Carbon nanotubes and graphene-based chemical sensors

The chemical sensing behaviour of the carbon nano-tube and graphene-based sensors for detecting various chemical analytes is presented in this article. A focus on detection mechanisms has been provided to assess their relative potential under different environmental conditions. The performance of these two carbon allotropes is compared based on their sensitivity towards various types of electron donating and accepting molecules. Although these carbon materials still have to meet crucial challenges in fabrication and optimization, continued progress in this field may lead to a sensor with superior sensitivity for a wide range of applications.

Semiconductor-like Sensitivity in Metallic Ultrathin Gold Nanowire-Based Sensors

Due to the ease of modification of electronic structure upon analyte adsorption, semiconductors have been the preferred materials as chemical sensors. At reduced dimension, however, the sensitivity of semiconductor-based sensors deteriorates significantly due to passivation, and often by increased band gap caused by quantum confinement. Using first-principles density functional theory combined with Boltzmann transport calculations, we demonstrate semiconductor-like sensitivity toward chemical species in ultrathin gold nanowires (AuNWs). The sensing mechanism is governed by the modification of the electronic structure of the AuNW as well as scattering of the charge carriers by analyte adsorption. Most importantly, the sensitivity exhibits a linear relationship with the electron affinities of the respective analytes. Based on this relationship, we propose an empirical parameter, which can predict an analyte-specific sensitivity of a AuNW, rendering them as effective sensors for a wide range of chemical an alytes.

Mechanisms of molecular doping of graphene: A first-principles study

Doping graphene with electron donating or accepting molecules is an interesting approach to introduce carriers into it, analogous to electrochemical doping accomplished in graphene when used in a field-effect transistor. Here, we use first-principles density-functional theory to determine changes in the electronic-structure and vibrational properties of graphene that arise from the adsorption of aromatic molecules such as aniline and nitrobenzene. Identifying the roles of various mechanisms of chemical interaction between graphene and a molecule, we bring out the contrast between electrochemical and molecular doping of graphene. Our estimates of various contributions to shifts in the Raman-active modes of graphene with molecular doping are fundamental to the possible use of Raman spectroscopy in (a) characterization of the nature and concentration of carriers in graphene with molecular doping, and (b) graphene-based chemical sensors.

Cd concentration sensor based on fiber grating technology

Fiber Bragg grating (FBG) and Long Period Grating (LPG) chemical sensors are one of the most exciting developments in the field of optical fiber sensors. In this paper we have proposed a simple and effective chemical sensor based on FBG and LPG techniques for detecting the traces of cadmium (Cd) in drinking water at ppm level. The sensitiveness of these two has been compared. Also, these results have been compared with the results obtained by sophisticated spectroscopic atomic absorption and emission spectrometer instruments. For proper designing of FBG to act as a concentration sensor, the cladding region of the grating has been etched using HF solution. We have characterized the FBG concentration sensor sensitivities for different solutions of Cd concentrations varying from 0.01 ppm to 0.04 ppm and observed reflected spectrum in FBG and transmitted spectrum in LPG using Optical Spectrum Analyzer. Proper reagents have been used in the solutions for detection of the Cd species. The overall shift in wavelength is 10 nm in case of LPG and the shift of Bragg wavelength is 0.07 nm in case of FBG for 0.01-0.04 ppm concentrations. (C) 2011 Elsevier B.V. All rights reserved.

Design of temperature-compensated reference electrodes for non-isothermal galvanic sensors

The criterion for the design of a temperature-compensated reference electrode for non-isothermal galvanic sensors is deduced from the basic flux equations of irreversible thermodynamics. It is shown that when the Seebeck coefficient of the non-isothermal cell using a solid oxygen ion-conducting electrolyte under pure oxygen is equal to the relative partial molar entropy of oxygen in the reference electrode divided by 4F, then the EMF of the non-isothermal cell is the same as that of an isothermal cell with the same electrodes operating at the higher temperature. By measuring the temperature of the melt alone and the EMF of the non-isothermal galvanic sensor, one can derive the chemical potential or the concentration of oxygen in a corrosive medium. The theory is experimentally checked using sensors for oxygen in liquid copper constructed with various metal+oxide electrodes and fully stabilised (CaO)ZrO2 as the electrolyte. To satisfy the exact condition for temperature compensation it is often necessary to have the metal or oxide as a solid solution in the reference electrode.

Room-temperature gas sensors based on gallium nitride nanoparticles

Room-temperature sensing characteristics for H-2, ethanol, NH3, H2S and water have been investigated with thick-film sensors based on GaN nanoparticles, prepared by a simple chemical route. In general, GaN nanoparticles exhibit satisfactory sensor properties for these gases and vapors even at room temperature. The sensitivity for ethanol is found to be highest, the sensitivity and recovery times being smallest. Gas sensor properties of GaN seem to be related to intrinsic defects, which act as sorption sites for the gas molecules. (c) 2010 Elsevier Ltd. All rights reserved.

The Blackett Memorial Lecture, 1991: Chemical Insights into High-Temperature Superconductors

The high-temperature superconductors are complex oxides, generally containing two-dimensional CuO2 sheets. Various families of the cuprate superconductors are described, paying special attention to aspects related to oxygen stoichiometry, phase stability, synthesis and chemical manipulation of charge carriers. Other aspects discussed are chemical applications of cuprates, possibly as gas sensors and copper-free oxide superconductors. All but the substituted Nd and Pr cuprates are hole-superconductors. Several families of cuprates show a nearly constant n(h) at maximum T(c). Besides this universality, the cuprates exhibit a number of striking common features. Based on Cu(2p) photoemission studies, it is found that the Cu-O charge-transfer energy, DELTA, and the Cu(3d)-O(2p) hybridization strength, t(pd), are key factors in the superconductivity of cuprates. The relative intensity of the satellite in the Cu(2p) core-level spectra, the polarizability of the CuO2 sheets as well as the hole concentration are related to DELTA/t(pd). These chemical bonding factors have to be explicitly taken into account in any model for superconductivity of the cuprates.

V2o5-Based Hydrocarbon Sensors

V2O5 supported on ZrO2 is found to be an excellent sensor for n-propane-butane mixtures at 625 K; in-situ X-ray diffraction studies show that V2O5 is reduced to VO2 with a metastable monoclinic structure on contact with the hydrocarbons and is oxidised back to the parent oxide on exposure to air.

Solid State Electrochemical Sensors in Process Control

The basic principles of operation of gas sensors based on solid-state galvanic cells are described. The polarisation of the electrodes can be minimised by the use of point electrodes made of the solid electrolyte, the use of a reference system with chemical potential close to that of the sample system and the use of graded condensed phase reference electrodes. Factors affecting the speed of response of galvanic sensors in equilibrium and non-equilibrium gas mixtures are considered with reference to products of combustion of fossil fuels. An expression for the emf of non-isothermal galvanic sensors and the criterion for the design of temperature compensated reference electrodes for non-isothermal galvanic sensors are briefly outlined. Non-isothermal sensors are useful for the continuous monitoring of concentrations or chemical potentials in reactive systems at high temperatures. Sensors for oxygen, carbon, and alloying elements (Zn and Si) in liquid metals and alloys are discussed. The use of auxiliary electrodes permits the detection of chemical species in the gas phase which are not mobile in the solid electrolyte. Finally, the cause of common errors in galvanic measurements, and tests for correct functioning of galvanic sensors are given. 60 ref.--AA

Fiber Bragg Grating Sensors for Real Time Monitoring of Evacuation Process

Fiber bragg grating (FBG) sensors have been widely used for number of sensing applications like temperature, pressure, acousto-ultrasonic, static and dynamic strain, refractive index change measurements and so on. Present work demonstrates the use of FBG sensors in in-situ measurement of vacuum process with simultaneous leak detection capability. Experiments were conducted in a bell jar vacuum chamber facilitated with conventional Pirani gauge for vacuum measurement. Three different experiments have been conducted to validate the performance of FBG sensor in monitoring vacuum creating process and air bleeding. The preliminary results of FBG sensors in vacuum monitoring have been compared with that of commercial Pirani gauge sensor. This novel technique offers a simple alternative to conventional method for real time monitoring of evacuation process. Proposed FBG based vacuum sensor has potential applications in vacuum systems involving hazardous environment such as chemical and gas plants, automobile industries, aeronautical establishments and leak monitoring in process industries, where the electrical or MEMS based sensors are prone to explosion and corrosion.

Applications of solid electrolytes in galvanic sensors

The concepts and theoretical origins of conduction domains for solid electrolytes and electrode polarization are outlined briefly. The point electrode made of the ' solid electrolyte material is useful for deflecting the semipermeability flux away from the electrode. The emf of galvanic sensors consisting of two solid electrolytes in intimate contact with each other and in which transport occurs by a common ion is reviewed. The voltage of such cells depends on the chemical potential of the active species at the interface between the two electrolytes, which can be evaluated from the transport properties of electrolytes using a numerical procedure. The factors governing the speed of response of solid electrolyte gas sensors are analyzed. A rigorous expression for the emf of non-isothermal galvanic sensors and the criterion for the design of temperature compensated reference electrodes for nonisothermal galvanic sensors are outlined. Non-isothermal sensors are useful for the continuous monitoring of concentrations or chemical potentials in reactive systems at high temperatures. The principles of operation of galvanic sensors for oxygen, sulphur, oxides of sulphur (SOx,x=2,3), carbon, oxides uf carbon (COx,x= 1,2), oxides of nitrogen (NOx,x= 1,2) and silicon are discussed. The use of auxiliary electrodes in galvanic sensors to expand the detection capability of known solid electrolytes to a large number of species is explained with reference to sensors for sulphur and oxides of sulphur (SOx,x=2,3).Finally the cause of the common errors in galvanic measurements and test for the correct functioning of galvanic sensors is given.

Fluorescent Tris-Imidazolium Sensors for Picric Acid Explosive

Two new anthracene-functionalized fluorescent tris-imidazolium salts have been synthesized, characterized, and proven to be selective sensors for picric acid, which is a common constituent of many powerful explosives. Theoretical studies revealed an unusual ground-state electron transfer from picrate anion to the sensor molecules.

Nanocomposite based flexible ultrasensitive resistive gas sensor for chemical reactions studies

Room temperature operation, low detection limit and fast response time are highly desirable for a wide range of gas sensing applications. However, the available gas sensors suffer mainly from high temperature operation or external stimulation for response/recovery. Here, we report an ultrasensitive-flexible-silver-nanoparticle based nanocomposite resistive sensor for ammonia detection and established the sensing mechanism. We show that the nanocomposite can detect ammonia as low as 500 parts-per-trillion at room temperature in a minute time. Furthermore, the evolution of ammonia from different chemical reactions has been demonstrated using the nanocomposite sensor as an example. Our results demonstrate the proof-of-concept for the new detector to be used in several applications including homeland security, environmental pollution and leak detection in research laboratories and many others.

Dual Binding Site Assisted Chromogenic and Fluorogenic Recognition and Discrimination of Fluoride and Cyanide by a Peripherally Borylated Metalloporphyrin: Overcoming Anion Interference in Organoboron Based Sensors

Peripherally triarylborane decorated porphyrin (2) and its Zn(II) complex (3) have been synthesized. Compound 3 contains of two different Lewis acidic binding sites (Zn(II) and boron center). Unlike all previously known triarylborane based sensors, the optical responses of 3 toward fluoride and cyanide are distinctively different, thus enabling the discrimination of these two interfering anions. Metalloporphyrin 3 shows a multiple channel fluorogenic response toward fluoride and cyanide and also a selective visual colorimetric response toward cyanide. By comparison with model systems and from detailed photophysical studies on 2 and 3, we conclude that the preferential binding of fluoride occurs at the peripheral borane moieties resulting in the cessation of the EET (electronic energy transfer) process from borane to porphyrin core and with negligible negetive cooperative effects. On the other hand, cyanide binding occurs at the Zn(II) core leading to drastic changes in its absorption behavior which can be followed by the naked eye. Such changes are not observed when the boryl substituent is absent (e.g., Zn-TPP and TPP). Compounds 2 and 3 were also found to be capable of extracting fluoride from aqueous medium.