Xu 2013

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Materials Chemistry A
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Mater. Chem. A, 2013, DOI: 10.1039/C3TA13188B.
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Journal of Materials Chemistry A

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Chemical exfoliation of graphitic carbon nitride for efficient heterogeneous

photocatalysis
Department of Chemistry, Tsinghua University, Beijing, 100084, PR China
Jing Xu, Liwu Zhang, Rui Shi, Yongfa Zhu*
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ABSTRACT. Single atomic layer nanosheet materials show great application potential in
many fields due to their enhanced intrinsic properties from their counterparts and newly born
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properties. Herein, g-C3N4 nanosheets with single atomic layer structure is prepared by a
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simple chemical exfoliation method. The as-prepared nanosheets show single atomic
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thickness of 0.4 nm and lateral size of micrometers. The structure and photocatalytic
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properties of the as-prepared single layer g-C3N4 are then studied. Compared with the bulk g-
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C3N4, single layer g-C3N4 nanosheets show great superiority in photogenerated charge carriers
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transfer and separation. Accordingly, the photocatalytic H2 production and pollutant
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decomposition activities, and photocurrent generation of single layer g-C3N4 nanosheets are
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much higher than that of the bulk g-C3N4, indicating the great application potential of single
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layer g-C3N4 nanosheets in photocatalysis and photosynthesis.
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Keywords: Carbon nitride; Single atomic layer; Nanosheet; Photocatalysis
Journal of Materials Chemistry A Accepted Manuscript
Published on 26 September 2013. Downloaded by University of Hong Kong Libraries on 01/10/2013 03:11:19.
DOI: 10.1039/C3TA13188B
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1. INTRODUCTION
structural and physiochemical properties.1 Since the discovery of the two-dimensional atomic
crystal graphene,2 which represents many intriguing properties different from bulk graphite
and potentials in diverse applications, great efforts have been performed to synthesize
nanosheets with single atomic layer structure.3-7 By exfoliating layered materials into
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nanosheets, exotic electronic properties and high specific surface areas accompanying with
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greatly enhanced host capabilities have been obtained and show great potential in application
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in electronics, energy storage, solar energy conversion, etc.8, 9
Single atomic layer nanosheets have attracted extensive attention due to their unique
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Graphite-like carbon nitride (g-C3N4), a metal-free polymer semiconductor, has attracted
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plenty of attention due to its potential application in solar energy conversion, photosynthesis,
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electrocatalysis, bioimaging and biomedical application.10-21 The g-C3N4 has been shown to be
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able to produce H2 by water splitting and decompose organic pollutants under visible light
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irradiation by pioneering works of Wang and coworkers.22 More potential applications of g-
18
C3N4 are emerging as researches carry on in structure engineering and activity improving.
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23-31
12,
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Motivated by graphene, researchers have tried to prepare the nanosheet form of g-C3N4 to
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fully explore the potential of g-C3N4. Compared with graphite, the layer of g-C3N4 is
22
composed by C-N bonds instead of C-C bonds, while weak van der Waals force exists
23
between the layers. Encourage by the exfoliation of graphite into graphene layers by the
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widely used Hummers method,32 Liu and coworkers employed the Hummers method to
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exfoliate bulk g-C3N4.33 However, instead of nanosheets, particles with several hundred
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nanometers thickness were obtained and the planar atomic structure of g-C3N4 has been
27
destroyed, indicating that the Hummers method may destroy the intrinsic structure of g-C3N4.
28
The failure is attributed to the not strong enough hydrogen bonding between the layers of
29
strands of polymeric melon units with NH/NH2 groups proposed by Lostsch et al.,34 which is
30
different from the planar pure covalent bonding cohesion within the graphite. Liu and
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coworkers thus developed a direct thermal oxidation etching process of bulk g-C3N4 to get
32
g-C3N4 nanosheets with a thickness of around 2 nm, implying a multilayer of g-C3N4 (6-7
33
layers).33 Ultrathin g-C3N4 nanosheets were also prepared by ultrasound exfoliation or liquid
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exfoliation routes from bulk g-C3N4.11, 35 The resulted nanosheets possess thickness of >2 nm.
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Instead of the top-down fabrication of g-C3N4 nanosheets, Wang and Coworkers found that
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a bottom-up method by modifying polycondensation of g-C3N4 precursors could result in

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thin C3N4 nanosheets with thickness of around 3.6 nm.36 Although different methods have
successfully been developed to get g-C3N4 nanosheets, the as-prepared g-C3N4 nanosheets are
still thicker than 2nm and composed of more than 6 C-N layers. It is still a great challenge to
prepare real graphene-like g-C3N4 material with single atomic layer.
Herein, we have for the first time obtained the single atomic layer g-C3N4 nanosheets
(Monolayer-C3N4) by a simple chemical exfoliation method. Since g-C3N4 is not strong
enough against the strong oxidation effect exerted by KMnO4 oxidant used in the Hummers
method for graphite exfoliation, KMnO4 is no more used in the chemical exfoliation method.
The obtained Monolayer-C3N4 is then characterized and performances in photosynthesis and
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photocatalysis under visible light irradiation are investigated.
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2. EXPERIMENTAL SECTION
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Synthesis of single atomic layer g-C3N4 nanosheets. g-C3N4 was prepared by heating
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dicyandiamide (Tianjin Fuchen Chemical Reagents factory, China) in a muffle furnace for 4 h
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to 550 C and keep at this temperature for another 4 h in air. g-C3N4 monolayer nanosheets
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were synthesized via the chemical exfoliation method. The as-prepared g-C3N4 (1 g) was
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mixed with 10mL of H2SO4 (98 wt %) in a 50mL flask and stirred for 8 h at room temperature.
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Then the mixture was slowly poured into 100 mL of deionized water and sonicated for
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exfoliation. The temperature of the suspension increased rapidly, and the color changed from
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yellow to light yellow. The obtained suspension was then subjected to 10 min of centrifugation
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at 3,000 r.p.m. to remove any unexfoliated g-C3N4. The obtained light yellow suspension was
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centrifuged, washed thoroughly with deionized water to remove the residual acid, and finally
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drying at 80 C in air overnight. In order to eliminate the structural defects, the obtained
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powders (0.3 g) were put into a flask with 150 mL of methanol and refluxed on a mantle heater
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at 65 C for 6 h. After centrifuged and dried at 80 C, the obtained products were g-C3N4
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nanosheets.
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Characterization of the Samples. The samples were characterized by powder X-ray
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diffraction (XRD) on a Bruker D8-advance X-ray diffractometer at 40 kV and 40 mA for
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monochromatized Cu K ( = 1.5406 ) radiation. The Brunauer-Emmett-Teller (BET)
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specific surface area and pore volume of the samples were characterized by nitrogen
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adsorption at 77 K with Micromeritics 3020 instrument. Transmission electron microscopy
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(TEM) images were obtained by Hitachi HT-7700 electron microscope operated at an
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accelerating voltage of 100 kV. Atomic Force Microscope (AFM) images were acquired in
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phase mode in air using a Digital Instrument Shimadzu SPM-9600 (The samples were
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prepared by drop-casting corresponding dilute dispersions onto freshly cleaved mica surface).
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Fourier transformed infrared (FTIR) spectra were recorded on a Bruker VERTEX 700
spectrometer between 4000 and 600 cm-1. Diffuse reflection spectra (DRS) were obtained on a
Hitachi U-3010 UV-vis spectrophotometer. Photoluminescence spectra (PL) of the samples
were obtained at room temperature excited by incident light of 318 nm using a fluorescence
spectrometer (JASCO FP-6500). Elemental analysis results were collected from an EA 3000
analyzer.
Photocatalytic tests and Photoelectrochemical Performance. The photocatalytic
activities for H2 production were evaluated under visible light irradiation ( > 420 nm). Visible
irradiation was provided by a 500 W xenon lamp with a 420 nm cutoff filter and the average
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visible light intensity was 40.0 mW cm-2. 20 mg of the photocatalyst powder was dispersed in
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an aqueous solution (20 mL) containing triethanolamine (10 vol. %) as a sacrificial electron
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donor. 3 wt. % Pt was loaded on the surface of the photocatalyst sample by the in situ
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photodeposition method using H2PtCl6. The suspension solution was then purged with N2 for
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at least 30 min to remove air and then sealed with a rubber septum. The temperature of the
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reaction solution was maintained at room temperature by a flow of cooling water during the
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photocatalytic reaction. The amount of evolved hydrogen was analyzed by a Shimadzu GC-
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2014 gas chromatography equipped with a thermal conductive (TCD) detector and a 5
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molecular sieve column, using N2 as the carrier gas.
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The photocatalytic activities were further evaluated by the degradation of phenol and
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methylene blue (MB) under visible light irradiation. In each run, 50 mL of MB solution
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(2.0105 M) or phenol solution (2.0 mg L-1) containing 25 mg of as-synthesized photocatalyst
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were placed in a glass beaker. Before irradiation, the suspensions were magnetically stirred in
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the dark for 2 h to ensure equilibrium between the photocatalyst and the model molecules. At
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certain time intervals, 2 mL of the suspensions were taken and centrifuged to remove the
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particles. The concentration of phenol was analyzed using a HPLC with a UV absorbance
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detector operated at 270 nm coupled to a Venusil XBP-C18 column. The concentration of the
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MB was analyzed by recording the absorption intensity at 663 nm using a Hitachi U-3010 UV-
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vis spectrophotometer.
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The photoelectrochemical properties were performed on a CHI 660B electrochemical
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system (Shanghai, China) using a standard three-electrode cell with a working electrode, a
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platinum wire counter electrode, and a standard calomel electrode (SCE) reference electrode.
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0.1 M Na2SO4 was used electrolyte. The working electrodes were prepared as follows: 2 mg of
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as-prepared photocatalyst was suspended in 1 mL of water to produce slurry, which was then
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dip-coated on a 20 mm 40 mm indium-tin oxide (ITO) glass electrode. Electrodes were

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exposed in air for 1 day to eliminate water and subsequently heated at 200 C for 1 day. All
investigated working electrodes were of similar thickness. The electrochemical impedance
spectroscopy (EIS) was carried out at the open circuit potential. A sinusoidal ac perturbation of
5 mV was applied to the electrode over the frequency range 0.05-105 Hz.
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3. RESULTS AND DISCUSSION
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Figure 1. Illustration of synthetic strategy. (a) Intercalation of H2SO4 (98 wt %) in the interplanar space of gC3N4. (b) Intercalated g-C3N4 was exfoliated into single layer due to the rapid heating effect of H2SO4 (98 wt %)
mixing with water.
Bulk C3N4
H2SO4 intercalated
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30
32
34
2Theta / degree
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Figure 2. XRD patterns of the bulk g-C3N4 before and after H2SO4 intercalation.
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The synthetic strategy is illustrated in Figure 1. First, the bulk g-C3N4 was mixed with
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H2SO4 (98 wt %) and stirred for 8 hours at room temperature to allow the intercalation of
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H2SO4 in the interlayer space of g-C3N4. The intercalation mechanism is generally similar
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with the widely reported H2SO4 intercalated graphite.37 The intercalation of H2SO4 into bulk
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g-C3N4 is confirmed by X-ray diffraction (XRD) (Figure 2). It is found that the (002)
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diffraction at around 27.4 o relating to the characteristic interlayer stacking structure is shifted
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to 25.0 o, indicating that the interlayer distance is expanded from 0.325 nm to 0.356 nm. Then
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the mixture was slowly poured into deionized water and sonicated, due to the sonication and
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rapid heating effect when concentrated H2SO4 is mixed with water, the intercalated bulk g5
Intensity / a.u.
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C3N4 was exfoliated into single layer. The obtained dispersion was then subjected to
centrifugation to remove any unexfoliated and aggregated g-C3N4. The exfoliation is found to
significantly depend on the concentration of sulfuric acid. H2SO4 with lower concentrations
(75 wt% and 50 wt%) were also studied, however the results show that lower concentration
H2SO4 failed to exfoliate bulk g-C3N4 into single layer (Figure S1 and S2 in Supporting
Information). Compared with the reported thermal oxidation etching process33, ultrasound
exfoliation11 or bottom-up method36 for the fabrication of g-C3N4 nanosheets, the chemical
exfoliation method allows intercalation of H2SO4 in the interlayer space of g-C3N4, thus
higher possibility to obtain single layer nanosheet after exfoliation. Moreover, the chemical
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exfoliation is also more cost-efficient than the reported methods mentioned above.
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Figure 3. Typical AFM images (a) and TEM images (b) of the as-prepared Monolayer-C3N4 nanosheets. The
tables and curves in the right panel show the height and width information of different nanosheets from the AFM
images.
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Figure 3a shows the typical atomic force microscope (AFM) image of the exfoliated g-
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C3N4 nanosheets. The lateral size of these sheets is ranging from tens of nanometers to several
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micrometers. The thickness analysis of the nanosheets by AFM reveal an average thickness of
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about 0.4 nm, which is very close to the theoretical thickness of monolayer g-C3N4 (about
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0.325 nm). Statistical studies of the thickness of single layer g-C3N4 nanosheets by measuring
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different samples confirm this observation (Figure S3 in the supporting information). Some
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multilayered g-C3N4 nanosheets with thickness from 1 nm to 4 nm are also observed in the
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AFM studies, which comprise ca. 40% of the sample, indicating the current chemical
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exfoliation can produce g-C3N4 nanosheets with 60% single layer C3N4. TEM image (Figure
3b) illustrates the very transparent feature of the nanosheets, indicating the ultrathin thickness
of the nanosheets. The darker part in the TEM image can be attributed to the overlap of
several g-C3N4 nanosheets or a multilayer nanosheet. The bulk g-C3N4 before exfoliation
shows a thickness of more than 10 nm (Figure S4 and S5), indicating the effectiveness of the
current chemical exfoliation method. The EDX studies (Figure S6) confirmed the elemental
composition of the nanosheets, which are shown to be composed of C and N elements, while
the Cu detected can be attributed to the copper substrate for TEM investigation. Notably,
oxygen is not detected in the element analysis of the nanosheets, implying the g-C3N4 is not
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oxidized by concentrated H2SO4 employed for exfoliation.
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a)
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b)
Bulk g-C3N4
10
20
30 40 50
2 Theta / degree
22
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24
25
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27
C-N
60
70
4000
3000
triazine
2000
Wavenumber / cm
1000
-1
c)
Intensity / a.u.
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Bulk g-C3N4
Monolayer-C3N4
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20
Monolayer-C3N4
Intensity / a.u.
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Monolayer-C3N4
Bulk g-C3N4
807
1632
1320
1572 1405
1253
1800
1600
1400
1200
1000
Wavenumber / cm
800
-1
Figure 4. a). XRD patterns, b). FTIR spectra, c). Enlarged FTIR spectra of the bulk g-C3N4
and Monolayer-C3N4.
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The structure, composition and chemical states of the Monolayer-C3N4 is further
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investigated by XRD, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared
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(FTIR) etc. In the XRD patterns (Figure 4a), the (002) diffraction at around 27.4 o relates to
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the characteristic interlayer stacking structure, while the (100) diffraction at 13.0 o indicates
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the interplanar structural packing. It has been reported in some other monolayer structures that
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due to the formation of agglomerates and crumples of the monolayer nanosheets by van der
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Waals force during preparing sample for XRD measurment, the XRD pattern of the
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monolayer nanosheets could resemble that of bulk form.38-40 However, it is observed that the
intensity of (002) diffraction related to the interlayer stacking is significantly weakened after
exfoliation as expected. The multilayer components in the sample also contribute to the
observed (002) diffraction.
The strong FTIR absorption bands of Monolayer-C3N4 in Figure 4b and 4c further revealed
a typical molecular structure of graphitic carbon nitride. The absorption band near 1572 and
1632 cm-1 are attributed to C=N stretching, while the three bands at 1253, 1320 and 1425 cm-1
correspond to aromatic C-N stretching. The peak at 807 cm-1 belongs to triazine ring mode,
which correspond to condensed CN heterocycles. The broad band at 3000 3500 cm-1
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corresponds to uncondensed terminal amino groups (-NH2 or =NH groups). The FTIR results
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are in fairly good accordance with the reports of g-C3N4 material prepared by
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polycondensation and polymerization reactions.25,26 The Raman spectra are also invesitigated
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to confirm the molecular structure of g-C3N4 (Figure S7 in supporting information). In the
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Raman spectra for both bulk and monolayer g-C3N4, there are two characteristic bands related
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to the disordered D (around 1300 cm-1) and graphitic G (around 1500 cm-1) bands, indicating
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the formation of graphitic structure. The Raman bands at 600 800 cm-1 can be attributed to
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the in-plane rotation of sixfold rings in a graphitic carbon nitride layer.41
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b) N 1s
a) C 1s
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22
288.0
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284.6
Monolayer-C 3N4
Intensity/a.u.
20
292
Monolayer-C 3N4
bulk g-C3N4
bulk g-C3N4
296
398.6
288
Binding energy/eV
408
284
404
400
Binding energy/eV
396
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Figure 5. a) C1s XPS spectra; b) N1s XPS spectra of the bulk g-C3N4 and Manolayer-C3N4 nanosheets.
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The chemical states of the Monolayer-C3N4 and the bulk g-C3N4 were studied by XPS
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(Figure 5). The C1s spectra show two peaks locating at about 284.6 eV and 288.0 eV. The
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288.0 eV peak is further deconvoluted into two Gaussian-Lorenzian peaks. The main
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contribution peak at 287.9 eV is attibuted to the sp2 hybridized carbon bonded to N inside the
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triazine rings, while the peak at 288.6 is assigned to the sp2 hybridized carbon in the triazine
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The peak at 284.6 eV is typically ascribed to sp2 C=C
ring bonded to the NH2 group.
bonds. The peak of 398.6 eV in the N1s spectra can also be deconvoluted into two Gaussian-
Lorenzian peaks. The dominant peak at 398.7 eV corresponds to the sp2-bonded N involved in
the triazine rings (C-N=C), while the peak at 399.7 eV is attributed to the bridging N atomes
in N-(C)3 or N bonded with hydrogen.35
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a)
b)
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12
13
14
15
300
400
Bulk g-C3N4
Bulk g-C3N4
Monolayer-C3N4
200
Monolayer-C3N4
Intensity / a.u.
500
600
700
800
350
400
450
500
550
600
Wavelength / nm
Wavelength / nm
Figure 6. a). DRS spectra and b). PL spectra of the bulk g-C3N4 and Monolayer-C3N4.
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The optical properties have been investigated by UV-Vis diffuse reflectance spectra (DRS)
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and photoluminenscence (PL) measurements (Figure 6a and 6b). It is found that the
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absorption edge of Monolayer-C3N4 shows a remarkable blue shift from 470 to 425 nm,
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corresponding to an increase in the band gap from 2.64 eV to 2.92 eV compared with that of
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bulk g-C3N4. This blue shift performance can be presumably ascribed to the decrease of
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conjugation length and the strong quantum confinement effect due to the single layer structure
23
of g-C3N4 nanosheets. The PL spectra demonstrate that under photoexcitation at 318 nm, the
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emission peak of the bulk g-C3N4 locates at around 464 nm, while the position of the emission
25
peak is blue shifted to to 438nm in the case of Monolayer-C3N4. The blue shift of the
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emission peak by 26 nm is in well agreement with the larger bandgap by 0.28 eV of
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Monolayer-C3N4 nanosheets.
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The photocatalytic H2 production from water in the presence of the bulk g-C3N4 or
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Monolayer-C3N4 were studied under visible-light irradiation ( > 420 nm), as shown in Figure
30
7a. 3 wt.% Pt was loaded on the surface of the photocatalyst samples by the in situ
31
photodeposition method from H2PtCl6 solution. It is found that Monolayer-C3N4 shows a
32
significant improvement over the reference bulk g-C3N4. The rate of H2 evolution on
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Monolayer-C3N4 reaches 230 molg-1h-1, which is about 2.6 times the rate of the bulk g-C3N4
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(90 molg-1h-1).
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a) 300
150
-0.6
Bulk g-C3N4
-0.9
4th
5th
0.75
Blank
Bulk g-C3N4
0.60
Monolayer-C3N4
0.45
50
0.30
-1.2
Sample
7
8
9
3rd
Time / h
Time
Figure 7. a) Photocatalytic H2 production on bulk-C3N4 and monolayer-C3N4. b) Photocatalytic decomposition of

phenol under visible light irradiation ( > 420 nm). c) Stability measurement.
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The superiority of Monolayer-C3N4 for photocatalysis application is further confirmed by
12
the photodegradation of phenol under visible light irradiation. A first-order linear relationship
13
was revealed by the plots of ln(C/C0) versus irradiation time (Figure 7b). The determined
14
reaction-rate constants, k, were 0.0633 and 0.2589 h-1, respectively, for bulk g-C3N4 and
15
Monolayer-C3N4. The photocatalytic decomposition rate over the monolayer nanosheet was
16
more than four times as fast as the bulk g-C3N4. The Monolayer-C3N4 also shows a more than
17
threefold enhancement in the photocatalytic degradation of methylene blue under visible light
18
irradiation, as shown in Figure S8 in supporting information. The stability of the Monolayer-
19
C3N4 as a photocatalyst is also evaluated under visible light irradiation (Figure 7c). It is found
20
that the photocatalytic activity only very slightly decreased after five successive cycles of
21
photocatalysis degradation tests, indicating the Monolayer-C3N4 is fairly stable under the
22
studied conditions.
23
It is well known that the photocatalytic activity is greatly related to surface area, charge
24
transporting, light absorption and so on. The properties and photocatalytic activity of the
25
single atomic layer g-C3N4 is different with multilayer g-C3N4 mainly in three aspects: i) The
26
electron and hole mobility in the monolayer is significantly greater than that in the multilayer,
27
which has been proved in the study of graphene. ii) The surface area of monolayer is bigger
28
than that of multilayer, which is also very important for a photocatalyst. iii) The light
29
absorption is different due to the quantum size effect, the absorption edge is expected to be
30
more blue-shifted in the case of monolayer, which could affect the photocatalytic activity by
31
shifting the position of conduction and valence bands of g-C3N4. Since the Monolayer-C3N4
32
was obtained from bulk g-C3N4 by chemical exfoliation, the crystallinity should be similar in
33
both materials, which is also confirmed by the XRD patterns. Therefore, the greatly enhanced
34
photocatalytic activity of Monolayer-C3N4 than the bulk g-C3N4 in both H2 production and
35
phenol degradation can be attributed to several reasons: First, the increased surface area, the
10
2nd
0.90
-0.3
200
100
1st
Monolayer-C3N4
ln(C/C )
o
H2 evolved / umolg h
-1 -1
250
c)
1.05
b)
0.0
C/C0
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measured surface area of Monolayer-C3N4 is 205.8 m2/g, which is almost 50 times larger than
that of bulk-C3N4 (4.3 m2/g), suggesting more active sites in the Monolayer-C3N4 for
photocatalytic reaction. Secondly, the improved photogenerated charge carriers transportation
and separation due to the monolayer nanosheet structure. The monolayer nanosheet structure
can significantly reduce the distance for the charge carriers to transfer from the place
generated to the solid-liquid interface due to the ultrathin structure. Finally, the negatively
shifted conduction band due to the quantum size effect can increase the activity of
photogenerated electrons.
The improved charge carrier separation in Monolayer-C3N4 is investigated by the
10
photocurrent and electrochemical impedance spectroscopy (EIS) measurements (Figure 9).
11
The potential of the electrodes against a Pt counter electrode was set at 0.0 V vs saturated
12
calomel electrode (SCE). As shown in Figure 9a, a fast and uniform photocurrent response
13
was observed for each switch-on and switch-off event in both bulk g-C3N4 and Monolayer-
14
C3N4 electrodes. This photoresponsive phenomenon was entirely reversible. The photocurrent
15
of the Monolayer-C3N4 is about four times as high as that of the bulk g-C3N4 electrode, which
16
indicates that the separation efficiency of photoinduced electrons and holes is significantly
17
improved in the Monolayer-C3N4 nanosheet.
18
20
21
22
23
24
25
26
27
28
20 a)
b)
off
M onolayer-C 3 N 4
(i) (ii)
16
2k
-Z"/ohm
19
12
8
(iii)
(iv)
1k
bu lk g-C 3 N 4
Light on
0
0
30
60
90
T im e /s
120
200
400
Z ' /o hm
60 0
Figure 8. a) Photocurrent response under chopped illumination. b) The EIS response of bulk g-C3N4 ((i) dark,
(ii) under visible light irradiation) and Monolayer-C3N4 electrodes ((iii) dark, (iv) under visible light irradiation).
29
30
The effect of monolayer nanosheet structure on the kinetics of interfacial charge transfer
31
was confirmed by EIS. Figure 8b shows the EIS Nyquist plots of the bulk g-C3N4 and
32
Monolayer-C3N4 electrodes in dark or under visible light irradiation. The Nyquist plot was
33
also fitted to the equivalent Randle circuit (Figure 8b, inset), where Rs is the electrolyte
34
solution resistance, CPE is the constant phase element for the electrode and electrolyte
35
interface, and Rct is the interfacial charge transfer resistance across the electrode/electrolyte. A
11
Current/A
DOI: 10.1039/C3TA13188B
Page 12 of 16
View Article Online
lower value of Rct suggests more efficient charge transfer across the electrode/electrolyte
interface, reducing the possibility of charge recombination and thus enhancing the
photocurrent response.42 The fitted Rct values for the bulk g-C3N4 and Monolayer-C3N4 under
visible light irradiation are 2570.7 and 980.2 , respectively, indicating that the Monolayer-
C3N4 possesses more efficient charge transfer than that of the bulk g-C3N4. One possible
reason for the more efficient charge transport in nanosheets than the bulk g-C3N4 could be the
electron-phonon interaction in the material. The lattice photons are different in the low
dimension material, which could affect the conductivity of the material. The efficient charge
mobility has been observed in low dimension materials, one typical example is graphene,
10
which shows very high electron mobility.2 However, the exact mechanism is still not very
11
clear.
12
13
4. CONCLUSION
14
In summary, we have successfully obtained single atomic layer g-C3N4 nanosheets by a
15
simple chemical exfoliation of the bulk g-C3N4. Although there are still 40% of multilayer
16
nanosheets existing in the product, it is for the first time single layer g-C3N4 nanosheets are
17
produced. Compared with the bulk g-C3N4, single layer g-C3N4 nanosheets show much larger
18
surface area and great superiority in photogenerated charge carriers transport. Accordingly, the
19
photocatalytic activity and photocurrent of single layer g-C3N4 nanosheets are significantly
20
enhanced. A threefold enhancement in photocatalytic H2 production is observed in the single
21
layer nanosheet as photocatalyst. Experiments trying to seperate the single layer nanosheets
22
from the multilayer ones are undergway. The single layer g-C3N4 shows great potential in the
23
application both in environment purification and solar energy conversion.
24
25
ASSOCIATED CONTENT
26
Supporting Information.
27
This material is available free of charge via the Internet.
28
AUTHOR INFORMATION
29
Corresponding Author
30
E-mail: zhuyf@mail.tsinghua.edu.cn
31
E-mail: zhanglw04@gmail.com
12
DOI: 10.1039/C3TA13188B
Page 13 of 16

View Article Online
Present address of Liwu Zhang: Cavendish Laboratory, University of Cambridge, JJ
Thomson Ave, Cambridge, CB3 0HE, UK
Author Contributions
These authors have contributed equally to this work.
5
6
ACKNOWLEDGMENT
The project was supported by the National Basic Research Program of China (973)
(2013CB632403), National High Technology Research and Development Program of China
(863) (2012AA062701), Special Project on Innovative Method from the Ministry of Science
10
and Technology of China (No.2009IM030500), and Atmospheric Environment Monitoring &
11
Pollution Control Program of Jiangsu Province (AEMPC201103).
12
13
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DOI: 10.1039/C3TA13188B
By a simple chemical exfoliation method, for the first time the single atomic layer g-C3N4
nanosheets are prepared.

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Volume 1 | Number 1 | January 2013 | Pages 00000000

Journal of Materials Chemistry A

Chemical exfoliation of graphitic carbon nitride for efficient heterogeneous

Department of Chemistry, Tsinghua University, Beijing, 100084, PR China

Jing Xu, Liwu Zhang, Rui Shi, Yongfa Zhu*

transfer and separation. Accordingly, the photocatalytic H2 production and pollutant

layer g-C3N4 nanosheets in photocatalysis and photosynthesis.

Keywords: Carbon nitride; Single atomic layer; Nanosheet; Photocatalysis

Journal of Materials Chemistry A Accepted Manuscript

Journal of Materials Chemistry A

in electronics, energy storage, solar energy conversion, etc.8, 9

Graphite-like carbon nitride (g-C3N4), a metal-free polymer semiconductor, has attracted

irradiation by pioneering works of Wang and coworkers.22 More potential applications of g-

a bottom-up method by modifying polycondensation of g-C3N4 precursors could result in

Journal of Materials Chemistry A Accepted Manuscript

Journal of Materials Chemistry A

prepare real graphene-like g-C3N4 material with single atomic layer.

(Monolayer-C3N4) by a simple chemical exfoliation method. Since g-C3N4 is not strong

The obtained Monolayer-C3N4 is then characterized and performances in photosynthesis and

photocatalysis under visible light irradiation are investigated.

Characterization of the Samples. The samples were characterized by powder X-ray

diffraction (XRD) on a Bruker D8-advance X-ray diffractometer at 40 kV and 40 mA for

monochromatized Cu K ( = 1.5406 ) radiation. The Brunauer-Emmett-Teller (BET)

adsorption at 77 K with Micromeritics 3020 instrument. Transmission electron microscopy

(TEM) images were obtained by Hitachi HT-7700 electron microscope operated at an

Journal of Materials Chemistry A Accepted Manuscript

Journal of Materials Chemistry A

Hitachi U-3010 UV-vis spectrophotometer. Photoluminescence spectra (PL) of the samples

Photocatalytic tests and Photoelectrochemical Performance. The photocatalytic

molecular sieve column, using N2 as the carrier gas.

(2.0105 M) or phenol solution (2.0 mg L-1) containing 25 mg of as-synthesized photocatalyst

The photoelectrochemical properties were performed on a CHI 660B electrochemical

dip-coated on a 20 mm 40 mm indium-tin oxide (ITO) glass electrode. Electrodes were

Journal of Materials Chemistry A Accepted Manuscript

Journal of Materials Chemistry A

investigated working electrodes were of similar thickness. The electrochemical impedance

3. RESULTS AND DISCUSSION

Journal of Materials Chemistry A Accepted Manuscript

Journal of Materials Chemistry A

Journal of Materials Chemistry A Accepted Manuscript

Journal of Materials Chemistry A

oxidized by concentrated H2SO4 employed for exfoliation.

The structure, composition and chemical states of the Monolayer-C3N4 is further

investigated by XRD, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared

Journal of Materials Chemistry A Accepted Manuscript

Journal of Materials Chemistry A

observed (002) diffraction.

to confirm the molecular structure of g-C3N4 (Figure S7 in supporting information). In the

the in-plane rotation of sixfold rings in a graphitic carbon nitride layer.41

Journal of Materials Chemistry A Accepted Manuscript

Journal of Materials Chemistry A

The peak at 284.6 eV is typically ascribed to sp2 C=C

ring bonded to the NH2 group.

in N-(C)3 or N bonded with hydrogen.35

emission peak by 26 nm is in well agreement with the larger bandgap by 0.28 eV of

photodeposition method from H2PtCl6 solution. It is found that Monolayer-C3N4 shows a

Journal of Materials Chemistry A Accepted Manuscript

Journal of Materials Chemistry A

Figure 7. a) Photocatalytic H2 production on bulk-C3N4 and monolayer-C3N4. b) Photocatalytic decomposition of

The superiority of Monolayer-C3N4 for photocatalysis application is further confirmed by

irradiation, as shown in Figure S8 in supporting information. The stability of the Monolayer-

Journal of Materials Chemistry A Accepted Manuscript