Covalent Functionalization of Carbon Nitride Frameworks through Cross-Coupling Reactions

Article abstract of DOI:10.1002/chem.201803201

A new and simple synthetic route is introduced to covalently functionalize the carbon nitride (CN) framework by the implementation of halogenated phenyl groups (Cl, Br and I), which serve as a chemically reactive center, within the CN framework. The coval

Full text of DOI:10.1002/chem.201803201

A Journal of
Accepted Article
Title: Covalent Functionalization of Carbon Nitride Frameworks through
Cross-Coupling Reaction
Authors: Jingwen Sun, Ravindra Phatake, Adi Azoulay, Guiming Peng,
Chenhui Han, Jesus Barrio, Jingsan Xu, Xin Wang, and
Menny Shalom
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To be cited as: Chem. Eur. J. 10.1002/chem.201803201
Link to VoR: http://dx.doi.org/10.1002/chem.201803201
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COMMUNICATION
Covalent Functionalization of Carbon Nitride Frameworks through
Cross-Coupling Reaction
Jingwen Sun,[a] Ravindra Phatake,[a] Adi Azoulay,[a] Guiming Peng,[a] Chenhui Han,[a] Jesús Barrio,[a]
Jingsan Xu,[b] Xin Wang[c] and Menny Shalom*[a]
Abstract: Here we introduce a new and simple synthetic route to
covalently functionalize the carbon nitride (CN) framework by the
implementation of halogenated phenyl groups (Cl, Br and I), which
serve as a chemically reactive center, within the CN framework. The
covalent modification is demonstrated here by substituting phenyl and
tert-butyl propionate onto the modified-CN framework through Suzuki
and Reductive-Heck cross-coupling reactions, respectively. The
effective functionalization leads to a facile exfoliation of the CN
framework into thinner layers and greatly enhances the dispersibility
in many solvents as well as the photocatalytic activity compared to the
unmodified CN. The general covalent modification opens the
possibility for tailor-made design of the CN materials dispersibility as
well as the photophysical and chemical properties toward their
exploitation in many fields, such as photocatalysis, bio-imaging,
sensing and heterogeneous catalysis.
structures by liquid-based techniques (i.e. NMR).[7] Moreover, the
strong van der Waals interaction between the CN layers alongside
with their low dispersibility impede their exfoliation into a stable
2D material.[7]
Intensive efforts have been devoted to optimizing the
photophysical and catalytic properties of bulk CN frameworks as
well as to improving their dispersibility, including physical and
chemical cleavage,[8a] nanostructuring,[8b-d] surface protonation,[9]
heteroatom incorporation,[10a-e] heterojunctions[10f] and other
electronic structures construction,[11] copolymerization of CN
monomers prior to their condensation at high temperature[12] and
non-covalent interaction with different molecules.[13] However,
most of the modifications involve either the bottom-up approach –
condensation of molecules with different heteroatoms and
molecular structure or by non-covalent post-modifications of the
final CN frameworks.[14] In contrast to the above-mentioned
approaches, post-condensation, covalent functionalization is
considered as more robust and permanent modification due to the
establishment of a non-reversible chemical bond between the
material and the selected molecule.[15] In addition, it allows the
introduction of groups that would be decomposed or condensate
during the calcination process (such as nitriles, esters,
carboxylates, boronic acid, etc.). The nature of the introduced
molecule can affect several properties of the modified material,
e.g. its electronic properties, surface charge, charge separation
under illumination, optical properties (i.e. band gap) and its
dispersibility in different solvents.[16] Several pioneering works
demonstrated the covalent functionalization of graphene and
other carbon allotropes such as carbon nanotubes.[17] This
successful approach paves the way for further development of
functional graphene derivatives. However, a direct covalent
modification of CN-based organic framework is challenging and
rarely reported before,[16,18] due to the chemical inertness of sp2
carbon-nitrogen bonds within the CN framework and the strong
interaction between its layers. Therefore, we envision that in order
to overcome these obstacles, the CN framework should
encompass a chemically reactive group that can be further
covalently functionalized.
Here, we demonstrate a new and facile strategy to covalently
functionalize CN organic framework by the insertion of a halogen-
(Cl, Br and I) substituted phenyl into the CN framework. Prior to
the covalent functionalization, the reactive CN framework is
prepared by the calcination of a new series of derivatives based
on modified 2,4-diamino-6-phenyl-1,3,5-triazine where the phenyl
group is substituted with different halogens. The introduction of
the halogenated phenyl group significantly improves the
dispersibility of the new CN framework in various solvents and
facilitates the exfoliation of the CN material into 2D sheets, most
likely because these bulky groups sterically hinder the interaction
between the layers. The great potential of this method is
exemplified here by functionalizing the CN organic framework
with a phenylboronic acid and a tert-butyl acrylate through Suzuki
Two-dimensional (2D) carbon nitride (CN) based semiconductors
possess a great promise in various fields as solar fuels production,
bio-imaging, sensing, light-emitting diodes and solar cells due to
their unique electronic, optical and structural properties,[1] as well
as to their low price, environmentally friendly nature and high
stability to oxidation and harsh chemical condition.[2,3] The
synthesis of CN frameworks usually relies on the condensation of
nitrogen-rich organic molecules such as urea, dicyandiamide or
melamine at elevated temperatures.[4] Their photophysical and
electronic properties are derived from the carbon-to-nitrogen ratio
and spatial organization in the final material. The traditional solid-
state synthesis of bulk CN framework usually leads to
disorganized textures with small grain sizes, poor electronic and
catalytic properties, which limits their performance in different
applications.[5] Additionally, the dispersibility of CN frameworks in
most solvents is relatively low owing to the strong van der Waals
and hydrogen bonds interaction between their layers.[6] The low
dispersibility strongly restricts the use of CN frameworks in
potential applications and hinders the elucidation of their local
[a]
Dr. J. Sun, Dr. R. Phatake, A. Azoulay, Dr. G. Peng, J. Barrio, Prof.
Dr. M. Shalom
Chemistry Department and and Ilse Katz Institute for Nanoscale
Science and Technology,
Ben-Gurion University of the Negev
Beersheva 009728, Israel
E-mail: mennysh@bgu.ac.il
[b]
[c]
C.Han, Prof. Dr. J. Xu
Chemistry Department,
Queensland University of Technology
Brisbane QLD 4001, Australia
Prof. Dr. X. Wang
Key Laboratory of Soft Chemistry and Functional Materials
Nanjing University of Science and Technology
Nanjing 210094, China
Supporting information for this article is given via a link at the end of
the document.
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10.1002/chem.201803201
Chemistry - A European Journal
COMMUNICATION
and Reductive-Heck cross-coupling reactions, respectively. The
final products after the covalent modification present ultrathin
sheet-like structure and enhanced dispersibility in many solvents,
such as DMSO, THF, n-hexane and diethyl ether. The advantage
of the enhanced dispersibility is exemplified here by the efficient
photooxidation of benzyl alcohol as a model reaction.
The new 2,4-diamino-6-phenyl-1,3,5-triazine derivatives
(DPT-X, X = Cl, Br, I) were synthesized by reacting dicyandiamide
with nitriles under microwave irradiation (Figure 1a).[19] The
chemical structure of the new monomers was confirmed by gas
chromatography–mass spectrometry (GC-MS), X-ray Diffraction
(XRD) and Fourier-transform infrared spectroscopy (FTIR)
spectra (Figure S1 and S2).
Sheet-like CN-Ph and CN-Ph-X morphologies were observed via
TEM and SEM (Figure 1b-e and Figure S6a-d). Energy-dispersive
X-Ray spectroscopy (EDXS) elemental mapping of CN-Ph-X
(Figure 1f and Figure S6e, f) displays a homogeneous halogen
distribution, further confirming the successful incorporation of the
phenyl-halogen groups within the framework. Additional evidence
for the layered structure of CN-Ph and CN-Ph-X framework is
given by the XRD patterns (Figure 1g). Identical predominant
diffraction at ~27º is detected in all samples, speaking for the
graphitic stacking feature,[13] in accordance with the TEM images.
The halogen incorporation leads to a small increase of the
distance between the CN frameworks layers, which facilitates
their exfoliation.
Figure 2. XPS spectra of (a) C 1s, (b) N 1s and (c) Br 3d in CN-Ph-Br. (d) Band
structure diagram of CN-Ph and CN-Ph-X. (e) Digital photograph images of bulk
CN (calcination from melamine) and CN-Ph (calcination from DPT) suspensions
in diverse solvents. (f) Pictures of CN-Ph and CN-Ph-X powder as well as the
corresponding suspension in DMSO.
Figure 1. (a) Illustration of the synthesis of DPT-X and the corresponding CN-
Ph-X. TEM images of (b) CN-Ph, (c) CN-Ph-Cl, (d) CN-Ph-Br and (e) CN-Ph-I.
SEM mapping of (f) CN-Ph-Br. (g) XRD patterns and (h) FTIR spectra of CN-
Ph, CN-Ph-Cl, CN-Ph-Br and CN-Ph-I.
The chemical structure of CN-Ph-Xs was further elucidated by
FTIR and XPS analysis as shown in Figure 1h, Figure 2a-c and
Figures S7-S9. The characteristic FTIR vibration peaks of CN
framework at 3400 cm−1, between 1000 and 1700 cm−1 or at
800 cm-1, corresponding to the N-H, C-N and C=N, as well as the
breathing mode of triazine units,[21] respectively, were detected.
The C 1s XPS analysis of CN-Ph-Br shows the intrinsic sp2 C-C
and N=C-N species together with C-Br bond at binding energies
(BEs) of 286.20 eV (Figure 2a).[22] The peaks at 400.3 eV and
398.6 eV in N 1s XPS spectra can be assigned to N-(C)3 and C=N-
C[23] (Figure 2b). The missing N-H peak implies the loss of N-H
groups during the condensation process. The existence of N-(C)3
indicates the fusion of the amine group by the formation of
heptazine unit as previously described for carbon nitride
materials.[24] The Br 3d core-level spectrum exhibits two peaks
centered at 70.4 eV and 71.5 eV, corresponding to the Br 3d5/2
and Br 3d3/2, respectively (Figure 2c). More evidence for the
successful introduction of Br can also be deduced from the
appearance of three additional signals with BEs at about 70, 189
and 256 eV in the wide-scan spectrum (Figure S7), attributable to
Br 3d, Br 3p, and Br 3s, respectively.[25] Additionally, the
integration of Cl and I atoms in the CN framework was also
confirmed by the XPS measurements (Figures S8-S9). The Cl 2p
peaks can be resolved into two peaks, centered at BEs of 200.5
The modified carbon and nitrogen based frameworks
(referred here as CN-Ph and CN-Ph-X, X= Cl, Br, I) were acquired
by the calcination of DPT and DPT-X for 4 h at 350 °C under
nitrogen atmosphere. We note that the condensation of the
precursors into organic CN framework takes place between 250-
350 °C as suggested by TGA measurement (Figure S3-S4) and
elemental analysis (EA), as detailed below. Different from the
commercial DPT, weight loss is observed below 100 °C for the
synthesized DPT-X, due to the desorption of moisture.
Furthermore, the decomposition slightly shifted compared to DPT
owing to the different intramolecular interactions. The high
amount of carbon in the starting materials leads to the formation
of a semiconductor already at 350 °C, while at higher calcination
temperatures a more nitrogen-doped carbon is obtained (Figure
S5). EA data of the CN frameworks is shown in Table S1.
Compared to the original CN-Ph, the relative amount of hydrogen
in all three halogenated materials is significantly reduced and the
C/N ratio increases from 1.54 to ~1.64. The EA data together with
the TGA measurements indicate that the DPT-X condensed
during the thermal treatment with the release of amino groups,
which is similar to the condensation progress of melamine.[20]
Simultaneously, the amount of halogen groups remained steady,
underpinning their preservation after 4 h calcination at 350 °C.
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10.1002/chem.201803201
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and 201.8 eV, belonging to the Cl 2p3/2 and Cl 2p1/2 species.[22]
Likewise, the I 3d spectrum entails two multiple peaks centered at
as calculated from the EA results. Therefore, here we introduced
30-40 mg phenylboronic acid or tert-butyl acrylate, around three
molar equivalents of Br for 25 mg CN-Ph-Br. Using similar
reaction conditions, both coupling reaction were shown to fully
substitute the bromophenyl group when conducted on small
molecules.[28]
621.5 and 633.3 eV, corresponding to I 3d5/2 and I 3d3/2
,
respectively.[26] Having all data at hand we can safely conclude
that the halogen-phenyl groups are fully integrated into the final
CN organic framework structure.
To investigate the effect of the halogens on the optical and
electronic properties of the final CN framework, UV-vis absorption
and Mott−Schottky analysis were performed (Figure S10 and
S11). The high amount of carbon in the starting monomers leads
to the formation of semiconductors with bandgaps ranging from
2.5 to 2.05 eV already at 350 °C. The redshift of the optical
absorption edge can be attributed to the withdrawing character of
the halogen groups. Similar to other carbon nitride materials, the
conduction band (CB) edge position of the new materials is highly
negative, indicating their strong reducing properties. Interestingly,
the halogen groups mainly affect the CB edge while the valence
band (VB) position for all materials is similar (Figure 2d). Very
importantly, the new CN frameworks are much more readily
dispersed (1 mg/ml) in a variety of solvents, such as DMSO, DMF,
THF, MeOH, NMP, toluene and IPA (Figure 2e, f). We note that
bulk CN, calcinated from melamine at 550 °C, is almost insoluble
in these solvents.
The final morphology of the composed materials (denoted as
CN-Ph-Suzuki and CN-Ph-RHeck) are shown in Figure 3b, c and
Figure S12a, b. An ultrathin sheet-like morphology of CN-Ph-
Suzuki and CN-Ph- RHeck indicates their good exfoliation to few
layers. A broader XRD peak at ~27º was observed for the CN-Ph-
Suzuki and CN-Ph-RHeck compared to the original CN-Ph-Br
(Figure S12c), supporting the improved exfoliation to a few
layers.[13]
The successful Suzuki and Reductive-Heck reactions and the
1
final chemical structure were investigated by FTIR and H NMR
measurements (Figure 3d and Figure 4). New absorption peaks
of CN-Ph-Suzuki around 780 and 750 cm-1 were attributed to the
introduction of another substituted phenyl group. Meanwhile, after
the Reductive-Heck reaction, a C=O absorption peak at 1725 cm-
1
was detected (Figure 3d).[29] Furthermore, the successful
covalent modification of the CN-Ph-Br was supported by 1H NMR
measurements of CN-Ph-Br, CN-Ph-Suzuki and CN-Ph-RHeck in
DMSO-d6 as shown in Figure 4 and Figure S13-S15. In contrast
to the starting material, CN-Ph-Br, the covalently modified CN-Ph-
Br samples show new 1H NMR signals belonging to the aromatic
(consistent with the formation of a new biphenyl moiety) or
aliphatic (consistent with the addition of the tert-butyl and
methylene groups) regions for the CN-Ph-Suzuki and CN-Ph-
RHeck materials, respectively. The 1H NMR and FTIR
measurements strongly support the successful covalent
functionalization of the CN-Ph-Br framework.
Figure 3. (a) Illustration of the post-covalent functionalization of CN-Ph-Br via
Suzuki and Reductive-Heck reaction. TEM images of CN-Ph-Br after the (b)
Suzuki reaction and (c) Reductive-Heck reaction. (d) FTIR spectra of CN-Ph-Br,
CN-Ph-Suzuki and CN-Ph-RHeck.
Figure 4. 1H NMR of CN-Ph-Br, (a) CN-Ph-Suzuki and (b) CN-Ph-RHeck (400
MHz, DMSO-d6, details with chemical shift are shown in the SI).
The existence of halogen in the CN-Ph framework, alongside
with its positive effect on the dispersibility of the material in various
solvents, opens a unique possibility to covalently functionalize the
material by the replacement of the halogen groups with other
molecules. Brominated aromatics are particularly conducive to
take part in a series of organic reactions, especially in cross-
coupling reactions such as Suzuki and Reductive-Heck
reaction.[27] Thus, here we chose CN-Ph-Br as a substrate for
further chemical modifications. With the assistance of Pd(OAc)2
and K2CO3 as catalyst and base, a Suzuki cross-coupling reaction
conducted with phenylboronic acid and tert-butyl acrylate was
selected to react with CN-Ph-Br for a typical Reductive-Heck
reaction, in both cases under microwave irradiation (Figure 3a).
The estimated weight percent of Br in CN-Ph-Br is around 30 %,
The functionalization of CN organic framework with bromo,
phenyl group and tert-butyl propionate lead to further
enhancement of their dispersibility in serious of organic solvents,
e.g., THF, n-hexane, diethyl ether and DMSO as shown in Figure
5a. The high dispersibility of these CN materials enables their
exploitation for various applications such as catalysis in organic
solvents. Especially in THF and DMSO, CN-Ph-Br, CN-Ph-Suzuki
and CN-Ph-RHeck, were spontaneously dispersed and formed a
clear yellow solution with a concentration of 1 mg/mL. Upon
standing for more than one month, all materials in THF and DMSO
were extremely stable without any observable aggregation. Even
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in less or non-polar solvents such as diethyl ether and n-hexane,
CN-Ph-Suzuki and CN-Ph-RHeck are well dispersed.
the reaction system (toluene) and further increase the
reaction kinetics. TEM images and FTIR measurements of the
CN-Suzuki after the recycle tests indicate the stability of the
catalyst (Fig. S20 and S21). The similar morphology and chemical
structure suggest that the CN-Suzuki is chemically stable and can
be reused without noticeable change.
The introduction of phenyl group and tert-butyl propionate
results in the alteration of the photophysical properties. A strong
fluorescent quenching (Figure 5a and Figure S16b) for both
materials was observed, implying that the relaxation of a fraction
of photocarriers occurs via a non-radiative pathway, probably
from the charge transfer of electrons and holes to the new surface
states.21 Figure S16a displays the UV-vis absorption spectra of
CN-Ph-Br, CN-Ph-Suzuki and CN-Ph-RHeck powders. For both
materials, the new group leads to a color change and a redshift of
the absorption edge. The absorption properties of the
corresponding materials in THF and DMSO were also
investigated (Figure 5b, c). The absorption edge of the modified
CNs in solution is strongly blue-shifted compared to the solid
materials, speaking for the successful exfoliation of the CN
framework into freestanding sheets.[30] In both solvents, there is a
notable redshift and increased absorption ranging from 330 to 430
nm, due to the introduced conjugative effect from phenyl group
and tert-butyl propionate compared to the CN-Ph-Br.[31] The
different absorption spectra of the materials in THF and DMSO
indicate the strong interaction between the material and the
solvent. The sharp peak at 256 nm is attributed to the aromatic π
Figure 5. (a) Pictures of 1 mg/ml of CN-Ph-Br, CN-Ph-Suzuki and CN-Ph-
RHeck in THF, n-hexane, diethyl ether, DMSO and corresponding solutions
under UV light, 365 nm. UV-vis absorption spectra of CN-Ph-Br, CN-Ph-Suzuki
and CN-Ph-RHeck in (b) THF and (c) DMSO. (d) A colloidal suspension of CN-
Ph in THF/water 1:1 mixture and their Tyndall effect. In higher water
concentration the formation of floccules is obtained.
→ π
to the nitrogen nonbonding orbital to the aromatic nonbonding (n
→ π
) transition.[32] As a polar aprotic organic solvent, DMSO can
reduce both the energies of excited states in π → π transition and
the ground-state energy in n → π transition, resulting in a redshift
⃰ transition whereas another peak at 295 nm can be assigned
⃰
⃰
⃰
of the absorption and the disappearance of the fine electronic
structure compared to the one in THF. The good dispersibility of
the functionalized CN materials in other solvents as THF opens
the possibility to improve their dispersibility in water by using THF
as co-solvents as shown in Figure 5d. The functionalized CN
materials can be well-dispersed in a THF/H2O mixture (v/v ratio =
1:1) to form a colloidal suspension with a significant Tyndall effect
In summary, we present a straightforward synthetic strategy
to covalently functionalize carbon nitride frameworks through the
implementation of chemically reactive groups, i.e. a halogenated
phenyl group, within the material framework prior to the materials
condensation at high temperature. The introduction of the
chemically reactive groups was allowed by the synthesis of a
series of halogen modified 2,4-diamino-6-phenyl-1,3,5-triazine
molecules that serve as the CN monomers and can be fully
preserved after calcination at 350 ºC. The new CN materials
demonstrate a good dispersibility in a wide range of solvents
thanks to the weakened interaction between CN layers. The
strength of this method is exemplified here by the post-
modification of CN framework with phenyl group and tert-butyl
propionate through Suzuki and Reductive-Heck cross-coupling
reactions, respectively. The successful integration of the new
groups into the CN framework significantly improves the
dispersibility of the modified CN in various solvents and facilitates
its exfoliation into 2D materials with different photophysical
properties. The potential of this approach is exemplified here by
the efficient photooxidation of benzyl alcohol as a model reaction
in an organic solvent. This new, simple approach paves the way
for tailored design of the chemical, photophysical and electronic
properties as well as the dispersibility in various solvents of
carbon nitride based materials toward their utilization in various
applications such as bio-imaging, sensing, photocatalysis and
electronic devices.
without showing any aggregation after
3 days at room
temperature. Once the mixture was further diluted with double
amount of H2O, tiny floccules could be slowly collected. After a
gentle vacuum drying, the precipitate revealed a homogeneous
highly-ordered morphology as shown in Fig. S17. This
phenomenon opens new opportunities to prepare colloids of
carbon and nitrogen based materials in different solvents and to
hybridize it with other materials for a broader range of applications.
Furthermore, the photocatalytic activity of synthesized CN-
Suzuki was evaluated using oxidation of benzyl alcohol as a
model reaction, which is a fundamental transformation in organic
chemistry and has wide application in flavour and fragrance
industry.[33] As shown in Fig. S18, the CN-Suzuki produces
approximately 100 μmol of benzaldehyde in 24 h under white LED
irradiation at 40 oC, almost twice higher than that of the traditional
g-C3N4 as well as good recyclability (Fig. S19). This activity
enhancement is mainly contributed from two aspects. First,
compared to the g-C3N4, more carbon was introduced into the CN-
Suzuki framework via the covalent functionalization, deducing a
narrower band gap. Therefore, once under light irradiation, the
CN-Suzuki would generate more electron and hole pairs, which
benefits the photo-induced oxidation reaction. Secondly, unlike g-
C3N4 which tends to aggregate and attaches to the wall of reactor
in the organic solvent, CN-Suzuki can be uniformly dispersed in
Experimental Section
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This article is protected by copyright. All rights reserved.

10.1002/chem.201803201
Chemistry - A European Journal
COMMUNICATION
COMMUNICATION
A new, general synthetic route to
covalently functionalize carbon nitride
Jingwen Sun, Ravindra Phatake, Adi
Azoulay, Guiming Peng, Chenhui Han,
Jesús Barrio, Jingsan Xu, Xin Wang and
Menny Shalom*
based semiconductors
by the
implementation of halogenated phenyl
groups (Cl, Br and I), which serve as a
chemically reactive center, within the
CN framework is reported. The
effective functionalization greatly
enhances its dispersibility in many
solvents as well as the photocatalytic
activity.
Page No. – Page No.
Covalent Functionalization of
Carbon Nitride Frameworks through
Cross-Coupling Reaction
This article is protected by copyright. All rights reserved.