Application of CNTs Gas Sensor in Online Monitoring of SF6 Insulated Equipment

The detection and analysis of SF6 decomposition components are of great significance in online condition assessment and fault diagnosis of GIS. Considering the shortcomings of general detection methods, carbon nanotubes (CNTs) gas sensor was studied to detect the SF6 decomposition components because of its advantages in large surface activity and abundant pore structure, et al. The large surface area has a strong adsorption and desorption capacity. In this chapter, SF6 decomposed gases, namely SO2F2, SOF2, SO2, H2S and CF4 are chosen as probe gases because they are the main by-products in the decomposition of SF6 under partial density (PD). First, the properties and preparation methods of CNTs are introduced to verify the advantages of CNTs for SF6 decomposition components detection. Then, both theoretical calculation and sensing experiment were adopted to study the microadsorption mechanism and macrogas-sensing properties. Based on the intrinsic CNTs, study for SF6 decomposition components adsorption, Pd, Ni, Al, Pt and Au metal doping CNTs and plasma-modified CNTs are discussed in order to enhance the gas sensing and selectivity of CNTs

Nanocomposites of Carbon Nanotube (CNTs)/CuO with High Sensitivity to Organic Volatiles at Room Temperature

AbstractIn order to enhance the sensitivity of carbon nanotube based chemical sensors at room temperature operation, CNTs/CuO nanocomposite was prepared under hydrothermal reaction condition. The resulted-product was characterized with TEM (transmission electron microscopy), XRD (X-ray diffraction) and so on. A chemical prototype sensor was constructed based on CNTs/CuO nanocomposite and an interdigital electrode on flexible polymer substrate. The gas-sensing behavior of the sensor to some typical organic volatiles was investigated at room temperature operation. The results indicated that the carbon nanotube was dispersed well in CuO matrix, the CuO was uniformly coated on the surface of carbon nanotube, and the tubular structure of carbon nanotube was clearly observed. From morphology of TEM images, it can also be observed that a good interfacial adhesion between CNT and CuO matrix was formed, which maybe due to the results of strong interaction between CNTs with carboxyl groups and CuO containing some hydroxy groups. The CNTs/CuO nanocomposite showed dramatically enhanced sensitivity to some typical organic volatiles. This study would provide a simple, low-cost and general approach to functionalize the carbon nanotube. It is also in favor of developing chemical sensors with high sensitivity or catalysts with high activity to organic volatiles at low temperature

The Development of Polymer-coated Electrodes for Chemical Detection

This research focuses on the development of simple and cost effective approaches for making electrochemical sensors with a great sensitivity and selectivity. As an economic and abundant starting material, organic substrates were investigated to making conductive polymers that showed promising electrocatalytic activities. Firstly, a poly(4-bromoaniline) film was successfully synthesized on a gold electrode and the porous film which was made up of nano-ribbons on the Au electrode was used for the recognition of amino acids enantiomers. Secondly, different halogen ions were introduced to manifest the properties of the synthesized polymers. The results show that bromide ions have significantly inhibited the transition of leucoemeraldine to emeraldine, letting the PANI polymer to be in Pernigraniline form, which exhibited much improved performance in pH sensing. In addition, a simple way to controllably deposit copper nanoparticles inside poly-2,5-dimethoxyaniline matrix, which can be employed as a glucose sensor, was developed

Design, fabrication and characterisation of gas sensors based on nanohybrid materials

Hoy en día, la necesidad de monitorizar y controlar el medio ambiente es a cada vezmás importante debido al creciente nivel de gases tóxicos que provienen de la expansiónde las actividades industriales, amenazando así el medio ambiente y la salud humana. Eldesarrollo de la nano-tecnología ha permitido fabricar sensores de gases portables,altamente sensibles, selectivos, de bajo coste y de bajo consumo de potencia.Los nanotubos de carbono (NTC) están ganando un interés a cada vez más considerablepor parte de la comunidad científica debido a su geometría y morfología únicas y susexcelentes propiedades electrónicas, mecánicas, térmicas i ópticas. Esto hace de ellosunos candidatos prometedores para un amplio rango de aplicaciones como por ejemplonuevos sensores de gases con propiedades mejoradas. En este contexto, mediante lapresente tesis, se ha realizado un profundo estudio para explorar las propiedades dediferentes sensores basados en nano-materiales híbridos constituidos por nanotubos decarbono junto a otros materiales con el fin de detectar gases tóxicos de manera eficiente.El trabajo realizado consistió en el diseño, la fabricación, la caracterización, y laoptimización de nanosensores híbridos.Esta tesis fue financiada en el marco del proyecto Europeo "Nano2hybrids", cuyoobjetivo era de diseñar la interfaz de las nano-partículas del metal con los nanotubos decarbono a través del control de los defectos estructurales y químicos producidos por ladescarga de un plasma de radiofrecuencia y aplicarlo a la detección de gases. Elbenceno fue elegido como gas principal, debido a sus graves efectos tóxicos a niveles depocas ppb y también debido a la no existencia en el mercado de un detector de bajocoste para benceno. De hecho, no hay en el estado de la técnica, un sensor de gas quepuede detectar de forma selectiva este gas a nivel operativo de ppb y trabajando atemperatura ambiente. Así, el reto de esta tesis era obtener un sensor altamente sensible,selectivo y estable, portátil y de bajo coste para la detección de benceno.En este sentido, se estudiaron exhaustivamente diferentes materiales basados ennanotubos de carbono funcionalizados, decorados con nanopartículas de metal o biendecorados o mezclados con óxidos metálicos, en términos de su adecuación para ladetección de gases (por ejemplo, sus sensibilidad, selectividad, estabilidad, y elmecanismo de detección, etc.). En particular se estudió la detección de diferentes gasescomo (benceno (C6H6 ), monóxido de carbono (CO), dióxido de nitrógeno (NO2), eletileno (C2H4), el sulfuro de hidrógeno (H2S), amoníaco (NH3) y agua (H2O)). Nuestrastareas consistieron en investigar experimentalmente y teóricamente el efecto de lascondiciones de preparación de los materiales (p.e. el tratamiento con plasma, lanaturaleza del precursor y tamaño de las nanoparticulas de metales), fabricación delsensor (p.e., técnica de deposición, el efecto del tipo de metal del los electrodos delsensor), y de las condiciones de caracterización del sensor (p.e., temperatura deoperación, flujo de gas,) sobre las propiedades sensoras de los mismos. Todo ello hapermitido adquirir conocimientos, explicar los mecanismos de funcionamiento en elsensado de gases de los diferentes materiales investigados y con ello desarrollar unsensor de gases adecuado para la detección de benceno.Hemos encontrado que los materiales híbridos que consisten en nanotubos tratados conplasma de oxígeno y decorados con diferentes nanopartículas de metal, muestran unamayor capacitad de detección a temperatura ambiente respecto a los nanotubos decarbono en bruto o los funcionalizados sólo con plasma. Las propiedades interfacialesde los materiales híbridos resultantes pueden ser adaptadas, lo que ofrece una enormeflexibilidad para el ajuste de sus propiedades sensoras. Cuando se combinaron en unamatriz de micro-sensores que opera a temperatura ambiente, nanotubos decorados condiferentes metales, de forma que unos resulten sensibles al benceno y otros insensibles,esto permitió por primera vez la realización de un prototipo de bajo coste capaz dedetectar selectivamente y a temperatura ambiente el benceno presente a nivel de trazas(por debajo de 50 ppbs) en una mezcla de gases. El prototipo realizado presenta unostiempos de respuesta y de recuperación de 60 s y 10 minutos respectivamente además deuna buena estabilidad y reproducibilidad. Este prototipo se encuentra protegido por unapatente que ha sido licenciada a una compañía que se encargará de la comercializaciónindustrial del producto.In the last few years, there has been a growing demand for monitoring the environment,especially with the increasing concern by the release of toxic gases emitted by manmadeactivities. The development of nanotechnology has created a huge potential for buildinghighly sensitive, selective, low cost, and portable gas sensors with low powerconsumption.Nowadays, carbon nanotubes are receiving an intense interest from the scientificcommunity, due to their unique geometry, morphology, electronic, mechanical, thermaland optical properties, which make them a promising candidate for many industrialapplications including new gas sensors for the detection of toxic species. In this context,in this thesis a deep study is devoted to explore the sensing properties of differenthybrid nanomaterials based on carbon nanotubes for an efficient detection of toxicgases. The design, fabrication, characterization, and optimization of gas sensors usinghybrid materials have been carried out.This thesis was financially supported by the European project "Nano2hybrids", whichexploits the interface design of metal nanocluster-carbon nanotube hybrids via controlof structural and chemical defects in a plasma discharge, for designing gas sensors withsuperior performance. Benzene was chosen as the principal target gas due to its serioustoxic effects at low ppb levels and the fact that there are no reliable, low cost andselective benzene detectors in the market. In fact, no gas sensor able to selectivelydetect this gas at ppb levels and operating at ambient temperature has been reported upto now in the literature. So, the challenge of the project was to fabricate sensitive,highly selective, stable, portable, and low cost benzene gas sensor employing hybridnanomaterials.Herein, functionalized MWCNTs, metal decorated MWCNTs, and metal oxidedecorated MWCNTs or metal oxide and MWCNT mixtures were deeply investigated interms of their gas sensing performances (e.g, sensitivity, selectivity, stability, detectionmechanism,. etc) towards the detection of different gases (benzene (C6H6), carbonmonoxide (CO), nitrogen dioxide (NO2), ethylene (C2H4), hydrogen sulfide (H2S),ammonia (NH3), and water (H2O)). Our tasks were to investigate experimentally andtheoretically the effects of material preparation conditions (e.g., plasma treatment,nanocluster precursor and size), sensor fabrication (e.g., deposition technique,electrodes sensor metal), and sensor characterization conditions (e.g., operatingtemperature, gas flow) on the gas sensing properties of our devices, and to acquireknowledge in order to develop a selective benzene detector. Based on experimental andtheoretical results, different mechanisms for the interaction between gases and thehybrid materials tested have been proposed.We found that hybrid materials consisting of oxygen plasma treated multiwalled carbonnanotubes decorated with different metal nanoparticles showed room temperaturesensing capability. Responsiveness to gases of these hybrid materials was higher thanthat of pristine or plasma functionalized carbon nanotubes. Metal decoated CNTs can betailored for the recognition of different gases and vapors with different reactivities,which offers enormous flexibility for tuning the interfacial properties of the resultinghybrid materials and thus, of their sensing properties. When combined in a microsensorarray operating at room temperature, the use of benzene-sensitive and benzeneinsensitivemetal-decorated multiwalled carbon nanotubes, allowed for the first time theimplementation of a low cost detector prototype, which can selectively detect benzenewhen present at trace levels (below 50 ppb) in a gas mixture. Sensors present responseand recovery times of 60 s and 10 min respectively, good stability and reproducibility.This type of sensors are protected by a patent, and licensed to a company for industrialcommercialization

Zinc oxide nanostructures with carbon nanotube and gold additives for co gas sensing application

Abstract: Zinc oxide (ZnO) nanostructures were synthesised for gas sensing application. In an attempt to improve the surface area and the electrical conductivity of the ZnO, nanomaterials such as the carbon nanotubes (CNTs) and gold nanoparticles (AuNPs) were used separately to produce CNTs/ZnO and Au/ZnO nanocomposites, respectively. The addition of these nanomaterials onto the ZnO nanostructures significantly improved the gas sensing properties such as the sensitivity and response time. Synthesis of gold nanoparticles was successfully achieved via gold salt (HAuCl4.3H2O) reduction using the Turkevich method. Citrate molecules were used as the stabiliser and to systematically control the sizes of the AuNPs. The sizes of AuNPs were found to increase from 14 nm to 40 nm when the concentration of citrate ions was reduced from 1 mM to 0.3 mM. The size distribution of AuNPs was relatively wider as the particle size increased. The synthesized AuNPs were stable for over a period of 4 weeks. Carbon nanotubes synthesis was achieved using chemical vapour deposition (CVD) method using acetylene gas as the carbon source and ferrocene as the catalyst. An increase in the flowrate of the precursor gas (acetylene) yielded an increase in amorphous carbon, which was attached to the walls of the carbon nanotubes. The optimum flowrate of acetylene was found to be 150 m3/min that yielded CNTs with an average diameter of 95 nm and a relatively narrow size distribution. The hydrothermal chemical precipitation method was used to synthesise ZnO nanostructures. Zinc sulphate (ZnSO4) and sodium hydroxide (NaOH) were used as a metal precursor and reducing agent, respectively. The NaOH concentration of 0.3 M yielded ZnO nanosheets with relatively the highest surface area of 102 m2/g. Gas sensing analysis was conducted using carbon monoxide (CO) gas at 250°C. The sensitivity and response time were calculated to be 9.8% and 114 seconds, respectively, at a CO concentration of 200 ppm. The composites CNTs/ZnO and Au/ZnO were prepared, separately. The average surface area of the Au/ZnO composite was 131 m2/g and that of CNTs/ZnO composite was 153 m2/g. The CNTs/ZnO composite showed an optimum sensitivity of 9.9% and the response time of 49 seconds when exposed to 200 ppm of CO gas at 250°C.M.Tech. (Chemical Engineering

An experimental study of the measurement of low concentration hydrogen sulfide in an aqueous solution

Endogenously generated H2S has been found not just a toxic substance but may play positive roles, such as the neuromodulator and vasorelaxant in the physiological system since 1990s. Then the precise control of the amount of Hydrogen Sulfide in the animal body raises great interests recently. However, the traditional methods for the Hydrogen Sulfide measurement need a large amount of tissue samples and take a complex procedure; it is impossible to develop any in-vivo real-time approach to measure H2S along the avenue of these methods. There is a great significance to develop new methods toward the measurement of Hydrogen Sulfide in in-vivo, real time, non- or less invasive manner with high resolution. One general idea to make the measurement less invasive is to take blood as sample – i.e., to measure Hydrogen Sulfide in blood. The study presented in this thesis aimed to conceive of new measurement methods for Hydrogen Sulfide in an aqueous solution along with their experimental verification. Though the blood sample will eventually be taken, the present study focused on an aqueous solution, which is a first step towards the final goal to measure Hydrogen Sulfide in blood. The study conducted a thorough literature review, resulting in the proposal of five methods, including: (i) the Hydrogen Sulfide measurement by Atomic Force Microscopy, (ii) the H2S measurement by Raman spectroscopy directly, (iii) the Hydrogen Sulfide measurement by Gas Chromatography/Mass Spectroscopy directly (with the static headspace technique), (iv) the Hydrogen Sulfide measurement by Mass Spectroscopy with Carbon Nanotubes, and (v) the Hydrogen Sulfide measurement by Raman spectroscopy with Carbon Nanotubes. The experiments for each of these methods were carried out, and the results were analyzed. Consequently, this study shows that method (v) is very promising to measure low concentration Hydrogen Sulfide in an aqueous solution, especially with the concentration level down to 10 μM and the presence of a linear relationship between the Hydrogen Sulfide concentration and its luminescent intensity

Wearable Nano-Based Gas Sensors for Environmental Monitoring and Encountered Challenges in Optimization

With a rising emphasis on public safety and quality of life, there is an urgent need to ensure optimal air quality, both indoors and outdoors. Detecting toxic gaseous compounds plays a pivotal role in shaping our sustainable future. This review aims to elucidate the advancements in smart wearable (nano)sensors for monitoring harmful gaseous pollutants, such as ammonia (NH3), nitric oxide (NO), nitrous oxide (N2O), nitrogen dioxide (NO2), carbon monoxide (CO), carbon dioxide (CO2), hydrogen sulfide (H2S), sulfur dioxide (SO2), ozone (O3), hydrocarbons (CxHy), and hydrogen fluoride (HF). Differentiating this review from its predecessors, we shed light on the challenges faced in enhancing sensor performance and offer a deep dive into the evolution of sensing materials, wearable substrates, electrodes, and types of sensors. Noteworthy materials for robust detection systems encompass 2D nanostructures, carbon nanomaterials, conducting polymers, nanohybrids, and metal oxide semiconductors. A dedicated section dissects the significance of circuit integration, miniaturization, real-time sensing, repeatability, reusability, power efficiency, gas-sensitive material deposition, selectivity, sensitivity, stability, and response/recovery time, pinpointing gaps in the current knowledge and offering avenues for further research. To conclude, we provide insights and suggestions for the prospective trajectory of smart wearable nanosensors in addressing the extant challenges

Gas Sensors Based on Electrospun Nanofibers

Nanofibers fabricated via electrospinning have specific surface approximately one to two orders of the magnitude larger than flat films, making them excellent candidates for potential applications in sensors. This review is an attempt to give an overview on gas sensors using electrospun nanofibers comprising polyelectrolytes, conducting polymer composites, and semiconductors based on various sensing techniques such as acoustic wave, resistive, photoelectric, and optical techniques. The results of sensing experiments indicate that the nanofiber-based sensors showed much higher sensitivity and quicker responses to target gases, compared with sensors based on flat films

APPLICATION OF SINGLE WALLED CARBON NANOTUBES IN ENVIRONMENTAL ENGINEERING: ADSORPTION AND DESORPTION OF ENVIRONMENTALLY RELEVANT SPECIES STUDIED BY INFRARED SPECTROSCOPY AND TEMPERATURE PROGRAMMED DESORPTION

This study evaluated the environmental applications of carbon nanotubes through the adsorption and desorption of representative environmentally relevant adsorbates; ammonia, hydrogen sulfide and acetone under ultra high vacuum (UHV) and high pressure conditions. The results showed that functionalities/defects sites on nanotube surfaces play an important role on the interaction between molecules and carbon nanotubes. The oxygen containing functional groups on single-walled carbon nanotubes (SWNTs) are studied by Fourier Transform Infrared (FTIR) spectroscopy under vacuum. Vacuum heating to ~ 1300 K removes most of the functionalities in the samples. The similarities in the infrared spectra of the Rice Tubes after a 1400 K treatment with spectra for HiPco nanotubes suggest the observation of intrinsic SWNT IR bands.Ammonia adsorption on single walled carbon nanotubes (SWNTs) was studied in order to investigate the environmental application of nanotubes, mainly possible uses as sensors. At 94 K, vacuum annealed SWNTs showed no detectable ammonia uptake. However, the ammonia adsorption was found to be sensitive to the functionalities and defects on the nanotube surfaces. NH3 desorbed from those nanotubes above 140 K, indicating a weak adsorbate-nanotube interaction (~30 kJ/mol). This work suggests the influence of functionalities and/or defect densities on the sensitivity of SWNT chemical gas sensors. Both physisorption and chemisorption of acetone on nanotubes were observed. It was found that H2S adsorbed on nanotube surfaces at cryogenic temperature but not at room temperature. The low desorption temperature suggests only physisorption of H2S on nanotubes.In this study, low concentration of functionalities on carbon material surfaces was detected by fluorescent labeling technique. Florescent labeling indicated the presence of COOH and CHO groups on the ACF 25 fiber surface. Neither the infrared spectrum nor the X-ray photoelectron spectrum showed evidence of the existence of those low concentration groups. The key findings of this work make it possible that applying scientific information obtained from studies under ideal conditions to industrial sorbents/sensors under realistic process conditions. Nanotube surfaces can be modified chemically to enhance their affinities for certain kinds of gas molecules