Multioxide combinatorial libraries: fusing synthetic approaches and additive technologies for highly orthogonal electronic noses.

This study evaluates the performance advancement of electronic noses, on-chip engineered multisensor systems, exploiting a combinatorial approach. We analyze a spectrum of metal oxide semiconductor materials produced by individual methods of liquid-phase synthesis and a combination of chemical deposition and sol-gel methods with hydrothermal treatment. These methods are demonstrated to enable obtaining a fairly wide range of nanomaterials that differ significantly in chemical composition, crystal structure, and morphological features. While synthesis routes foster diversity in material properties, microplotter printing ensures targeted precision in making on-chip arrays for evaluation of a combinatorial selectivity concept in the task of organic vapor, like alcohol homologs, acetone, and benzene, classification. The synthesized nanomaterials demonstrate a high chemiresistive response, with a limit of detection beyond ppm level. A specific combination of materials is demonstrated to be relevant when the number of sensors is low; however, such importance diminishes with an increase in the number of sensors. We show that on-chip material combinations could favor selectivity to a specific analyte, disregarding the others. Hence, modern synthesis methods and printing protocols supported by combinatorial analysis might pave the way for fabricating on-chip orthogonal multisensor systems.

Poly(vinyl chloride)/Nanocarbon Composites for Advanced Potentiometric Membrane Sensor Design.

Polymer nanocomposites filled with carbon nanoparticles (CNPs) are a hot topic in materials science. This article discusses the current research on the use of these materials as interfacial electron transfer films for solid contact potentiometric membrane sensors (SC-PMSs). The results of a comparative study of plasticized poly (vinyl chloride) (pPVC) matrices modified with single-walled carbon nanotubes (SWCNTs), fullerenes-C60, and their hybrid ensemble (SWCNTs-C60) are reported. The morphological characteristics and electrical conductivity of the prepared nanostructured composite films are reported. It was found that the specific electrical conductivity of the pPVC/SWCNTs-C60 polymer film was higher than that of pPVC filled with individual nanocomponents. The effectiveness of this composite material as an electron transfer film in a new potentiometric membrane sensor for detecting phenylpyruvic acid (in anionic form) was demonstrated. Screening for this metabolic product of phenylalanine in body fluids is of significant diagnostic interest in phenylketonuria (dementia), viral hepatitis, and alcoholism. The developed sensor showed a stable and fast Nernstian response for phenylpyruvate ions in aqueous solutions over the wide linear concentration range of 5 × 10-7-1 × 10-3 M, with a detection limit of 10-7.2 M.

Current Trends and Promising Electrode Materials in Micro-Supercapacitor Printing.

The development of scientific and technological foundations for the creation of high-performance energy storage devices is becoming increasingly important due to the rapid development of microelectronics, including flexible and wearable microelectronics. Supercapacitors are indispensable devices for the power supply of systems requiring high power, high charging-discharging rates, cyclic stability, and long service life and a wide range of operating temperatures (from -40 to 70 °C). The use of printing technologies gives an opportunity to move the production of such devices to a new level due to the possibility of the automated formation of micro-supercapacitors (including flexible, stretchable, wearable) with the required type of geometric implementation, to reduce time and labour costs for their creation, and to expand the prospects of their commercialization and widespread use. Within the framework of this review, we have focused on the consideration of the key commonly used supercapacitor electrode materials and highlighted examples of their successful printing in the process of assembling miniature energy storage devices.

Hydrothermal Synthesis of a Cellular NiO Film on Carbon Paper as a Promising Way to Obtain a Hierarchically Organized Electrode for a Flexible Supercapacitor.

The formation of a cellular hierarchically organized NiO film on a carbon paper substrate under hydrothermal conditions using triethanolamine as a base has been studied. The thermal behavior of the carbon paper substrate with the applied semi-product shell was studied using synchronous thermal analysis (TGA/DSC) and it was demonstrated that such modification of the material surface leads to a noticeable increase in its thermal stability. Using scanning electron microscopy (SEM), it was shown that the NiO film grown on the carbon fiber surface is characterized by a complex cellular morphology, organized by partially layered individual nanosheets of about 4-5 nm thickness and lateral dimensions up to 1-2 µm, some edges and folds of which are located vertically relative to the carbon fiber surface. The surface of the obtained material was also examined using atomic force microscopy (AFM), and the electronic work function of the oxide shell surface was evaluated using the Kelvin probe force microscopy (KPFM) method. The electrochemical parameters of the obtained flexible NiO/CP electrode were analyzed: the dependence of the specific capacitance on the current density was determined and the stability of the material during cycling was studied, which showed that the proposed approach is promising for manufacturing hierarchically organized electrodes for flexible supercapacitors.

Gas-Sensitive Properties of ZnO/Ti2CTx Nanocomposites.

At present, a new class of 2D nanomaterials, MXenes, is of great scientific and applied interest, and their application prospects are very broad, including as effective doping components for receptor materials of MOS sensors. In this work we have studied the influence on the gas-sensitive properties of nanocrystalline zinc oxide synthesized by atmospheric pressure solvothermal synthesis, with the addition of 1-5% of multilayer two-dimensional titanium carbide Ti2CTx, obtained by etching Ti2AlC with NaF solution in hydrochloric acid. It was found that all the obtained materials have high sensitivity and selectivity with respect to 4-20 ppm NO2 at a detection temperature of 200 °C. It is shown that the selectivity towards this compound is best for the sample containing the highest amount of Ti2CTx dopant. It has been found that as the MXene content increases, there is an increase in nitrogen dioxide (4 ppm) from 1.6 (ZnO) to 20.5 (ZnO-5 mol% Ti2CTx). reactions which the responses to nitrogen dioxide increase. This may be due to the increase in the specific surface area of the receptor layers, the presence of MXene surface functional groups, as well as the formation of the Schottky barrier at the interface between the phases of the components.

Low Temperature Chemoresistive Oxygen Sensors Based on Titanium-Containing Ti2CTx and Ti3C2Tx MXenes.

The chemoresistive properties of multilayer titanium-containing Ti2CTx and Ti3C2Tx MXenes, synthesized by etching the corresponding MAX phases with NaF solution in hydrochloric acid, and the composites based on them, obtained by partial oxidation directly in a sensor cell in an air flow at 150 °C, were studied. Significant differences were observed for the initial MXenes, both in microstructure and in the composition of surface functional groups, as well as in gas sensitivity. For single Ti2CTx and Ti3C2Tx MXenes, significant responses to oxygen and ammonia were observed. For their partial oxidation at a moderate temperature of 150 °C, a high humidity sensitivity (T, RH = 55%) is observed for Ti2CTx and a high and selective response to oxygen for Ti3C2Tx at 125 °C (RH = 0%). Overall, these titanium-containing MXenes and composites based on them are considered promising as receptor materials for low temperature oxygen sensors.

Microplotter Printing of a Miniature Flexible Supercapacitor Electrode Based on Hierarchically Organized NiCo2O4 Nanostructures.

The hydrothermal synthesis of a nanosized NiCo2O4 oxide with several levels of hierarchical self-organization was studied. Using X-ray diffraction analysis (XRD) and Fourier-transform infrared (FTIR) spectroscopy, it was determined that under the selected synthesis conditions, a nickel-cobalt carbonate hydroxide hydrate of the composition M(CO3)0.5(OH)·0.11H2O (where M-Ni2+ and Co2+) is formed as a semi-product. The conditions of semi-product transformation into the target oxide were determined by simultaneous thermal analysis. It was found by means of scanning electron microscopy (SEM) that the main powder fraction consists of hierarchically organized microspheres of 3-10 µm in diameter, and individual nanorods are observed as the second fraction of the powder. Nanorod microstructure was further studied by transmission electron microscopy (TEM). A hierarchically organized NiCo2O4 film was printed on the surface of a flexible carbon paper (CP) using an optimized microplotter printing technique and functional inks based on the obtained oxide powder. It was shown by XRD, TEM, and atomic force microscopy (AFM) that the crystalline structure and microstructural features of the oxide particles are preserved when deposited on the surface of the flexible substrate. It was found that the obtained electrode sample is characterized by a specific capacitance value of 420 F/g at a current density of 1 A/g, and the capacitance loss during 2000 charge-discharge cycles at 10 A/g is 10%, which indicates a high material stability. It was established that the proposed synthesis and printing technology enables the efficient automated formation of corresponding miniature electrode nanostructures as promising components for flexible planar supercapacitors.

Hydrothermal Synthesis of Nickel Oxide and Its Application in the Additive Manufacturing of Planar Nanostructures.

The hydrothermal synthesis of nickel oxide in the presence of triethanolamine was studied. Furthermore, the relationship between the synthesis conditions, thermal behavior, crystal structure features, phase composition and microstructure of semi-products, and the target oxide nanopowders was established. The thermal behavior of the semi-products was studied using a simultaneous thermal analysis (in particular, using one that involved thermogravimetric analysis and differential scanning calorimetry, TGA/DSC). An X-ray diffraction (XRD) analysis revealed that varying the triethanolamine and nickel chloride concentration in the reaction system can govern the formation of α- and ß-Ni(OH)2-based semi-products that contain Ni(HCO3)2 or Ni2(CO3)(OH)2 as additional components. The set of functional groups in the powders was determined using a Fourier-transform infrared (FTIR) spectroscopy analysis. Using microextrusion printing, a composite NiO-(CeO2)0.80(Sm2O3)0.20 anode film was fabricated. Using XRD, scanning electron microscopy (SEM), and atomic force microscopy (AFM) analyses, it was demonstrated that the crystal structure, dispersity, and microstructure character of the obtained material correspond to the initial nanopowders. Using Kelvin probe force microscopy (KPFM) and scanning capacitance microscopy (SCM), the local electrophysical properties of the printed composite film were examined. The value of its conductivity was evaluated using the four-probe method on a direct current in the temperature range of 300-650 °C. The activation energy for the 500-650 °C region, which is of most interest in the context of intermediate-temperature SOFCs working temperatures, has been estimated.

Application of Titanium Carbide MXenes in Chemiresistive Gas Sensors.

The titanium carbide MXenes currently attract an extreme amount of interest from the material science community due to their promising functional properties arising from the two-dimensionality of these layered structures. In particular, the interaction between MXene and gaseous molecules, even at the physisorption level, yields a substantial shift in electrical parameters, which makes it possible to design gas sensors working at RT as a prerequisite to low-powered detection units. Herein, we consider to review such sensors, primarily based on Ti3C2Tx and Ti2CTx crystals as the most studied ones to date, delivering a chemiresistive type of signal. We analyze the ways reported in the literature to modify these 2D nanomaterials for (i) detecting various analyte gases, (ii) improving stability and sensitivity, (iii) reducing response/recovery times, and (iv) advancing a sensitivity to atmospheric humidity. The most powerful approach based on designing hetero-layers of MXenes with other crystals is discussed with regard to employing semiconductor metal oxides and chalcogenides, noble metal nanoparticles, carbon materials (graphene and nanotubes), and polymeric components. The current concepts on the detection mechanisms of MXenes and their hetero-composites are considered, and the background reasons for improving gas-sensing functionality in the hetero-composite when compared with pristine MXenes are classified. We formulate state-of-the-art advances and challenges in the field while proposing some possible solutions, in particular via employing a multisensor array paradigm.

Atmospheric Pressure Solvothermal Synthesis of Nanoscale SnO2 and Its Application in Microextrusion Printing of a Thick-Film Chemosensor Material for Effective Ethanol Detection.

The atmospheric pressure solvothermal (APS) synthesis of nanocrystalline SnO2 (average size of coherent scattering regions (CSR)-7.5 ± 0.6 nm) using tin acetylacetonate as a precursor was studied. The resulting nanopowder was used as a functional ink component in microextrusion printing of a tin dioxide thick film on the surface of a Pt/Al2O3/Pt chip. Synchronous thermal analysis shows that the resulting semiproduct is transformed completely into tin dioxide nanopowder at 400 °C within 1 h. The SnO2 powder and the resulting film were shown to have a cassiterite-type structure according to X-ray diffraction analysis, and IR spectroscopy was used to establish the set of functional groups in the material composition. The microstructural features of the tin dioxide powder were analyzed using scanning (SEM) and transmission (TEM) electron microscopy: the average size of the oxide powder particles was 8.2 ± 0.7 nm. Various atomic force microscopy (AFM) techniques were employed to investigate the topography of the oxide film and to build maps of surface capacitance and potential distribution. The temperature dependence of the electrical conductivity of the printed SnO2 film was studied using impedance spectroscopy. The chemosensory properties of the formed material when detecting H2, CO, NH3, C6H6, C3H6O and C2H5OH, including at varying humidity, were also examined. It was demonstrated that the obtained SnO2 film has an increased sensitivity (the sensory response value was 1.4-63.5) and selectivity for detection of 4-100 ppm C2H5OH at an operating temperature of 200 °C.