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Nanostructured SnO2 for CO Sensors

This document discusses the synthesis of nanostructured SnO2 using a polyol technique for CO gas sensor applications. The synthesized SnO2 demonstrated a sensitivity of 52.84% at 150 °C with a response time of 8 minutes and a recovery time of 7 minutes. Characterization techniques such as XRD, SEM, and BET were employed to analyze the material's properties and confirm its effectiveness as a gas sensor.

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9 views5 pages

Nanostructured SnO2 for CO Sensors

This document discusses the synthesis of nanostructured SnO2 using a polyol technique for CO gas sensor applications. The synthesized SnO2 demonstrated a sensitivity of 52.84% at 150 °C with a response time of 8 minutes and a recovery time of 7 minutes. Characterization techniques such as XRD, SEM, and BET were employed to analyze the material's properties and confirm its effectiveness as a gas sensor.

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annisa z
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© All Rights Reserved
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ScienceDirect
Procedia Engineering 170 (2017) 60 – 64


Engineering Physics International Conference, EPIC 2016

Investigation of Nanostructured SnO2 Synthesized with Polyol Technique


for CO Gas Sensor Applications
Aminuddin Debatarajaa,b, Daryl Widia Zulhendria, Brian Yuliartoa,d, Nugrahaa,d, Hiskiac, Bambang
Sunendara,d
a
Department of Engineering Physics, Faculty of Industrial Technology, Institut Teknologi Bandung, Indonesia
b
Electrical Engineering, State Polytechnic of Jakarta, Depok, Indonesia
c
Research Centre for Electronics and Telecommunication, Indonesian Institute of Sciences, Bandung, Indonesia
d
Research Center of Nanosciences and Nanotechnology, Institut Teknologi Bandung, Indonesia

Abstract

In the development of gas sensors, many material based on Metal Oxide Semiconductor is often used, one of them is Tin Oxide (SnO2). SnO2
is widely used for CO gas sensor because of several advantages including long life expectancy, relatively stable, high durability, resistance to
corrosive gases, and good mechanical resistance. Performance improvement of CO gas sensor has been carried out by synthesizing SnO2 by
polyol technique to produce nanostructured powder followed by deposition on alumina substrate using doctor blade coating technique. In order
to determine the performance of the sensor material, the sample was characterized using x-ray diffraction, scanning electron microscopy, and
BET calculation of N2 adsorption-desorption. The XRD analysis showed the tetragonal crystal phase of SnO 2, and BET analysis result in 24,53
m2/g surface area. Furthermore, SEM image showed the nanorod shape of SnO2 morphology with diameter 50 nm – 2 μm. Sensor
characterization with 30 ppm CO gas showed that the sample can work in 150 oC working temperature with sensitivity of 52.84%.
© 2017 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
© 2016 The Authors. Published by Elsevier Ltd.
([Link]
Peer-review under responsibility of the organizing committee of the Engineering Physics International Conference 2016
Keywords: CO gas sensor, Polyol technique, SnO2 nanostructure, sensitivity.

1. Introduction

Various types of materials have been used for gas sensors application. The material that widely used is based on Metal Oxide
Semiconductor (MOS) such as SnO2, ZnO, WO3, CuO, Co3O4 and NiO to detect variety of gases, such as NO2 , NH3, CO, H2,
and C2H5OH[1]. Various attempt in synthesizing, processing, characterization and modification of nanoscale Metal Oxide
Semiconductor (MOS) materials in order to improve the performance as gas sensors [2]. The SnO2 nanopowder is an active
material that widely used for CO gas sensor because of good sensitivity[3]. SnO2-based gas sensors have several advantages
including long life expectancy, performance stability, high durability, good chemical and mechanical resistance, relative
inexpensive production cost, small in dimension, fast to operate, and easy to maintain. However there are also disadvantages,
such as if use to detect H2 gas, the operating temperature is high (350 oC) and the resistance also relatively high (100 Mega
Ohm) [4]. Currently the available CO gas sensors works in high temperature of about 300 oC [5-8]. The current development
trends to improve CO gas sensors performances are improvement of sensitivity, reduction of response time, as well as lowering
the limit of detection [9]. The working principle of SnO2 as CO gas sensor is the change in sensor electrical conductivity as a
result of reaction between oxygen and reduction of gas ions on the surface. SnO2 nanoparticles have a high surface area, hence
will have better sensitivity. The large surface area can be reached by reducing the size of the particles [10]. The extraction of
metal oxide powder by reflux process utilized polymer-solvent alcohols (polyols) which have hydroxyl group. The types of
polyol solvent including diethylene glycol (DEG) and ethylene glycol (EG). The polyol itself will act as stabilizer, limiting the

1877-7058 © 2017 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
([Link]
Peer-review under responsibility of the organizing committee of the Engineering Physics International Conference 2016
doi:10.1016/[Link].2017.03.011
Aminuddin Debataraja et al. / Procedia Engineering 170 (2017) 60 – 64 61

particle growth and agglomeration. The boiling point of the solvents that exceeds 150 oC is temperature in which some type of
metal oxides will begin forming crystals [11]. The chemical reaction that occurs in formation of SnO2 with polyol solvent is
shown in Figure 1. This experiment, synthesized SnO2 material by polyol technique to obtain nanoparticles from SnCl22H2O
precursor. The precursor was solved in EG, then refluxed at boiling point temperature (197 oC) for a certain time. Reflux process
kept the amount of the solvent constant. The result of the reflux then filtrated, and filtered residue was heat-treated [12].

Fig 1 Reaction formation of SnO2 with ethylene glycol solvent

The initial step of synthesis is dissolving the precursor (SnCl2.2H2O) into a solution (EG). Reflux process will untied Sn and Cl
atoms becoming Cl- and Sn2+ ions which tend to bind to the hydroxyl groups of EG, lead into polymerization of EG becoming
tin glycolate compound. The role of EG is not only as complexion agent to form polymer network, but also to maintain distance
between metal ions to prevent the aggregation of metal oxide particles. The next process after reflux is removal of organic
substances (the hydroxyl groups of EG), and then formation of SnO2 powder with heat treatment [13]. The interface of two
different materials is often referred as heterojunction and the structure of the two materials is heterostructure. When the two
materials are combined and connected, the Fermi energy level at the contact surface will shift, so that the level becomes equal.
This phenomenon will cause charge transfer, hence cause depletion of the joint layer [14]. The improvement of gas detection
performance of a material, can be caused by several factors such as charge carrier separation, enhancement of potential barrier,
layer depletion at the interface of the materials, chemical effect such as lower activation energy, catalyst activity, synergist
surface reaction, and geometry effects such as grain refinement [15].

2. Methods

The experiment was carried out in three stages: synthesis of nanostructured SnO2, material characterization, and CO gas
response characterization.

2.1. Equipments

The equipments used in material synthesis are: digital scales (Kern 440-21A, 0.001 gram precision), beaker, ultrasonic
cleaner (Branson 2510, 40 kHz), mini water pump (Aquila P1200, 13 watt, 600 liters/hour), erlenmeyer and condensing tube,
furnace (temperature controller Fuji PXR-9, power controller Omron G3PX -220EH), low speed centrifuge (10,000 rpm), and
microwave oven. For gas characterization system the equipments are: 2 of 6m3 gas cylinders, valve, gas hose, three way valve,
hose and bubler, and test chamber consist of: sensor holder, probe, heater plate, temperature controller (Fuji PXR-9), power
controller (Omron G3PX-220EH), gas analyzer (Bacharach PCA 3), mini air compressor (Multi Pro MC-102-MPAB, 23
liters/minute), and data logger (Picotest M3500A).

2.2. Materials

Tin (II) chloride dehydrate (SnCl2.2H2O), EMSURE, Merck; sodium hydroxide (NaOH) 3.5 M; nitric acid (HNO3) 65wt%,
Merck; ethanol PA, Merck; aqua bidestilata; technical ethanol; ethylene glycol, Merck; alumina plate; silver paste, El Coat;
carbon monoxide gas 1000 ppm with N2 for balance.

2.3. Synthesis of Tin Oxide nanostructure

0.5 mole (4,513 grams) SnCl2.2H2O was dissolved in 40 mL of EG. 5 drops of NaOH 3.5 M was added into the solution to
reached pH=3. The solution was then refluxed for 3 hours at 197 OC, until the color changed from clear to orange and contained
62 Aminuddin Debataraja et al. / Procedia Engineering 170 (2017) 60 – 64

white precipitate. After reflux, the solution was centrifuged: firstly to separate the the precipitate from the solvent, then the mix
of precipitate with ethanol and water consecutively. After that, the precipitate was dried in oven so that the residual of ethanol
and water would evaporate. Finally the heat treatment was carried out at 550 OC for 2 hours, to eliminate the organic elements
and to form SnO2 particles.

2.4. Material Deposition

The obtained SnO2 powder was mixed with EG and then deposited with doctor blade coating on alumina substrate with silver
electrode on it. The distance between the electrodes is 6 mm. The deposited material on the substrate was then heated at 200 OC
for two hours.

2.5. Material characterization

There four instruments used for characterization: X-Ray diffraction (XRD), Brunauer-Emmett-Teller (BET), Scanning
Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS). To determine the phase of the formed cystal, XRD
characterization (Philips Analytical X-Ray, Cu, λ = 1.54060 Å, 40 kV, 30 mA, 10o-90o, 0.02 step with 0.4 second per step) was
done in Metallurgical Characterization Laboratory, Faculty of Mining and Petroleum Engineering, Institut Teknologi Bandung.
BET (Quantachrome Instruments, NovaWin 11:03) calculation of nitrogen adsorption-desorption was conducted to determine
the specific surface area of the synthesized material. SEM was used to determine the morphology and the size of the formed
particles, by taking a picture of the material at a certain area and certain magnification. EDS was used to analyze the elemental
composition of the sample.

3. Results and Discussion

3.1. Synthesis and Characterization of SnO2 nanostructure.

In 3 hours reflux process, the addition of NaOH was meant to be catalyst to speed up the process, and the change of color
occured because of Cl- ion released to the solution. The reflux temperature that reached 197 °C, yielded tin glycolate formation
in precipitates. The centrifuge process of precipitate with ethanol and water was meant to clean the the undesired residual.
Calcination process caused the glycolate to evaporate leaving the tin to be oxidized resulting in SnO2 formation.

Fig 2. X-ray diffraction pattern of SnO2 sample synthesized by polyol method.

The XRD results of SnO2 sample in Figure 2, shows the diffraction pattern of SnO2 peaks at (110), (101), (200), (211), (220),
and (301) at 2θ diffraction angle 26.7o, 33.97o, 38o, 51.8o, 54.8o, 66.1o consecutively. These peaks is belong to cassiterite crystal
phase with tetragonal rutile structure (JCPDS No. 41-1445). The result of EDS shows that the synthesized sample consists of Sn,
and O elements with 24.1% and 75.9% composition respectively. The BET calculation of Nitrogen absorption-desorption
process, result in 24.528 m2/g specific surface area. Figure 3 depict the SEM result of the sample. The surface morphology of the
sample indicates that: the particle size of SnO2 is in the range of 50 nm -2 μm, and agglomeration occurs in some places.
Aminuddin Debataraja et al. / Procedia Engineering 170 (2017) 60 – 64 63

Fig 3. Morphology of SnO2

3.2. Response to CO Gas

SnO2 nanostructures on the alumina (Al2O3) substrate coated with Ag electrode was successfully tested on the exposure of the
CO gas. The dynamic response of the sensor was recorded at operating temperature of 150 oC and exposure of 30 ppm CO gas.
The dynamic response is shown in Fig 4. The response sensitivity (ratio of the difference of sensor resistance with initial
resistance before the exposure of the CO gas) reach 52.84%, with 8 minutes response time (time required to reach 90% of the
response peak), and 7 minutes recovery time (time required by to reach 90% from peak response to the original state).

Fig 4. Dynamic Response of SnO2 to 30 ppm Carbon Monoxide

4. Conclusion

From the experiment and the result, several points can be concluded as follows:
1. SnO2 composite materials have been successfully synthesized by the polyol method
2. The XRD results confirmed that the synthesized material has cassiterite crystals phase with tetragonal rutile structure,
which indeed tin oxide crystal phase
3. SEM result showed that the sythesized material is in the form of small dots and distributed on the surface in the form of
nanorods
4. The EDS confirmed that the elemental composition of synthesized material consists of Sn, and O elements with 24.1%,
and 75.9% composition respectively
5. BET calculation from the N2 adsorption-desorption result of the synthesized material informed that the specific surface
area is 24.528 m2/g
6. The gas testing result at 150 oC and 30 ppm CO: 52.84% sensitivity, 8 minutes response time, and 7 minutes recovery
time.
64 Aminuddin Debataraja et al. / Procedia Engineering 170 (2017) 60 – 64

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Common questions

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The SnO2 synthesis via the polyol method, involving the use of ethylene glycol as a stabilizer and heating at 197 °C, results in a controlled reaction and formation of nanostructures. The use of x-ray diffraction confirms the formation of cassiterite crystal phase with tetragonal rutile structure, and SEM reveals a nanorod morphology, both of which contribute to increased surface area and gas interaction. The BET analysis, indicating a specific surface area of 24.528 m2/g, further supports this outcome. These structural enhancements enable high sensitivity, exemplified by the sensor's 52.84% sensitivity to CO at 150 °C .

Several experimental findings support the suitability of SnO2 synthesized via the polyol method for CO gas sensor applications. X-ray diffraction confirms the presence of a cassiterite crystal phase with a tetragonal rutile structure, crucial for stable sensing performance. SEM shows the nanostructured morphology advantageous for high surface interactions. The evaluated specific surface area of 24.528 m2/g from BET analysis also points to the surface area enhancement critical for sensor performance. Additionally, the CO gas testing at 150 °C showed a significant sensitivity of 52.84%, with acceptable response and recovery times, underscoring the functional sensor design .

X-ray diffraction (XRD) analysis elucidates the crystal structure of the SnO2 material. The diffraction pattern reveals specific peaks corresponding to known angles and intensities, confirming the material's crystalline phase. The presence of cassiterite phase with tetragonal rutile structure, detected through peaks at specific 2θ angles, demonstrates compactness and structural stability necessary for consistent sensor behavior. These structural insights enable a prediction of the sensor’s operational reliability and efficiency due to well-ordered atomic arrangements .

SnO2 is preferred for gas sensors due to its several advantages: it has a long life expectancy, stability under operational conditions, high durability, and resistance to corrosive gases. Its production is relatively inexpensive, and the metal oxide offers a high surface area favorable for sensing applications. The nanostructured form of SnO2—characterized by a high specific surface area as demonstrated in the study (24.528 m2/g)—increases the reactive surface available for gas interactions, making it a highly sensitive sensor material .

SnO2-based CO gas sensors function by the change in electrical conductivity of SnO2 due to reactions between oxygen molecules adsorbed on the surface and the target gas molecules, specifically CO in this case. The synthesis of SnO2 by the polyol method enhances this sensor performance due to the resulting nanostructures, which provide a higher surface area, thereby increasing sensitivity. The polyol method involves refluxing SnCl2.2H2O in ethylene glycol (EG), leading to polymerization which reduces agglomeration, ultimately producing SnO2 with high surface area and nanoscale features .

Ethylene glycol (EG) plays a pivotal role in the synthesis of SnO2 by acting both as a solvent and a stabilizer to control particle growth and agglomeration. During synthesis, EG promotes the formation of small, uniformly distributed SnO2 nanoparticles. The study reports that EG prevents agglomeration and results in a nanorod morphology with particle sizes between 50 nm and 2 μm, as shown in SEM images. This morphology is crucial for maximizing the reactive surface area, which enhances the sensitivity of SnO2 in sensor applications .

The polyol-synthesized SnO2 demonstrates enhanced sensitivity to CO gas compared to current high-temperature CO sensors. Traditionally, these sensors operate at around 300 °C, whereas the polyol-synthesized SnO2 operates effectively at 150 °C, showcasing reduced energy consumption and enhanced sensitivity. The performance metrics include a sensitivity of 52.84% to CO gas at a concentration of 30 ppm, with a rapid response time of 8 minutes and a recovery time of 7 minutes. These metrics indicate significant advancements in terms of operational temperature, efficiency, and response characteristics .

The integration of SnO2 nanostructures with alumina substrates helps in optimizing the sensor's response characteristics. The deposition method using a doctor blade technique ensures a uniform layer of SnO2 on the substrate, which is equipped with silver electrodes to facilitate charge transfer. This integration allows effective interaction between the SnO2 surface and CO gas, resulting in a sensitivity of 52.84% at 150 °C with a response time of 8 minutes and recovery time of 7 minutes, highlighting the sensor's rapid response and recovery profile .

While SnO2 nanostructures offer significant advantages for CO gas detection, they present limitations for broader applications. One noted issue is their generally high operational temperature requirement for gases like H2, which is about 350 °C, making them less energy-efficient. Additionally, there could be challenges related to specificity, as the semiconductor's response isn't exclusive to CO but also interacts with other gases, potentially leading to cross-sensitivity and false readings. Addressing these limitations would require additional modifications or the incorporation of dopants to enhance selectivity and operational efficiency .

The refluxing process in the synthesis of SnO2 nanoparticles is critical as it maintains the solvent system while ensuring thorough mixing and controlled thermal conditions. At a temperature of 197 °C, refluxing promotes the dissociation of Sn2+ ions and polymerization with ethylene glycol, resulting in a well-defined tin glycolate precursor. This process prevents rapid phase transitions that could lead to agglomeration, essentially controlling particle size and morphology. By stabilizing intermediate compounds, refluxing is essential for achieving the desired nanorod structure and surface area enhancements necessary for effective CO gas sensing .

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