Metal-Oxide Based Nanomaterials: Synthesis, Characterization and Their Applications in Electrical and Electrochemical Sensors.

Pure, mixed and doped metal oxides (MOX) have attracted great interest for the development of electrical and electrochemical sensors since they are cheaper, faster, easier to operate and capable of online analysis and real-time identification. This review focuses on highly sensitive chemoresistive type sensors based on doped-SnO2, RhO, ZnO-Ca, Smx-CoFe2-xO4 semiconductors used to detect toxic gases (H2, CO, NO2) and volatile organic compounds (VOCs) (e.g., acetone, ethanol) in monitoring of gaseous markers in the breath of patients with specific pathologies and for environmental pollution control. Interesting results about the monitoring of biochemical substances as dopamine, epinephrine, serotonin and glucose have been also reported using electrochemical sensors based on hybrid MOX nanocomposite modified glassy carbon and screen-printed carbon electrodes. The fundamental sensing mechanisms and commercial limitations of the MOX-based electrical and electrochemical sensors are discussed providing research directions to bridge the existing gap between new sensing concepts and real-world analytical applications.

Electrochemical Sensing of Serotonin by a Modified MnO2-Graphene Electrode.

The development of MnO2-graphene (MnO2-GR) composite by microwave irradiation method and its application as an electrode material for the selective determination of serotonin (SE), popularly known as "happy chemical", is reported. Anchoring MnO2 nanoparticles on graphene, yielded MnO2-GR composite with a large surface area, improved electron transport, high conductivity and numerous channels for rapid diffusion of electrolyte ions. The composite was characterized by X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and scanning electron microscopy (SEM) for assessing the actual composition, structure and morphology. The MnO2-GR composite modified glassy carbon electrode (GCE) exhibited an excellent electrochemical activity towards the detection of SE in phosphate buffer saline (PBS) at physiological pH of 7.0. Under optimum conditions, the modified electrode could be applied to the quantification of serotonin by square wave voltammetry over a wide linear range of 0.1 to 800 µM with the lowest detection limit of 10 nM (S/N = 3). The newly fabricated sensor also exhibited attractive features such as good anti-interference ability, high reproducibility and long-term stability.

Monitoring of Chemical Risk Factors for Sudden Infant Death Syndrome (SIDS) by Hydroxyapatite-Graphene-MWCNT Composite-Based Sensors.

Sensing properties of chemical sensors based on ternary hydroxyapatite-graphene-multiwalled carbon nanotube (HA-GN-MWCNT) nanocomposite in the detection of chemical substances representing risk factors for sudden infant death syndrome (SIDS), have been evaluated. Characterization data of the synthesized composite have shown that the graphene-MWCNT network serves as a matrix to uniformly disperse the hydroxyapatite nanoparticles and provide suitable electrical properties required for developing novel electrochemical and conductometric sensors. A HA-GN-MWCNT composite-modified glassy carbon electrode (HA-GN-MWCNT/GCE) has been fabricated and tested for the simultaneous monitoring of nicotine and caffeine by cyclic voltammetry (CV) and square wave voltammetry (SWV), whereas a HA-GN-MWCNT conductive gas sensor has been tested for the detection of CO2 in ambient air. Reported results suggest that the synergic combination of the chemical properties of HA and electrical/electrochemical characteristics of the mixed graphene-MWCNT network play a prominent role in enhancing the electrochemical and gas sensing behavior of the ternary HA-GN-MWCNT hybrid nanostructure. The high performances of the developed sensors make them suitable for monitoring unhealthy actions (e. g. smoking, drinking coffee) in breastfeeding women and environmental factors (bad air quality), which are associated with an enhanced risk for SIDS.

Effects of UV Irradiation on the Sensing Properties of In2O3 for CO Detection at Low Temperature.

In this study, UV irradiation was used to improve the response of indium oxide (In2O3) used as a CO sensing material for a resistive sensor operating in a low temperature range, from 25 °C to 150 °C. Different experimental conditions have been compared, varying UV irradiation mode and sensor operating temperature. Results demonstrated that operating the sensor under continuous UV radiation did not improve the response to target gas. The most advantageous condition was obtained when the UV LED irradiated the sensor in regeneration and was turned off during CO detection. In this operating mode, the semiconductor layer showed an apparent "p-type" behavior due to the UV irradiation. Overall, the effect was an improvement of the indium oxide response at 100 °C toward low CO concentrations (from 1 to 10 ppm) that showed higher results than in the dark, which is promising to extend the detection of CO with an In2O3-based sensor in the sub-ppm range.

Photo-Electrochemical Sensing of Dopamine by a Novel Porous TiO2 Array-Modified Screen-Printed Ti Electrode.

In this paper, the development of a nanoporous TiO2 array-modified Ti electrode for photo-electrochemical (PEC) sensing of dopamine (DA) is reported. A porous TiO2 array-modified electrode was fabricated from the controlled anodic oxidation of a Ti working electrode of commercial screen-printed electrodes (SPE). The anodization process and the related morphological and microstructural transformation of the bare Ti electrode into a TiO2/Ti electrode was followed by scanning electron microscopy (SEM) and UV-visible reflectance spectroscopy (DR-UV-Vis). The modified electrode was irradiated with a low-power (120 mW) UV-Vis LED lamp (λ = 400 nm) and showed good performance for the detection of DA with a large linear response range, a sensitivity of 462 nA mM-1 cm-2, and a limit of detection of 20 µM. Moreover, it showed higher photocurrents in the presence of DA in comparison to some foreign species such as ascorbic acid, uric acid, glucose, K⁺, Na⁺, and Cl-. Thus, this proposed low-cost photo-electrochemical sensor, with the advantage of very simple fabrication, demonstrates potential applications for the determination of dopamine in real samples.

CO2 sensing properties of electro-spun Ca-doped ZnO fibres.

The availability of low-cost, high-performing sensors for carbon dioxide detection in the environment may play a crucial role for reducing CO2 emissions and limiting global warming. In this study, calcium-doped zinc oxide nanofibres with different Ca to Zn loading ratios (1:40 or 1:20) are synthesised via electro-spinning, thoroughly characterised and, for the first time, tested as an active material for the detection of carbon dioxide. The results of their characterisation show that the highly porous fibres consist of interconnected grains of oxide with the hexagonal wurtzite structure of zincite. Depending on the Ca:Zn loading ratio, calcium fully or partly segregates to form calcite on the fibre surface. The high response of the sensor based on the fibres with the highest Ca-doping level can be attributed to the synergy between the fibre morphology and the basicity of Ca-ion sites, which favour the diffusion of the gas molecules within the sensing layer and the CO2 adsorption, respectively.

Hybrid Noble-Metals/Metal-Oxide Bifunctional Nano-Heterostructure Displaying Outperforming Gas-Sensing and Photochromic Performances.

As nanomaterials are dominating 21st century's scene, multiple functionality in a single (nano)structure is becoming very appealing. Inspired by the Land of the Rising Sun, we designed a bifunctional (gas-sensor/photochromic) nanomaterial, made with TiO2 whose surface was simultaneously decorated with copper and silver (the Cu/Ag molar ratio being 3:1). This nanomaterial outperformed previous state-of-the-art TiO2-based sensors for the detection of acetone, as well as the Cu-TiO2-based photochromic material. It indeed possessed splendid sensitivity toward acetone (detection limit of 100 ppb, 5 times lower than previous state-of-the-art TiO2-based acetone sensors), as well as reduced response/recovery times at very low working temperature, 150 °C, for acetone sensing. Still, the same material showed itself to be able to (reversibly) change in color when stimulated by both UV-A and, most remarkably, visible light. Indeed, the visible-light photochromic performance was almost 3 times faster compared to the standard Cu-TiO2 photochromic material-that is, 4.0 min versus 10.8 min, respectively. It was eventually proposed that the photochromic behavior was triggered by different mechanisms, depending on the light source used.

Synthesis, Characterization and Gas Sensing Properties of Ag@α-Fe2O3 Core-Shell Nanocomposites.

Ag@α-Fe2O3 nanocomposite having a core-shell structure was synthesized by a two-step reduction-sol gel approach, including Ag nanoparticles synthesis by sodium borohydride as the reducing agent in a first step and the subsequent mixing with a Fe+3 sol for α-Fe2O3 coating. The synthesized Ag@α-Fe2O3 nanocomposite has been characterized by various techniques, such as SEM, TEM and UV-Vis spectroscopy. The electrical and gas sensing properties of the synthesized composite towards low concentrations of ethanol have been evaluated. The Ag@α-Fe2O3 nanocomposite showed better sensing characteristics than the pure α-Fe2O3. The peculiar hierarchical nano-architecture and the chemical and electronic sensitization effect of Ag nanoparticles in Ag@α-Fe2O3 sensors were postulated to play a key role in modulating gas-sensing properties in comparison to pristine α-Fe2O3 sensors.

CO and NO2 Selective Monitoring by ZnO-Based Sensors.

ZnO nanomaterials with different shapes were synthesized, characterized and tested in the selective monitoring of low concentration of CO and NO2 in air. ZnO nanoparticles (NPs) and nanofibers (NFs) were synthesized by a modified sol-gel method in supercritical conditions and electrospinning technique, respectively. CO and NO2 sensing tests have demonstrated that the annealing temperature and shape of zinc oxide nanomaterials are the key factors in modulating the electrical and sensing properties. Specifically, ZnO NPs annealed at high temperature (700 °C) have been found sensitive to CO, while they displayed negligible response to NO2. The opposite behavior has been registered for the one-dimensional ZnO NFs annealed at medium temperature (400 °C). Due to their adaptable sensitivity/selectivity characteristics, the developed sensors show promising applications in dual air quality control systems for closed ambient such as automotive cabin, parking garage and tunnels.

Room-temperature hydrogen sensing with heteronanostructures based on reduced graphene oxide and tin oxide.

There's something in the air … A nanocomposite consisting of well-dispersed SnO(2) and Pt nanoparticles on reduced graphene oxide (see the high-resolution TEM image) exhibited very high responses to hydrogen at concentrations between 0.5 and 3% in air, with response times of 3-7 s and recovery times of 2-6 s. The sensor was prepared by a straightforward microwave-assisted non-aqueous sol-gel approach.