Solid State Sciences 46 (2015) 84e88

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Solid State Sciences

journal homepage: www.elsevier.com/locate/ssscie

CVD growth of large-area graphene over Cu foil by atmospheric

pressure and its application in H2 evolution
Shu Ye a, Kefayat Ullah a, Lei Zhu a, Asghar Ali a, Won Kweon Jang b, Won-Chun Oh a, *
a
Department of Advanced Materials Science & Engineering, Hanseo University, Chungnam 356-706, Korea
b
Division of Electronic, Computer and Communication Engineering, Hanseo University, Chungnam 356-706, Korea

a r t i c l e i n f o a b s t r a c t

Article history: This study reports that the atmospheric pressure chemical vapor deposition (CVD) growth of large area
Received 24 March 2015 graphene (LAG) over a Cu foil. The obtained large area graphene was further decorated with TiO2
Received in revised form nanoparticles via ultrasonic method. The surface structure, crystal phase, and elemental identification of
22 May 2015
these obtained LAG/TiO2 composite were characterized by X-ray diffraction (XRD), scanning electron
Accepted 24 May 2015
Available online 28 May 2015
microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray (EDX) analysis, and
Raman spectra. The photocatalytic H2 evolution result illustrates Cu-LAG/TiO2 has been found to be a
potential catalyst for conversion of solar energy to clean hydrogen energy under visible light-driven
Keywords:
CVD
despite that the H2 evolution activity is not high enough in this stage.
Ultrasound © 2015 Elsevier Masson SAS. All rights reserved.
Graphene
Cu foil
H2 evolution

1. Introduction been carried out [21e24]. However, many problems remain unre-
solved for practical applications such as narrow light response
The successful growth of large-area graphene [1e4] has the range and low separation probability of the photoinduced elec-
potential to revolutionize applications of graphene in electronic tronehole pairs in the TiO2 photocatalytic system. In order to
and mechanical devices. Recently, CVD growth has been used to improve the photocatalytic activity and the response into the
realize such films on metal surfaces. Most of the CVD growth uses visible light region, TiO2 doping with transition metals has been
polycrystalline Ni [5e8], Fe [9], and Cu [10e14] films/foils, and it widely investigated [25].
has been considered that Ni and Fe give inhomogeneous graphene In this study，the LAG materials were grown on Cu foil by using
films with multi-layer flakes. The LAG has also been obtained using a single step CVD method under atmospheric pressure. The hybrid
a solid-phase layer-stacking approach with ethanol wetting [15]. material was further decorated with TiO2 via an ultrasound method
However, these nanocarbon hybrids required multiple fabrication/ at a low temperature. The catalysts were characterized by X-ray
synthesis steps or used rGO as the non-ideal substitute of graphene. diffraction (XRD), energy dispersive X-ray analysis (EDX), scanning
Titanium dioxide (TiO2) is the most widely used semiconductor electron microscopy (SEM), and transmission electron microscopy
in environmental pollution control, conversion and energy storage, (TEM) techniques. The catalytic efficiency of the Cu-LAG/TiO2
sensors, photovoltaics, and Li batteries because of its unique photo- composites was evaluated by H2 evolution under visible light.
electric properties, high chemical stability, low cost, and low
toxicity towards both humans and the environment [16e20]. The
2. Experimental procedures
improvement and optimization of TiO2 as a photocatalyst is a major
task for technical applications of heterogeneous photocatalysis in
2.1. Materials and reagents
the future. In this sense, many investigations for the enhancement
of photocatalytic activity either in the UV or visible region have
Benzene used as a carbon precursor material was purchased
from Dae-Jung Chemical and Metals Co. Ltd Korea. Titanium (IV) n-
butoxide (TNB, C16H36O4Ti), which was used as a titanium precur-
* Corresponding author. sor, was purchased from Samchun Pure Chemical Co. Ltd., Korea.
E-mail address: [email protected] (W.-C. Oh). The Cu foil (99.9%), annealed uncoated, was used as the substrate

http://dx.doi.org/10.1016/j.solidstatesciences.2015.05.010
1293-2558/© 2015 Elsevier Masson SAS. All rights reserved.
 S. Ye et al. / Solid State Sciences 46 (2015) 84e88 85

material to grow LAG. Argon and nitrogen gas were purchased from 2:10. These obtained composites were named Cu-LAG/TiO2.
Samchun Pure Chemical Co. Ltd., Korea. A specially designed split Si
tube furnace divided into two parts, the inner tube and the outer 2.4. Characterization
tube, was used. The dimensions of the tube were 30 cm length and
4 cm outer diameter, with two nozzles, one for the inlet of benzene The crystal structures and phases of the samples were obtained
vapors and the other for the inlet of Ar and N2 gas. The inner by XRD (Shimata XD-D1, Japan) with Cu Ka radiation (l ¼ 1.54056)
furnace, also called the heating center, having a 8-cm length and 5- in the range of 2q from 10 to 80
at a scan speed of 1.20 m1. The
cm diameter, was used to grow LAG on Cu foil. Ethylene glycol was decomposition kinetics for the photocatalytic activity was
purchased from Dae-Jung Chemical and Metals Co. Ltd, Korea. All measured in the range between 300 and 700 nm using a spec-
chemicals were used without further purification. trometer (Optizen POP, Mecasys, Korea). Energy dispersive X-ray
spectroscopy (EDX) was also employed for elemental analysis. High
2.2. Preparation of LAG material Resolution Transmission Electron Microscopy (HRTEM, JEOL, JEM-
2010, Japan) was used to observe the surface state and structure
Briefly, the benzene was first heated below its boiling temper- of the photocatalyst composites at an acceleration voltage of
ature, and vapors were produced. The vapors were then transferred 200 kV.
to the tube simultaneously with Ar gas, which also acted as a carrier
for benzene vapors and prevented the Cu foil from reacting with 3. Results and discussion
water molecules. The vapor flow and the Ar gas ratio were
controlled through the control valve. The furnace temperature was 3.1. Characterization of Cu-LAG/TiO2 composite
increased to 500
C at the first step, and Ar gas was released into the
Si furnace. After reaching the temperature of around 500
C, a Cu The XRD patterns of he Cu-LAG/TiO2 composite are shown in
foil was inserted into the inner tube by flowing a controlled amount Fig. 1. The patterns clearly showed peaks of TiO2, namely, the planes
of Ar gas and benzene vapors. After 5 min, the coated Cu foil was (101), (004), (200), (211), (204), (220), and (215) at 2 q values of
checked and scratched using a blade, and then the powder was about 25.38, 37.82, 48.18, 54.4, 62.92, 69.92, and 74.91, respectively.
scratched from the coated Cu foil before being dried at 100
C in a According to JCPDS-21-1272, all patterns were assigned to the
dry oven [26]. polycrystalline anatase phase structure of TiO2. The crystallite size
of the samples was calculated from the full-width at half maxima of
2.3. Attachment of TiO2 on graphene sheet the (101) peak of anatase TiO2 by the DebyeeSherrer equation:

2 mL of TNB (about 6.5  105 mol) was added to 10 mL of the d¼kl ¼ bcosq (1)
ethanol solution, followed by magnetic stirring for 5 min; after that,
10 mL distilled water was dropwised added to the solution with where d represents the crystallite size of; l represents the wave-
constant stirring. Then, we added 0.4 g of as-prepared LAG and length of the incident X-ray; b is the full-width at half maximum
30 mL ethylene glycol into the solution. This step was then followed (FWHM) of the diffraction peak; and y represents the scattering
by constant stirring and ultrasonication (using 750 W, Ultrasonic angle. The average crystalline size calculated from the above
Processor VCX 750, Korea) for 4 h. After completion, the black so- equation for pure TiO2 was 9.5 nm, and the average crystalline size
lution was filtered, washed 3 times with deionized water and of Cu-LAG/TiO2 composite was 7.7 nm [27]. Furthermore, the
ethanol, and then dried at 873 K. Finally, the sample was heated at absence of graphene peaks in the XRD patterns of composite cat-
873 K for 1 h. The weight ratios of LAG to TNB were approximately alysts showed that CVD-made graphene did not change the

Fig. 1. X-ray diffraction patterns of the Cu-LAG/TiO2 composite.

86 S. Ye et al. / Solid State Sciences 46 (2015) 84e88

Fig. 2. Energy dispersive X-ray elemental analysis of Cu-LAG/TiO2composite.

Table 1 Cu2O or CuO nanoparticles on the LAG can be observed in Fig. 3d

Energy dispersive X-ray elemental microanalysis (wt%) of the Cu-LAG/TiO2 and e, which were consistent with the XRD patterns. This
composites.
morphology was expected to be beneficial for the photoinduced
Sample Element electron transfer between the TiO2 and Cu2O or CuO nanoparticles
C O Ti Cu Zn Total to the LAG. In addition, the HRTEM images clearly showed the
presence of smaller particles with diameters of approximately
LAG/T2 26.38 17.87 9.68 45.43 0.54 100.00
15 nm as evidenced by Fig. 3e, which show the TiO2 nanoparticles
derived from the TNB material.

structure of TiO2 [28].

The EDX analysis of the Cu-LAG/TiO2 composite indicated that 3.2. Photochemical hydrogen production
the nanocomposites were synthesized successfully. Fig. 2 shows
that the composite were rich in C, O, Cu, and Ti elements rather The 0.05 g Cu-LAG/TiO2 nanocomposites were well dispersed in
than any other metal elements [29]. Very low concentrations of 100 ml aqueous solution containing Na2S/Na2SO3 as a sacrificial
impurities were observed, and these impurities may have been due reagent. The TiO2 nanoparticles on the LAG surface act as H2 evo-
to starting the experiment with CVD-made lager-area graphene lution centers, as decorated by the microwave-assisted method. A
[30]. The elemental contents of the Cu-LAG/TiO2 is listed in Table 1. 356-nm light source was adjusted so that the maximum area of the
The morphology of CVD-grown graphene on Cu foil was sealed container would be exposed. Quantum yield (QY) was
observed by HRTEM. Fig. 3a and b is a typical HRTEM image of 5-nm observed using the equation
CVD-grown graphene on a copper foil substrate at 500
C. Fig. 3a
and b gives a larger-area graphene with some dark region consid- np ¼ t  S  Q (2)
ered to be valleys between the two graphene domains. It is well

known that the graphene films are easily grown on copper foil by QYð%Þ ¼ nH np  100 (3)
CVD [31]. From Fig. 3c, d, and e, the TEM images show that the LAG
in the nanocomposite were rippled and resembled crumpled silk where, np is the amount of incident photons, t is irradiation time, s
veil waves, which were appropriate for immobilizing the nano- is irradiation area in m2, and Q is photon flux of the incident light.
particles [32]. Furthermore, a highly dense deposit of the TiO2 and The Q (Y) was calculated from the ratio of the number of reacted

Fig. 3. HRTEM images of (a), (b) LAG; TEM images of (c), (d) and (e) Cu-LAG/TiO2.
 S. Ye et al. / Solid State Sciences 46 (2015) 84e88 87

Fig. 4. Photocatalytic H2 evolution of Cu-LAG/TiO2 and P-25 using Na2S/Na2SO3 as the Fig. 6. Quantum yields for hydrogen evolution by Cu-LAG/TiO2 and P-25 with 20%
sacrificial reagent. methanol.

electrons during hydrogen evolution to the number of incident

photons according to Equation (3), where nH is the amount of
photogenerated H2 [33e35]. After 9 h irradiation, the photo-
catalytic H2 evolution and quantum yield efficiency (QYs) for the
Cu-LAG/TiO2 nanocomposites and P-25 are shown in Figs. 4 and 5,
respectively. The QYs of individual Cu-LAG/TiO2 nanocomposite
were 6.2%, using Na2S/Na2SO3 as the reagent.
In contrast, H2 evolution and QYs for P-25 were smaller than
those of the Cu-LAG/TiO2 nanocomposite under the same condi-
tions. The decrease in H2 evolution and corresponding QY efficiency
may have been attributed to the fast recombination rate of the
excited electrons and hole pair in TiO2. These results highlight the
importance of Cu-LAG, which is absent in P-25. The sacrificial re-
agent provided electrons to consume the photogenerated holes,
and TiO2 acted as a reaction center to produce H2 from water. The
H2 evolution plot for a 20% methanol solution with Cu-LAG/TiO2
and P-25 as a photocatalyst is shown in Fig. 6. Fig. 7. Cyclic test of the Cu-LAG/TiO2 nanocomposite using Na2S/Na2SO3 as the sacri-
ficial reagent under UV light irradiation.
Cyclic photocatalytic hydrogen evolution experiments were
carried out to further demonstrate the photostability and cyclic
performance of the Cu-LAG/TiO2 composite photocatalysts. As stability of the catalysts and their benefit in practical applications.
shown in Fig. 7, the photocatalysts exhibited a minor loss of pho- The possible reasons for H2 evolution of composite catalyst under
tocatalytic activity for hydrogen evolution under the same condi- visible light irradiation are the following. Firstly, the photocatalytic
tions after three runs, indicating the photocatalytic stability of our activity of Cu-LAG/TiO2 composite catalyst might be attributed to
nanocomposite. The reused catalyst did not show any noticeable extended light absorption into visible light region due to copper
change in QYs efficiency, which emphasizes the excellent chemical and LAG incorporation. Secondly, in Cu-LAG/TiO2 system, the
excited electrons of TiO2 could transfer from the conduction band
to LAG through percolation mechanism [36,37]. Thus, in the com-
posite, LAG served as an acceptor of generated electrons of TiO2 and
effectively suppressed the charge recombination, leaving more
charge carriers to form reactive species and promote the H2 evo-
lution [38].

4. Conclusions

In conclusion, we successfully investigated a new and short

route to produce LAG. The LAG materials were grown on Cu foil by
using a single step CVD method under atmospheric pressure. This
large-area graphene can be produced in industries at a large scale
by further controlling experimental parameters to optimum values.
We demonstrated the production of large-area graphene at a very
short reaction time in a nitrogen/argon environment using a
chemical vapor deposition method. The HRTEM images showed the
multi-layer graphene growth on Cu foil. The obtained large-area
Fig. 5. Quantum yields for hydrogen evolution by Cu-LAG/TiO2 and P-25 with the graphene was decorated with TiO2 nanoparticles successfully via
Na2S/Na2SO3 aqueous solution. an ultrasonic method. Cu-LAG/TiO2 is a stable efficient
88 S. Ye et al. / Solid State Sciences 46 (2015) 84e88

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