Applications of COFs

The capacity of COFs materials begins from its high porosity and capable molecular framework.
[31-34] Besides, the adaptable and controllable organizations can be functionalized to present
catalytic destinations for additional utilization as catalytic materials. [35-39] As opposed to
conventional heterogeneous catalyst, the COFs show advanced durability and reusing capacity.
Significantly, COFs with imine or hydrazone linkage are impervious to deterioration in air and in
different protic or aprotic solvents, Accordingly, they have arisen as a class of robust
multifunctional materials with extraordinary properties, and subsequently opening up
tremendous probabilities in the field of catalytic application. [40-43] A variety of useful COF
materials with customized functionalities could be attained. With tunable chemical and actual
properties, these COF materials are new contenders for additional applications, for example, in
gas stockpiling, photoelectricity, and catalysis.
Gas storage
Hydrogen storage
The requirement for the decrease of air contamination and the growing requirements for energy
have prompted the inquiry of new and clean energy sources. Because of its clean burning and
high synthetic energy frequency, hydrogen has been sought as an optimal substitute for
conventional petroleum derivatives, particularly in transportation. [1,2] For commercial
utilization of hydrogen as an energy source, efficient and safe stockpiling of hydrogen is one of
the primary bottlenecks. Enormous studies have zeroed in on the hydrogen storage with
permeable materials. [2-4] The chance of applying COF materials for hydrogen stockpiling has
additionally been sought after as of late. Table 1 (segment 4) sums up the capacities of hydrogen
storage announced for the COF materials. [5-7]

Table1: Hydrogen, methane, and carbon dioxide uptakes

of COFs

BET surface Pore volume H2 uptakea CH4 uptakec CO2 uptaked

Material area (m2 g1) (Vp, cm3 g1) (wt%) (mg g1) (mg g1) Ref.

COF-1 750 0.30 1.48b 40 230 07

COF-6 750 0.32 2.26b 65 310 07

COF-10 1760 1.44 3.92b 80 1010 07

COF-102 3620 1.55 7.24b 187 1200 07

COF-1 628 0.36 1.28 (1 bar) — — 06

COF-11Å 105 0.05 1.22 (1 bar) — — 57

COF-16Å 753 0.39 1.40 (1 bar) — — 57

CTC-COF 1710 1.03 1.12 (1.05 bar) — — 05

a b c d
H2 uptake measured at 77 K. H2 uptake at saturation. CH4 uptake at 35 bar and 298 K. CO2 uptake at 55
bar and 298 K

As a general rule, COFs with bigger surface regions have higher hydrogen uptake limits when
estimated under similar conditions. For instance, COF-18å with a BET surface space of 1263 m 2
g-1 shows the most noteworthy hydrogen take-up (1.55 wt% at 1 bar, 77 K) among comparative
2D COFs with different alkyl chain lengths.[57] Interestingly, COF-11å with the surface space of
105 m2 g-1 shows the hydrogen take-up of 1.22 wt% at 1 bar and 77 K. In this specific outlook,
3D COFs may have better potential for hydrogen storage due to the higher surface regions and
lower densities. For sure, numerous investigations have centered on the anticipated and estimated
hydrogen takes-up of 3D COFs. [8,9] For instance, 3D COF-102 material shows the most
notable hydrogen take-up of 7.24 wt% at saturation (B35 bar, 77 K) which is marginally higher
than that of undefined PAF-1 (7.0 wt%).135 Noteworthily, the amorphous PAF-1 has the highest
BET surface region (5600 m2 g-1) among all permeable natural polymers,[58] while the
glasslike 3DCOF-102 has a BET surface space of 3620 m 2 g-1.[7] On the other hand, a latest
study by Zheng and colleagues proposes that the limit of hydrogen storage can be upgraded by
fusing undulated macrocyclic cyclotricatechylene into 2D COFs. The acquired CTC-COF shows
higher hydrogen take-up (1.12 wt%) at low pressure (1.05 bar) than those of 2D COFs with
comparable designs. The worth of hydrogen uptake under this condition for CTC-COF is really
close to those of 3D COF materials.[5]
The US Department of Energy (DOE) has set an objective for hydrogen storage of 5.5 wt% at a
working temperature of - 40 to 60°C under pressure of 100 atm until 2017. In any case, the
majority of the hydrogen uptake announced for permeable materials was estimated at 77 K, far
away from the best temperature range needed for the pragmatic applications. Nonetheless,
hypothetical examinations on the COF frameworks show that the hydrogen storage at a
temperature scope of 273 to 298 K is basically possible,107 especially for the metal-doped
COFs. For instance, it has been hypothetically anticipated that lithium doped COFs ought to have
further developed limit of hydrogen storage, which is credited to the proposed arrangement of a
dative connection between the H2 and the Li atom.123 The determined hydrogen uptake for Li-
doped COF-105 and COF-108 (6.84 and 6.73 wt%, separately, at 298 K and 100 bar) are better
than those for MOF materials and non-doped COFs. Albeit the trial and hypothetical outcomes
have revealed insight into utilizing COFs as the best possibility for hydrogen storage, the viable
utilization of COF materials toward this objective is as yet distant.
Methane Storage
As the primary part of natural gas, methane is ample and economical in comparison with
customary petroleum products. The current US DOE focus for methane storage is 180 (v/v) at 35
bar and 298 K. To utilize methane into driving autos in a practical way, effective and safe
storage frameworks should be created. [10] Therefore, the capacity of methane stockpiling in
certain COF materials has been analyzed (Table 1, section 5). [7]
Similar to the instances of hydrogen storage, the limits of methane storage in 3D COFs are
higher than those of 2D COFs. For instance, the gravimetric takes-up of methane at 35 bar and
298 K in 3D COF-102 (187 mg g-1) and COF-103 (175 mg g-1) are higher than that of 2D COF-5
(89 mg g-1), yet somewhat lower than that of 3D MOF PCN-14 (253 mg g -1 at 290 K). [11]
Although the limits of methane stockpiling in these COF materials pretty much reach the DOE
target, reducing the expenses and efforts in blending the COF materials remain a major threat
towards the practical applications.
Carbon Dioxide Storage
Recently carbon dioxide producing from the burning of fossil fuels is believed to be a major
addition to an unnatural weather change. So, to efficiently catch and store carbon dioxide is a
dire issue for research. [12] The capacity of CO 2 has been broadly researched using a wide scope
of permeable materials, like porous carbons silicas, and MOFs. [13-15] The utilization of COF
materials as the capacity media has also been endeavored. The detailed CO 2 uptake for COF is
summed up in Table 2 (section 6), showing a highest amount of 1200 mg g-1 for COF-102 at 55
bar and 298 K. [7] As exhibited in other permeable materials like ZIFs, [16,17] fusion of
functional moieties into COFs may turn into a best decision to improve their ability of CO 2
storage.
Ammonia Storage
Ammonia is broadly utilized in industrial applications, for example, in the creation of nitrogen
fertilizers. For transportation and application, compacted liquid ammonia is regularly required.
Nevertheless, the liquid ammonia is difficult to deal with because of its erosive and destructive
nature. Efficient and adaptable storage of alkali in adsorbents is a viable method to resolve this
issue. Lately, Yaghi and co-workers detailed that a boron containing COF, COF-10, has
particularly high ammonia take-up in contrast to other permeable materials. The entire alkali
take-up limit of COF-10 is 15 mol kg -1 at 298 K and 1 bar, which is maximum among the
permeable materials recorded, like Amberlyst 15 (11 mol kg -1), zeolite 13X (9 mol kg-1), and
MCM-41 (7.9 mol kg-1).

Figure 1: The proposed ammonia–boron interaction upon the adsorption of ammonia on COF-10
Additionally, the ammonia uptake of COF-10 can be delivered and re-adsorbed in a reversible
way with a slight decrease (4.5%) in the complete take-up limit. The layered morphology of
COF-10 was found disturbed during the adsorption cycles; although, the nuclear network and
periodicity are preserved. The particularly high take-up of ammonia in COF-10 was clarified by
the development of a symmetrical ammonia-borane coordination bond (Figure 1).
Photoelectric Applications
The photocatalytic reactions with ability of changing solar energy into synthetic fuels are
expected to be an engaging method to address the overall energy and ecological issues. It has
been demonstrated that the COFs with light-reaping and charge detachment abilities have
effectively taken enormous steps towards producing useful photoactive materials in
photocatalytic frameworks. [44-45] With certain photoelectric moieties implanted into the
structure, useful COF materials can show extraordinary optical and electrical properties.
Jiang and colleagues spearheaded the research by incorporating the pyrene-functionalized COFs
for photoelectric applications. PPy-COF was acquired by means of the self-condensation of
pyrene-2,7-diboronic corrosive (PDBA, 21), [19] while the TP-COF was attained through the co-
condensation of 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP, 3) and PDBA21 (Fig. 2). [20]
Both PPy-COF and TP-COF have 2D eclipsed structures with the BET surface spaces of 868 m 2
g-1 and 932 m2 g-1, separately. Surprisingly, TP-COF is profoundly phosphorescent with a limit of
assembling photons from UV to visible spectrum. Besides, TP-COF shows the p-type
semiconductive characters due to eclipsed structure of triphenylene and pyrene units.

Figure 2: Building units and extended structures of PPy-COF and TP-COF.

Phthalocyanine compounds ought to have high absorption of visible light. The planar p-
electronic macrocycles make them appealing structural units for developing functional COF
materials. Using a Lewis acid-catalyzed protocol, Spitler and Dichtel synthesized an eclipsed 2D
COF (Pc-PBBA-COF) containing metal-free phthalocyanine groups from phthalocyaninetetra
(acetonide) (Fig.3). [18]

Figure 3:Building units and extended structures of phthalocyanine-based COFs.

Catalysis
The utilization of functional porous materials with huge surface regions for heterogeneous
catalysis has been recognized for a long time. [21] For instance, inorganic zeolites have been
broadly applied as strong catalysts in refining and petrochemical industries.[22] Porous however
amorphous natural polymers have been recommended as new contender for efficient
heterogeneous catalysts in fine compound synthesis. [23-26] Recent exploration has likewise
exhibited the chance of utilizing hybrid translucent MOFs for catalysis. [27-30]. Therefore,
functional COF materials develop have high potential as efficient and effective catalysts. As for
other permeable solids, appropriate COFs for catalytic applications should consolidate potent
reactant destinations and show perseverance to high thermal conditions, water, and majority of
the natural solvents. Besides, the direct access to the catalytic region and the efficient mass
transfer inside the permeable catalyst ensures the best catalytic performance.
Electrocatalytic Reactions
Electrocatalytic reactions green energy technologies, like metal-air batteries and fuel cells, etc.
are being rapidly developed. However, this clean technology requires high productivity
electrocatalysts to advance major synthetic reactions, in particular oxygen reduction and
evolution reaction, which decides the proficiency of the apparatus. Exceptionally, many COF
based electrocatalysts have displayed unmistakable execution in contrast with those recently
utilized, and evolving many directing works. [47-48] In 2015, Mao and collaborators changed a
cobalt porphyrin-based covalent organic structure (Co-COF) into proficient oxygen reduction
reaction electrocatalyst. [49]
Numerous functionalized COFs have been utilized as electrocatalysts in water splitting. For
instance, an azined-based COF was developed and used as a heterogeneous oxygen advancement
reaction electrocatalyst by joining dynamic Ni3N nanoparticles into its permeable framework.
[46] Benefiting from its similar graphenes structure and solid π–π collaborations, the subsequent
layered COFs showed remarkable stability. The high electrocatalytic action of a close record low
over potential at 230 mV@10 mA cm−2 was accomplished, obviously supporting the construction
driven electronic synergism between the π-conjugated COF and the active metal sites.
Organocatalysis
Many multifunctional COFs polymers possess high potentials as efficient robust catalysts and
have been widely utilized in different types of organic chemical reaction. [50-54] Generally,
incorporating nitrogen-containing molecular units, such as amine, imine and triazine groups,
within a tunable COF could facilitate to lock metal active sites. Thus, the heterogeneous
functionalized catalysts rooted in covalent polymer carriers display high activities and are also
easily to be recovered and reused.
Photoluminescent
Concerning luminescent potential applications, fluorescent nanoparticles of a novel type of
melamine COF-type porous architecture, so called SNW-1, obtained by a rapid microwave-
assisted approach, was used as effective sensor material. The as-synthesized SNW-1
nanoparticles exhibited high sensitivity and selectivity, as well as fast response to nitroaromatic
explosives, such as 2,4,6-trinitrotoluene (TNT), 2,4,6 trinitrophenylmethylnitramine (Tetryl) and
picric acid (PA) [55]. Furthermore, the incorporation of pyrene and triphenylene units by
solvothermal polymeric condensation favored the formation of belt-shape hexagonal mesoporous
COFs, which exhibited photonic absorption, emitting blue luminescence and acting as
semiconducting material. [19]
The self-condensation of pyrenediboronic acid allowed the crystallization of 2D COF materials
based on aligned polypyrene sheets in micrometer-scale cubes. This spatial distribution of
uniform nanolayers facilitated exciton migration and carrier transportation. This polypyrrole
COFs exhibited visible light harvesting and photocurrent production with a fast response to
irradiation with visible light, without apparent structure deterioration (Fig. 4) [20].
Figure 4: Scheme of (a) preparation and (b) structure of PPy-COF. (Boron: white; Oxygen: red; Pyrene: blue).

In the same line, 2D COFs with pyrene units occupying structural vertices and diazabutadiene (-
C=N-N=C-) moieties located in edges of rhombic sheets, favored the formation of AA-stacking
modes to form periodically ordered pyrene columns and 1D microporous channels. Owing to
pyrene columnar ordering, the azine-connected networks were highly luminescent, whereas the
azine fragments were useful as open anchoring points for hydrogen-bonding interactions. These
cooperative functions located on vertices and edges allowed the use of this pyrene-COFs as
chemosensors for the detection of explosive molecules such as 2,4,6-trinitrophenol [56].
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