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Zinc oxide/graphene nanocomposite fabricated via hydrothermal method for gas sensor.

Zinc oxide decorated graphene as a potential gas sensor


Acetylene gas sensor based on the composition of Zinc oxide nanoparticles and graphene.
ZnO nanoparticles and graphene hybrid architecture for high-sensitive gas sensors
Hydrothermal route of ZnO/Grephene nanocomposite for C2H2 gas sensor
Property enhancement of ZnO nanoparticles/Grephene nanocomposite and potential
application in gas sensor.

Abstract

1. Introduction
Graphene/ metal oxide semiconductors (MOS) based solid state gas sensors have attracted
increasing attention worldwide because of their wide range of applications, including the
detection of hazardous gases, environmental gas monitoring, humidity and air quality control,
and chemical process control [1-4]. In recent years, ZnO as a key wide-band gap (3.4 eV at 2 K)
semiconductor with high sensitivity, chemical stability, low production cost and miniature size
has proven to be an excellent gas sensing material utilizing ZnO nanoparticles, one-dimensional
(1D) nanorods, nanowires, nanobelts, nanotubes, two-dimensional (2D) nanoakes, nanoplates,
and nanosheets for both oxidative and reductive detecting gases [5-15]. However, it has high
power consumption due to its high working temperature (250-600 0C). Accordingly, the
development of metal/MOS sensors that can operate at room temperatures with high sensitivity
and low production cost has attracted much attention.
Graphene-based metal oxide nanocomposites consist of the highly conductive carbon lm
serving as an anchor for the metal oxide nanocrystals. For the nanoparticles, suppressing the
aggregation of nano blocks under specic operation conditions ranging from 200 to 450o C is
benecial in retaining high sensing performances; this is because gas sensitivity is enhanced
dramatically when the particle size is comparable to or less than two times of the Debye length
[7].
Acetylene, as an important industrial raw material, is used widely to synthesize valuable
chemicals, such as acetaldehyde, acetic acid, acraldehyde, chloroethylene, chloroprene, and
so on. Moreover, acetylene is the most effective and versatile fuel gas, enabling manual
applications in welding, cutting, straightening, and other localized heating process.
Constitutionally, acetylene is highly combustible and explosive, possessing wide range of
ammability limits in air. At present, many nanostructure gas sensors have been obtained
successfully in detecting C2H5OH, HCHO, CH4, CO, NO2, and NH3. However,
information on acetylene (C2H2) sensors is still very limited.

In this work, nanoparticle-decorated ZnO microdisks with hierarchical structures were


successfully synthesized using a simple citric acid-assisted hydrothermal method. The ZnO
microdisks show a hexagonal wurtzite structure with high crystallinity. More importantly,
the hierarchical nanoparticle-on-microdisk structures suppress the aggregation of ZnO
nanoparticles. This characteristic endows the sensor based on nanoparticle-decorated ZnO
microdisks with high response values, rapid responserecovery, good selectivity, and longterm stability in the range of 14000 ppm at 420 C. It is worth noting that the sensor
even exhibits high response (S = 7.9) to acetylene as low as 1 ppm.

2. Experimental
2.1. Materials
Extra pure graphite powder (99.5%) was obtained from Merck. H 2SO4 (95%-97%), H2O2 (30%)
and HNO3 (68%-70%) were purchased from Dongwoo Fine-Chem. KMnO4 (97%) and
Zn(NO3)2.6H2O (98%) were purchased from Sigma Aldrich. HCl (35-37%) was purchased Wako
Pure Chem. Inds. Ltd. NaOH pellet was obtained from Dae Jung Chem. & Inds. Co. Ltd.
C2H5OH (99.9%) was purchased from DC Chemicals Co. Ltd. All the chemicals were used as
received.
2.2. Preparation of ZnO/RGO nanocomposite
Graphene oxide (GO) was prepared by Hummers and Offeman method [3, 4]. ZnO/RGO
composite was prepared via a hydrothermal method with zinc nitrate hexahydrate
[Zn(NO3)2.6H2O] and GO as the precursors.
0.6 wt.% GO in ethanol was taken and mixed with (40 ml, 0.01 M) Zn(NO 3)2.6H2O. The
resulting solution was kept in sonication bath for 10 min at room temperature. After sonication,
(40 ml, 0.025 M) NaOH solution in ethanol was added to the above solution base. The nal
solution was then transferred into a 100 mL of Teon-lined stainless-steel autoclave at 120 o C
for 10 h and naturally cooled to room temperature, attaining a suspension of ZnO/RGO
nanocomposite with little precipitation. Varying concentration, composites were synthesized by
carefully adjusting the molar ratio of ZnO to GO. The GO/ZnO ratio was varied from 0.6 to 2.6
wt.%, with resultant as ZnO/RGO-1 (GO-0.6 wt.%), ZnO/RGO-2 (GO-1.2 wt.%), ZnO/RGO-3
(GO-2 wt.%) and ZnO/RGO-4 (GO-2.6 wt.%). The composition with 2 wt.% GO termed as

ZnO/RGO-3 was found to be most optimal for gas sensing applications with regard to sensitivity
and selectivity.
The possible reaction process can be expressed as follows [5]:
Zn(NO3)2.6H2O + NaOH Zn(OH)2 + NaNO3 + H2O

(1)

Zn(OH)2 + H2O Zn2+ + OH + H2O


Zn(OH)42 + H+
Zn(OH)42 ZnO + H2O + OH

(2)
(3)

2.3. Characterization
Fourier transform infrared spectra (FT-IR) were recorded using Varian 2000 Scimitar
spectrometer in the range of 4000 cm1 to 350 cm1. The analysis of the phase transition was
carried out by the X-Ray diffractometer (Rigaku Ultima IV) with Cu K radiation ( = 1.54056
A) with a 2 scanning range of 1080o. The morphologies of GO, RGO, ZnO and ZnO/RGO
nanocomposites were observed using eld-emission scanning electron microscopy (FESEM,
Hitachi S4800) with an accelerating voltage of 10 kV and energy-dispersive spectrometer (EDS)
for compositional analysis. High resolution transmission electron microscopy (HRTEM) images
were obtained from a Fecnai F20 with an accelerating voltage of 200 kV. Raman spectra were
obtained on RS JDbin-yvon LabRamHRUV system with a 514 nm wavelength laser in the range
from 3500 cm1 to 300 cm1. BrunauerEmmettTeller (BET) surface area and pore diameter
distribution measurements were performed using an ASIC-2 gas adsorption analyzer (N2 as
absorbate, operating temperature: 196o C). The UVvis spectrum (1901100 nm) was
measured using a UV1800 Shimadzu UV spectrophotometer. Ethanol was used for background
signal. The photoluminescence (PL) spectra were obtained at an excitation wavelength of 340
nm on Perkin Elmer LS 55 setup with a 390 nm lter on emission side.
2.4. Fabrication of gas sensors and measurements of sensing properties
As-prepared ZnO/RGO suspension was drop-coated onto the patterned platinum electrodes on
Al2O3 substrate, followed by heating at 100o C for 2 h to obtain resistive-type C2H2 sensors.
Gas sensing properties were investigated in linear sweep mode from -10 to +10 V. Keithley 4200
(semiconductor characterization system) was used for all IV measurements and data
acquisition. Dry nitrogen was used for ushing. The response magnitude of the sensors is dened

Z g Zc
Zc

100

as S =
, where Zg and Zc are the impedance in C2H2 gas and carrier gas,
respectively. The response time and recovery time of sensors are dened as the time to reach
90% of total impedance change.
3. Results and discussions
3.1. Characterization of ZnO/RGO nanocomposite
XRD
The XRD patterns of pure ZnO and ZnO/RGO composites are shown in Figure 1. The two
characteristic reflection peaks at (002) plane of graphene appear at 2 values of 24.6 o and 43.3o
are theoretically expected to be observed in the XRD pattern of ZnO/RGO composites [6]. The
absence of the (002) reection peak suggests that GO nanosheets are fully oxidized after the
thermal treatment and the distance between the carbon sheets has increased due to the insertion
of the inter-planar groups [7] and fully covered with ZnO nanoparticles for all samples. But the
pattern has a new lower intensity peak centered at 12.3o, which corresponds to a d-spacing of
8.29 , which is attributed to the (001) reection of GO. No other reection peaks, including the
(001) GO reections, are observed indicating the formation of high purity ZnO and the reduction
by hydrothermal process. As the concentration of GO increases in the composites, the intensity
of the reection peaks of RGO increased.

FTIR
Figure 2 shows the FT-IR spectra of GO and ZnO/RGO composite with different GO
concentration. The oxygen-containing functional group of GO (a) represents in band at 1095 cm1
, 1404 cm-1 and 1740 cm-1, corresponding to functional oxide after oxidation, epoxy and carboxy
groups, respectively. The broad absorption band at 3400 cm -1 indicates the presence of O-H
group in graphene oxide [8,9]. However, the oxygen-containing functional groups were almost
entirely removed during the thermal reduction process. In the spectrum of ZnO/RGO (b-e)
samples, the characteristic of the Zn-O stretching vibration of ZnO shifted to lower wave number
447 cm1 from the reported values of 457 cm1 [10] due to the presence of the carboxylic
functional groups in the functionalized hybrid composites involved in the formation of Zn-O-C
carbonaceous bonds [11]. The peak at 1740 cm-1, C=O stretching vibrations of the COOH
groups is absent, which may be due to the anchoring of ZnO on the graphene sheets [12, 13]. The
peak at 28853703 cm-1, O-H band is also turn into narrow band due to the functionalization of
ZnO groups.

SEM
EDS
UV-vis
HRTEM

3.2. Gas sensing properties

3.3. Optical properties

3.4. Electrical properties

4. Conclusions

Acknowledgements
This work is nancially supported by the .
We would also like to acknowledge Mr.for assistance during experiments.

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List of figure with caption

Figure 1: XRD pattern of pure ZnO (a), ZnO/RGO nanocomposites with concentration 0.6 wt%
(b), 1.2 wt% (c), 2 wt% (d) and 2.6 wt% (e).

Figure 2: FT-IR pattern of pure GO (a), ZnO/RGO nanocomposites with concentration 0.6 wt%
(b), 1.2 wt% (c), 2 wt% (d) and 2.6 wt% (e).

Figure 3:

Figure 4: EDS spectra of ZnO/RGO nanocomposite at GO concentration of 0.6 wt% .

Figure 5:
Figure 6:
Figure 7:
Figure 8:
Figure 9:

Table 1: EDS analysis for ZnO/RGO composite

GO 0.6 wt%

GO 2.6 wt%

Elements
Weight %

Atom %

Weight %

Atom %

2.10

5.31

3.88

9.59

9.51

18.04

5.44

10.11

Zn

20.23

9.39

13.08

5.95

Si

61.24

66.19

69.00

73.04

Pt

6.92

1.07

8.60

1.31

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