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Chemically Derived Graphene for the Detection of NO 2

Chemically Derived Graphene for the Detection of NO 2 Alexander Zöpfl 1 *, Wendy Patterson 1

Alexander Zöpfl 1 *, Wendy Patterson 1 , Thomas Hirsch 1 , Günther Ruhl 2 , Otto S. Wolfbeis 1 , Frank-Michael Matysik 1

1)

Institute of Analytical Chemistry, Chemo- and Biosensors, University of Regensburg, 93040 Regensburg, Germany

2) Infineon Technologies AG, 93049 Regensburg, Germany

2) Infineon Technologies AG, 93049 Regensburg, Germany Introduction Detection of gases is an important task to
2) Infineon Technologies AG, 93049 Regensburg, Germany Introduction Detection of gases is an important task to
2) Infineon Technologies AG, 93049 Regensburg, Germany Introduction Detection of gases is an important task to
Introduction Detection of gases is an important task to improve the safety and quality of
Introduction
Detection of gases is an important task to improve the safety and quality of human life. Graphene based sensors provide a low cost alternative for online monitoring of hazardous or
explosive gases. One major component of outdoor air pollution is NO 2 , which is formed by the burning of fossil fuels and is highly toxic. Therefore, a selective detection is needed in
terms of air monitoring. Highly sensitive metal oxide based gas sensors are well established and widely implemented. However, they operate at high temperatures (250 – 600 °C),
which requires excessive energy and degrades their long term stability. In this regard, graphene based gas sensors, which operate at low temperatures (25 – 85 ° C), could provide
an attractive alternative. In this study, selectivity was introduced by chemical functionalization of graphene by inserting molecular receptors or by doping with metals and metal oxides.
Preparation of Graphene Modified Micro- Electrodes Preparation of Graphene via Hummers Method Oxidation Reduction
Preparation of Graphene Modified Micro-
Electrodes
Preparation of Graphene via Hummers Method
Oxidation
Reduction
Graphite
Graphene
Oxide
red.
Graphene
KMnO
4 ,
D T, N 2 H 4
H 2 SO 4
(GO)
Oxide
The properties of chemically derived
graphene (rGO) depend on many
experimental details such as the graphite
precursor material, the synthesis strategy,
and the post-treatment.
Following Hummers method, subsequent
reduction of the resulting graphene oxide
(GO) leads to graphene material with many
defects evident in the Raman spectrum.
Nevertheless, due to the simplicity of this
procedure, it is one of the most important
routes for graphene preparation.
Comparison of the Raman spectra of rGO and GO to a
graphene flake prepared by the classical Scotch-Tape
method reveals many defects within the graphene.
Fabrication of Graphene Electrodes via Spin-coating
In order to investigate the electrical
properties of rGO, the material needs to
be electrically connected. Micro-
electrodes with gold conducting paths
evaporated on a silicon wafer were used.
Spin coating of rGO suspensions onto
the micro-elecrodes resulted in
reproducible deposition of thin layers.
Au-electrode
SiO 2
Spin-coating
of
rGO-suspension
R
Sensor Properties In the gas sensors developed herein, it was found that many parameters affect
Sensor Properties
In the gas sensors developed herein, it was found that many parameters affect the
electrical resistance, e.g. humidity and temperature. A change in the temperature from
25 °C to 85 °C leads to an enormous drop in resistance, which is a characteristic
feature of metalloids. It is suggested that the charge transport within rGO happens
through variable range hopping. In this manner, hopping occurs between graphene
structures which are separated by defects and this is affected by temperature.
Another parameter influencing the conductance is air humidity. The adsorption of
water onto graphene leads to a decrease in resistance due to its electron-withdrawing
effect. Increased temperature also results in improved signal regeneration.
Lower resistance and less background noise can be
obtained at higher temperature.
Humidity leads to a more efficient regeneration of
the signal.
Gas Detection Using Unmodified Graphene To assess the effect of gas adsorption on the conductance
Gas Detection Using Unmodified
Graphene
To assess the effect of gas adsorption on the conductance of rGO , the electrical
resistance of coated micro-electrodes was measured while mixing a test gas into a
constant flow of synthetic air. Gas adsorption onto rGO leads to a change in
conductance. Therefore, gas molecules adsorb onto the graphene surface and change
its electronic structure by electron-withdrawing or -pushing effects. Chemically derived
graphene shows more p-type semiconducting behavior and therefore mainly positive
charge carriers (holes) are involved. The electron transfer from rGO to adsorbed gas
molecules leads to more positive charge carriers, and results in an improved
conductance of the electrode, as was observed for NO 2 . Also the resistance drops
faster for higher concentrations and leads to different signals for different
concentrations. Graphene exhibits high affinity to almost any gas adsorption (NO 2 ,
CO 2 , CO, CH 4 , H 2 ) and therefore changes in resistance can be observed. This makes
the unmodified sensor very unselective.
Normalized change in electrical resistance of microelectrodes coated with rGO in the presence of 100 ppm
NO 2 at different temperature and different concentrations of NO 2 .
Functionalization of Graphene SEM picture of rGO electro- chemically doped with Ni nanoparticles. Chemical
Functionalization of Graphene
SEM picture of rGO electro-
chemically doped with Ni
nanoparticles.
Chemical modicifaction
with
e.g.
octadecyl-
amine (ODA).
SEM picture
of
rGO
Doping with metals and metal
oxides is easily achievable.
electrochemically doped
with Pt nanoparticles.
Changing the sensor surface by chemical functionalization leads to different
responses to various gases, and therefore, to improved selectivity. Chemical
modifications were implemented by attaching functional groups and by doping with
metals and metal oxides. Functionalization was performed by wet chemical and
electrochemical methods.
Change of electrical resistance of micro-electrodes coated with functionalized rGO in the presence of 100 ppm NO 2 .
Conclusion Here, graphene based gas sensors have been implemented to monitor various gases and operate
Conclusion
Here, graphene based gas sensors have been implemented to monitor various gases and operate at low temperatures.
Selectivity was introduced by various chemical modifications. Due to the simplicity of Hummers method, large scale production
is possible, and a pathway towards obtaining graphene for low-cost applications is realized. Although many parameters
influence the gas sensor measurements, e.g. temperature and air humidity, but these are easily controllable. Further, by simple
arrangement of different modified graphene electrodes in an array, an artificial nose for gas detection could be realized.
Acknowledgements This work was supported by Infineon and DFG Research Training Electronic Properties of Carbon
Acknowledgements
This work was supported by
Infineon
and
DFG
Research
Training Electronic Properties of
Carbon Based Nanostructures
(GRK 1570).
*email: alexander.zoepfl@ur.de
*email:
alexander.zoepfl@ur.de

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