Two-dimensional carbide crystals (MXenes) are emerging as a promising platform for the development of novel gas sensors, offering advantages in energy efficiency and tunable analyte selectivity. One of the most effective strategies to enhance and tailor their functional performance involves forming hetero-structured composites with metal oxides. In this work, we explore a chemiresistive effect in double-metal MXene of Ti0.2V1.8C and its composites with 2 mol. % SnO2 and Co3O4 nanocrystalline oxides toward feasibility tests with alcohol and ammonia vapor probes. The materials were characterized by simultaneous thermal analysis, X-ray diffraction analysis, Raman spectroscopy, and scanning/transmission electron microscopy. Gas-sensing experiments were carried out on composite layers deposited on multi-electrode substrates to be exposed to the test gases, 200–2000 ppm concentrations, at an operating temperature of 370 °C. The developed sensor array demonstrated clear analyte discrimination. The distinct sensor responses enabled a selective identification of vapors through linear discriminant analysis, demonstrating the further potential of MXene-based materials for integrated electronic nose applications.

Gas sensors which could efficiently operate at room temperature (RT) are highly requested by numerous end-users including various industries, Internet of Things, and personal gadgets. Therefore, 2D MXenes of metal carbides are suggested as a possible emerging option to be alternative to conventional metal oxides. Here, we consider i-MXene structures of W1.33C with in-plane ordered vacancies at the metal sites for additional functionalization of the material. The materials were properly characterized by XRD, XPS, and electron microscopy and further drop-casted over on-chip multielectrode array to be exposed upon gaseous analytes, representative of alcohols, ketones, arenes, and humidity at RT. It is shown that W1.33C structures are mostly sensitive to H2O vapors with the limit of detection going down below 1 ppm. The selectivity to distinguish various analytes is demonstrated via applying a multisensor approach while processing the vector response yielded by the entire array of on-chip W1.33C-based sensor elements.

Background The multisensor concept has been developed as a powerful alternative to well-known gas-analytical instrumentation for applications where a fast but accurate and reliable assessment of the environment is required. The concept follows a biology-inspired approach where the selectivity towards various gases/odors is attained via pattern recognition of multisensory signal vectors. Herein, we discuss how to design a selective multisensor library based on various metal oxide nanostructures like a lab-on-chip using a simple but efficient bottom-up growth of materials over the multi-electrode chip under robust dc electrochemical protocols. Results In addition to a conventional growth of oxide layers over the metal electrodes, we show that the fine nanowall-like oxide structures appear as a quasi-matrixed percolation film over the SiO2 substrate surface in the inter-electrode gaps to constitute a chemiresistive film. We have tested two directions while applying the technique to grow Co, Ni, Mn, and Zn oxides to develop on-chip sensor arrays of, (i) monoxide type employing the oxide films with gradual change of growth time, and (ii) multi-oxide type based on the four oxides. The materials were thoroughly characterized by electron microscopy, X-ray diffraction, thermogravimetric analysis, and X-ray photoelectron spectroscopy/mapping to prove the composition and structure. Among tested oxides, ZnO readily appears not only at the electric potential-targeted chip zone but also in other areas to dope the films for yielding heterojunctions with other oxides that enhances a variability of functional properties in the on-chip sensor array. The gas-sensing performance of the chips has been tested versus various chemically akin alcohol vapors at the sub- and low ppm range of concentrations in a mixture with air. Significance We show that the grown oxide nanostructures exhibit a high-sensitive chemiresistive signal which allows one to build a multisensor vector signal, selective to the kind of alcohols, even at sub-ppm concentrations. Moreover, the multi-oxide library yields options for a superior selectivity under LDA metrics than the gradient-grown mono-oxide one due to the versatility of materials while the low-cost growth protocols remain to be the same in both cases. The delivered method to produce multisensor arrays allows one producing low-cost but efficient electronic nose units for numerous applications.

Electronic nose (EN) units mimicking the operation of a mammalian olfaction system find widespread applications in various fields. However, these devices face problems with the steadiness of sensor response that significantly reduces their abilities when compared to custom analytical instrumentation. We discuss approaches to handling non-stationary signals generated by a multisensor array of EN and study the efficiency of single-and multi-stage classifiers based on gradient-boosted tree model and linear discriminant analysis. Employing an experimental setting with a graphene-based on-chip unit, we show that our methods allow to obtain a high-quality classification of analyte (97.0% precision and 94.6% recall of 5 analytes with a latency of under 3 min) after a carefully designed calibration.

The emerging versatile realm of graphene/metal oxide nanoparticles (NPs) composites has boosted the development of energy storage and gas sensing systems. However, with the advancements in deriving composites of more complex designs, the explicit understanding of their physics with respect to chemistry and morphology began to fade. Here, we aspire to hint at the effect of ZnO nanoparticles on aminated graphene, bundling theoretical modeling with thorough experimental examination (Transmission electron microscopy, X-ray photoelectron, X-ray absorption fine structure and valence-band photoemission spectroscopies, and temperature-dependent sheet resistance measurements). Starting with setting up the framework for modeling the Am-ZnO composite with its thorough verification by experimental probing, we stepwise examine the material's properties. The effect of ZnO surface chemistry on bonding, often neglected theoretically, is highlighted by core-level spectroscopy. In turn, band structure and charge localization alterations induced by ZnO NPs are pointed out experimentally, supplemented with the developed method for conductivity calculations. Given these results, the role of graphene, NPs, and their interface in chemiresistive signal appearance is further featured. Taken together, our results give a hint at the mechanisms underlying the interaction between the metal oxide NPs and derivatized graphene, advancing the engineering of such composites for practical applications.

While preparing oxide layers as gas sensors by a sol-gel approach, a high-temperature annealing makes a challenge to apply in numerous applications like flexible electronics with a heavy influence on the oxide microstructure. Therefore, its replacing by UV irradiation combined with a mild heating as “photo-annealing” paves the way to develop soft protocols when designing oxide-based gas sensors bearing a fine nanocrystallinity. Herein, we consider hierarchical sol-gel derived ZnO films which were a subject of conventional annealing and photoannealing to compare their gas-sensor performance when exposed to alcohol vapors. It is found that films obtained by photoannealing have an X-ray amorphous character, in contrast to ones being thermally annealed; although, the hierarchical organization of both samples revealed by SEM is almost identical. The DFTB modeling performed for ZnO crystal exposed to alcohol molecules and water has indicated the chemiresistive effect to be enhanced with a molecular weight of analytes. These observations were validated in experiment with sol-gel ZnO layers which exhibited an alcohol response in sub-ppm concentration range down to 10 ppb. To selectively compare the impact of various alcohols, we successfully applied a linear-discriminant analysis to the vector signal of the on-chip multisensor array.

MXenes are two-dimensional (2D) materials with a great potential for sensor applications due to their high aspect ratio and fully functionalized surface that can be tuned for specific gas adsorption. Here, we demonstrate that the Nb2CTz-based sensor exhibits high performance towards alcohol vapors at temperatures up to 300–350 °C, with the best sensitivity towards ethanol. We attribute the observed remarkable chemiresistive effect of this material to the formation of quasi-2D Nb2O5 sheets as the result of the oxidation of Nb-based MXenes. These findings are supported by synchrotron X-ray photoelectron spectroscopy studies together with X-ray diffraction and electron microscopy observations. For analyte selectivity, we employ a multisensor approach where the gas recognition is achieved by linear discriminant analysis of the vector response of the on-chip sensor array. The reported protocol demonstrates that MXene layers are efficient precursors for the derivation of 2D oxide architectures, which are suitable for developing gas sensors and sensor arrays.

Composites based on carbon nanomaterials exhibit many advantageous properties for gas sensing, such as high and fast response, room-temperature operation, and tailoring sensitivity by energy level engineering. However, only the first attempts to employ such chemosensors for gas-sensing applications have been made. In this work, an on-chip multisensor array of carboxylated carbon nanotubes (CNT), aminated reduced graphene oxide (rGO-Am), and CNT/rGO-Am nanocomposite was fabricated using a simple and low-cost spray deposition method. The CNT/rGO-Am sensor demonstrated a fast and high response to NH3 in dry air at low (25 ppm) and high (400 ppm) concentrations of 70 and 115%, respectively. The response to NH3 in humid air increased and reached 160% at 400 ppm. The chemosensor exhibited high sensitivity and selectivity toward ammonia with a low detection limit estimated to be below 0.2 ppb. Linear discriminant analysis of the sensor responses to different concentrations of NH3, dry and humid air revealed better discrimination when CNT/rGO-Am composites were used in combination with CNT and rGO-Am sensors in an array. This study demonstrates that composite sensors with junctions between carbon nanomaterials have great potential for practical applications in fast and selective gas detection at room temperature and different humidity.

Herein, we represent the creating and gas-sensing properties of On-chip multisensor arrays based on a phosphorylated graphene (Gr-P) film with a gradually changed thickness. Selective detection of the alcohols, from methanol to butanol, mixed with air to match permissible exposure OSHA limits is demonstrated for the chip operating at room temperature.

The rational design of composites based on graphene/metal oxides is one of the pillars for advancing their application in various practical fields, particularly gas sensing. In this study, a uniform distribution of ZnO nanoparticles (NPs) through the graphene layer was achieved, taking advantage of amine functionalization. The beneficial effect of amine groups on the arrangement of ZnO NPs and the efficiency of their immobilization was revealed by core-level spectroscopy, pointing out strong ionic bonding between the aminated graphene (AmG) and ZnO. The stability of the resulting Am-ZnO nanocomposite was confirmed by demonstrating that its morphology remains unchanged even after prolonged heating up to 350 °C, as observed by electron microscopy. On-chip multisensor arrays composed of both AmG and Am-ZnO were fabricated and thoroughly tested, showing almost tenfold enhancement of the chemiresistive response upon decorating the AmG layer with ZnO nanoparticles, due to the formation of p-n heterojunctions. Operating at room temperature, the fabricated multisensor chips exhibited high robustness and a detection limit of 3.6 ppm and 5.1 ppm for ammonia and ethanol, respectively. Precise identification of the studied analytes was achieved by employing the pattern recognition technique based on linear discriminant analysis to process the acquired multisensor response.

The detection of inert gases presents a challenging task because these molecules do not react with most known sensor-based units aimed at environment monitoring. Here, we ionize these molecules in a low-potential discharge mode to force their interaction with semiconducting SnO2 single-crystal nanobelts (NBs) deposited as a mat over a multielectrode chip and show the ion-induced resistivity changes similar to a conventional operation of the metal oxide sensor. In particular, the conductance of the percolating NB mats is significantly enhanced under irradiation with He+, Ne+, and Ar+ ions at a low-pressure oxygen background. The phenomenon is well explained via ab initio calculations performed in the framework of density functional theory (DFT), which clarify the interaction of various ions with SnO2 nanocrystals related primarily to the appearance of electronic states and redistribution of their density dependent on the kind of ions. The differences in ion interaction with the SnO2 surface is the background for options to distinguish the inert gases with a SnO2 NB-based multisensor array as a low-cost selective detector via transferring the variations in a charge exchange at the adsorbate/adsorbent interface into a varied chemiresistive vector signal like a (mass) spectrometer performs.

The results of experimental studies of the effect of degradation of macroscopic charge transport in ensembles of close-packed anatase nanoparticles under long-term action of a constant electric field are presented. The degradation is presumably due to the increasing degree of blocking of statistically independent conduction channels formed in ensembles of particles under the field action. A phenomenological model is considered for estimating the number of active conduction channels in an ensemble of particles near the percolation threshold in the system. Keywords: nanoparticles, anatase, charge transfer, percolation threshold.

The 2D structure of MXenes attracts wide research attention toward an application of these materials in gas sensors. These structures are extremely sensitive to minor variations in their composition, which are employed for tuning their functional properties. Here, we consider the partially substituted MXenes of the composition of TixV2-xC, where x = 0.2, via quantum chemical calculations, and test their chemiresistive characteristics as a receptor component of the planar-type sensor and on-chip multisensor array. We thoroughly discuss the synthesis process of Ti0.2V1.8AlC MAX-phase and the corresponding MXenes, to prepare functional inks and, furthermore, deposit the films by microextrusion printing over an array of planar multi-electrode structures at the surface of a pen-sized chip. The crystal structure of the obtained materials is evaluated via X-ray diffraction analysis. The developed chip has been exposed upon few gaseous analytes, of alcohol VOCs, NH3, and H2O, of a 500–16,000 ppm concentration, at room temperature to ensure that we could observe the positive chemiresistive effect matured from resistance enhancing, with up to 10% vs. water vapors. The calculations carried in the framework of the density-functional theory for V2C, Ti2C, and Ti0.2V1.8C crystals ensured that the variations in their electronic structure were almost consistent with the experiment fundings: the most prominent effect is observed in relation to the H2O vapors. Therefore, these Ti0.2V1.8C structures could be considered for applying them in room temperature-operated hygrometers.

The results of experimental studies of the effect of degradation of macroscopic charge transport in ensembles of close-packed anatase nanoparticles under long-term action of a constant electric field are presented. The degradation is presumably due to the increasing degree of blocking of statistically independent conduction channels formed in ensembles of particles under the field action. A phenomenological model is considered for estimating the number of active conduction channels in an ensemble of particles near the percolation threshold in the system.

The artificial olfaction units (or e-noses) capable of room-temperature operation are highly demanded to meet the requests of society in numerous vital applications and developing Internet-of-Things. Derivatized 2D crystals are considered as sensing elements of choice in this regard, unlocking the potential of the advanced e-nose technologies limited by the current semiconductor technologies. Herein, we consider fabrication and gas-sensing properties of On-chip multisensor arrays based on a hole-matrixed carbonylated (C-ny) graphene film with a gradually changed thickness and concentration of ketone groups of up to 12.5 at.%. The enhanced chemiresistive response of C-ny graphene toward methanol and ethanol, of hundred ppm concentration when mixing with air to match permissible exposure OSHA limits, at room-temperature operation is signified. Following thorough characterization via core-level techniques and density functional theory, the predominant role of the C-ny graphene-perforated structure and abundance of ketone groups in advancing the chemiresistive effect is established. Advancing practice applications, selective discrimination of the studied alcohols is approached by linear discriminant analysis employing a multisensor array's vector signal, and the fabricated chip's long-term performance is shown.

Уважаемые коллеги!Благодарим Вас за проявленный интерес к Четвертой российской конференции «Графен: молекула и 2D кристалл» и желание принять участие в её работе.Конференция проходит в научно-образовательном центре города Новосибирска -Академгородке.Мероприятие посвящено актуальным направлениям исследований и разработок в области углеродных и низкоразмерных материалов.Проведение конференции поможет координации усилий ученых в решении современных проблем материаловедения и привлечению молодых исследователей для решения актуальных научных задач.Оргкомитет выражает особую благодарность НГУ, Центру компетенций НТИ «Моделирование и разработка новых функциональных материалов с заданными свойствами», компаниям «Диаэм», «НТ-МДТ Спектрум Инструментс» и корпорации "Графеновая Долина" за финансовую поддержку и журналам Аналитика, Наноиндустрия и РЭНСИТ за информационную поддержку.Искренне надеемся, что пребывание в Новосибирском Академгородке и в стенах Новосибирского государственного университета оставит множество положительных эмоций и

The results of experimental studies of ohmic conductivity degradation in the ensembles of nanostructured anatase bridges under a long-term effect of direct current are presented. Stochastic sets of partially conducting inter-electrode bridges consisting of close-packed anatase nanoparticles were formed by means of the seeding particles from drying aqueous suspensions on the surfaces of silica substrates with interdigital platinum electrodes. Multiple-run experiments conducted at room temperature have shown that ohmic conductivity degradation in these systems is irreversible. It is presumably due to the accumulated capture of conduction electrons by deep traps in anatase nanoparticles. The scaling analysis of voltage drops across the samples at the final stage of degradation gives a critical exponent for ohmic conductivity as ≈1.597. This value satisfactorily agrees with the reported model data for percolation systems. At an early stage of degradation, the spectral density of conduction current fluctuations observed within the frequency range of 0.01–1 Hz decreases approximately as 1/ω, while near the percolation threshold, the decreasing trend changes to ≈1/ω2. This transition is interpreted in terms of the increasing contribution of blockages and subsequent avalanche-like breakdowns of part of the local conduction channels in the bridges into electron transport near the percolation threshold.

We consider an on-chip sensor array based on a mesoporous layer of SnO2 nanoparticles to be screen printed on the multielectrode-supplied Si/SiO2 substrate as a chemiresistive building platform for portable and personalized in situ instruments. To differentiate the local oxide layer properties we apply Nd:YAG laser whose scanning etched various layer areas at varied power driven by working current in 24.8 A-26.7 A range. As a result, the SnO2 layer has dual-grad modified properties as, (i) a spatial modification of thickness down to nm-range, and (ii) the change of oxidation state with appearance of traces of SnO, which both result in a great varying of gas -sensing properties of local sensor elements over the array. To test the functionality of the chip, we could detect vapors of four ketones (acetone, cyclopentanone, cyclohexanone, 2-octanone) and four alcohols (methanol, ethanol, isopropanol, butanol), at sub-, down to ca. 100 ppb, and low, up to 10, ppm concentrations with their selective recognition via processing the array's vector signal by linear discriminant algorithm. Primarily, we show differences in the interaction of ketones and alcohols with SnO2 surface by first-principle calculations in frames of density functional theory to serve as fundamental receptor pre-requisites for the analyte's selective discrimination by the oxide layer under the multisensor concept to employ here. We consistently show that two modes of the sensor operation could be rather equally applied to the array as, (i) UV LED, 366 nm wavelength, irradiation at room temperature, and (ii) heating up to approx. 583 K. While the heating provides faster and higher chemiresistive responses, the UV-excited mode provides more selective vector signals, lower energy consumption, and a higher signal-to-noise ratio.

Detection of heavy meals in aqueous media challenges worldwide research in developing particularly fast and affordable methods. Fluorescent sensors look to be an appropriate instrument for such a task, as recently they have been found to have made large progress in the detection of chemical analytes, primarily in the environment, along with biological fluids, which still suffer from not enough selectivity. In this work, we propose a new fluorescent method to selectively recognize heavy metals in an aqueous solution via employing an array of several fluorescent probes: acridine yellow, eosin, and methylene blue, which were taken as examples, being sensitive to a microsurrounding of the probe molecules. The exemplary sensor array generated six channels of spectral information through the use of various combinations of excitation and detection wavelengths. Following the known multisensor approach, we applied a linear discriminant analysis to selectively distinguish the vector signals from the sensor array from salts of heavy metals—Cu, Pb, Zn, Cd, and Cz—at the concentration ranges of 2.41 × 10−6–1.07 × 10−5 M, 2.8 × 10−5–5.87 × 10−4 M, 1.46 × 10−6–6.46 × 10−6 M, 1.17 × 10−8–5.2 × 10−8 M, and 2.11 × 10−6–9.33 × 10−6 M, respectively. The suggested approach was found to be promising due to it employing only one cuvette containing the test solution, simplifying a sample preparation when compared to preparing a variety of solutions in tests with single fluorescence probes.

Graphene derivatization to either engineer its physical and chemical properties or overcome the problem of the facile synthesis of nanographenes is a subject of significant attention in the nanomaterials research community. In this paper, we propose a facile and scalable method for the synthesis of thiolated graphene via a two-step liquid-phase treatment of graphene oxide (GO). Employing the core-level methods, the introduction of up to 5.1 at.% of thiols is indicated with the simultaneous rise of the C/O ratio to 16.8. The crumpling of the graphene layer upon thiolation without its perforation is pointed out by microscopic and Raman studies. The conductance of thiolated graphene is revealed to be driven by the Mott hopping mechanism with the sheet resistance values of 2.15 kΩ/sq and dependable on the environment. The preliminary results on the chemiresistive effect of these films upon exposure to ethanol vapors in the mix with dry and humid air are shown. Finally, the work function value and valence band structure of thiolated graphene are analyzed. Taken together, the developed method and findings of the morphology and physics of the thiolated graphene guide the further application of this derivative in energy storage, sensing devices, and smart materials.