Environmentally benign and economic synthesis of covalent triazine-based frameworks

Article abstract of DOI:10.1016/S1872-2067(17)62771-2

Covalent triazine-based frameworks (CTFs) are important microporous materials with a wide range of applications. Here, we demonstrate an environmentally benign and economic synthetic pathway to CTFs. The monomers used for CTFs, aromatic nitriles, were obtained by cyanation using nontoxic potassium hexacyanoferrate(II) in place of commonly used toxic cyanides. Then, the CTFs were synthesized by trimerization of the corresponding cyano monomers in molten zinc chloride. A series of CTFs was synthesized, and the highest Brunauer-Emmett-Teller surface area measured in this series was 2404 m²/g. Among the synthesized CTFs, CTF_DCP exhibited excellent CO₂ adsorption properties, with a CO₂ uptake of 225 mg/g at 0 °C.

Full text of DOI:10.1016/S1872-2067(17)62771-2

Chinese Journal of Catalysis 38 (2017) 583–588
a v a i l a b l e a t w w w . s c i e n c e d i r e c t . c o m
j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / c h n j c
Article
Environmentally benign and economic synthesis of covalent
triazine‐based frameworks
Ling Zhanga,b, Xue Liub, Rui‐Xia Yangb, Nian‐Yu Huanga, Wei‐Qiao Dengb,*
a Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges
University, Yichang 443002, Hubei, China
b State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning,
China
A R T I C L E I N F O
A B S T R A C T
Article history:
Covalent triazine‐based frameworks (CTFs) are important microporous materials with a wide range
of applications. Here, we demonstrate an environmentally benign and economic synthetic pathway
to CTFs. The monomers used for CTFs, aromatic nitriles, were obtained by cyanation using nontoxic
potassium hexacyanoferrate(II) in place of commonly used toxic cyanides. Then, the CTFs were
synthesized by trimerization of the corresponding cyano monomers in molten zinc chloride. A se‐
ries of CTFs was synthesized, and the highest Brunauer‐Emmett‐Teller surface area measured in
this series was 2404 m2/g. Among the synthesized CTFs, CTFDCP exhibited excellent CO2 adsorption
properties, with a CO2 uptake of 225 mg/g at 0 °C.
Received 30 November 2016
Accepted 25 December 2016
Published 5 March 2017
Keywords:
Covalent triazine‐based framework
Aryl bromide
Cyanation
Potassium hexacyanoferrate(II)
Palladium acetate
© 2017, Dalian Institute of Chemical Physics, Chinese Academy of Sciences.
Published by Elsevier B.V. All rights reserved.
1. Introduction
reversible condensation reactions that have to be carried out
under thermodynamic rather than kinetic control [8].
The field of microporous materials has recently seen re‐
markable development owing to the potential applications of
these materials in gas storage, separation and catalysis [1–4].
Compared with traditional porous materials, organic mi‐
croporous materials have the advantages of high specific sur‐
face areas, good solubility, diverse synthetic methods and wide
applicability [2]. With the ever increasing sophistication of
synthetic methods available for the construction of organic
porous materials, porous materials with various functions can
now be synthesized according to researchers’ diverse needs.
Covalent organic frameworks (COFs) are a unique class of
crystalline porous organic polymers with inherent porosity and
periodic molecular ordering [5–7]. It is, however, difficult to
construct crystalline COFs because their syntheses require
Covalent triazine‐based frameworks (CTFs) are a special
and emerging class of COFs [9] that are produced by ionother‐
mal trimerization of aromatic polynitriles in molten ZnCl2 to
give triazine rings [10]. For example, the first reported CTF,
CTF‐1 [10], was prepared by trimerization of p‐dicyanoben‐
zene. CTFs are gaining an increasing amount of attention be‐
cause of their excellent chemical and thermal stabilities, ul‐
tra‐high Brunauer‐Emmett‐Teller (BET) surface areas and po‐
rosities, as well as the high amount of nitrogen functionalities
in their networks. Owing to these remarkable properties, CTFs
have been applied in many fields, including catalysis [11–13],
gas adsorption and storage [14–16], sorbent materials [17,18],
organic semiconductors [19], electrical materials [20,21] and
others [22–24].
* Corresponding author. Tel: +86‐411‐84379571; Fax: +86‐411‐84675584; E‐mail: dengwq@dicp.ac.cn
This work was supported by the National Natural Science Foundation of China (21373202, 21525315).
DOI: 10.1016/S1872‐2067(17)62771‐2 | http://www.sciencedirect.com/science/journal/18722067 | Chin. J. Catal., Vol. 38, No. 3, March 2017

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Ling Zhang et al. / Chinese Journal of Catalysis 38 (2017) 583–588
To synthesize CTFs on a large scale for potential commer‐
2.2. Analytical methods
cialization, an economical synthetic pathway is required. The
key monomers used in CTFs are multiple cyano‐substituted
benzenes, but these are not available on a large scale. The tra‐
ditional synthetic routes to cyano‐substituted benzenes include
Rosenmund von Braun reactions [25–27] from aryl halides,
diazotization of anilines and the Sandmeyer reaction [28].
However, these synthetic methodologies are associated with
the use of overstoichiometric amounts of toxic cyanides, such
as Zn(CN)2 [29], CuCN [30], KCN [31], NaCN [32] and trime‐
thylsilyl cyanide (TMSCN) [33], as the cyanide source, which is
a serious environmental concern. Recently, nontoxic potassium
hexacyanoferrate(II) was introduced as a cyanation agent by
Beller’s group [34–36]. They demonstrated that aryl halides
can react with potassium hexacyanoferrate(II) to give cyano
compounds in the presence of catalytic amounts of palladium
catalysts and ligands such as 1,5‐bis(diphenylphosphino)pen‐
tane (dpppe), 1,1′‐bis(diphenylphosphino)ferrocene (dppf),
triphenylphosphine (PPh3), tricyclohexylphosphine (PCy3) and
GC‐MS analysis was performed on a GCMS‐QP2010SE spec‐
trometer. n‐Hexadecane was selected as the internal standard
for GC‐MS after optimization. The NMR spectra (1H, 400 MHz;
13C, 100 MHz) were recorded on a Bruker Mercury Plus
400‐MHz spectrometer. CDCl3 was used as the solvent with
tetramethylsilane (TMS) as the internal standard. The synthesis
of CTFs was carried out in a muffle burner (TSX1200). The spe‐
cific surface area of the CTFs was measured on an adsorption
instrument (Quantachrome Quadrasorb SI).
2.3. Typical procedure for palladium acetate‐catalyzed
cyanation of aryl bromides
Aryl bromide (6.0 mmol), K4[Fe(CN)6]·3H2O (2.4 mmol),
Na2CO3 (6.0 mmol) and Pd(OAc)2 catalyst (0.2 mol% relative to
the aryl bromide) were mixed in NMP (12 mL) in a 25‐mL
flame‐dried double‐neck round‐bottom flask and heated with
stirring at 130 °C under argon. The progress of the reaction was
monitored by GC‐MS. At the end of the reaction, the mixture
was cooled to room temperature. Samples were quenched with
H2O (or with sat. NH4Cl when pyridines were used as sub‐
strates), and extracted with EtOAc (25 mL × 3). The organic
layer was washed with water (15 mL × 3) and 5% NH3·H2O (15
mL × 2), and then dried over Na2SO4. Evaporation of the solvent
left the crude product, which was further purified by column
chromatography over silica gel (60–120 mesh) eluting with
petroleum ether/ethyl acetate to afford the pure aryl nitrile.
1,4‐Dicyanobenzene (1b, DCB). 1H NMR (CDCl3, 400 MHz): δ
= 7.80 (s, 4H); 13C NMR (101 MHz, CDCl3): δ = 132.81, 117.00,
116.76.
2,6‐Dicyanopyridine (2b, DCP). 1H NMR (CDCl3, 400 MHz): δ
= 8.15 (dd, J = 8.4, 7.4 Hz, 1H), 7.99 (d, J = 7.8 Hz, 2H); 13C NMR
(101 MHz, CDCl3): δ = 139.13, 135.22, 131.29, 115.53.
1,4‐Dicyanonaphthalene (3b, DCN). 1H NMR (CDCl3, 400
MHz): δ = 8.35 (dd, J = 6.4, 3.2 Hz, 2H), 7.98 (s, 2H), 7.87 (dd, J =
6.4, 3.2 Hz, 2H); 13C NMR (101 MHz, CDCl3): δ = 132.00, 131.09,
130.30, 126.03, 116.27, 115.20.
2,2′‐bis(diphenylphosphino)diphenyl ether (Bpephos).
A
drawback of this procedure is the need for expensive ligands,
which not only greatly increases the cost of the experiments,
but also limits the scale of the reaction. Recently, several tria‐
zine‐functionalized porous polymers were synthesized using
imide‐functionalized 1,3,5‐triazine frameworks and showed
high CO2‐adsorption capacities [37,38]. Modak et al. [37] re‐
ported a one‐pot bottom‐up synthetic strategy for the tria‐
zine‐functionalized porphyrin‐based porous organic polymer
TPOP‐1, which showed a CO2 uptake of up to 6.2 mmol/g at 3 ×
105 Pa and 0 °C. Gomes et al. [38] reported the synthesis of the
polymer TRITER‐1 by condensation polymerization of 1,3,5‐
tris‐(4‐aminophenyl)triazine (TAPT) and terephthaldehyde.
In this work, we have developed a new synthetic pathway
for CTFs. First, multiple cyano‐substituted aromatics were
synthesized using inexpensive and nontoxic K4[Fe(CN)6]·3H2O
as the cyanide source for cyanation of aryl bromides. This reac‐
tion was catalyzed by Pd(OAc)2 without addition of other lig‐
ands. Second, CTFs were synthesized by polymerization of the
multiple cyano‐substituted aromatics in molten ZnCl2, which
acts as both a catalyst and a solvent at temperatures of
400–600 °C [10]. The obtained CTFs exhibited excellent CO2‐
adsorption properties.
2.4. Synthetic procedure for CTFs
Traditional CTF synthesis has been described elsewhere
[10]. In this work, aryl nitriles (7.8 mmol) and anhydrous ZnCl2
(39.0 mmol) were transferred into a quartz ampoule (15 cm3)
under an inert atmosphere. The ampoule was evacuated, sealed
and heated to 400 °C for 20 h and then to 600 °C for another 20
h. The ampoule was then cooled to room temperature and
opened carefully (Caution: the ampoule is under pressure,
which is released on opening). The reaction mixture was then
ground and washed thoroughly with large amounts of water to
remove most of the ZnCl2. It was then stirred in dilute HCl for
15 h to remove the residual salt. After this purification step, the
resulting black powder was filtered, washed successively with
water and THF and dried in vacuum at 120 °C. The yield of the
reaction was high (> 91%) to quantitative.
2. Experimental
2.1. Reagents
All reagents were purchased from Alfa Aesar, J&K Scientific
Ltd., Aladdin Reagent and Sigma Aldrich, and were used with‐
out further purification. 1,4‐Dicyanobenzene (1b), 2,6‐dicyan‐
opyridine (2b) and 1,4‐dicyanonaphthalene (3b) were pre‐
pared from their corresponding aryl bromides with
K4[Fe(CN)6]·3H2O in the presence of Pd(OAc)2 according to a
previously reported method [34,39]. 1b–3b were isolated from
the reaction mixtures and characterized by H NMR and 13C
NMR spectroscopy.
1

Ling Zhang et al. / Chinese Journal of Catalysis 38 (2017) 583–588
585
3. Results and discussion
Table 2
Pd(OAc)2‐catalyzed cyanation of various aryl bromides a.
3.1. Pd(OAc)2‐catalyzed cyanation of 1,4‐dibromobenzene with
Ar Br
Ar CN
K4[Fe(CN)6]·3H2O
a
b
Br
We used 1,4‐dibromobenzene as a model substrate to
screen suitable reaction conditions for the cyanation of aryl
bromides (Table 1). We obtained similar yields using
N,N‐dimethylformamide (DMF) and 1‐methyl‐2‐pyrrolidinone
(NMP) as the solvent (around 60%, Table 1, Entries 1 and 3);
however, the yield decreased to only 41% after replacing the
solvent with N,N‐dimethylacetamide (DMAc) (Table 1, Entry 2).
To our surprise, a high yield of 1,4‐dicyanobenzene was ob‐
tained at a relatively low catalyst concentration when the reac‐
tion time was prolonged (Table 1, Entries 5 and 6). However,
increasing the amount of Pd(OAc)2 led to a decrease in the yield
(Table 1, Entries 7–9). This might have been caused by exces‐
sive catalyst aggregation and transformation to insoluble palla‐
dium black [34,40]. In practice, the use of (0.1–0.2) mol% lig‐
and‐free Pd(OAc)2 gives good yields in the cyanation reaction
of 1,4‐dibromobenzene with K4[Fe(CN)6]·3H2O (NMP, Na2CO3,
130 °C). No desired product was observed when the cyanation
was performed in DMSO, toluene or ethylene glycol owing to
the poor solubility of 1,4‐dibromobenzene and K4[Fe(CN)6]
(Table 1, Entries 10–12). The best reaction conditions were
thus determined to be 0.2 mol% Pd(OAc)2 and NMP as the sol‐
vent, with a reaction time of 2 h (> 99%) (Table 1, Entry 4).
Br
1a
CN
CN
NC
N
CN
2b (Y: 34% (58%)b; 9 h)c
3b (Y: 76% (90%)b; 5 h)
DCP
DCN
a
Reaction conditions: 6.0 mmol aryl bromide, 2.4 mmol
K4[Fe(CN)6]·3H2O, 6.0 mmol Na2CO3, 0.2 mol% Pd(OAc)2, 12 mL NMP,
under Ar, 130 °C. Y = yield of the isolated product.
Values in parentheses were determined by GC with n‐hexadecane as
the internal standard. All products were identified by NMR spectroscopy.
c 0.4 mol% Pd(OAc)2.
b
pletely converted to 1,4‐dicyanonaphthalene (3b). However,
the yield of 2,6‐dicyanopyridine (2b) was less than 58%, even
after 9 h of reaction time.
3.3. N2 adsorption of CTFs
CTFDCB, CTFDCP [10] and CTFDCN frameworks (Table 2) were
synthesized by heating a mixture of the nitrile monomers DCB,
DCP and DCN and ZnCl2 in quartz ampules at 400–600 °C for 40
h. The molten ZnCl2 acts as both solvent and catalyst for the
self‐polymerization of the triazine rings. The molar ratio of
ZnCl2 to the nitrile monomer was 5:1, which allowed the reac‐
tion to proceed smoothly.
3.2. Pd(OAc)2‐catalyzed cyanation of aryl bromides with
K4[Fe(CN)6]·3H2O
Based on the above result, we extended the substrate scope
to heteroaromatic compound 2,6‐dibromopyridine (2a) and
polycyclic aromatic hydrocarbon 1,4‐dibromonaphthalene
(3a), and the reactions were performed under the optimized
reaction conditions (Table 2). Accordingly, 3a was almost com‐
The porosity, that is, the surface area and pore volume, and
the pore size distribution of all CTFs were characterized by N2
adsorption measurements (Fig. 1). All CTFs were outgassed in
vacuum at 150 °C for 10 h, and the results are listed in Table 3.
As shown in Fig. 1(a), the N2 isotherms indicate that the three
polymers are microporous; this is also demonstrated by the
sharp adsorption/desorption step in the low relative pressure
region (P/P0 = 0–0.05). The isotherms for CTFDCB and CTFDCN
also exhibit hysteresis loops, which indicate the presence of
mesopores. The H2‐type hysteresis loops present in the CTFDCB
and CTFDCN desorption isotherms may be caused by the differ‐
ent mechanisms of the condensation and evaporation process‐
es in the micro‐ and mesopores [41]. The surface areas of the
CTFs, calculated using the BET equation, were 2404, 1650 and
780 m2/g for CTFDCB, CTFDCP and CTFDCN, respectively. The pore
size distributions of CTFDCB, CTFDCP and CTFDCN were calculated
by HK methods. As shown in Fig. 1(b), all three CTFs exhibit
small micropore diameters centered around 0.5 nm; for exam‐
ple, CTFDCB had a maximum pore size of 0.57 nm. Moreover, the
overall micropore volume of CTFDCB was 0.85 cm3/g, and those
of CTFDCP and CTFDCN were 0.76 and 0.52 cm3/g, respectively
(Table 3). The porosity and texture of the CTFs were homoge‐
neous and the presence of small micropores was confirmed by
the high‐resolution transmission electron microscopy images
shown in Fig. 2.
Table 1
Optimization of the reaction conditions for the cyanation of 1,4‐dibro‐
mobenzene a.
.
Br
Br +
NC
CN
K4[Fe(CN)6] 3H2O
Pd(OAc)2
(mol%)
0.2
Time
(h)
2
2
1
2
4
4
4
4
4
2
Conv.
Yieldb
(%)
60
41
63
> 99
71
89
78
76
53
0
Entry
Solvent
(%)
62
43
66
100
72
89
79
77
55
0
1
2
3
4
5
6
7
8
DMF
DMAc
NMP
NMP
NMP
NMP
NMP
NMP
NMP
0.2
0.2
0.2
0.05
0.1
0.3
0.4
0.5
0.2
9
10
11
DMSO
Toluene
0.2
2
0
0
12
0.2
Ethylene glycol
2
0
0
a
Reaction conditions: 6.0 mmol 1,4‐dibromobenzene, 2.4 mmol
K4[Fe(CN)6]·3H2O, 6.0 mmol Na2CO3, 12 mL solvent, Pd(OAc)2, under Ar,
130 °C.
b Determined by GC‐MS with n‐hexadecane as the internal standard.

586
Ling Zhang et al. / Chinese Journal of Catalysis 38 (2017) 583–588
1.6
1400
1200
1000
800
600
400
200
0
(b)
CTF
CTF
CTF
CTF
CTF
CTF
ads
des
ads
des
ads
des
(a)
DCB
DCB
DCP
DCP
DCN
DCN
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
CTF
CTF
CTF
DCB
DCP
DCN
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
0.0
0.2
0.4
0.6
0.8
1.0
Relative pressure (P/P0)
Pore diameter (nm)
Fig. 1. (a) N2 adsorption isotherms of CTFs at –196 °C; (b) Pore size distributions of CTFDCB, CTFDCP and CTFDCN
.
opyridine, reached 225 and 154 mg/g under 1  105 Pa at 0 and
25 °C, respectively. However, the CO2 uptake of CTFDCB, which
had the highest BET surface area among the three CTFs stud‐
ied, was only 148 mg/g at 0 °C and 99 mg/g at 25 °C, close to
the 129 mg/g at 0 °C and 97 mg/g at 25 °C measured for
CTFDCN. The high adsorption ability of CTFDCP, compared with
those of CTFDCB and CTFDCN, derives from the extra nitrogen
atoms in the structure, which serve as active alkali sites and
attract CO2 molecules [42]. Comparison of the CO2 uptake of
these CTFs with those of metal organic frameworks (MOFs),
conjugated microporous polymers (CMPs) [43] and zeolites
[44], as well as those obtained under identical conditions for
our previously reported CMPs, Co‐CMP and Al‐CMP [45], shows
that the CTFs have good CO2 capture abilities at both 0 and 25
°C (Table 4). To better understand the adsorption properties,
the isosteric heats of adsorption were calculated using a variant
of the Clausius Clapeyron equation [46] from fits of the CO2
isotherms at different temperatures. As shown in Fig. 3(c), the
Table 3
Porosity data for CTFs from N2 isotherms measured at –196 °C.
Surface area a Micropore volume b Pore size c
CTFs
Monomer
(m2/g)
2404
1650
780
(m3/g)
0.85
(nm)
0.57
0.45
0.54
CTFDCB
CTFDCP
CTFDCN
DCB
DCP
DCN
0.76
0.52
a Determined by the BET equation over the relative pressure range
described in reference.
b Determined at P/P0 = 0.99.
c Determined by nonlocal density functional theory.
3.4. CO2 adsorption of CTFs
As shown in Fig. 3(a) and (b), CO2 adsorption by CTFs was
also investigated using volumetric methods at 0 and 25 °C. All
of the CTFs showed reversible CO2 adsorption isotherms. The
CO2 uptake of CTFDCP, which was synthesized from 2,6‐dicyan‐
(a)
(b)
(c)
Fig. 2. High‐resolution transmission electron micrographs of CTFDCB (a), CTFDCP (b) and CTFDCN (c).
160
120
80
40
0
50
40
30
20
10
0
240
200
160
120
80
(b)
CTF
CTF
CTF
(a)
(c)
CTF
CTF
CTF
CTF
CTF
CTF
DCB
DCP
DCN
DCB
DCP
DCN
DCB
DCP
DCN
40
0
20 40 60 80 100 120 140 160
CO2 adsorbed (mg/g)
0.2
0.4
0.6
0.8
1.0
0.2
0.4
0.6
0.8
1.0
Relative pressure (P/P0)
Relative pressure (P/P0)
Fig. 3. CO2 adsorption isotherms of CTFs at 0 °C (a) and 25 °C (b), and corresponding heats of adsorption (c).

Ling Zhang et al. / Chinese Journal of Catalysis 38 (2017) 583–588
587
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We have developed an environmentally friendly method for
the direct synthesis of multiple cyano‐substituted aromatic
compounds. This method uses palladium acetate without any
additional ligands as the catalyst and nontoxic potassium hex‐
acyanoferrate(II) as the cyanide source, thus removing the
need for special precautions. Notably, aromatic nitriles could be
obtained in excellent yields using catalyst amounts of only
(0.2–0.4) mol%. Moreover, three CTFs were synthesized from
the obtained cyano‐aromatic compounds. These CTFs exhibited
high specific surface areas and excellent CO2 absorption abili‐
ties. Furthermore, the synthesized porous polymers had good
stability and multiple active sites for metal coordination; we
thus expect them to find application in catalyst supports.
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Graphical Abstract
Chin. J. Catal., 2017, 38: 583–588 doi: 10.1016/S1872‐2067(17)62771‐2
Environmentally benign and economic synthesis of covalent triazine‐based
frameworks
CN
CN
Ling Zhang, Xue Liu, Rui‐Xia Yang, Nian‐Yu Huang, Wei‐Qiao Deng *
China Three Gorges University; Dalian Institute of Chemical Physics, Chinese
Academy of Sciences
K4[Fe(CN)6]·3H2O
Covalent triazine‐based frameworks were prepared from the corresponding
dicyano monomers by cyanation of aryl bromides with nontoxic potassium hex‐
acyanoferrate(II) in the presence of palladium acetate.

588
Ling Zhang et al. / Chinese Journal of Catalysis 38 (2017) 583–588
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