Large-scale synthesis of azine-linked covalent organic frameworks in water and promoted by water

Article abstract of DOI:10.1039/c9nj00830f

A hydrothermal procedure has been developed to produce azine-linked COFs by conducting condensation reactions of hydrazine with hydroxy-substituted 1,3,5-triformylbenzene in water. The synthesis of one representative COF was drastically promoted by water in comparison with the traditional solvothermal reactions in organic solvents. This synthesis has advantages of large-scale production, catalyst-free reaction, short reaction time, and the obtained COF exhibits higher crystallinity and surface area.

Full text of DOI:10.1039/c9nj00830f

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Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
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DOI: 10.1039/C9NJ00830F
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Large-scale synthesis of azine-linked covalent organic frameworks
in water and promoted by water
Received 00th January 20xx,
Accepted 00th January 20xx
‡
‡
Jian Lu,a,b Feng Lin,b Qiang Wen,b Qiao-Yan Qi,b Jia-Qiang Xu*a and Xin Zhao*b
DOI: 10.1039/x0xx00000x
www.rsc.org/
continuous flow synthesis illustrated by Zhao and co-workers very
A hydrothermal procedure has been developed to produce azine-
linked COFs by conducting condensation reactions of hydrazine
with hydroxy-substituted 1,3,5-triformylbenzene in water. The
synthesis of one representative COF is dramatically promoted by
water in comparison with the traditional solvothermal reactions in
organic solvents, which is revealed by the large-scale production,
free of catalyst, short reaction time, and higher crystallinity and
surface area of the COF.
O
O
O
H
N
O
N
H
O
N
H
HO
O
OH
O
H
O
H
N
O
O
N
N
OH
+
H
O
O
H
O
O
H2O
N
N
H
O
O
N
H
O
H
N
O
O
H
N
H2N NH2
N
H
Covalent organic frameworks (COFs) are a class of crystalline porous
organic materials which hold reticular structures.1 Over the past
decade COFs have drawn considerable attention because of their
versatile applications ranging from adsorption,2 separation,3
sensors,4 catalysis,5 drug delivery,6 proton conduction,7 to
photoelectric materials.8 The construction of COFs follows the
principle of reticular chemistry,9 for which dynamic covalent bonds
such as the formation of boronate,10 imine,11 hydrazone,12 and even
imide,13 have been utilized. Since the first two COFs were reported
in 2005,14 a variety of COFs have been synthesized and many
potential applications have been demonstrated.15 However, for the
COFs reported so far, although different building blocks and bond
types have been employed, they are almost entirely prepared
under solvothermal conditions in organic solvents and the
production scales are usually limited to tens to hundred
milligrams.16 So far only a few procedures have been developed to
decrease/eliminate the use of organic solvents and/or to increase
the production scale of COFs, as represented by solid state
mixing/grinding procedures developed by Banerjee et al.,17 and a
O
O
HCOF-1
Scheme 1 Synthesis of HCOF-1 via a hydrothermal procedure.
recently.18 As far as practical applications of COFs are concerned,
one of the bottlenecks is how to realize their feasibly large-scale
production. The use of a large quantity of flammable organic
solvents not only increases production cost, but also incurs safety
problem and environmental hazards. Replacing organic solvents
with water as the solvent for chemical reactions is a fundamental
goal in green chemistry. Although this goal has already been
achieved for a variety of organic reactions,19 fabrication of COFs in
water has rarely been achieved. To the best of our knowledge,
there is only one study reported by Banerjee and co-workers, which
afforded COFs through heating 1,3,5-triformylphloroglucinol and
o
aromatic amines in water at 120 C for 3 days in the presence of
AcOH as a catalyst.20 In this communication, we report the synthesis
of three azine-linked COFs by using only water as the solvent for the
condensation reactions. The COFs can be produced in large-scale
and no acidic catalyst is required. Furthermore, a representative
COF exhibits higher quality (crystallinity and specific surface area)
than those synthesized in organic solvents. It is also found that the
use of water dramatically promotes the production efficiency of the
COF by reducing the reaction time to several hours, which
otherwise needs several days when organic solvents are used. Such
advantages, especially the large-scale production, offer practical
applications of the COF, which has further been demonstrated by
its use as column stuffing for highly efficient separation of
methylene blue (MB) from the other dyes.
a. NEST Laboratory, Department of Chemistry, College of Science,
Shanghai University, Shanghai 20044 China. E-mail: xujiaqiang@shu.edu.cn.
b Key Laboratory of Synthetic and Self-Assembly Chemistry for Organic Functional
Molecules, Center for Excellence in Molecular Synthesis, Shanghai Institute of
Organic Chemistry, Chinese Academy of Science, 345 Lingling Road, Shanghai
200032 China. Email: xzhao@sioc.ac.cn
Electronic Supplementary Information (ESI) available: Preparation of the monomer
and COF, FTIR spectra, solid state 13C NMR, screening of condensation conditions,
TGA trace, N2 adsorption−desorption isotherms (77 K) plots, BET plots, and
fractional atomic coordinates. See DOI: 10.1039/x0xx00000x
‡ These authors contributed equally to this work.
This journal is © The Royal Society of Chemistry 20018
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0.5h
1h
2h
4h
8h
The hydrothermal synthesis of HCOF-1 was conducted by the co-
condensation of 1,3,5-triformylphloroglucinol with hydrazine
hydrate in water (Scheme 1). This COF has been previously
View Article Online
DOI: 10.1039/C9NJ00830F
12h
24h
synthesized
under
solvothermal
conditions
by
using
tetrahydrofuran-methanol (named as COF-JLU2)21 or dioxane-
mesitylene (named as ATFG-COF or RIO-13)22 as the solvents and
catalyzed by aqueous acetic acid. In order to produce materials with
o
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good crystallinity, keeping the reaction at 120 C for at least the 3
days is needed and extending reaction time is suggested to afford
materials with higher crystallinity. This COF has been demonstrated
to exhibit remarkably high CO2 and methane uptakes. Such
excellent performance makes the COF very promising for practical
applications. However, the solvothermal synthesis provides the
target COF with scales up to only hundred milligrams, as indicated
by the fact that a 1-gram-synthesis requires parallelizing the
condensation reaction for 6 times.22a The small-scale synthesis of
this COF significantly limits its practical applications.
To optimize the hydrothermal conditions, reaction conditions
including temperature, concentration of catalyst, and reaction time
were screened, respectively. For the screening processes,
experiments of small-scale (tens milligrams) synthesis were
5
10
15
20
25
30
2-Theta
Fig. 1 PXRD profiles of HCOF-1 synthesized under different reaction time.
Fig. 2 Photographs showing the proceeding of a 10-gram-scale synthesis of
HCOF-1.
conducted
to
save
1,3,5-triformylphloroglucinol.
Three
temperatures, 80, 120 and 150 oC were screened when the
concentration of AcOH was fixed at 6 M and reaction time was kept
based on the data derived from its N2 isotherm (Fig. S3, ESI). The
BET surface area value is higher than that of COF-JLU2 and ATFG-
COF, which are 415 and 520 m2g-1, respectively.21,22a,23 A 10-gram-
scale synthesis was further conducted (Fig. 2). The resulting COF
also exhibits good crystallinity and remarkably it displays an even
higher BET surface area (763 m2g-1) (Fig. S4, ESI). These results
clearly indicate that the COF prepared from water possesses higher
quality than those from organic solvents. Moreover, it is also found
that the hydrothermal method gives rise to much higher yield of the
product than that of the solvothermal reactions in organic solvents,
with the former up to 97% while the latter reported to be 70%.21
The scale-up process strongly suggests that mass production of the
o
for 3 days. It is found that 120 C is more suitable than the other
two, as indicated by their powder X-ray diffraction (PXRD) profiles
(Fig. S1, ESI). In the next step, the influence of concentration of
catalyst AcOH on the production of HCOF-1 was investigated by
setting the reaction temperature to be 120 oC. Very interestingly,
the porous material with the highest crystallinity is obtained from
the entry which runs the condensation reaction without AcOH. For
the condensation reactions in the presence of AcOH, the
crystallinity of HCOF-1 decreases with the increase of the
concentration of AcOH (Fig. S2, ESI). The dispensing with acidic
catalyst is a big advantage for industrial production, for which acid-
induced corrosion of equipment is usually a severe issue.
COF can be reached if
triformylphloroglucinol is available.
a
large amount of 1,3,5-
o
Fixing the reaction temperature to be 120 C and no AcOH being
added, 1,3,5-triformylphloroglucinol and hydrazine were co-
condensated in water for different length of time. As revealed by
the PXRD data of the as-obtained materials (Fig. 1), a reaction time
of 0.5 h already gives rise to crystalline product. The crystallinities
of the products increase with the extending time and no significant
difference is observed between the samples obtained from the
entries of 8, 12 and 24 hours, suggesting a time of 812 hours is
long enough to complete the condensation reaction. In comparison
to the previous COFs under solvothermal conditions in organic
solvents, this hydrothermal process dramatically shortens the
reaction time, which not only significantly decreases energy cost
but also promotes efficiency for mass production.
After the reaction conditions have been optimized, scale-up of
the newly developed hydrothermal process was conducted, with
fixing the reaction time to be 12 h. Firstly, a 1-gram-scale synthesis
was carrying out. The as-prepared material exhibits good
crystallinity and its BET surface area is calculated to be 617 m2g-1
HCOF-1 was characterized with Fourier transform infrared (FT-IR)
spectroscopy and solid state 13C cross polarization magic angle
spinning (CP-MAS) NMR technique. Theoretically, HCOF-1 has two
tautomers.22 As shown in its infrared spectrum, no significant peaks
corresponding to O-H or N-H are observed due to the
tautomerization (Fig. S6, ESI). A broad peak centred at 1590 cm-1 is
assigned to C=N bond and C=C bond, indicating coexistence of the
two kinds of tautomers. The coexistence of keto-enhydrazine and
enol-hydrazone tautomers has also been corroborated by the solid
state
13C
CP-MAS
NMR
spectrum.
While
1,3,5-
triformylphloroglucinol displays peaks at 192, 174 and 103 ppm for
the three different types of carbon atoms (Fig. S7, ESI), resonance
signals corresponding to keto-carbon (180 ppm), imine-carbon and
enol-carbon (163 ppm) are observed for HCOF-1 (Fig. S8, ESI), which
is in accord with the previous study on ATFG-COF.22 UV-Vis spectra
of 1,3,5-triformylphloroglucinol and HCOF-1 were also compared,
which revealed that the COF exhibited a broad absorption band
2 | Chem. Comm., 2018, 54, 1-4
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covering the range of 300-800 nm (Fig. S9, ESI). SEM and TEM
View Article Online
DOI: 10.1039/C9NJ00830F
100
a
b
reveal that HCOF-1 exhibits flake-like morphology (Fig. S10, ESI).
Elemental analysis of HCOF-1 gives rise to C, H, and N contents to
be 52.88%, 4.25% and 19.27%, respectively, which are very close to
the theoretical values of the expected 2D COF (C: 52.95%, H: 2.96%
and N: 20.58%). The porosity of HCOF-1 is reflected by pore size
distribution obtained from the N2 adsorption−desorption data.
Fitting the data with nonlocal density functional theory (NLDFT)
calculations gave a narrow pore size distribution centered at 10.2 Å
(Fig. S11, ESI), which is consistent with the theoretical pore size
(11.8 Å) estimated from the simulation. Thermogravimetric analysis
(TGA) reveals that HCOF-1 is thermally quite stable (Fig. S12, ESI).
More than 92% weight is maintained when the temperature
increases from 35 to 300 °C under nitrogen atmosphere.
The crystal structure of HCOF-1 described as a hexagonal
structure with a P6 symmetry for the eclipsed AA layer stacking was
confirmed by the PXRD measurement. The experimental PXRD
pattern of HCOF-1 displays diffraction peaks at 2 6.93, 11.78 and
26.9°, which fits well with the theoretically simulated PXRD pattern
(Fig. 3). The experimental PXRD pattern was refined by Pawley
method to yield unit cell parameters of a = b = 15.415 Å, c = 3.345 Å,
and α = β = 90o, γ = 120o, with Rp = 1.94% and Rwp = 2.47%. As
indicated by the difference plot, the experimental and refined
diffraction patterns match each other quite well.
To extend this hydrothermal procedure to other COFs, another
two COFs, termed as HCOF-2 and HCOF-3,22b were prepared from
the condensations of hydrazine hydrate with 2,4,6-
triformylresorcinol and 2-hydroxy-1,3,5-triformylbenzene in water,
respectively. The target COFs were successfully obtained, as
evidenced by the characterization data (Fig. S13-S25, ESI). These
results demonstrate that this hydrothermal method could also be
applicable to the synthesis of other azine-based COFs. However, it
should be noted that, with the decrease of the numbers of hydroxyl
groups in the monomers, extended reaction time is required to
afford COFs with good quality. It might be ascribed to decreasing
water solubility of the monomers with less hydroxyl groups.
The facile large-scale synthesis of the COFs encourages us to
exploit its practical applications, for example, as an adsorbent or
column stuffing for separation. In this context, selective adsorption
and separation of organic dyes was investigated. The adsorption
experiment was carried out by immersing HCOF-1 (10 mg) in an
aqueous solution of MB (1  10-4 M), and the progress was
monitored with UV-vis spectroscopy. The concentration of MB
decreases dramatically in 1 min, and the blue solution of MB fades
to colorlessness within 10 min (Fig. 4a). In sharp contrast, HCOF-1
exhibits much lower uptakes towards the other water soluble dyes
Methyl Orange (MO) and Acid Red 1 (AR1) (Fig. S26, ESI). The
application of HCOF-1 as column stuffing was further illustrated.
Columns packed with HCOF-1 (1.0 cm in height) were made, which
were then used to remove MB from water and to separate MB from
the mixture of MB and MO or MB and AR1. As shown in Figure 4b,
complete removal of MB from water is reached by passing a
solution of MB through the column (Fig. 4b, left). On the other hand,
complete separation of MB from its mixture with MO or AR1 can
001
110
AA stacking
c
d
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2 Theta
AB stacking
Fig. 3 (a) Experimental (black) and refined (red) PXRD patterns of HCOF-1, (b)
difference plot between the experimental and refined PXRD patterns, and
simulated PXRD patterns of (c) HCOF-1 with AA stacking, (d) HCOF-1 with AB
stacking.
2.5
a
b
0 min
1 min
10 min
1 h
2 h
3 h
2.0
1.5
1.0
0.5
0.0
4 h
5 h
-1
550 575 600 625 650 675 700 725 750
Wavelength (nm)
Fig. 4 (a) Time-dependent UV-vis absorption spectra of MB (the inserted
photographs show the color change before and after the dye uptake). (b)
Removing MB from water (left), and separating MB from MB-MO mixture
(middle), and MB-AR1 mixture (right) by passing the columns which are packed
with HCOF-1.
also be facilely realized by passing the mixtures through the
column (Fig. 4b, middle and right). Since the three dyes bear
different structures and functional groups, the adsorption
selectivity should be a concerted effect of multiple factors.
However, on the basis of the fact that the HCOF-1 exhibited
high adsorption efficiency for positively charged MB but much
lower uptakes toward the two negatively charged dyes MO
and AR1, charge selectivity is likely to be the major factor.
In summary, a green process for the synthesis of azine-
linked COFs has been developed. Compared with the most
widely used solvothermal synthesis of COFs in organic
solvents, the new procedure uses only water as the solvent
and thus possesses the advantages of safety, low cost, and
friendly to the environment. This hydrothermal procedure
allows large-scale production of the COFs, which breaks the
limitation of ten-to-hundred-milligram-scale preparations
under the current solvothermal conditions. Moreover, the use
of water as solvent for the COF synthesis also brings in several
other advantages such as dramatically shortening reaction
time from several days to several hours, improving the quality
of the COFs, and dispensing with acidic catalyst. These
advantages offer mass production of COFs in laboratory and
even industrialization production in the near future, which lay
a foundation for practical applications of COFs.
We thank the National Natural Science Foundation of China
(21632004) and the Strategic Priority Research Program of the
Chinese Academy of Sciences (XDB20000000) for financial
support.
Conflicts of interest
This journal is © The Royal Society of Chemistry 2018
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There are no conflicts to declare.
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4 | Chem. Comm., 2018, 54, 1-4
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Page 5 of 5
New Journal of Chemistry
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DOI: 10.1039/C9NJ00830F
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Table of contents entry
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Large-scale synthesis
in water & promoted by water
O
O
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N
N
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O
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O
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A hydrothermal procedure has been developed to synthesize covalent organic
frameworks in water, with the advantages of large-scale production, short reaction time,
free of acidic catalyst, and higher quality of the product.