In this paper, a nitrogen dioxide (NO 2 ) gas sensor using nitrogen-doped double-walled carbon nanotubes (N-DWCNTs) with different types of nitrogen is demonstrated, and the sensor performance to the pyridinic nitrogen is related. The ratio of nitrogen is controlled by the temperature applied for the synthesis. It is found that the fabricated sensor from N-DWCNTs enable an approximately threefold improvement in NO 2 detection compared to the sensor from DWCNTs. Also, the improvement of sensor response of N-DWCNTs more depends on the pyridinic site than the other types of nitrogen, because it can strongly interact with the NO 2 molecule. The sensing mechanism is attributed to the charge transfer between the NO 2 molecule and the sensing materials (especially with pyridinic site), which shifts the Fermi level, resulting in a decrease of the electrical resistance. Furthermore, the relation between the sensor response and the concentration of NO 2 is derived based on Langmuir adsorption isotherm, and the calculated detection limit can be down to 0.14 ppm, which suggests that the N-DWCNTs-based sensor is a promising approach for low concentration NO 2 detection at room temperature.
A hybrid sensor based on the integration of functionalized multiwalled carbon nanotubes (MWCNTs) with ethyl cellulose (EC) was fabricated for sensitivity enhancement of benzene detection. To functionalize the surface of MWCNTs, MWCNTs were treated with hydrochloric acid for 60 min (A60-MWCNTs), while other MWCNTs were treated with oxygen plasma for 30, 60, 90, and 120 min (P30-MWCNTs, P60-MWCNTs, P90-MWCNTs, and P120-MWCNTs, resp.). Pristine MWCNTs, A-MWCNTs, and P-MWCNTs were dispersed in 1,2-dichloroethane, then dropped onto a printed circuit board consisting of Cu/Au electrodes used as the sensor platform. Next, EC was separately spin coated on the pristine MWCNTs, A-MWCNTs, and P-MWCNTs (EC/MWCNTs, EC/A-MWCNTs, and EC/P-MWCNTs, resp.). All sensors responded to benzene vapor at room temperature by increasing their electrical resistance which was sensitive to benzene vapor. The EC/P90-MWCNTs enabled an approximately 11-fold improvement in benzene detection compared to EC/MWCNTs. The sensitivity of all sensors would be attributed to the swelling of EC, resulting in the loosening of the MWCNT network after benzene vapor exposure. The differences of the sensing responses of the EC/MWCNTs, EC/A-MWCNTs, and EC/P-MWCNTs would be ascribed to the differences in crystallinity and functionalization of MWCNT sidewalls, suggesting that acid and oxygen plasma treatments of MWCNTs would be promising techniques for the improvement of benzene detection.
Effect of acid and heat treatments of multi-walled carbon nanotubes (MWCNTs) on benzene detection was investigated. For acid treatment, MWCNTs were treated by hydrochloric acid (HCl) for 1 h meanwhile other batches of MWCNTs were treated by heating under air ambient at 500°C for 1 h. Pristine, HCl-treated and heat-treated MWCNTs were separately coated with ethyl cellulose (EC) by spin-coating prior to fabrication of three different sensors named as EC/pristine MWCNTs, EC/HCl-MWCNTs and EC/heat-MWCNTs sensors, respectively. Each fabricated sensor was exposed to benzene vapor at room temperature for testing its sensing performance based on an increase in its electrical resistance which was sensitive to benzene vapor. Response of the sensors fabricated from EC/HCl-MWCNTs and EC/heat-MWCNTs were 3.66 and 1.92 times higher than that of EC/pristine MWCNTs, respectively. Sensitivity of all sensors would be attributed to swelling of EC, resulting in loosening of MWCNT network after benzene vapor exposure. In addition, the difference of sensing response of the EC/pristine MWCNTs when compared with those of EC/HCl-MWCNTs and EC/heat-MWCNTs would be ascribed to different crystallinity and functionalization of MWCNTs sidewalls, suggesting that acid and heat treatments of MWCNTs would be promising techniques for improvement of benzene detection.
A highly sensitive and selective formaldehyde sensor was successfully fabricated using hybrid materials of nitrogen-doped double-walled carbon nanotubes (N-DWCNTs) and polyvinylpyrrolidone (PVP). Double-walled carbon nanotubes (DWCNTs) and N-DWCNTs were produced by high-vacuum chemical vapor deposition using ethanol and benzylamine, respectively. Purified DWCNTs and N-DWCNTs were dropped separately onto the sensing substrate. PVP was then dropped onto pre-dropped DWCNT and N-DWCNTs (hereafter referred to as PVP/DWCNTs and PVP/N-DWCNTs, respectively). As-fabricated sensors were used to find 1,2-dichloroethane, dichloromethane, formaldehyde and toluene vapors in parts per million (ppm) at room temperature for detection measurement. The sensor response of N-DWCNTs, PVP/DWCNTs and PVP/N-DWCNTs sensors show a high response to formaldehyde but a low response to 1,2-dichloroethane, dichloromethane and toluene. Remarkably, PVP/N-DWCNTs sensors respond sensitively and selectively towards formaldehyde vapor, which is 15 times higher than when using DWCNTs sensors. This improvement could be attributed to the synergistic effect of the polymer swelling and nitrogen-sites in the N-DWCNTs. The limit of detection (LOD) of PVP/N-DWCNTs was 15 ppm, which is 34-fold higher than when using DWCNTs with a LOD of 506 ppm. This study demonstrated the high sensitivity and selectivity for formaldehyde-sensing applications of high-performance PVP/N-DWCNTs hybrid materials.
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