–V profile of PPy-COF between two Pt electrodes (black: without PPy-
Phthalocyanine compounds have strong absorption capa- COF; blue: with PPy-COF; red: with iodine-doped PPy-COF). (b) Electric current
cities of visible light. The planar p-electronic macrocycles make with the bias voltage (2 V) on–off. (c) I–V profile of PPy-COF between sandwich-
type Al/Au electrodes (black: without light irradiation; red: with light irradiation).
(d) Photocurrent response with the light on–off. (Reprinted with permission from
ref. 89. Copyright 2009 Wiley-VCH.)

them fascinating building units for constructing functional

COF materials. Using a Lewis acid-catalysed protocol, Spitler
and Dichtel synthesized an eclipsed 2D COF (Pc-PBBA-COF)
containing metal-free phthalocyanine groups from phthalo-
cyanine tetra(acetonide) 29a and 1 (Fig. 28).48 Jiang and co-workers
synthesized nickel phthalocyanine-based COFs (NiPc COF and

Fig. 25 Building units and extended structures of PPy-COF and TP-COF. (Adapted
with permission from ref. 51 and 89. Copyright 2008 and 2009 Wiley-VCH.)

Fig. 26 (a) Fluorescence microscopic image of PPy-COF (inset: enlargement of Fig. 28 Building units and extended structures of phthalocyanine-based COFs.
individual cubes) and (b) normalised fluorescence spectra of PPy-COF (red) and (Adapted with permission from ref. 48, 94 and 93. Copyright 2010 Nat. Chem.
PDBA 21 (black) upon the excitation at 414 nm at 25 1C. (Reprinted with Macmillan Publishers Ltd., 2011 Wiley-VCH, and 2011 American Chemical
permission from ref. 89. Copyright 2009 Wiley-VCH.) Society.)

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2D-NiPc-BTDA COF) via the boronate esterification reaction of Recent research indicates that porphyrins are also suitable
(2,3,9,10,16,17,23,24-octahydroxyphthalocyaninato) nickel(II) building units for constructing functional COFs. Jiang and
28a with 1 or benzothiadiazole diboronic acid (BTDADA, 2) co-workers reported the first porphyrin-based COF (ZnP-COF)
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(Fig. 28).93,94 Pc-PBBA-COF, NiPc COF, and 2D-NiPc-BTDA COF constructed via the boronate esterification reaction of zinc(II)
all possess eclipsed structures with the BET surface areas of 5,10,15,20-tetrakis(4-(dihydroxyboryl)phenyl) porphyrin 30b and
469, 624, and 877 m2 g 1, respectively, and with the average 1,2,4,5-tetra-hydroxybenzene 14a (Fig. 29).72 ZnP-COF reveals a
pore sizes of 2.1, 1.9, and 2.2 nm, respectively. Due to the tetragonal 2D eclipsed structure with a large BET surface area of
eclipsed structure, Pc-PBBA-COF shows a blue shift with 1742 m2 g 1 and an average pore size of 2.5 nm. The photo-
the absorption maxima comparable to the phthalocyanine electronic properties of ZnP-COF and other two porphyrin-
tetra(acetonide) powder and shows an absorption band of most based COFs (H2-COF and CuP-COF) have been studied in a
of the solar spectrum. Similarly, the eclipsed stacking of more recent work.149 The eclipsed alignment of these COF
phthalocyanine units renders NiPc COF with an enhanced materials provides the possibility of carrier transportation
light-harvesting capability in the visible and near-infrared within porphyrin macrocycles. Moreover, H2-COF with metal-
regions. Meanwhile, NiPc COF reveals high photoconductivity free porphyrin macrocycles exhibits a hole transport. Due to the
and extreme sensitivity to visible and near-infrared photons. By formation of metal-on-metal channels in the metal-porphyrin
introducing electron-deficient benzothiadiazole units at the macrocycles with different electron densities, ZnP-COF and
edges of 2D tetragonal metallophthalocyanine eclipsed struc- CuP-COF show high-rate ambipolar and electron conduction,
ture, 2D-NiPc-BTDA COF turns to be an n-type semiconductor respectively. Another two 2D non-metal porphyrin COF
and exhibits great changes in the carrier-transport mode with a materials (COF-366 and COF-66) with high charge carrier
broad and enhanced absorbance up to 1000 nm. Moreover, mobility have been synthesized by Yaghi and co-workers.96
2D-NiPc-BTDA COF shows panchromatic photoconductivity COF-366 was obtained via the formation of imine bonds
and high sensitivity to near-infrared photons. between tetra(p-amino-phenyl)porphyrin 31 and terephthaldehyde
Porphyrins are another interesting type of large, planar 6. COF-66 was synthesized via the boronic esterification reaction of
macrocyclic compounds with 18-electron p systems and there- tetra(p-boronic acid-phenyl)porphyrin 30a and 2,3,4,5-tetrahydroxy
fore, have been applied in the synthesis of porous materials anthracene 15a. Both COF-366 and COF-66 show the hole
such as MOFs144–147 and conjugated nanoporous polymers.148 conducting with high mobilities.

Fig. 29 Building units and chemical structures of porphyrin-based COFs.96,149

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These studies suggest that the structural features of 2D the Pd(II)-coordinated COF-LZU1 via a simple treatment with
eclipsed COFs are beneficial to carrier transportation. The Pd(OAc)2 at room temperature. The structural preservation and
unique properties of the optoelectronic COFs represent an robust Pd(II)-incorporation in the obtained Pd/COF-LZU1 were
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important step toward the applications of functional COFs in further verified by the PXRD, solid-state NMR, and XPS
optoelectronics and photovoltaics. analyses.
Pd/COF-LZU1 was then tested for catalysing the Suzuki–
7.3 Catalysis Miyaura coupling reaction (Table 3). The excellent catalytic
The use of functional porous materials with large surface areas performance was elucidated by the broad scope of the reactants,
for heterogeneous catalysis has been acknowledged for several the excellent yields (96–98%) of the reaction products, together
decades.59 For example, inorganic zeolites have been widely with the high stability and easy recyclability of the catalyst.
applied as robust catalysts in refining and petrochemical
industries.55 Porous but amorphous organic polymers have Table 3 Catalytic activity of Pd/COF-LZU1 in the Suzuki–Miyaura coupling
been suggested as new candidates for efficient heterogeneous reaction66
catalysts in fine chemical synthesis.39,40,62,148 Recent research
has also demonstrated the possibility of employing hybrid
crystalline MOFs for catalysis.150–153 In this context, functional Entrya R X Time (h) Yieldb (%)
COF materials should also possess high potentials as efficient
and robust catalysts. As the cases of other porous solids, 1 I 3 96
suitable COF candidates for catalytic applications should incor-
porate robust catalytic sites and possess high stability to 2 I 2 97
thermal treatments, water, and most of the organic solvents.
3 Br 3 97
Furthermore, the easy accessibility to the catalytic sites and the
efficient mass transport inside the porous catalyst should also 4 Br 3 97
be guaranteed for the ideal catalytic performance.
5 Br 3 97
Recently, we realized the first application of COF materials
for highly efficient catalysis (Fig. 30).66 Intrigued by using the 6 Br 2.5 98
Schiff-base metal complex as the homogeneous catalysts, we
synthesized a new imine-linked COF material (COF-LZU1) from 7 Br 2.5 97
simple building units 18 and 9. The 2D eclipsed layered-sheet 8 Br 4 96
structure of COF-LZU1 renders the distance of nitrogen atoms a
Reaction conditions: aryl halide (1.0 mmol), phenylboronic acid
to be 3.7 Å in the adjacent layers, which is suitable for the (1.5 mmol), K2CO3 (2.0 mmol), and Pd/COF-LZU1 (0.5 mol%), 4 mL of
strong coordination of metal ions. Accordingly, we synthesized p-xylene, 150 1C. b Isolated yield.

Fig. 30 Chemical and extended structures of COF-LZU1 and Pd/COF-LZU1. (Adapted with permission from ref. 66. Copyright 2011 American Chemical Society.)

564 Chem. Soc. Rev., 2013, 42, 548--568 This journal is c The Royal Society of Chemistry 2013
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Noteworthily, in comparison with the Pd(II)-containing MOF,154 for further applications, also, the synthesis of functionality-
Pd/COF-LZU1 required less catalyst-loading, shorter reaction incorporated COFs with high periodicity and stability is the
time and showed higher reaction yield. The superior activity of vital issue in this research area.
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the Pd/COF-LZU1 catalyst should be attributed to its unique In terms of the designed synthesis, as described in this
structure. The eclipsed layered-sheet arrangement and the review, great success has been achieved in constructing the
distance between nitrogen atoms in adjacent layers provide boron-containing COFs, many of which have also been sub-
COF-LZU1 as a robust scaffold for incorporating catalytic sites. jected to further applications. It is therefore expected that new
The regular channels with a diameter of 1.8 nm ensure efficient progress be made towards the diversity-oriented synthesis of
access to these active sites together with fast diffusion of the functional boron-containing COFs applicable to a variety of
bulky products. desired applications. Further development of triazine-based
Although this is so far the only example of utilising the COF and imine-based COFs may be more directed toward expanding
material for catalysis, the design strategy used may find further the scope of applicable building units and optimising the
applications for synthesizing functional COF materials in synthetic conditions. As mentioned in Section 5.3, the existing
catalysing a wide scope of reactions, and even under harsh examples of amorphous imine-based polymers could have
reaction conditions. The further progress in this area may given a hint on the designed synthesis of new imine-based
eventually bring COF materials into practical applications. COFs. Of course, new synthetic strategies for constructing novel
COF networks are, as always, highly desired.
8. Conclusions and perspectives In terms of the synthetic methods, further development
towards the efficient synthesis of COF materials with increased
First discovered by Yaghi and co-workers in 2005,9 the covalent crystallinity and in large scale production would be of great
organic frameworks (COFs) represent a fascinating new type of interest. Seeking for appropriate conditions to facilitate the
crystalline porous materials. In comparison with other crystal- weak interactions, such as p–p stacking and hydrogen binding,
line porous solids (inorganic zeolites and hybrid MOFs), the may be helpful to obtain the COFs with higher periodicity. The
COF materials possess the advantages of low density, large templating or seeding method applicable in zeolite synthesis17
surface areas, tunable properties and functionality because of may also work in the COF cases. For advanced applications in
the versatile covalent-bonding of organic building units con- certain circumstance, morphology-controlled synthesis is sub-
sisting of light elements (C, Si, O, B, and N) only. These jected to further development. In-depth understanding of the
advantages together with the regular pore structures have formation mechanism would provide insightful information
offered the COF materials with superior potentials in advanced for the COF synthesis.
applications, such as gas storage,133 adsorption,67 optoelectricity,51 In terms of characterisation issues, sophisticated techniques
catalysis,66 and so on. The exciting development in this area are still in urgent need to gain more detailed information about
has attracted intensive interest from researchers with diverse the COF structures and properties. Analysis of PXRD data
expertise. By covering most of the reported work on COFs, this assisted with computational simulation should help to reduce
review summarises the state-of-the-art development on the the uncertainty in structural determination, especially for the
design, synthesis, characterisation, and application of the complex 3D COFs. It is worth mentioning that, as demon-
crystalline porous COF materials. strated in the cases of zeolites and other (porous) solids,
To date, the biggest challenge in the COF synthesis is the solid-state NMR spectroscopy106 is a powerful technique in
construction of functional COF materials with highly periodic studying the local structures, the information of which is
and robust frameworks. Although the synthesized COFs could complementary to those obtained by other characterisation
give reasonable PXRD patterns due to the partial crystallinity, techniques. More importantly, solid-state NMR spectroscopy
the overall structural regularity is still poor in many cases. could be further applied to investigate the host–guest inter-
As a matter of fact, the experimental values of the pore size actions and the catalytic mechanisms155 of functional COF
distribution and the surface area are often different from those materials. Also the 129Xe NMR technique may provide uniquely
predicted theoretically. The main reason lies in that the tailor- the insightful information on the voids of the COF materials.
made control of the thermodynamic and kinetic properties of In terms of applications, further development towards the
the reversible reaction is hard to achieve towards the perfect practical use of COF materials in gas storage, adsorption,
formation of covalently-bonded COF frameworks with high optoelectricity, and catalysis is highly desired. Moreover, syn-
(overall) periodicity. Moreover, most of the synthesized COFs thesis of new functional COFs, such as the chiral COFs for
so far possess the 2D layered crystalline structures. In compari- asymmetric catalysis, will further boost the advanced applica-
son with the effects governed by dynamic covalent chemistry,13 tions of COF materials.
the noncovalent p–p stacking interaction between layers can be Last but not the least, continuous efforts on the computa-
relatively weak for the integrated construction of highly tional modelling of COF materials would provide valuable
periodic and porous structures. In this regard, efforts for the information for the characterisation and application of COF
construction of 3D COFs might be encouraged. However, these materials in a predictive manner.107
attempts would be associated with extra difficulties in the In summary, though many challenges still exist, the rapid
designed synthesis and structural identification. As a prerequisite development of COFs in recent years has predicted well for the

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