WO2016197181A1

WO2016197181A1 - Nox gas sensor

Info

Publication number: WO2016197181A1
Application number: PCT/AU2016/000199
Authority: WO
Inventors: Kourosh Kalantar-Zadeh; Jian Zhen OU; Nam Ha; Yongxiang Li
Original assignee: Royal Melbourne Institute of Technology Ltd
Current assignee: Royal Melbourne Institute of Technology
Priority date: 2015-06-12
Filing date: 2016-06-10
Publication date: 2016-12-15
Anticipated expiration: 2017-12-12
Also published as: US20180299395A1; EP3307673A1; EP3307673A4; CN107709228A; JP2018517142A; CA2989191A1; AU2016275551A1; BR112017026554A2

Abstract

This invention provides a highly-selective and sensitive Nitrogen oxide gas sensor based on the resistive transducing platforms using two-dimensional (2D) tin disulphide (SnS₂) flakes that can operate below 150 °C. This sensor operates based on the physisorption of nitrogen oxide on the surface of the sensitive layer. The fabrication of the sensors is low-cost. The tin disulphide is preferably produced by reacting tin dichloride at elevated temperature with powdered sulphur in a liquid phase to form tin disulphide nano particles and separating the tin disulphide nano particles from the liquid phase.

Description

NOx GAS SENSOR

This invention relates to gas sensors for detecting nitrogen oxides.

Background to the invention

Nitrogen dioxide (NO2) is an industrially and biologically important gas that is mostly released during the combustion of fossil fuels. This gas can be particularly dangerous and at levels greater than 1 ppm, causing damage to the human respiration system and worsening respiratory diseases. NO2 is also a recognized air pollutant. It plays an important role in the chemistry of the atmosphere, contributing to the formation of ozone (O3), which is the major cause of photochemical smog and acid rain.

NO2 is an important material for the synthesis of nitric acid that is used in the production of fertilisers and explosives for both military and mining uses.

Furthermore, NO2 is an essential gas for many biosystems, as nitrogen monoxide (NO) appears as a gasotransmitter in many cell signalling paths can convert to NO2 rapidly in the presence of environmental perturbance. As such, the sensing of nitrogen oxides (NOx, a group mainly consists of NO2 and NO) can be potentially implemented as a diagnostic process. For instance, the detection of NOx in exhaled breath (at the ppb level) is helpful for identifying infections of lung tissus. In addition, the NOx can possibly be used as a biomarker for some of the gastrointestinal disorder symptoms such as irritable bowel disease (IBD).

The current NO2 gas sensor technologies can be categorized into

chemiluminescent, electrochemical, resistive, and optical detection.

The patents of US4236895 and W01999053297 reported chemiluminescent sensors for NO2 detection. In brief, the sensing mechanism relies on the reaction of NO with O3 to produce an excited form of NO2. As the excited molecule returns to its ground state, fluorescent radiation is emitted. The intensity of the light is

proportional to the concentration of NO. These sensors are bulky and need gas converters that can be used to convert NO2 catalytically to NO, making them expensive and relatively cumbersome for many applications.

The patents of US5906718 and EP1688736 reported NO2 sensors that are based on the use of electrochemical cells. The operation principle relies on the

electrochemical reduction of NO2 between two electrodes immersed in a liquid electrolyte reservoir. NO2 passes through a capillary diffusion barrier into the reaction cell, where it is reduced at the working electrode. The migrating electrons produced by the reaction result in a net current flow, which is proportional to the NO2 concentration. However, these sensors are poorly selective and have cross-talk to other possibly co-existing gases (e.g. H2 gas in the automotive industry and clinical diagnostics). In addition, the operation lifetime of the sensors are very short (3-6 months), which potentially increases the maintenance cost of sensing system. The poor gas selectivity and short lifetime issues can be improved by using zirconia- based solid electrolytes (US6413397 and US6843900). These sensors can also operate in the oxygen-free environment. However, their operation temperatures are usually very high (in the range of 500-900 °C), which results in high operation costs. It is generally energy inefficient, limiting their applications to combustion and automotive monitoring systems.

Non-dispersive infrared sensing of NO2 is another highly selective gas sensing method (US6469303), which relies on the unique infrared light absorption fingerprint of NO2 gas molecules. Nevertheless, it needs a long enough interaction pathway between the gas molecules and infrared light beam otherwise its sensitivity will be greatly degraded. This makes them bulky and expensive. As smaller sizes, the general detection limit of these sensors is within the ppth range (part per thousand), which is not suitable for most of the applications.

Another common NO2 sensors are the chemiresistor type based on semiconducting metal oxides (US7704214 and US8758261), such as tin oxide (Sn02), tungsten oxide (WO3) and zinc oxide (ZnO). In these sensors, the gas diffuses into the oxide and modulates the grain boundary resistances by transferring charge carriers from the semiconductor to the adsorbed species. However, the surface affinity of these metal oxide materials is also high to gas species other than NO2, making these sensors poorly selective. Furthermore, the presence of oxygen is crucial during the operation, which will not be suitable for some particular applications with the need of oxygen-free environment such as the gastrointestinal tracts and fermentation chambers. Finally in order to improve the response and recover kinetics of the sensors, the operation temperatures are usually high (> 200 °C). The recent replacement with carbon nanotube (CNT) and graphene (US20140103330,

US8178157 and CN104181209) can significantly reduce the consumption of energy and oxygen. Nevertheless, the issue of poor gas selectivity has yet been addressed. Additionally, CNT and graphene based devices are generally not reversible sensors without extensive surface functionalization.

It is an object of this invention to provide a nitrogen sensor that can operate at lower temperatures.

It is another object of this invention to provide a gas sensor that shows selectivity for nitrogen oxides.

Brief description of the invention

To this end this invention provides a nano structured tin disulphide nitrogen oxide gas sensor.

This nanostructured gas sensor demonstrates selectivity for NOx and can operate at temperatures below 150 °C. The sensor operation is based on the physisorption of nitrogen oxide on the surface of the sensitive layer.

There is no selective NO2 gas sensors available in the market or reported in literature that are highly sensitive and can operate reliably at relatively low

temperatures regardless of the presence of ambient oxygen. This invention provides a highly-selective and sensitive NO2 gas sensor based on the resistive transducing platforms using two-dimensional (2D) tin disulphide (SnS2) flakes that can operate below 150 °C. The fabrication of the sensors is low-cost.

The tin disulphide is preferably produced by reacting tin dichloride at elevated temperature with powdered sulphur in a liquid phase to form tin disulphide nano particles and separating the tin disulphide nano particles from the liquid phase. Detailed description of the invention

A preferred embodiment of the invention will be described in which

Figure 1 is schematic representation of the sensor of this invention;

Figure 2 illustrates the gas sensing response of 2D SnS2 flakes. To synthesize nanostructured SnS2 flakes, many methods can be used. Methods that make large surface to volume ratio are the most suitable for making gas sensors and generally two dimensional materials (2D) fall into this category. A 2D structure is atomically thin and the lateral dimension is much larger than this thickness. An example for the synthesis of 2D SnS2 is presented here. Tin chloride (SnCl4*5H20, 0.5 mM) can be added to a mixture of oleic acid (OAc-5 ml_) and octadecene (ODE-10 ml_) in a 100 ml_ three-neck flask to produce tin precursor. A standard Schlenk line can be used to protect the reaction from oxygen and moisture under a flow of high-purity N2. The mixed solution can be degassed at > 100 °C for a while to remove moisture and oxygen. Subsequently, the solution is stirred at elevated temperature. Then, sulphide powder can be injected into the reaction system. After cooling the solution to room temperature, the SnS2 flakes can be collected and separated from the solution by centrifugation.

The gas sensor is shown in figure 1.

The 2D SnS2 gas sensors are fabricated by drop-casting the solution containing 2D SnS2 flakes on the resistive transducing substrates (Figure 1). The substrates are made of alumina with surface input interdigitated transducer (IDT) patterns. The resistance of the device is measured using a multimeter and the gas response factor is calculated using R_g/R_a for R_g > R_a, or R_a/R_g for R_g < R_a, where R_a and R_g represent the resistances of the device to air and the analyte gas, respectively. We tested the operation temperature of sensors from that of room to 160 °C. For the temperatures lower than 80 °C, the device does not show acceptable

recovery/recovery time and additionally R_g is very large, while there is an

observable transition from SnS2 to sub-stoichiometric tin oxides (SnO_x) when the operation temperature exceeds 180 °C.

Figure 2 shows the gas sensing response of the sensor of this invention. The response factor and response time of sensors made of 2D SnS2 flakes in the presence of 10 ppm NO2 in synthetic air balance as a function of operation temperature; b. The dynamic sensing performance of 2D SnS2 flakes toward NO2 gas with the concentrations ranged from 0.6 to 10 ppm at the operation temperature of 120 °C; c. The cross-talk of 2D SnS₂ flakes towards H₂ (1%), CH₄ ( 0%), CO2 (10%), H2S (56 ppm) and NO2 (10 ppm); d. The calculated molecule-surface adsorption energies of 2D SnS2 flakes towards the aforementioned gases together with NH3. Table 1. The gas sensing performance of 2D SnS2 flakes toward 10 ppm N0₂ at different temperatures

Operation temperature (°C) Response factor Response time (s) Recovery time (s)

80 27.2 243 723

100 28.7 220 358

120 36.3 172 138

140 20.7 180 115

160 8.2 187 98

From Fig. 2a and Table 1 , the initial response factor of the sensor at 80 °C after the exposure of 10 ppm NO2 in synthetic air balance is found to be ~28, indicating the resistance of the device after NO2 gas exposure is approximately 28 times larger than that in the presence of synthetic air. In this case, the surface adsorbed NO2 gas molecule acts as an electron acceptor and accepts electrons from 2D SnS2 flakes. Such a charge reduces the number of free electrons in the flake, thus increasing its resistance. The response factor is enhanced as well as the response and recovery time are decreased with the increase of operation temperature for up to 120 °C, suggesting that the increase of operation temperature facilitates the adsorption of NO2 gas molecules onto the 2D SnS2 surface. However when further increasing the operation temperature beyond 120 °C, the response factor is dramatically dropped and the response time is slightly increased, implying that the surface desorption process of NO2 gas becomes comparable to its adsorption process at such elevated temperatures. The dynamic performance of the sensor towards NO2 gas with concentrations ranged from 0.6 to 10 ppm at the optimum operation temperature of 120 °C is also investigated and shown in Fig. 2b. With the increase in the concentration of NO2, more charges are transferred from SnS2 to NO2. The charges are transferred to different NO2 molecules as the concentration increases. The measured response factor of the sensor is observed to be almost linear with the exposure concentrations of NO2 gas, while the response and recovery time are gradually decreased and eventually reach the saturation stage when the NO2 concentration exceeds 2.5 ppm (Table 2). Table 2. The gas sensing performance of 2D SnS₂ flakes toward different concentrations of NO2.

NO2 concentration (ppra) Response factor Response time (s) Recovery time (s)

0.6 6.7 317 465

1.2 10.8 182 181

2.5 15.1 162 144

5 22.1 169 145

7.5 30.0 170 139

10 36.3 172 138

The NO2 gas sensing performance of SnS2 flakes is highly selective as only minimal responses toward other gases, including H2 (1%), CHU (10%), CO2 (10%) and H₂S (56 ppm), are observed compared to that of NO2 (Fig. 2c).

To understand such a unique response of 2D SnS2 flakes toward NO2 gas, we calculated the molecule-surface binding energies using density function theory to calculate the dispersion forces, which are shown in Fig. 2d and Table 3.

Table 3. The calculated molecule-surface adsorption energies of 2D SnS2 flakes towards H2, CH4, CO2, H2S, NH3, NO2 and O2.

Molecule Binding energy (eV)

C0₂ -0.191

H₂ -0.053

H₂S -0.199

NH₃ -0.215

N0₂ -0.367

0₂ 1.430

The closest distance between the molecules and the surface, for the bound species, ranged from 2.17 to 2.87 A which is within the typical range for physisorped molecules. The values of the binding energies also indicate the physisorption has occurred between the molecule and the surface for CH4, CO2, H2S, NH3 and NO2, with NO2 being the most strongly bound species. The binding energy for NO2 is approximately 140 meV greater than for the next most bound species (NH3), while H2 and O2 are non-binding due to its relatively small adsorption energy (~50 meV) and positive adsorption energy (Table 3), respectively. The calculated surface binding energies toward different gas molecules are in accordance with the measurement results, confirming that the impressive NO2 gas response of 2D SnS2 flakes is originated from its unique physical surface affinity to the gas molecules. Figure 2 shows the gas sensing response of the sensor of this invention. The response factor and response time of sensors made of 2D SnS2 flakes in the presence of 10 ppm NO2 in synthetic air balance as a function of operation temperature; b. The dynamic sensing performance of 2D SnS2 flakes toward NO2 gas with the concentrations ranged from 0.6 to 10 ppm at the operation temperature of 120 °C; c. The cross-talk of 2D SnS2 flakes towards H₂ (1%), CH₄ (10%), CO2 (10%), H2S (56 ppm) and NO2 (10 ppm); d. The calculated molecule-surface adsorption energies of 2D SnS2 flakes towards the aforementioned gases together with NH3.

From the above it can be seen that this invention provides a gas sensor with good selectivity for nitrogen oxide gases and which is able to operate at low

temperatures.

Those skilled in the art will appreciate that this invention can be implemented in embodiments other than those described without departing from the core teachings of this invention.

Claims

1. A nitrogen oxide gas sensor which includes nano structured tin disulphide.

2. A gas sensor as claimed in claim 1 which consists of a transducing platform incorporating two-dimensional (2D) tin disulphide (SnS2) flakes.

3. A gas sensor as claimed in claim 2 in which the transducing platform consists of resistive transducing substrates made of alumina with surface input interdigitated transducer (IDT) patterns.

4. A gas sensor as claimed in claim 1 in which the tin disulphide nano particles are produced by reacting tin dichloride at elevated temperature with powdered sulphur in a liquid phase to form tin disulphide nano particles and separating the tin disulphide nano particles from the liquid phase.