Accepted Manuscript

Preparation of nanoscale-dispersed g–C3N4/graphene oxide composite photo-

Hui Wang, Qianhong Shen, Zengyu You, Yuxuan Su, Yang Yu, Abbas
Babapour, Fang Zhang, Di Cheng, Hui Yang

PII: S0167-577X(18)30044-2
DOI: https://doi.org/10.1016/j.matlet.2018.01.037
Reference: MLBLUE 23685

To appear in: Materials Letters

Received Date: 19 October 2017

Please cite this article as: H. Wang, Q. Shen, Z. You, Y. Su, Y. Yu, A. Babapour, F. Zhang, D. Cheng, H. Yang,
Preparation of nanoscale-dispersed g–C3N4/graphene oxide composite photocatalyst with enhanced visible-light
photocatalytic activity, Materials Letters (2018), doi: https://doi.org/10.1016/j.matlet.2018.01.037

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Preparation of nanoscale-dispersed g-C3N 4/graphene oxide composite

photocatalyst with enhanced visible-light photocatalytic activity

Hui Wang,a Qianhong Shen,*a, b Zengyu You,a Yuxuan Su,a Yang Yu

,a Abbas Babapour,a Fang Zhang,b Di Cheng, b and Hui Yang*a, b

Zhejiang University, Hangzhou P.R. China 310027

China 310058

Abstract: A novel metal-free photocatalyst of g-C3N4/graphene oxide nanocomposite

(CNNP/GO) was fabricated by loading g-C3N4 nanoparticles on graphene oxide

through electrostatic self-assembly strategy. XRD, FT-IR, SEM, TEM, and PL were

adopted to analyze the structure and properties of the CNNP/GO nanocomposite.

Photocatalytic activity of CNNP/GO nanocomposite was evaluated by the degradation

of methylene blue (MB) under visible-light irradiation. The results show that the

nanonization of bulk g-C3N4 widens the band gap of g-C3N4 from 2.75 eV to 3.40 eV,

and the obtained CNNP exhibits an obvious blue-shift in the absorption band edge

compared with bulk g-C3N4, resulting in the weak response to visible light.

Introducing GO into CNNP can efficiently reduce the band gap to 2.55 eV, thereby

enhancing the utilization of visible light. Moreover, the GO can be served as an

electron acceptor in the CNNP/GO nanocomposite, leading to significantly

improvement in separation efficiency of photo-generated carriers. Hence, the best

photocatalytic degradation rate of MB over CNNP/GO nanocomposite is about 2 and

6 times higher than that over bulk g-C3N4 and CNNP samples, respectively.

Furthermore, this work also indicates that the novel CNNP could be an excellent

material to combine with other semiconductors to construct high efficient

KEYWORDS: graphitic carbon nitride, graphene oxide, nanocomposite, visible-light response,

photocatalysis

INTRODUCTION

At present, energy and environmental problems have greatly restricted the

development of society. Among various problem-solving strategies, semiconductor-

based photocatalysis has gained considerable attention for its diverse potential in

energy and environmental applications. Recently, graphitic carbon nitride (g-C3N4)

has become a promising visible-light photocatalyst due to its appropriate band gap

(2.7 eV) and excellent chemical/thermal stability[1, 2]. More importantly, this metal-

free semiconductor, consisting of only carbon and nitrogen, is obviously green and

abundant[3]. However, the widely used polycondensation preparation method of g-

C3N4 always form bulk g-C3N4 with low specific surface area, poor quantum yield

and high recombination rate of photo-generated carriers as well as poor photocatalytic

reaction efficiency[4]. Therefore, nano g-C3N4 (such as nanorods,[5] nanosheets[6, 7])

attracted more and more attentions due to its high specific surface area. Furthermore,

nano g-C3N4 with smaller size can also shorten the transfer path of photo-generated

carriers, resulting in high efficient separation of photo-generated electrons and holes.

In our preliminary study, g-C3N4 nanoparticles have been synthesized by using a

facile method, and the recombination of photo-generated carriers was therefore

efficiently inhibited. However, it was also found that the nanonization of bulk g-C3N4

widened the band gap of g-C3N4, leading to poor photocatalytic activity under visible-

light irradiation, whereas the g-C3N4 nanoparticles exhibited high photocatalytic

activity when excited by UV-light. To the best of our knowledge, this is the first time

to report this special phenomenon of the g-C3N4 nanoparticles. Therefore, based on

such unique g-C3N4 nanoparticles, constructing a high efficient composite

property will be an interesting work. In recent years, graphene have attracted great

interest and been used to combine with other materials due to its amazing conduction

properties, high strength and toughness structure, and large specific surface area[8].

Especially for the graphene-based composite photocatalytic materials, graphene can

not only promote transfer and separation of photo-generated electrons and holes, but

also narrow the bandgap of semiconductor photocatalyst to obtain high photocatalytic

activities under visible-light irradiation[9].

Herein, g-C3N4 nanoparticles/graphene oxide (CNNP/GO) nanocomposites with

enhanced visible-light photocatalytic activity were synthesized by loading g-C3N4

nanoparticles (CNNP) on graphene oxide (GO). The relationships between structural

features, electronic properties, and photocatalytic activities of the CNNP/GO

nanocomposites were discussed. Compared with the bulk g-C3N4, CNNP can be better

combined with GO, and thus obtaining a nanoscale-dispersed composite

photocatalytic materials with intimate interracial contact and more exposed reactive

centers. Actually, the CNNP can also be loaded on many other semiconductors with

matched energy band structure to construct high-efficient nano heterojunctions, and

thus providing a new idea for fabricating g-C3N4 based composite photocatalytic

materials.

Experimental

CN was prepared by direct thermal condense of melamine in a semi-closed

system. In detail, 5 g of melamine was placed in a 20 ml crucible with cover, and then

was put in a muffle furnace and heated to 600 ℃ for 2 h at a heating rate of 3 ℃/min.

After cooling to room temperature, the resultant light yellow agglomerates were

collected and grounded into powders for further use.[10] CNNP was prepared by a
simple disintegration-exfoliation process. In detail, 1 g of CN was added to a mixture

of concentrated sulfuric acid (H2SO4) (20 ml) and nitric acid (HNO3) (20 ml)

firstly.[10] The mixture was magnetically stirred and refluxed at 80 ℃ for 2 h, and

then poured into 1 L deionized water. Finally, the product was washed with deionized

water to near-neutral pH and dispersed in 20 ml of deionized water followed by

sonication for 2 h. The concentration of CNNP is about 10 mg/ml. CNNP/GO

composite photocatalyst was synthesized via self-assembly process. Typically, 10 mg

of GO was initially dispersed in 50 ml of water and ultrasonicated for 1 hour. Then, a

certain amount of CNNP was added into the above suspension and ultrasonicated for

another hour. After that, the mixture was magnetically stirred for 12 hours. The

CNNP/GO composite photocatalyst was obtained after centrifugation and drying. As-

prepared composites with different CNNP/GO mass ratio of 2:1, 4:1 and 6:1 were

denoted as CNNP/GO-2, CNNP/GO-4 and CNNP/GO-6, respectively.

Results and discussions

Fig.1 shows the TEM images of samples with the lamellar structures, the

uniformed CNNP was displayed after the acid etching and it showed the thin-layer

structure (Fig. 1a). As shown in Fig. 1 (c-e), the CNNP is uniformly loaded on the GO.

With increasing the content of CNNP, there are more CNNP on the GO, and it is very

conform to the results of the SEM observation (Fig. S1).

Figure 1 TEM images of (a) CN, (b) CNNP,

(c) CNNP/GO-2, (d) CNNP/GO-4, (e) CNNP/GO-6.

The XRD patterns of the samples of CN, CNNP, GO and CNNP/GO are shown
in Fig. S2. The CN sample displays a typical feature of g-C3N4 with two peaks at

27.41° and 13.21°, corresponding to the (002) and (100) diffraction planes (JCPDS

87-1526) respectively[11]. The XRD pattern of the obtained CNNP only shows the

characteristic peak at 27.41°, suggesting that the typical layered structure of g-C3N4 is

well kept. Whereas the low angle diffraction peak at 13.21° becomes weak, because

planar size of the layers is simultaneously decreased after the intense protonation[11].

For pure GO, only a sharp diffraction peak at around 10.8° can be observed,

corresponding to the (002) reflection of GO[12]. The characteristic peak at 27.3° is

observed clearly for CNNP/GO composite, indicating the preservation of well-

crystalline g-C3N4 structure in the composites. Furthermore, the weakened

characteristic peak of GO at 10.8° can also be distinguished.

Fig. 2a shows the UV-Vis diffuse reflectance spectra of CN, CNNP, and

CNNP/GO nanocomposites. Compared with CN, the absorption edge of CNNP shows

a distinct blue shift. GO modification can significantly affect the optical properties of

g-C3N4, and the absorption edge of all CNNP/GO nanocomposites occur red shift

relative to CNNP. Fig. 2b shows the plots of the transformed Kubelka-Munk function

as a function of light energy. It can be seen that the band gap of CN, CNNP,

CNNP/GO-2, CNNP/GO-4 and CNNP/GO-6 are estimated to be about 2.75 eV, 3.40

eV, 1.95 eV, 2.55 eV and 3.03 eV, respectively. According to FTIR (Fig. S3), the

typical peak of C-OH decreases dramatically in intensity, while the peak of C–O–C at

1214 cm-1 relatively increases simultaneously. Therefore, it is indicated that the -OH

groups may act as a cross-linker to connect GO and CNNP by forming C-O-C

bonds[9, 13]. Theoretical calculations have illustrated that oxygen near the conduction

and valence bands originated from the C − O – C covalent bonding which introduces

extra p states can decrease the bandgap of semiconductor[14]. Hence, the oxygen-rich
active sites on the GO surface (e.g., − OH, − COOH) can play a key role of cross-

linker to form C−O−C covalent bonding between GO and CNNP, which could be the

reason for the bandgap narrowing and enhanced visible-light absorption of the

CNNP/GO nanocomposite [15].

Figure 2 (a) UV-vis diffuse reflectance spectra of CN, CNNP, and CNNP/GO nanocomposites.

(b) The plots of transformed Kubelka-Munk functions versus the light energy.

Fig. S4 shows the photoluminescence spectra (PL) of as-prepared samples. CN

has a typical emission peak at 464 nm, while the emission peak of CNNP blue-shifts

to 430 nm, indicating a larger bandgap caused by the quantum confinement effect

with conduction[14]. And it can also be seen from the PL spectra that all the

CNNP/GO samples present a much lower intensity than that of CN and CNNP,

revealing that the radiative recombination of photo-generated electron-hole pairs is

largely inhibited.

The photocatalytic properties of as-prepared samples were evaluated by

photocatalytic decomposing MB (15mg/L) under visible-light (λ> 420 nm) irradiation

(Fig. 3). As shown in Fig. 3, only 12% of MB is decomposed by CNNP under visible-

light irradiation for 3 h due to its low absorption in visible light and some existent

residual CN. Besides, just 36% of MB is decomposed by CN owing to the rapid

recombination of photo-generated carriers. Compared with CN and CNNP, all the

CNNP/GO samples have much higher degradation efficiency for MB under the same

conditions. In the CNNP/GO samples, CNNP, as a photocatalyst, can generate

acts as a carrier of nanoparticles and furthermore facilitates the transfer of photo-

generated electrons. Moreover, there is an optimum CNNP content in CNNP/GO

samples based on their different roles. Among all the CNNP/GO samples, CNNP/GO-

4 reaches the highest degradation rate of 67% within 3 h due to its suitable band gap

and the enhanced separation efficiency of photo-generated carriers. As the mass ratio

of CNNP to GO is less than 4, the photocatalytic activity of CNNP/GO gradually

increases with the CNNP content. Further increasing the CNNP content, the

photocatalytic activity of CNNP/GO slightly decreases. The efficient charge

separation, improved visible-light absorption, as well as increased active sites

generated from nanoscale dispersion all contribute to the enhanced photocatalytic

activity.

Figure 3 Photocatalytic degradation of MB by nanocomposites

Conclusions

In summary, a facile synthesis method is presented to prepare CNNP/GO

nanocomposite with remarkable enhanced visible-light photocatalytic activity by

loading g-C3N4 nanoparticles on graphene oxide. The GO can narrow the bandgap of

CNNP and increase the visible-light utilization. Moreover, the GO can also facilitate

the separation of photo-generated carriers owing to the close interface formed

between GO and CNNP via C-O-C bonds. Another effect of the present work is to
propose a facile and efficient method to construct g-C3N4 based composite materials

through the assembly of g-C3N4 nanoparticles, and thus the CNNP can be loaded on

many other semiconductors with matched energy band structure to find new

photocatalysis systems with high-efficient nano heterojunctions.

Acknowledgements

This work is supported by The Key Research and Development Program of

Zhejiang Provence(No. 2017C01002).

Appendix A. Supplementary data

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HIGHLIGHTS:
1. g-C3N4 nanoparticles with low recombination of photo-generated carriers were
prepared.

2. A g-C3N4/graphene oxide composite with high-efficient heterojunctions was

3. A facile method was proposed to prepare g-C3N4 nanoparticles composite materials.

graphical abstract: