NOx adsorption behavior of LaFeO3 and LaMnO3+δ and its influence on potentiometric sensor response

NO_x adsorption behavior on LaFeO₃ (LFO) and LaMnO_3+δ (LMO) was characterized using temperature controlled methods and mass spectrometry. Temperature program desorption revealed decomposition of complex surface species formation when NO or NO₂ was adsorbed on LFO and LMO. LFO exhibited higher adsorption capacity for NO_x species than LMO and was shown to be more active for NO_x surface conversion. Both effects were attributed to the different B-site cations, with iron in LFO in the 3+ valence state, and manganese in LMO in the 3+ and 4+ valence states. Results from diffuse reflectance infrared spectroscopy were used to identify specific nitrite and nitrate species that are formed on the surfaces of LFO and LMO at room temperature. Temperature programmed reaction revealed a complex NO₂ decomposition mechanism to NO and O₂ for LFO and LMO in which the formation of nitrite and nitrate species serve as intermediates below ∼600 °C. NO_x sensing mechanisms were considered and predicted based on the types and quantities of surface species formed.     

Room temperature hydrogen gas sensor nanocomposite based on Pd-decorated multi-walled carbon nanotubes thin films

Multi-walled carbon nanotubes (MWCNTs) are successfully processed in the form of thin films (buckypapers), and their morphology and electrical behaviour are characterized. The MWCNTs are synthesized by the floating catalyst chemical vapour deposition process. The effects of a sequence of treatments applied for MWCNTs purification on the buckypapers electrical behaviour are also examined. Nanocomposite thin films constituted of pristine and purified MWCNTs and Pd nanoparticles are prepared in order to evaluate their viability as H₂ sensors at room temperature. For this purpose, the electrical resistance of the nanocomposite films in atmospheres with different H₂ concentrations, is determined. Scanning electron microscopy (SEM) images show that the buckypapers and the nanocomposite films are 2D structures constituted by randomly oriented MWCNTs. The buckypapers present a semiconductor-like electrical behaviour as determined by the standard four point method. Room temperature resistivity values of around 10⁻³ Ω m are assessed. Nanocomposite films show different electrical behaviour depending on the purification treatment applied to the MWCNTs employed. Furthermore, the electrical resistance of the nanocomposite films is found to increase when the measurements are performed in H₂ atmosphere. Values of H₂ sensitivity at room temperature of the nanocomposite films up to 2.15% are determined for H₂ average concentration higher than 350 ppm with short recovery time.     

Effect of aluminium doping on structural and gas sensing properties of zinc oxide thin films deposited by spray pyrolysis

A facile spray pyrolysis route is used to deposit aluminium doped ZnO (AZO) thin films on to the glass substrates. It is observed that on aluminium doping the particle size of ZnO reduces significantly; moreover, uniformity of particle also gets enhanced. Their XRD study reveals that intensity ratio of crystal planes depend on the aluminium doping concentration. The gas response studies of; ∼800 nm thick Al-doped ZnO films at different operating temperatures show that 5 at% Al-doped ZnO thin film exhibits highest response towards H₂S gas at 200 °C. The results suggest that the gas response strongly depends on the particle size and aluminium doping in the ZnO.     

In2O3 + xBaO (x = 0.5-5 at.%) - A novel material for trace level detection of NOx in the ambient

Indium oxide (In₂O₃) doped with 0.5-5 at.% of Ba was examined for their response towards trace levels of NO_x in the ambient. Crystallographic phase studies, electrical conductivity and sensor studies for NO_x with cross interference for hydrogen, petroleum gas (PG) and ammonia were carried out. Bulk compositions with x ≤ 1 at.% of Ba exhibited high response towards NO_x with extremely low cross interference for hydrogen, PG and ammonia, offering high selectivity. Thin films of 0.5 at.% Ba doped In₂O₃ were deposited using pulsed laser deposition technique using an excimer laser (KrF) operating at a wavelength of (λ) 248 nm with a fluence of ∼3 J/cm² and pulsed at 10 Hz. Thin film sensors exhibited better response towards 3 ppm NO_x quite reliably and reproducibly and offer the potential to develop NO_x sensors (Threshold limit value of NO₂ and NO is 3 and 25 ppm, respectively).     

Electrocatalytic reduction of hydrogen peroxide and its determination in antiseptic and soft-glass cleaning solutions at phosphotungstate-doped-glutaraldehyde-cross-linked poly-l-lysine film electrodes

The present work describes the electrocatalytic behavior of phosphotungstate-doped glutaraldehyde-cross-linked poly-l-lysine (PLL-GA-PW) film electrode towards reduction of hydrogen peroxide (H₂O₂) in acidic medium. The modified electrode was prepared by means of electrostatically trapping the phosphotungstate anion into the cationic PLL-GA coating on glassy carbon electrode. The PLL-GA-PW film electrode showed excellent electrocatalytic activity towards H₂O₂ reduction in 0.1 M H₂SO₄. Under the optimized conditions, the electrochemical sensor exhibited a linear response for H₂O₂ concentration over the range 2.5 × 10⁻⁶ to 6.85 × 10⁻³ M with a sensitivity of 1.69 μA mM⁻¹. The curvature in the calibration curve at high concentration is explained in terms of Michaelis-Menten (MM) saturation kinetics, and the kinetics parameters calculated by three different methods were compared. The PLL-GA-PW film electrode did not respond to potential interferents such as dopamine, ascorbic acid and uric acid. This unique feature of PLL-GA-PW film electrode allowed selective determination of H₂O₂. Finally, the proposed electrochemical sensor was successfully applied to determine H₂O₂ in commercially available antiseptic solution and soft-contact lenses cleaning solution and the method has been validated using independent estimation by classical potassium permanganate titration method. Major advantages of the method are simple electrode fabrication, stability and high selectivity towards hydrogen peroxide.     

The low temperature polysilicon (LTPS) thin film MOS Schottky diode on glass substrate for low cost and high performance CO sensing applications

The Au/SnO₂/n-LTPS MOS Schottky diode prepared on a glass substrate for carbon monoxide (CO) sensing applications is studied. The n-LTPS (n-type low temperature polysilicon) is prepared by excimer laser annealing and PH₃ plasma treatment of an amorphous Si thin film on glass substrate. The developed Schottky diode exhibits a high relative response ratio of ∼546% to 100 ppm CO ambient under condition of 200 °C and −3 V bias. The response ratio is better than the reported SnO₂ based resistive type CO sensors of 100% and 37%, respectively on poly-alumina and glass substrates or comparable to 390% of Pt-AlGaN/GaN Schottky diode CO sensor. Thus, the Au/SnO₂/n-LTPS Schottky diode has the potential to develop a low cost high performance CO sensor.     

Vic-dioximes: A new class of sensitive materials for chemical gas sensing

Vic-dioximes, a class of organic chemical compounds, are proposed and characterized for the first time as sensitive materials for volatile organic compound sensing with sorption based chemical gas sensors. Their peculiar sensing properties described in this work originate in the oxime functional group which is a powerful H bond donor interacting strongly but reversibly with H bond acceptors. These specific interactions result in a high preferential enrichment of analyte molecules with H bonding acceptor capabilities in the sensitive material. Accordingly, sensitivity and selectivity for these compounds of vic-dioxime based sensors are high. The advantageous sensing properties are demonstrated in this work with quartz crystal microbalance sensors using 11 selected volatile organic compounds and a set of vic-dioximes varied in their substituents. Vic-dioximes with short alkylthiol substituents were found highly sensitive to such H bond acceptors as organic amines, alcohols, and esters with partition coefficients up to 26,000. At the same time they showed low affinity for aromatic compounds and chlorocarbons. Vic-dioximes are considered powerful sensing materials and interesting for practical use in chemical gas sensor arrays.     

Flexible H2 sensor fabricated by layer-by-layer self-assembly of thin films of polypyrrole and modified in situ with Pt nanoparticles

A novel flexible H₂ gas sensor was fabricated by the layer-by-layer (LBL) self-assembly of a polypyrrole (PPy) thin film on a polyester (PET) substrate. A Pt-based complex was self-assembled in situ on the as-prepared PPy thin film, which was reduced to form a Pt-PPy thin film. Microstructural observations revealed that Pt nanoparticles formed on the surface of the PPy film. The sensitivity of the PPy thin film was improved by the Pt nanoparticles, providing catalytically active sites for H₂ gas molecules. The interfering gas NH₃ affected the limit of detection (LOD) of a targeted H₂ gas in a real-world binary gas mixture. A plausible H₂ gas sensing mechanism involves catalytic effects of Pt particles and the formation of charge carriers in the PPy thin film. The flexible H₂ gas sensor exhibited a strong sensitivity that was greater than that of sensors that were made of Pd-MWCNTs at room temperature.     

Synthesis of quantum size ZnO crystals and their gas sensing properties for NO2

Quantum size ZnO crystals have been synthesized successfully by a room temperature sol-gel process. Oleic acid (OA) has been used as capping agent to control the particle size of ZnO. The crystal structure and size of the ZnO are characterized by the X-ray diffraction (XRD) and transmission electron microscope (TEM). The XRD results show the as-synthesized ZnO has hexagonal wurtzite structure and the average crystallite size is 5.7 nm which is little less than TEM result. It is testified by photoluminescence (PL) and Raman spectra that the quantum size ZnO keeps the crystal structure of the bulk ZnO and possesses more surface defects. The quantum size ZnO has the highest response of 280 to NO₂ and the highest selectivity of 31 and 49 corresponding to CO and CH₄ at operating temperature of 290 °C. The effect of calcination temperatures on sensing property and transient response of the ZnO sensor are also investigated.     

Epitaxially grown graphene based gas sensors for ultra sensitive NO2 detection

Epitaxially grown single layer and multi layer graphene on SiC devices were fabricated and compared for response towards NO₂. Due to electron donation from SiC, single layer graphene is n-type with a very low carrier concentration. The choice of substrate is demonstrated to enable tailoring of the electronic properties of graphene, with a SiC substrate realising simple resistive devices tuned for extremely sensitive NO₂ detection. The gas exposed uppermost layer of the multi layer device is screened from the SiC by the intermediate layers leading to a p-type nature with a higher concentration of charge carriers and therefore, a lower gas response. The single layer graphene device is thought to undergo an n-p transition upon exposure to increasing concentrations of NO₂ indicated by a change in response direction. This transition is likely to be due to the transfer of electrons to NO₂ making holes the majority carriers.