Review on carbon-derived, solid-state, micro and nano sensors for electrochemical sensing applications

The aim of this review is to summarize the most relevant contributions in the development of electrochemical sensors based on carbon materials in the recent years. There have been increasing numbers of reports on the first application of carbon derived materials for the preparation of an electrochemical sensor. These include carbon nanotubes, diamond like carbon films and diamond film-based sensors demonstrating that the particular structure of these carbon material and their unique properties make them a very attractive material for the design of electrochemical biosensors and gas sensors. Carbon nanotubes (CNT) have become one of the most extensively studied nanostructures because of their unique properties. CNT can enhance the electrochemical reactivity of important biomolecules and can promote the electron-transfer reactions of proteins (including those where the redox center is embedded deep within the glycoprotein shell). In addition to enhanced electrochemical reactivity, CNT-modified electrodes have been shown useful to be coated with biomolecules (e.g., nucleic acids) and to alleviate surface fouling effects (such as those involved in the NADH oxidation process). The remarkable sensitivity of CNT conductivity with the surface adsorbates permits the use of CNT as highly sensitive nanoscale sensors. These properties make CNT extremely attractive for a wide range of electrochemical sensors ranging from amperometric enzyme electrodes to DNA hybridization biosensors. Recently, a CNT sensor based fast diagnosis method using non-treated blood assay has been developed for specific detection of hepatitis B virus (HBV) (human liver diseases, such as chronic hepatitis, cirrhosis, and hepatocellular carcinoma caused by hepatitis B virus). The linear detection limits for HBV plasma is in the range 0.5–3.0 μL−1 and for anti- HBVs 0.035–0.242 mg/mL in a 0.1 M NH4H2PO4 electrolyte solution. These detection limits enables early detection of HBV infection in suspected serum samples. Therefore, non-treated blood serum can be directly applied for real-time sensitive detection in medical diagnosis as well as in direct in vivo monitoring. Synthetic diamond has been recognized as an extremely attractive material for both (bio-) chemical sensing and as an interface to biological systems. Synthetic diamond have outstanding electrochemical properties, superior chemical inertness and biocompatibility. Recent advances in the synthesis of highly conducting nanocrystalline-diamond thin films and nano wires have lead to an entirely new class of electrochemical biosensors and bio-inorganic interfaces. In addition, it also combines with development of new chemical approaches to covalently attach biomolecules on the diamond surface also contributed to the advancement of diamond-based biosensors. The feasibility of a capacitive field-effect EDIS (electrolyte-diamond-insulatorsemiconductor) platform for multi-parameter sensing is demonstrated with an O-terminated nanocrystalline-diamond (NCD) film as transducer material for the detection of pH and penicillin concentration. This has also been extended for the label-free electrical monitoring of adsorption and binding of charged macromolecules. One more recent study demonstrated a novel bio-sensing platform, which is introduced by combination of a) geometrically controlled DNA bonding using vertically aligned diamond nano-wires and b) the superior electrochemical sensing properties of diamond as transducer material. Diamond nanowires can be a new approach towards next generation electrochemical gene sensor platforms. This review highlights the advantages of these carbon materials to promote different electron transfer reactions specially those related to biomolecules. Different strategies have been applied for constructing carbon material-based electrochemical sensors, their analytical performance and future prospects are discussed

Tuning the Performance of Nanocarbon-Based Gas Sensors Through Nanoparticle Decoration

Tin dioxide (SnO2) is a well–known gas sensing material, but it becomes sensitive only at elevated temperatures (e.g., above 200 &degC). Nanoparticles (NPs) combined with nanocarbons, such as carbon nanotubes (CNTs) and graphene, form a new class of hybrid nanomaterials that can exhibit fascinating gas sensing performance due to tunable electron transfer between NPs and nanocarbons induced by gas adsorption. Indeed, sensors made of SnO2 NPs&ndascoated CNTs have shown outstanding room–temperature sensing performance to various gases, including those that are undetectable by either SnO2 or CNTs alone. The objectives of this dissertation study are to synthesize various NP–nanocarbon hybrid materials and to fabricate and characterize sensing platforms based on the resulting hybrid nanomaterials. Two simple and efficient methods have been used for the hybrid synthesis. One is a simple NP synthesis and assembly system for NP–nanocarbon hybrid nanomaterials production through combining a mini–arc plasma reactor with electrostatic force–directed assembly. The other is a simple wet–chemical method for direct fabrication of doped SnO2 NP–decorated reduced graphene oxide (RGO) sheets. In particular, CNT/Ag NP and RGO/Ag NP hybrids have been produced for fast, sensitive, and selective detection of NH3. Furthermore, a ternary hybrid of Ag NPs and SnO2 NPs–decorated CNTs has been demonstrated and showed better sensing performance than CNT/SnO2 NP hybrids likely due to the enhanced gas adsorption and electron transfer. Additionally, hybrid sensors of In–doped SnO2 NPs on RGO are shown to exhibit high selectivity to NO2 sensing. Finally, the sensing mechanism for the NP–nanocarbon system has been extensively discussed. Based on this study, we conclude that the sensing performance (including sensitivity, selectivity, and response time) can be fine–tuned by coating nanocarbons with carefully–selected NPs (pure or doped). An attempt has been made to compare the sensing performance of hybrids based on various types of nanocarbons (e.g., multiwalled CNTs, semiconducting single–walled CNTs, RGO). Nanocarbons with superior semiconducting properties as building blocks of hybrid nanomaterials are shown to exhibit better gas sensing performance. This study provides a scientific foundation to engineer practical room–temperature gas sensors with enhanced performance

Nanotechnology Applications for Chemical and Biological Sensors

Recent discoveries indicate that when the materials are brought down to sizes in the range 1–100 nm, theseexhibit unique electrical, optical, magnetic, chemical, and mechanical properties. Methods have now beenestablished to obtain the monodisperse nanocrystals of various metallic and semiconducting materials, single-walled and multi-walled nanotubes of carbon and other metallic and non-metallic materials together withorganic nanomaterials such as supra-molecular nanostructures, dendrimers, hybrid composites with tailoredfunctionalities. The high surface-to-volume ratio with an added element of porosity makes these highly potentialcandidates for chemical and biological sensor applications with higher degree of sensitivity and selectivity ascompared to their bulk counterparts. The paper reviews the recent developments and applications of chemicaland biological sensors based on nanomaterials of various structural forms.Defence Science Journal, 2008, 58(5), pp.636-649, DOI:http://dx.doi.org/10.14429/dsj.58.168

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

Conductometric Gas Nanosensors

This paper presents a review of the current research activities in the field of gas nanosensors. Nanomaterials are characterized by physical and chemical properties that differ from their macroscopic counterparts and, in particular, by an enhanced chemical reactivity even at room temperature. This effect has stimulated the development of chemical sensors based on several different nanomaterials. Here we focus most attention on carbon nanotubes, silicon and metal oxide nanoparticles and metal nanowires. After introducing a few general definitions a discussion on the fundamental properties of the nanostate used in the sensor field is presented and several nanosensors, based on the aforementioned nanomaterials, are discussed. Finally, some personal conclusions will be drawn

Nanocomposite Films for Gas Sensing

Nanocomposite films are thin films formed by mixing two or more dissimilar materials having nano-dimensional phase(s) in order to control and develop new and improved structures and properties. The properties of nanocomposite films depend not only on the individual components used but also on the morphology and the interfacial characteristics. Nanocomposite films that combine materials with synergetic or complementary behaviours possess unique physical, chemical, optical, mechanical, magnetic and electrical properties unavailable from that of the component materials and have attracted much attention for a wide range of device applications such as gas sensors.NRC publication: Ye

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