Index Air Quality Monitoring for Light and Active Mobility.

Light and active mobility, as well as multimodal mobility, could significantly contribute to decarbonization. Air quality is a key parameter to monitor the environment in terms of health and leisure benefits. In a possible scenario, wearables and recharge stations could supply information about a distributed monitoring system of air quality. The availability of low-power, smart, low-cost, compact embedded systems, such as Arduino Nicla Sense ME, based on BME688 by Bosch, Reutlingen, Germany, and powered by suitable software tools, can provide the hardware to be easily integrated into wearables as well as in solar-powered EVSE (Electric Vehicle Supply Equipment) for scooters and e-bikes. In this way, each e-vehicle, bike, or EVSE can contribute to a distributed monitoring network providing real-time information about micro-climate and pollution. This work experimentally investigates the capability of the BME688 environmental sensor to provide useful and detailed information about air quality. Initial experimental results from measurements in non-controlled and controlled environments show that BME688 is suited to detect the human-perceived air quality. CO2 readout can also be significant for other gas (e.g., CO), while IAQ (Index for Air Quality, from 0 to 500) is heavily affected by relative humidity, and its significance below 250 is quite low for an outdoor uncontrolled environment.

Metal Oxide Nanowire-Based Sensor Array for Hydrogen Detection.

Accurate hydrogen leakage detection is a major requirement for the safe and widespread integration of this fuel in modern energy production devices, such as fuel cells. Quasi-1D nanowires of seven different metal oxides (CuO, WO3, Nb-added WO3, SnO2, ZnO, α-Bi2O3, NiO) were integrated into a conductometric sensor array to evaluate the hydrogen-sensing performances in the presence of interfering gaseous compounds, namely carbon monoxide, nitrogen dioxide, methane, acetone, and ethanol, at different operating temperatures (200-400 °C). Principal component analysis (PCA) was applied to data extracted from the array, demonstrating the ability to discriminate hydrogen over other interferent compounds. Moreover, a reduced array formed by only five sensors is proposed. This compact array may be easily implementable into artificial olfaction systems used in real hydrogen detection applications.

Synthesis of TiO2-(B) Nanobelts for Acetone Sensing.

Titanium dioxide nanobelts were prepared via the alkali-hydrothermal method for application in chemical gas sensing. The formation process of TiO2-(B) nanobelts and their sensing properties were investigated in detail. FE-SEM was used to study the surface of the obtained structures. The TEM and XRD analyses show that the prepared TiO2 nanobelts are in the monoclinic phase. Furthermore, TEM shows the formation of porous-like morphology due to crystal defects in the TiO2-(B) nanobelts. The gas-sensing performance of the structure toward various concentrations of hydrogen, ethanol, acetone, nitrogen dioxide, and methane gases was studied at a temperature range between 100 and 500 °C. The fabricated sensor shows a high response toward acetone at a relatively low working temperature (150 °C), which is important for the development of low-power-consumption functional devices. Moreover, the obtained results indicate that monoclinic TiO2-B is a promising material for applications in chemo-resistive gas detectors.

Fabrication of CuO (p)-ZnO (n) Core-Shell Nanowires and Their H2-Sensing Properties.

Unlike the conventional one-dimensional (1D) core-shell nanowires (NWs) composed of p-type shells and n-type cores, in this work, an inverse design is proposed by depositing n-type ZnO (shell) layers on the surface of p-type CuO (core) NWs, to have a comprehensive understanding of their conductometric gas-sensing kinetics. The surface morphologies of bare and core-shell NWs were investigated by field emission scanning electron microscope (FE-SEM). The ZnO shell layer was presented by overlay images taken by electron dispersive X-ray spectroscopy (EDX) and high-resolution transmission electron microscopy (HRTEM). The pronounced crystalline plane peaks of ZnO were recorded in the compared glancing incident X-ray diffraction (GI-XRD) spectra of CuO and CuO-ZnO core-shell NWs. The ZnO shell layers broaden the absorption curve of CuO NWs in the UV-vis absorption spectra. As a result of the heterostructure formation, the intrinsic p-type sensing behavior of CuO NWs towards 250 and 500 ppm of hydrogen (H2) switched to n-type due to the deposition of ZnO shell layers, at 400 °C in dry airflow.

Flower-like ZnO Nanostructures Local Surface Morphology and Chemistry.

This work presents the results of comparative studies using complementary methods, such as scanning electron microscopy (SEM), X-ray photoemission spectroscopy (XPS), and thermal desorption spectroscopy (TDS) to investigate the local surface morphology and chemistry of flower-like ZnO nanostructures synthesized by the thermal oxidation technique on native Si/SiO2 substrates. SEM studies showed that our flower-like ZnO nanostructures contained mostly isolated and irregular morphological low-dimensional forms, seen as rolled-up floss flowers, together with local, elongated, complex stalks similar to Liatris flowers, which contained joined short flosses in the form of nanodendrites. Beyond this, XPS studies showed that these nanostructures exhibited a slight surface nonstoichiometry, mostly related to the existence of oxygen-deficient regions, combined with strong undesired C surface contamination. In addition, the TDS studies showed that these undesired surface contaminations (including mainly C species and hydroxyl groups) are only slightly removed from the surface of our flower-like ZnO nanostructures, causing an expected modification of their nonstoichiometry. All of these effects are of great importance when using our flower-like ZnO nanostructures in gas sensor devices for detecting oxidizing gases because surface contamination leads to an undesired barrier for toxic gas adsorption, and it can additionally be responsible for the uncontrolled sensor aging effect.

Robust Room-Temperature NO2 Sensors from Exfoliated 2D Few-Layered CVD-Grown Bulk Tungsten Di-selenide (2H-WSe2).

We report a facile and robust room-temperature NO2 sensor fabricated using bi- and multi-layered 2H variant of tungsten di-selenide (2H-WSe2) nanosheets, exhibiting high sensing characteristics. A simple liquid-assisted exfoliation of 2H-WSe2, prepared using ambient pressure chemical vapor deposition, allows smooth integration of these nanosheets on transducers. Three sensor batches are fabricated by modulating the total number of layers (L) obtained from the total number of droplets from a homogeneous 2H-WSe2 dispersion, such as ∼2L, ∼5-6L, and ∼13-17L, respectively. The gas-sensing attributes of 2H-WSe2 nanosheets are investigated thoroughly. Room temperature (RT) experiments show that these devices are specifically tailored for NO2 detection. 2L WSe2 nanosheets deliver the best rapid response compared to ∼5-6L or ∼13-17L. The response of 2L WSe2 at RT is 250, 328, and 361% to 2, 4, and 6 ppm NO2, respectively. The sensor showed nearly the same response toward low NO2 concentration even after 9 months of testing, confirming its remarkable long-term stability. A selectivity study, performed at three working temperatures (RT, 100, and 150 °C), shows high selectivity at 150 and 100 °C. Full selectivity toward NO2 at RT confirms that 2H-WSe2 nanosheet-based sensors are ideal candidates for NO2 gas detection.

One Dimensional ZnO Nanostructures: Growth and Chemical Sensing Performances.

Recently, one-dimensional (1D) nanostructures have attracted the scientific community attention as sensitive materials for conductometric chemical sensors. However, finding facile and low-cost techniques for their production, controlling the morphology and the aspect ratio of these nanostructures is still challenging. In this study, we report the vapor-liquid-solid (VLS) synthesis of one dimensional (1D) zinc oxide (ZnO) nanorods (NRs) and nanowires (NWs) by using different metal catalysts and their impact on the performances of conductometric chemical sensors. In VLS mechanism, catalysts are of great interest due to their role in the nucleation and the crystallization of 1D nanostructures. Here, Au, Pt, Ag and Cu nanoparticles (NPs) were used to grow 1D ZnO. Depending on catalyst nature, different morphology, geometry, size and nanowires/nanorods abundance were established. The mechanism leading to the VLS growth of 1D ZnO nanostructures and the transition from nanorods to nanowires have been interpreted. The formation of ZnO crystals exhibiting a hexagonal crystal structure was confirmed by X-ray diffraction (XRD) and ZnO composition was identified using transmission electron microscopy (TEM) mapping. The chemical sensing characteristics showed that 1D ZnO has good and fast response, good stability and selectivity. ZnO (Au) showed the best performances towards hydrogen (H2). At the optimal working temperature of 350 °C, the measured response towards 500 ppm of H2 was 300 for ZnO NWs and 50 for ZnO NRs. Moreover, a good selectivity to hydrogen was demonstrated over CO, acetone and ethanol.

An Array of MOX Sensors and ANNs to Assess Grated Parmigiano Reggiano Cheese Packs' Compliance with CFPR Guidelines.

Parmigiano Reggiano cheese is one of the most appreciated Italian foods on account of its high nutrient content and taste. Due to its high cost, these characteristics make this product subject to counterfeiting in different forms. In this study, an approach based on an array of gas sensors has been employed to assess if it was possible to distinguish different samples based on their aroma. Samples were characterized in terms of rind percentage, seasoning, and rind working process. From the responses of the sensors, five features were extracted and the capability of these parameters to recognize target classes was tested with statistical analysis. Hence, the performance of the sensors' array was quantified using artificial neural networks. To simplify the problem, a hierarchical approach has been used: three steps of classification were performed, and in each step one parameter of the grated cheese was identified (firstly, seasoning; secondly, rind working process; finally, rind percentage). The accuracies ranged from 88.24% to 100%.

Seed-Assisted Growth of TiO2 Nanowires by Thermal Oxidation for Chemical Gas Sensing.

Herein, we report the catalyst assisted growth of TiO2 one-dimensional (1D) nanowires (NWs) on alumina substrates by the thermal oxidation technique. RF magnetron sputtering was used to deposit a thin Ti metallic layer on the alumina substrate, followed by an Au catalytic layer on the Ti metallic one. Thermal oxidation was carried out in an oxygen deficient environment. The optimal thermal growth temperature was 700 °C, in a mixture environment composed by Ar and O2. As a comparison, Ti films were also oxidized without the presence of the Au catalyst. However, without the Au catalyst, no growth of nanowires was observed. Furthermore, the effect of the oxidation temperature and the film thickness were also investigated. SEM, TEM, and EDX studies demonstrated the presence of Au nanoparticles on top of the NWs, indicating that the Au catalyst drove the growth process. Raman spectroscopy revealed the Rutile crystalline phase of TiO2 NWs. Gas testing measurements were carried out in the presence of a relative humidity of 40%, showing a reversible response to ethanol and H2 at various concentrations. Thanks to the moderate temperature and the easiness of the process, the presented synthesis technique is suitable to grow TiO2 NWs for many different applications.

Novel insight on the local surface properties of ZnO nanowires.

Novel insight on the local surface properties of ZnO nanowires (NW) deposited by the evaporation-condensation method on Ag-covered Si substrates is proposed, based on the results of comparative studies by using the scanning electron microscopy (SEM), x-ray photoemission spectroscopy (XPS) and thermal desorption spectroscopy (TDS) methods, respectively. SEM studies showed that ZnO nanowires (nanoribbons) are mostly isolated and irregular, having the average length µm and the average at the level of tens nm, respectively. Our XPS studies confirmed their evident surface non-stoichiometry, combined with strong C surface contaminations, which was related to the existence of oxygen-deficient regions. Additionally, TDS studies showed that undesired surface contaminations (including C species and hydroxyl groups) on the surface of ZnO NWs can be removed almost completely, leading to an increase of the final non-stoichiometry. Both effects are of great importance when using ZnO NWs for the detection of oxidizing gases, because the undesired C contaminations (including C-OH species) play the role of undesired barriers for the gas adsorption, especially at the low working temperature, additionally affecting the uncontrolled sensor ageing effect.

Nanostructured MOS Sensor for the Detection, Follow up, and Threshold Pursuing of Campylobacter Jejuni Development in Milk Samples.

Food poisoning is still the first cause of hospitalization worldwide and the most common microbial agent, Campylobacter jejuni, is the most commonly reported gastrointestinal disease in humans in the EU (European Union) as is reported by the European Union One Health 2018 Zoonoses Report styled by the EFSA (European Food Safety Authority) and ECDC (European Center for Disease Prevention and Control). One of the vehicles of transmission of this disease is milk. Nanostructured MOS (Metal Oxide Semiconductor) sensors have extensively demonstrated their ability to reveal the presence and follow the development of microbial species. The main objective of this work was to find a set up for the detection and development follow up of C. jejuni in milk samples. The work was structured in two different studies, the first one was a feasibility survey and the second one was to follow up the development of the bacteria inside milk samples. The obtained results of the first study demonstrate the ability of the sensor array to differentiate the contaminated samples from the control ones. Thanks to the second study, it has been possible to find the limit of microbial safety of the contaminated milk samples.

Hydrogen Gas Sensing Performances of p-Type Mn3O4 Nanosystems: The Role of Built-in Mn3O4/Ag and Mn3O4/SnO2 Junctions.

Among oxide semiconductors, p-type Mn3O4 systems have been exploited in chemo-resistive sensors for various analytes, but their use in the detection of H2, an important, though flammable, energy vector, has been scarcely investigated. Herein, we report for the first time on the plasma assisted-chemical vapor deposition (PA-CVD) of Mn3O4 nanomaterials, and on their on-top functionalization with Ag and SnO2 by radio frequency (RF)-sputtering, followed by air annealing. The obtained Mn3O4-Ag and Mn3O4-SnO2 nanocomposites were characterized by the occurrence of phase-pure tetragonal α-Mn3O4 (hausmannite) and a controlled Ag and SnO2 dispersion. The system functional properties were tested towards H2 sensing, yielding detection limits of 18 and 11 ppm for Mn3O4-Ag and Mn3O4-SnO2 specimens, three orders of magnitude lower than the H2 explosion threshold. These performances were accompanied by responses up to 25% to 500 ppm H2 at 200 °C, superior to bare Mn3O4, and good selectivity against CH4 and CO2 as potential interferents. A rationale for the observed behavior, based upon the concurrence of built-in Schottky (Mn3O4/Ag) and p-n junctions (Mn3O4/SnO2), and of a direct chemical interplay between the system components, is proposed to discuss the observed activity enhancement, which paves the way to the development of gas monitoring equipments for safety end-uses.

Chemical Gas Sensors Studied at SENSOR Lab, Brescia (Italy): From Conventional to Energy-Efficient and Biocompatible Composite Structures.

In this paper, we present the investigations on metal oxide-based gas sensors considering the works performed at SENSOR lab, University of Brescia (Italy). We reported the developments in synthesis techniques for the preparation of doped and functionalized low-dimensional metal oxide materials. Furthermore, we discussed our achievements in the fabrication of heterostructures with unique functional features. In particular, we focused on the strategies to improve the sensing performance of metal oxides at relatively low operating temperatures. We presented our studies on surface photoactivation of sensing structures considering the application of biocompatible materials in the architecture of the functional devices as well.

Manganese Oxide Nanoarchitectures as Chemoresistive Gas Sensors to Monitor Fruit Ripening.

The efficient detection of low-concentration ethylene is a challenging issue of key importance for food quality control end-uses. Herein, we report on the fabrication of MnO2-based nanoarchitectures by a two-step plasma-assisted process, consisting in the initial chemical vapor deposition of MnO2 (host) on polycrystalline Al2O3 substrates and the subsequent functionalization with Ag and Au-based nanoparticles (guest) by sputtering processes. The resulting composites, characterized by a high Ag/Au dispersion and an effective host-guest contact, were tested for the first time as chemoresistive gas sensors for ethylene recognition at low temperatures. The high sensitivity and promising responses, enhanced by metal particle introduction, candidate the target systems as attractive platforms for the eventual monitoring of vegetables/fruits ripening and ageing.

Integration of VLS-Grown WO3 Nanowires into Sensing Devices for the Detection of H2S and O3.

The inspiration behind this research is the development of tungsten oxide (WO3) nanowires based, highly sensitive and selective sensing devices directly on the active sensing platform. WO3 one-dimensional nanowires were synthesized via the vapour-phase growth technique. This approach allows the production of well-aligned and uniform nanowires on alumina substrates with their diameter and length in the nanometer range. The morphological and structural properties of nanowires have been investigated by means of the field effect electron microscopy, grazing incidence X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy. Finally, the fabricated WO3 nanowire sensing devices and their gas sensing performance were investigated in the presence of different oxidizing and reducing gases (especially environmental gases) at different temperatures. The WO3 sensors demonstrate high performance toward H2S and O3 at the optimal working temperatures of 400 and 200 °C, respectively, with the detection limit in the ppb level.

Low-Power Detection of Food Preservatives by a Novel Nanowire-Based Sensor Array.

Food preservatives are compounds that are used for the treatment of food to improve the shelf life. In the food industry, it is necessary to monitor all processes for both safety and quality of the product. An electronic nose (or e-nose) is a biomimetic olfactory system that could find numerous industrial applications, including food quality control. Commercial electronic noses are based on sensor arrays composed by a combination of different sensors, which include conductometric metal oxide devices. Metal oxide nanowires are considered among the most promising materials for the fabrication of novel sensing devices, which can enhance the overall performances of e-noses in food applications. The present work reports the fabrication of a novel sensor array based on SnO2, CuO, and WO3 nanowires deposited on top of µHPs provided by ams Sensor Solutions Germany GmbH. The array was tested for the discrimination of four typical compounds added to food products or used for their treatment to increase the shelf life: ethanol, acetone, nitrogen dioxide, and ozone. Results are very promising; the sensors array was able to operate for a long time, consuming less than 50 mW for each single sensor, and principal component analysis (PCA) confirmed that the device was able to discriminate between different compounds.

Sensing Nitrogen Mustard Gas Simulant at the ppb Scale via Selective Dual-Site Activation at Au/Mn3O4 Interfaces.

The efficient detection of chemical warfare agents (CWAs), putting at stake human life and global safety, is of paramount importance in the development of reliable sensing devices for safety applications. Herein, we present the fabrication of Mn3O4-based nanocomposites containing noble metal particles for the gas-phase detection of a simulant of vesicant nitrogen mustard, i.e., di(propylene glycol) monomethyl ether (DPGME). The target materials were fabricated by chemical vapor deposition of manganese oxide on Al2O3 substrates and subsequent functionalization with silver or gold via radio frequency sputtering. The obtained high purity composites, characterized by an intimate metal/oxide contact, yielded an outstanding efficiency in the detection of DPGME. In particular, sensing of the latter analyte with an ultralow detection limit of 0.6 ppb could be performed selectively with respect to other CWA simulants. In addition, the tuneability of selectivity patterns as a function of metal nanoparticle nature paves the way to the development of efficient and selective devices for practical end uses.

The Influence of Nb on the Synthesis of WO3 Nanowires and the Effects on Hydrogen Sensing Performance.

Hydrogen sensing is becoming one of the hottest topics in the chemical sensing field, due to its wide number of applications and the dangerousness of hydrogen leakages. For this reason, research activities are focusing on the development of high-performance materials that can be easily integrated in sensing devices. In this work, we investigated the influence of Nb on the sensing performances of WO3 nanowires (NWs) synthetized by a low-cost thermal oxidation method. The morphology and the structure of these Nb-WO3 nanowires were investigated by field emission scanning electron microscope (FE-SEM), high-resolution transmission electron microscope (HR-TEM), X-ray diffraction (XRD), Raman and X-ray photoelectron (XPS) spectroscopies, confirming that the addition of Nb does not modify significantly the monoclinic crystal structure of WO3. Moreover, we integrated these NWs into chemical sensors, and we assessed their performances toward hydrogen and some common interfering compounds. Although the hydrogen sensing performances of WO3 nanowires were already excellent, thanks to the presence of Nb they have been further enhanced, reaching the outstanding value of more than 80,000 towards 500 ppm @ 200 °C. This opens the possibility of their integration in commercial equipment, like electronic noses and portable devices.

"Metal oxide -based heterostructures for gas sensors"- A review.

This review focuses on the synthesis and chemical sensing characterization of metal oxide heterostructures reported since 2012. Heterostructures exhibit strong interactions between closely packed interfaces, showing superior performances compared to single structures. Surface effects appear thanks to the magnification of nanostructures' surface leading to an enhancement of surface related properties (the base of chemical sensors working mechanism). The combination of different metal oxides to form heterostructures further improves the selectivity and/or other important sensing parameters. A very large number of different morphologies and structures have been proposed, each one exhibiting peculiar sensing properties towards specific chemical compounds. Among the different preparation methodologies, a significant number has been performed by means of hydrothermal method. However, the combination of various fabrication methods seems a very efficient strategy to obtain metal oxide-based heterostructures with different morphologies and dimensions such as core-shell nanostructures, one-dimensional heterostructures, two-dimensional layered heterojunctions, and three-dimensional hierarchical heterostructures. Despite all extraordinary advances in both material science and nanotechnology and the results achieved with heterostructured chemical sensors, there are few points that still deserve further studies and investigations, such as possible diffusion across the junctions, reproducibility of the fabrication process, synergistic or catalytic effects among the materials forming the heterostructures and influence/stability of the contacts. Moreover, perfect control over their growth is mandatory for their application in commercial devices. Only a careful understanding of the growth and the interface properties could fill the existing gap between laboratory studies and real-world exploitation of these heterostructures.

Surface Properties of SnO2 Nanowires Deposited on Si Substrate Covered by Au Catalyst Studies by XPS, TDS and SEM.

The surface chemistry and the morphology of SnO2 nanowires of average length and diameter of several µm and around 100 nm, respectively, deposited by vapor phase deposition (VPD) method on Au-covered Si substrate, were studied before and after subsequent air exposure. For this purpose, surface-sensitive methods, including X-ray photoelectron spectroscopy (XPS), thermal desorption spectroscopy (TDS) and the scanning electron microscopy (SEM), were applied. The studies presented within this paper allowed to determine their surface non-stoichiometry combined with the presence of carbon contaminations, in a good correlation with their surface morphology. The relative concentrations of the main components [O]/[Sn]; [C]/[Sn]; [Au]/[Sn], together with the O⁻Sn; O⁻Si bonds, were analyzed. The results of TDS remained in a good agreement with the observations from XPS. Moreover, conclusions obtained for SnO2 nanowires deposited with the use of Au catalyst were compared to the previous obtained for Ag-assisted tin dioxide nanowires. The information obtained within these studies is of a great importance for the potential application of SnO2 nanowires in the field of novel chemical nanosensor devices, since the results can provide an interpretation of how aging effects influence gas sensor dynamic characteristics.