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A low-temperature solid-phase method to synthesize
Cite this: DOI: 10.1039/c3cc42266f
highly fluorescent carbon nitride dots with tunable
Published on 29 May 2013. Downloaded by Monash University on 10/06/2013 16:17:19.
emission†
Received 28th March 2013,
Accepted 28th May 2013 Juan Zhou,z Yong Yangz and Chun-yang Zhang*
DOI: 10.1039/c3cc42266f
www.rsc.org/chemcomm
Highly fluorescent graphitic carbon nitride quantum dots (g-CNQDs)
with a quantum yield of 42% are synthesized by a low-temperature
solid-phase method with urea and sodium citrate as the precursors.
Notably, the tunable emission of g-CNQDs can be achieved by simply
adjusting the molar ratio of the two reactants.
As a metal-free polymeric photocatalyst,1 graphitic carbon
nitrides have been widely used in water splitting, solar energy
transfer, and pollutant degradation.2 Recently, nanoscale graphitic
carbon nitride with distinct optical features, such as fluorescent
carbon nitride nanosheets and carbon nitride quantum dots
(g-CNQDs), has been explored due to its promising applications
in biosensing3 and bioimaging.4 In the past decades, semi-
conductor quantum dots (QDs) have attracted great attention
due to their unique optical properties.5 However, those QDs
might induce serious health and environmental problems due
to the involvement of heavy metals, which limit their widespread
application.6 Therefore, the development of novel metal-free and
fluorescent nanoparticles is of great significance. The g-CNQDs
have the advantages of bright fluorescence, good stability, water-
solubility, biocompatibility, and nontoxicity, making them good
candidates in place of traditional QDs. However, there are still
some bottlenecks for the g-CNQDs, such as the lack of effective
synthetic methods and the low quantum yield.
So far, the preparation of graphitic carbon nitrides has
usually relied on the pyrolysis of nitrogen-rich precursors such as
melamine, cyanamide, and dicyandiamide.7 Such a strategy is
simple, but requires a high temperature of 450–600 1C. The resultant
carbon nitrides have large particle sizes and poor luminescent
properties, and are not suitable for optical applications.8 Recently,
some new synthetic approaches for preparing fluorescent g-CNQDs
have been developed. Sun et al. developed a heat-treatment-based
Single-Molecule Detection and Imaging Laboratory, Shenzhen Institutes of Advanced
Technology, Chinese Academy of Sciences, Shenzhen 518055, China.
E-mail: zhangcy@siat.ac.cn; Fax: +86-755-86392299; Tel: +86-755-86392211
† Electronic supplementary information (ESI) available: Detailed experimental
procedures, quantum yield measurements and characterization. See DOI:
10.1039/c3cc42266f
‡ These authors contributed equally.
This journal is c The Royal Society of Chemistry 2013
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(refluxing, microwave and solvothermal heating) method9 with
nitrogen-containing organic molecules including dimethylamine,
1,2-ethylenediamine and N,N-dimethylformamide as the pre-
cursors. However, the quantum yield of the obtained g-CNQDs
can only reach 11%. Barman and Sadhukhan achieved an improved
quantum yield of 29% using the microwave-mediated method with
formamide as the precursor, but the obtained g-CNQDs had wide
size distributions from 2 nm to 15 nm.10 Xie et al. demonstrated an
ultrasonic method to liquid exfoliate bulk graphitic carbon nitrides
and obtained graphitic-phase carbon nitride nanosheets with a
quantum yield of 19.6%, and the diameter of the nanosheets ranged
from 70 nm to 160 nm.4 Therefore, more facile and effective
methods for preparing fluorescent g-CNQDs with extremely high
quantum yield are highly desirable.
In this communication, we demonstrate a new solid-phase
reaction strategy to produce highly fluorescent g-CNQDs at an
extremely low temperature. Urea is selected as the precursor due
to its low-cost, abundance, and the nitrogen-rich nature. Besides,
urea is an active molecule under thermal treatment,11 which enables
the reaction to proceed at low temperature as compared with the
conventional pyrolysis methods.9 So far, bulk graphitic carbon
nitrides have been usually achieved by thermally heating urea or
thiourea at high temperature (>400 1C).12 To the best of our knowl-
edge, the highly fluorescent g-CNQDs synthesized from urea at a
low temperature have never been reported. In addition, g-CNQDs
synthesized from urea have distinct characteristics of non-toxicity,
good water-solubility, and suitability for biological applications.
The solid mixture of urea and sodium citrate with a molar ratio of
6 : 1 was thermally treated at 180 1C in an autoclave for 1 h.
Fluorescent g-CNQDs were extracted from the resultant yellowish
powders (Fig. S1b, ESI†) by washing with alcohol and subsequently
dialyzing against pure water for 24 h. The collected g-CNQDs were
evaluated by high-resolution transmission electron microscopy
(HR-TEM), atomic force microscopy (AFM), X-ray powder diffraction
(XRD), X-ray photoelectron spectroscopy (XPS), and Fourier transform
infrared spectroscopy (FT-IR). The TEM image reveals that the
obtained g-CNQDs are well monodispersed and uniform in size
(Fig. 1a). As estimated from the TEM images, the diameters of
g-CNQDs are mainly distributed in the narrow range of 2.6–5.5 nm
Chem. Commun.

Communication
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Fig. 1 (a) TEM image of the g-CNQDs. The inset is a representative HR-TEM
image of an individual carbon nitride dot. (b) Size distribution histogram of
g-CNQDs. (c) AFM image of g-CNQDs deposited on a mica substrate and (d) the
height profile along the line in (c).
with an average size of 4.3 nm (Fig. 1b). The inset in Fig. 1a shows the
representative image of an individual nanoparticle, indicating the
high crystallinity with a lattice parameter of 0.34 nm, which is in
agreement with the 002 plane of graphitic carbon nitride.7 The
corresponding AFM image (Fig. 1c) reveals a typical topographic
height of 1.5–2.5 nm (Fig. 1d), suggesting that the g-CNQDs consist of
a few layers of C–N sheets.4,10 The characterization of the XRD pattern
further demonstrates two characteristic peaks at 27.41 and 13.11
(Fig. S1a, ESI†), consistent with the previous reports on graphitic
carbon nitride.13 The strong peak at 27.41 represents the character-
istic interplanar stacking of aromatic systems, indexed for graphitic
carbon nitride as the (002) peak, and the weak diffraction peak at
13.11 corresponds to an interplanar structural packing motif indexed
as the (100) peak. XPS measurements further confirm the chemical
structure and composition of the g-CNQDs (Fig. S1b, ESI†). The
binding energy peaks at 288.5, 399.5 and 531.1 eV correspond to C1s,
N1s and O1s, respectively. In contrast to the previously reported
g-CNQDs,9 a large amount of oxygen is measured in the obtained
g-CNQDs (Fig. S1b, ESI†). The C1s spectrum can be deconvoluted
into four peaks at 284.57, 286.07, 288.04 and 289.02 eV (Fig. S1c,
ESI†). Among them, the binding energy peak at 284.57 eV is ascribed
to sp2 C–C bonds, and the binding energy peak at 288.04 eV is
attributed to sp2 N–CQN bonds. Whereas the binding energy peaks
at 286.07 eV and 289.02 eV are attributed to C–O and O–CQO bonds,
respectively, indicating the existence of oxygen-rich groups. The N1s
spectrum demonstrates three peaks at 398.6, 399.5 and 400.5 eV
(Fig. S1d, ESI†), which are associated with CQN–C, C–N–C, N–(C)3
groups, respectively. Together with the presence of N–CQN bonds,
the above results indicate that the basic substructure of g-CNQDs is
the heptazine heterocyclic ring unit. These results are also supported
by the FT-IR spectroscopy (Fig. S2, ESI†). Zeta potential measure-
ments illustrate that the g-CNQDs are negatively charged with a
surface potential of 42.4  0.91 mV (Fig. S3, ESI†), providing two
pieces of vital information: (i) the obtained g-CNQDs are stable and
monodispersed by virtue of the negative electrostatic repulsions and
(ii) negatively charged oxygen-rich functional groups (such as carboxyl
or hydroxyl groups) are decorated on the surface of g-CNQDs.
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Fig. 2 (a) UV-vis absorption (red line) and photoluminescence (black line) spectra
of the obtained g-CNQDs. The inset is a digital picture of g-CNQDs dispersed in pure
water. (b) Photoluminescence spectra of the g-CNQDs at various excitation wave-
lengths from 360 nm to 500 nm. The inset is the normalized PL emission spectra.
The remarkable optical properties of the as-obtained g-CNQDs are
confirmed by the UV-Vis absorption and the steady-state fluorescent
spectra. As shown in Fig. 2a, UV-Vis spectra indicate a characteristic
absorption peak at 344 nm for the g-CNQDs. The narrow and
symmetrical fluorescence spectra show that the emission peak is at
467 nm at the excitation wavelength of 360 nm. The digital picture of
the aqueous dispersions further shows that the obtained g-CNQDs
are water-soluble and exhibit strong blue fluorescence under 365 nm
UV light. Notably, the quantum yield was measured to be 42% using
quinine sulfate as a standard (see details in the ESI†). To the best of
our knowledge, this is the highest quantum yield value for the
reported fluorescent g-CNQDs,9,10 whereas the highest reported
quantum yield of g-CNQDs is 29%.10 Fig. 2b shows the variation of
fluorescent emission spectra of the g-CNQDs with the excitation
wavelengths. Similar to most of the luminescent carbon dots and
graphene QDs,14 the fluorescent emission of g-CNQDs is excitation-
dependent. The emission peak of g-CNQDs was red-shifted from
467 nm to 574 nm with the excitation wavelength changing from
360 nm to 500 nm, which may be attributed to the optical selection of
differently-sized nanoparticles (quantum effect) and different emis-
sive traps on the g-CNQDs surface.15
Notably, the tunable emission of g-CNQDs can be achieved by
simply adjusting the molar ratio of the two reactants. Four repre-
sentative g-CNQDs were prepared by tuning the molar ratio of urea
to sodium citrate from 3 : 1 to 6 : 1, 9 : 1 and 12 : 1 (Fig. S4, ESI†).
Fig. 3a demonstrates that all of the obtained four g-CNQDs have
good water-solubility. Measurements of zeta potentials indicate that
the four g-CNQDs are negatively surface charged (Fig. S3, ESI†).
Fig. 3b and c shows that all of the obtained g-CNQDs show bright
Fig. 3 Tunable emission of g-CNQDs with different molar ratios of the two
reactants. (a) Digital photos of four g-CNQDs dispersions (5 mg mL1 dissolved in
water) under white light. (b) Digital photos of the corresponding g-CNQD dispersions
under a UV-lamp at the excitation wavelength of 365 nm. (c) The corresponding
fluorescent spectra of four g-CNQDs at the excitation wavelength of 365 nm.
This journal is c The Royal Society of Chemistry 2013

ChemComm
Scheme 1 Mechanism for the formation of highly fluorescent g-CNQDs.
fluorescence under ultraviolet light (Fig. 3b). When increasing the
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amount of sodium citrate, a distinct change of fluorescent emission
from green to dark blue can be observed at the same excitation
wavelength of 365 nm. As measured from the fluorescent spectra
(Fig. 3c), the fluorescent emission peaks of the four g-CNQDs are
located at 450 nm, 467 nm, 536 nm and 526 nm, further confirming
that tunable emission of g-CNQDs can be achieved by tuning the
molar ratio of the two reactants.
Finally, the mechanism for the formation of g-CNQDs with
tunable emission is investigated. It is well known that urea is an
active molecule under thermal treatment,11 while thermal decom-
position temperature of sodium citrate is higher than 200 1C.16 In
this research, urea as a nitrogen source was first decomposed at
180 1C producing a large amount of NH3,12 resulting in a high
pressure atmosphere in the autoclave, which further accelerates the
decomposition of sodium citrate. According to the aforementioned
characterization, the structure of obtained g-CNQDs is shown in
Scheme 1. Sodium citrate functions as the carbon source and
provides negative surface functional groups (carboxyl and hydroxyl
groups) for the g-CNQDs. Similar to that of carbon dots and
graphene QDs,17 the fluorescent performance of g-CNQDs strongly
depends on their surface states. The changes in the molar ratio of
the two reactants by using different amounts of sodium citrate
result in the alteration of the content of carbon and oxygen-rich
groups, which would affect the surface state of g-CNQDs. When
increasing the amount of sodium citrate (molar ratio of urea to
sodium citrate changes from 12 : 1 to 9 : 1), a slight red-shift of
g-CNQDs was observed, which may result from the increasing
amount of carbon content in g-CNQDs, similar to the previously
reported BCN nanoparticles.18 Whereas, upon further increasing the
amount of sodium citrate (molar ratio of urea to sodium citrate
changes from 9 : 1 to 3 : 1), an obvious blue-shift of g-CNQDs was
observed, which may result from the increase of oxygen-rich groups
on the surface, consistent with the reported N-doped graphene QDs
whose oxygen-rich groups contribute to the blue-shifted emission.19
To demonstrate the feasibility of obtained g-CNQDs for cell
imaging, HEK 293T cells were incubated with the g-CNQDs.
Bright blue, green and red emission of g-CNQDs can be
observed distinctly in the membrane and the cytoplasmic area
of HEK 293T cells by confocal microscopy at the excitation
wavelength of 405, 488, and 543 nm, respectively (Fig. S5, ESI†).
In contrast, only weak auto-fluorescence was observed in the
HEK 293T cells in the absence of g-CNQDs (Fig. S5, ESI†),
suggesting that the g-CNQDs can be applied for bioimaging.
In summary, a facile, non-toxic, low-temperature solid-phase
method has been developed for preparing highly fluorescent
g-CNQDs. The quantum yield of obtained g-CNQDs can reach 42%,
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which is the highest quantum yield reported so far for g-CNQDs.11,12
Moreover, the tunable emission of g-CNQDs can be achieved by
simply adjusting the molar ratio of the two reactants. Because of the
advantages of extremely high quantum yield, good biocompatibility,
and tunable fluorescent emission, the obtained g-CNQDs are pro-
mising in photodevices, optical sensors and biological applications.
This work was supported by the National Basic Research
Program 973 (Grant No. 2011CB933600 and 2010CB732600),
the Award for the Hundred Talent Program of the Chinese
Academy of Sciences, the Natural Science Foundation of China
(Grant No. 21075129 and 31000599), and the Fund for Shenzhen
Engineering Laboratory of Single-molecule Detection and Instru-
ment Development (Grant No. (2012) 433).
Notes and references
1 X. C. Wang, K. Maeda, F. Thomas, K. Takanabe, G. Xin, J. M.
Carlsson, K. Domen and M. Antonietti, Nat. Mater., 2009, 8, 76.
2 (a) X. C. Wang, K. Maeda, X. F. Cheng, K. Takzuhiro, K. Domen, Y. D.
Hou, X. Z. Fu and M. Antonietti, J. Am. Chem. Soc., 2009, 131, 1680;
(b) Y. Zheng, J. Liu, J. Liang, M. Jaroniec and S. Z. Qiao, Energy Environ.
Sci., 2012, 5, 6717; (c) F. Z. Su, S. C. Mathew, L. Möhlmann, M. Antonietti,
X. C. Wang and S. Blechert, Angew. Chem., Int. Ed., 2011, 50, 657.
3 (a) E. Z. Lee, Y. S. Jun, W. H. Hong, A. Thomas and M. M. Jin, Angew.
Chem., Int. Ed., 2010, 49, 9706; (b) C. M. Cheng, Y. Huang, X. Q. Tian,
B. Z. Zehng, Y. Li, H. Y. Yuan, D. Xiao, S. P. Xie and M. M. F. Choi, Anal.
Chem., 2012, 84, 4754; (c) E. Z. Lee, S. U. Lee, N. S. Heo, G. D. Stucky,
Y. S. Jun and W. H. Hong, Chem. Commun., 2012, 48, 3942.
4 X. D. Zhang, X. Xie, H. Wang, J. J. Zhang, B. C. Pan and Y. Xie, J. Am.
Chem. Soc., 2013, 135, 18.
5 (a) A. P. Alivisatos, Science, 1996, 271, 933; (b) X. G. Peng, L. Manna,
W. D. Yang, J. Wickham, E. Scher, A. Kadavanich and A. P. Alivisatos,
Nature, 2000, 404, 59; (c) W. C. W. Chan and S. Nie, Science, 1998,
281, 2016.
6 (a) A. M. Derfus, W. C. W. Chan and S. N. Bhatia, Nano Lett., 2004,
4, 11; (b) N. Lewinski, V. Colvin and R. Drezek, Small, 2008, 4, 26.
7 A. Thomas, A. Fischer, F. Goettmann, M. Antoietti, J. O. Muller,
R. Schlogl and J. M. Carlsson, J. Mater. Chem., 2008, 18, 4893.
8 (a) L. Yang, P. W. May, Y. Huang and L. Yin, J. Mater. Chem., 2007,
17, 1255; (b) S. M. Lyth, Y. Nabae, S. Moriya, S. Kuroki, M.-a. Kakimoto,
J.-i. Ozaki and S. Miyata, J. Phys. Chem. C, 2009, 113, 20148.
9 (a) S. Liu, J. Q. Tian, L. Wang, Y. L. Luo, J. F. Zhai and X. P. Sun,
J. Mater. Chem., 2011, 21, 11726; (b) S. Liu, J. Q. Tian, L. Wang, Y. L. Luo
and X. P. Sun, RSC Adv., 2012, 2, 411; (c) S. Liu, L. Wang, J. Q. Tian,
J. F. Zhai, Y. L. Luo, W. B. Lu and X. P. Sun, RSC Adv., 2011, 1, 951.
10 S. Barman and M. Sadhukhan, J. Mater. Chem., 2012, 22, 21832.
11 (a) B. Bann and S. A. Miller, Chem. Rev., 1958, 58, 131; (b) F. Kurzer,
Chem. Rev., 1956, 56, 95.
12 (a) J. H. Liu, T. D. Zhang, Z. C. Wang, G. Dawson and W. Chen,
J. Mater. Chem., 2011, 21, 14398; (b) G. G. Zhang, J. S. Zhang,
M. W. Zhang and X. C. Wang, J. Mater. Chem., 2012, 22, 8083.
13 (a) B. V. Lotsch, M. Doblinger, J. Sehnert, L. Seyfarth, J. Senker,
O. Oeckler and W. Schnick, Chem.–Eur. J., 2007, 13, 4969;
(b) S. C. Yan, Z. S. Li and Z. G. Zou, Langmuir, 2010, 26, 3894.
14 (a) D. Pan, J. Zhang, Z. Li, C. Wu, X. Yan and M. Wu, Chem.
Commun., 2009, 3681; (b) D. Pan, J. Zhang, X. Li and M. Wu,
Adv. Mater., 2009, 22, 734.
15 (a) L. B. Tang, R. B. Ji, X. K. Cao, J. Lin, H. X. Jiang, X. M. Li,
K. S. Teng, C. M. Luk, S. J. Zeng, J. H. Hao and S. P. Lau, ACS Nano,
2012, 6, 5102; (b) Y. M. Long, C. H. Zhou, Z. L. Zhang, Z. Q. Tian,
L. Bao, Y. Lin and D. W. Pang, J. Mater. Chem., 2012, 22, 5917.
16 A. B. Bourlinos, A. Stassinopoulos, D. Anglos, R. Zboril,
M. Karakassides and E. P. Giannelis, Small, 2008, 4, 455.
17 (a) L. Bao, Z. L. Zhang, Z. Q. Tian, L. Zhang, C. Liu, Y. Lin, B. P. Qi
and D. W. Pang, Adv. Mater., 2011, 23, 5801; (b) H. Tetsuka, R. Asahi,
A. Nagoya, D. Okamoto, I. Tajima, R. Ohta and A. Okamoto,
Adv. Mater., 2012, 39, 5333.
18 W. W. Lei, D. Portehault, R. Dimova and M. Antonietti, J. Am. Chem.
Soc., 2011, 133, 7121.
19 Y. Li, Y. Zhao, H. H. Cheng, Y. Hu, G. Q. Shi, L. M. Dai and L. T. Qu,
J. Am. Chem. Soc., 2012, 134, 15.
Chem. Commun.