Nanocrystalline TiO2/SnO2 composites for gas sensors

TiO₂/SnO₂ nanocomposites are studied as potential candidates for gas sensors. Commercial metal oxide nanopowders milled for 1?h in ethanol are used for preparing nanocomposites with varied composition from 100?mol% TiO₂ to 100?mol% SnO₂. Brunauer?CEmmett?CTeller (BET) adsorption isotherms served to determine specific surface area, SSA. The particle size distribution is established by means of Dynamic Light Scattering, DLS technique. Differential Thermal Analysis and Thermogravimetry, DTA/TG measurements within the temperature range of 20?C900?°C indicate better stability of nanomaterials composed of bigger particles or agglomerates. The total mass loss varies from 0.9 to 8.5% for 100?mol% SnO₂ and 100?mol% TiO₂, respectively. The only gaseous products of decomposition are water and carbon dioxide. X-ray diffraction analysis of nanocomposites indicates two separate phases of different crystallite size, i.e., smaller rutile TiO₂ (9?nm) and larger cassiterite SnO₂ (28?nm). Gas sensor dynamic responses at 400?°C to the reducing gas??ammonia (NH₃) are detected in the concentration range extending from 100?ppm to ?5000?ppm. Nanosensor of 50?mol% SnO₂/50?mol% TiO₂ is stable and sensitive to the interaction with NH₃ and gives the highest response at 400?°C.     

Chlorine gas sensors using one-dimensional tellurium nanostructures

Tellurium nanotubes have been grown by physical vapor deposition under inert environment at atmospheric pressure as well as under vacuum conditions. Different techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and optical absorption have been utilized for characterization of grown structures. Films prepared using both types of tellurium nanotubes were characterized for sensitivity to oxidizing and reducing gases and it was found that the relative response to gases depends on the microstructure. Nanotubes prepared at atmospheric pressure (of argon) showed high sensitivity and better selectivity to chlorine gas. Impedance spectroscopy studies showed that the response to chlorine is mainly contributed by grain boundaries and is therefore enhanced for nanotubes prepared under argon atmosphere.     

Optical sensors

Summary A fibre optic biosensor for ethanol was developed, which is based on the enzymatic oxidation of ethanol. The sensor layer contains an oxygen-sensitive fluorescing indicator which reports the decrease in the local oxygen partial pressure as the result of the enzymatic oxidation. The sensor measures in the 50–500 mmol/l ethanol range, with an accuracy of ± 4 mmol/l at 100 mmol/l. The detection limit is 10 mmol/l ethanol.

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Optische SensorenTeil 20. Ein faseroptischer Biosensor für Ethanol

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Presented in part at the Biosensor International Workshop 1987 at GBF, Braunschweig, June 1987     

Improved dynamic response of potentiometric ammonia sensors using pure teflon membranes

Several microporous membrane parameters are investigated in an attempt to improve the dynamic response of ammonia gas-sensing electrodes. Parameters of interest include hydrophobic and support membrane porosities as well as support polymer composition. Results show that the electrode recovery process represents the major component of the total dynamic response and that, of the teflon membranes currently available, the 0.02-μm pure teflon membrane is the membrane of choice for these electrodes.     

Towards ultra-responsive biodegradable polysaccharide humidity sensors

Sodium alginate is a biodegradable natural polymer that is derived from algae and is water soluble. Upon immersion in a CaCl₂ solution, a sodium alginate water solution is cross-linked to form water-insoluble calcium alginate. When the sodium alginate water solution is immersed in the CaCl₂ bath via a syringe pump, calcium alginate fibers are produced. By changing the CaCl₂ concentration, calcium alginate fibers with different degrees of cross-linking can be produced. Such fibers were found to differ in mechanical and morphological properties, and more interestingly, were found to possess humidity sensing and conductive properties. Interestingly, the higher the CaCl₂ concentration, the lower the degree of cross-linking, which produced softer fibers with better humidity sensing and conductive properties. The fibers were able to trap water in their structures, and a higher water content increased the conductivity due to the presence of an electrolyte salt in the fiber and due to the polyelectrolyte nature of the fiber itself. The cross-linking and percent shrinking degree, morphology and mechanical properties of the fibers were found to create significant changes in the conductivity and humidity sensing properties of the fibers. High humidity environments led to an increase in the conductivity of the fibers, whereas dry environments led to a decrease in the conductivity. The fibers, especially those with the highest CaCl₂ concentration, were determined to be ultra-responsive to humidity changes and exhibited very good repetition in humidity cycles. These tailored fibers are proposed as novel biodegradable conductive materials for various humidity sensing, robotic and bio-robotic applications.     

Resistive gas sensors based on the composites of nanostructured carbonized polyaniline and Nafion

Due to constant necessity to have reliable and sensitive gas sensors in many contemporary technologies, there is a permanent need for development of new sensing platforms with good sensing properties. Here, we demonstrate a novel type of resistive gas sensors based on carbonized polyaniline/Nafion composites. The sensing mechanism of such sensors is based on the sorption of gases by the composites which induce Nafion swelling and decreasing of conductivity. Chemosensitive properties can be tuned by the (i) choice of carbon materials with different conductivities, (ii) Nafion content in the composite, and (iii) thickness of the composite layer. We have shown that the sensors respond to water, acetone, ethanol, and methanol vapors. For the last two cases, we have achieved high sensitivity, fast response, wide concentration range, and good recovery. The use of simultaneous two- and four-point techniques for these sensors provides an internal control of the sensor integrity.     

The detection of hydrogen using catalytic flammable gas sensors

The response to hydrogen (0.1 – 2.0% in air) of flammable gas sensors consisting of pellistors coated with supported palladium has been investigated. An optimum diffusion-limited response of 15 – 30 mV/(% H₂), depending on reactor geometry, was obtained with pellistors operated at ≈200 °C under atmospheric pressure. Both ambient and generated water reduced catalytic activity and response, particularly at low temperature. Activity was also greatly reduced by overheating of the pellistor. The influence of these factors on recommended operating procedures is considered.     

Detection of organic gases using TiO2 nanotube-based gas sensors

We fabricated porous gas sensing films composed of TiO₂ nanotubes prepared by a hydrothermal treatment for the detection of organic gases, such as alcohol and toluene. The morphology of the sensing films was controlled with a ball-milling treatment and calcination at high temperature to improve the sensitivity of the films. The sensor using nanotubes with the ball-milling treatment exhibited the improved sensor responses to toluene at 500oC. The results obtained indicated the importance of the microstructure control of sensing layers in terms of particle packing density, pore size distribution, and particle size and shape for detecting large sized organic gas molecules.     

Selective recognition of xylene isomers using ZnO-SWNTs hybrid gas sensors

We demonstrate a hybrid ZnO nanoparticle decorated SWNT network device that can conductometrically differentiate between xylene isomers at room temperature with minimal interference from background VOCs. Field effect transistor measurements are conducted to identify the sensing mechanism which is attributed to enhanced SWNT transduction of chemical interaction with ZnO surfaces.     

Fabrication of an ammonia gas sensor using inkjet-printed polyaniline nanoparticles

This work details the fabrication and performance of a sensor for ammonia gas analysis which has been constructed via the inkjet-printed deposition of polyaniline nanoparticle films. The conducting films were assembled on interdigitated electrode arrays and characterised with respect to their layer thickness and thermal properties. The sensor was further combined with heater foils for operation at a range of temperatures. When operated in a conductimetric mode, the sensor was shown to exhibit temperature-dependent analytical performance to ammonia detection. At room temperature, the sensor responded rapidly to ammonia (t₅₀ = 15 s). Sensor recovery time, response linearity and sensitivity were all significantly improved by operating the sensor at temperatures up to 80 °C. The sensor was found to have a stable logarithmic response to ammonia in the range of interest (1-100 ppm). The sensor was also insensitive to moisture in the range from 35 to 98% relative humidity. The response of the sensor to a range of common potential interferents was also studied.     

Determination of ammonia in the air using piezoelectric resonance sensors coated with humic acids

Natural macromolecular compounds, humic acids (HA), have been used to form gas-sensitive layers of piezoelectric resonance gravimetric sensors. HA have been extracted from humus using alkaline extraction and purified by electrodialysis through ion-exchange membranes. Species have been deposited onto the electrode surface of piezoelectric quartz resonators by air-spraying their aqueous solutions, the layer thickness being 100–200 nm. In determining ammonia with the sensor obtained on the basis of purified HA species, the detection limit is ∼10 mg/m³. Gas-sensitive layers on the basis of humic acids are more stable as compared to the conventionally used gas-sensitive layers based on pyridoxine hydrochloride or ascorbic acid.     

Detection of organophosphorus compounds with semiconductor gas sensors using adsorption preconcentration

Effective concentrators for organophosphorus compounds, highly sensitive semiconductor sensors, and a prototype of a detector for specific determination of low concentrations of organophosphorus compounds in air were developed. It is preferable to use as concentrating sorbents silicates with low density of surface hydroxy groups, ensuring high degree of recovery of the target compound by thermal desorption without its decomposition. SnO₂ modified with RuO₂ is the most sensitive sensor material.     

Sampling small volumes of ambient ammonia using a miniaturized gas sampler

The development of a gas sampler for a miniaturized ambient ammonia detector is described. A micromachined channel system is realized in glass and silicon using powder blasting and anodic bonding. The analyte gas is directly mixed with purified water, dissolving the ammonia that will dissociate into ammonium ions. Carrier gas bubbles are subsequently removed from the liquid stream through a venting hole sealed with a microporous water repellent PTFE membrane. A flow restrictor is placed at the outlet of the sampler to create a small overpressure underneath the membrane, enabling the gas to leave through the membrane. Experiments with a gas flow of 1 ml min(-1), containing ammonia concentrations ranging from 9.4 ppm to 0.6 ppm in a nitrogen carrier flow have been carried out, at a water flow of 20 microl min(-1). The ammonium concentration in the sample solution is measured with an electrolyte conductivity detector. The measured values correspond with the concentration calculated from the initial ammonia concentration in the analyte gas, the fifty times concentration enhancement due to the gas-liquid volume difference and the theoretical dissociation equilibrium as a function of the resulting pH.     

Carbon nanotube gas and vapor sensors

Carbon nanotubes have aroused great interest since their discovery in 1991. Because of the vast potential of these materials, researchers from diverse disciplines have come together to further develop our understanding of the fundamental properties governing their electronic structure and susceptibility towards chemical reaction. Carbon nanotubes show extreme sensitivity towards changes in their local chemical environment that stems from the susceptibility of their electronic structure to interacting molecules. This chemical sensitivity has made them ideal candidates for incorporation into the design of chemical sensors. Towards this end, carbon nanotubes have made impressive strides in sensitivity and chemical selectivity to a diverse array of chemical species. Despite the lengthy list of accomplishments, several key challenges must be addressed before carbon nanotubes are capable of competing with state-of-the-art solid-state sensor materials. The development of carbon nanotube based sensors is still in its infancy, but continued progress may lead to their integration into commercially viable sensors of unrivalled sensitivity and vanishingly small dimensions.     

Fluorescence sensors for trace monitoring of dissolved ammonia

Even though monitoring of dissolved ammonia is acutely important for environmental studies, fish farms and for industrial surveillance, no system for the performance of online measurements at the concentrations needed exists so far. For many applications it is necessary to detect dissolved ammonia concentrations at sub mg/l-levels, because ammonia is reported to be toxic for aquatic organisms above 25 microg/l. We present new ammonia sensitive materials consisting of fluorescent pH indicators embedded into different cellulose esters. The low pK(a) value of the indicators and the high solubility of ammonia in the cellulose polymers lead to detection limits below 1 microg/l and a dynamic range between 5 and 1000 microg/l. Response times at these trace concentration levels are in the order of 20-30 min. The sensors are suitable for fresh and sea water monitoring by an additional silicon layer preventing the interference of protons and salinity. The fluorescent indicators Eosin ethylester and 2',7'-dichlorofluorescein methylester (DCF) were investigated to achieve sensors with a dynamic range matching the target concentrations. Sensors with improved performance were obtained by employing cellulose ester nanospheres with incorporated Eosin ethylester. The simple sensor design has a high potential to be applied in miniaturized optical measurement system for online ammonia detection.     

Optical ammonia gas sensor based on a porous silicon rugate filter coated with polymer-supported dye

An ammonia gas sensor chip was prepared by coating an electrochemically-etched porous Si rugate filter with a chitosan film that is crosslinked by glycidoxypropyltrimethoxysilane (GPTMS). The bromothylmol blue (BTB), a pH indicator, was loaded in the film as ammonia-sensing molecules. White light reflected from the porous Si has a narrow bandwidth spectrum with a peak at 610 nm. Monitoring reflective optical intensity at the peak position allows for direct, real-time observation of changes in the concentration of ammonia gas in air samples. The reflective optical intensity decreased linearly with increasing concentrations of ammonia gas over the range of 0–100 ppm. The lowest detection limit was 0.5 ppm for ammonia gas. At optimum conditions, the full response time of the ammonia gas sensor was less than 15 s. The sensor chip also exhibited a good long-term stability over 1 year. Therefore, the simple sensor design has potential application in miniaturized optical measurement for online ammonia gas detection.     

Optical sensors for dissolved sulfur dioxide

Colorimetric sensing membranes for the determination of sulfur dioxide were developed and characterized. These films can be used for sensing trace amounts of sulfur dioxide both in the gas phase and in aqueous solutions. Lipophilic pH indicator ion pairs were immobilized in hydrophobic gas-permeable silicone and phenyl substituted ormosil. On exposure to SO₂ the films undergo a visually detectable color change from blue to yellow. No cross-sensitivity to pH and CO₂ was observed. Response times depend on the thickness of the sensing membranes, the indicator concentration in the film as well as on the respective SO₂ concentration. Membranes with response times of < 1 min (t₉₀) were developed. The sensitivity to sulfur dioxide depends on the pK_a of the indicator. An increase in the pK_a results in a lower detection limit. The new optical SO₂ sensors are chemically and mechanically stable and are easy to manufacture. The storage stability of the membranes is at least 7 months if stored in the dark. Received: 17 December 1997 / Revised: 12 June 1998 / Accepted: 15 June 1998     

Optical and electrochemical sol-gel sensors for inorganic species

The use of sol-gels as a sensing matrix for the development of unique sensing strategies is discussed. Sol-gels offer almost limitless possibilities for sensing substrates due to the variety of physical properties that can be obtained by altering a number of discussed fabrication conditions and techniques. By careful consideration of the sensing requirements, novel detection methods have been developed for a variety of analytes and applications. Here, sol-gels have been used to monitor pH at the extreme ends of the scale ([H⁺] = 1–11 M and [OH⁻] = 1–10 M) and in mixed solvent/solute systems using dual sensing approaches. The use of ligand-grafted sol-gel monoliths for optical determination of metal ion species is also discussed. The electrochemical determination of Cr(VI) by electrodeposited sol-gel modified electrodes is also presented.     

无机物的光学和电化学传感器

本文讨论将溶胶凝胶作为一种基质来发展独特的传感策略．溶胶凝胶为传感基质的制备和发展提供了无限空间,这种空间得益于基质物理性质的多样性,可以通过改变一些传感器已知的制备条件和合成技术来实现．我们在对传感需求的认真考虑和研究的基础上,开发出了用于一些分析物的新的检测方法,同时发展了它们的应用．溶胶凝胶被用来监测浓强酸（[H^＋]=1～11M）,浓强碱（[OH^-]：1～10M）及采用双传感方法来测定混合溶剂／溶质系统．本文还讨论了使用配体嫁接的块状溶胶凝胶对金属离子进行光学测定．最后介绍了用电化学法和溶胶凝胶修饰的电极来测定六价铬的方法．     

Optical sensors and biosensors based on sol-gel films

The sol-gel technology is being increasingly used for the development of optical sensors and biosensors, due to its simplicity and versatility. By this process, porous thin films incorporating different chemical and biochemical sensing agents are easily obtained at room temperature, allowing final structures with mechanical and thermal stability as well as good optical characteristics. In this article, an overview of the state-of-the-art of sol-gel thin films-based optical sensors is presented. Applications reviewed include sensors for determination of pH, gases, ionic species and solvents, as well as biosensors.