Enhanced CO2 Sensing by Oxygen Plasma-Treated Perovskite-Graphene Nanocomposites.

Carbon dioxide (CO2) is a major greenhouse gas responsible for global warming and climate change. The development of sensitive CO2 sensors is crucial for environmental and industrial applications. This paper presents a novel CO2 sensor based on perovskite nanocrystals immobilized on graphene and functionalized with oxygen plasma treatment. The impact of this post-treatment method was thoroughly investigated using various characterization techniques, including Raman spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The detection of CO2 at parts per million (ppm) levels demonstrated that the hybrids subjected to 5 min of oxygen plasma treatment exhibited a 3-fold improvement in sensing performance compared to untreated layers. Consequently, the CO2 sensing capability of the oxygen-treated samples showed a limit of detection and limit of quantification of 6.9 and 22.9 ppm, respectively. Furthermore, the influence of ambient moisture on the CO2 sensing performance was also evaluated, revealing a significant effect of oxygen plasma treatment.

Advantages of Slow Sensing for Ambient Monitoring: A Practical Perspective.

Air pollution is a ubiquitous threat, affecting 99% of the global populace and causing millions of premature deaths annually. Monitoring ambient air quality is essential, aiding policymakers and environmental agencies in timely interventions. This study delves into the advantages of slower gas sensors over their ultrafast counterparts, with a keen focus on their practicality in real-world scenarios. Slow sensors offer accurate time-averaged exposure assessments, harmonizing with established regulatory benchmarks. Their heightened precision and reliability, complemented by their cost-effectiveness, render them eminently suitable for large-scale deployment. The slow sensing ensures compatibility with regulations, fostering robust risk management practices. In contrast, ultrafast sensors, while claiming rapid detection, despite touting swift detection capabilities, grapple with formidable challenges. The sensitivity of ultrafast sensors to uncontrolled atmospheric effects, fluctuations in pressure, rapid response times, and uniform gas dispersion poses significant hurdles to their reliability. Addressing these issues assumes paramount significance in upholding the integrity of air quality assessments.

Hydrogen Sensing Mechanism of WS2 Gas Sensors Analyzed with DFT and NAP-XPS.

Nanostructured tungsten disulfide (WS2) is one of the most promising candidates for being used as active nanomaterial in chemiresistive gas sensors, as it responds to hydrogen gas at room temperature. This study analyzes the hydrogen sensing mechanism of a nanostructured WS2 layer using near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) and density functional theory (DFT). The W 4f and S 2p NAP-XPS spectra suggest that hydrogen makes physisorption on the WS2 active surface at room temperature and chemisorption on tungsten atoms at temperatures above 150 °C. DFT calculations show that a hydrogen molecule physically adsorbs on the defect-free WS2 monolayer, while it splits and makes chemical bonds with the nearest tungsten atoms on the sulfur point defect. The hydrogen adsorption on the sulfur defect causes a large charge transfer from the WS2 monolayer to the adsorbed hydrogen. In addition, it decreases the intensity of the in-gap state, which is generated by the sulfur point defect. Furthermore, the calculations explain the increase in the resistance of the gas sensor when hydrogen interacts with the WS2 active layer.

ZnO-Loaded Graphene for NO2 Gas Sensing.

This paper investigates the effect of decorating graphene with zinc oxide (ZnO) nanoparticles (NPs) for the detection of NO2. In this regard, two graphene sensors with different ZnO loadings of 5 wt.% and 20 wt.% were prepared, and their responses towards NO2 at room temperature and different conditions were compared. The experimental results demonstrate that the graphene loaded with 5 wt.% ZnO NPs (G95/5) shows better performance at detecting low concentrations of the target gas than the one loaded with 20 wt.% ZnO NPs (G80/20). Moreover, measurements under dry and humid conditions of the G95/5 sensor revealed that the material is very sensitive to ambient moisture, showing an almost eight-fold increase in NO2 sensitivity when the background changes from dry to 70% relative humidity. Regarding sensor selectivity, it presents a significant selectivity towards NO2 compared to other gas compounds.

Octahedral Molybdenum Iodide Clusters Supported on Graphene for Resistive and Optical Gas Sensing.

This paper reports for the first time a gas-sensitive nanohybrid based on octahedral molybdenum iodide clusters supported on graphene flakes (Mo6@Graphene). The possibility of integrating this material into two different transducing schemes for gas sensing is proposed since the nanomaterial changes both its electrical resistivity and optical properties when exposed to gases and at room temperature. Particularly, when implemented in a chemoresistive device, the Mo6@Graphene hybrid showed an outstanding sensing performance toward NO2, revealing a limit of quantification of about 10 ppb and excellent response repeatability (0.9% of relative error). While the Mo6@Graphene chemoresistor was almost insensitive to NH3, the use of an optical transduction scheme (changes in photoluminescence) provided an outstanding detection of NH3 even for a low loading of Mo6. Nevertheless, the photoluminescence was not affected by the presence of NO2. In addition, the hybrid material revealed high stability of its gas sensing properties over time and under ambient moisture. Computational chemistry calculations were performed to better understand these results, and plausible sensing mechanisms were presented accordingly. These results pave the way to develop a new generation of multi-parameter sensors in which electronic and optical interrogation techniques can be implemented simultaneously, advancing toward the realization of highly selective and orthogonal gas sensing.

Unraveling the Gas-Sensing Mechanisms of Lead-Free Perovskites Supported on Graphene.

Lead halide perovskites have been attracting great attention due to their outstanding properties and have been utilized for a wide variety of applications. However, the high toxicity of lead promotes an urgent and necessary search for alternative nanomaterials. In this perspective, the emerging lead-free perovskites are an environmentally friendly and harmless option. The present work reports for the first time gas sensors based on lead-free perovskite nanocrystals supported on graphene, which acts as a transducing element owing to its high and efficient carrier transport properties. The use of nanocrystals enables achieving excellent sensitivity toward gas compounds and presents better properties than those of bulky perovskite thin films, owing to their quantum confinement effect and exciton binding energy. Specifically, an industrially scalable, facile, and inexpensive synthesis is proposed to support two different perovskites (Cs3CuBr5 and Cs2AgBiBr6) on graphene for effectively detecting a variety of harmful pollutants below the threshold limit values. H2 and H2S gases were detected for the first time by utilizing lead-free perovskites, and ultrasensitive detection of NO2 was also achieved at room temperature. In addition, the band-gap type, defect tolerance, and electronic surface traps at the nanocrystals were studied in detail for understanding the differences in the sensing performance observed. Finally, a comprehensive sensing mechanism is proposed.

Dysprosium Doped Zinc Oxide for NO2 Gas Sensing.

Pure and dysprosium-loaded ZnO films were grown by radio-frequency magnetron sputtering. The films were characterized using a wide variety of morphological, compositional, optical, and electrical techniques. The crystalline structure, surface homogeneity, and bandgap energies were studied in detail for the developed nanocomposites. The properties of pure and dysprosium-doped ZnO thin films were investigated to detect nitrogen dioxide (NO2) at the ppb range. In particular, ZnO sensors doped with rare-earth materials have been demonstrated as a feasible strategy to improve the sensitivity in comparison to their pure ZnO counterparts. In addition, the sensing performance was studied and discussed under dry and humid environments, revealing noteworthy stability and reliability under different experimental conditions. In this perspective, additional gaseous compounds such as ammonia and ethanol were measured, resulting in extremely low sensing responses. Therefore, the gas-sensing mechanisms were discussed in detail to better understand the NO2 selectivity given by the Dy-doped ZnO layer.

Metal loaded nano-carbon gas sensor array for pollutant detection.

Many research works report a sensitive detection of a wide variety of gas species. However, their in-lab detection is usually performed by using single gases and, therefore, selectivity often remains an unsolved issue. This paper reports a four-sensor array employing different nano-carbon sensitive layers (bare graphene, SnO2@Graphene, WO3@Graphene, and Au@CNTs). The different gas-sensitive films were characterised via several techniques such as FESEM, TEM, and Raman. First, an extensive study was performed to detect isolated NO2, CO2, and NH3molecules, unravelling the sensing mechanism at the operating temperatures applied. Besides, the effect of the ambient moisture was also evaluated. Afterwards, a model for target gas identification and concentration prediction was developed. Indeed, the sensor array was used in mixtures of NO2and CO2for studying the cross-sensitivity and developing a calibration model. As a result, the NO2detection with different background levels of CO2was achieved with anR2of 0.987 and an RMSE of about 22 ppb.

Graphene Loading with Polypyrrole Nanoparticles for Trace-Level Detection of Ammonia at Room Temperature.

The outstanding versatility of graphene for surface functionalization has been exploited by its decoration with synthesized polypyrrole (PPy) nanoparticles (NPs). A green, facile, and easily scalable for mass production nanocomposite development was proposed, and the resulting PPy@Graphene was implemented in chemoresistive gas sensors able to detect trace levels of ammonia (NH3) under room-temperature conditions. Gas exposure for 5 min revealed that the presence of nanoparticles decorating graphene entail greater sensitivity (13-fold) in comparison to the bare graphene performance. Noteworthy, excellent repeatability (0.7% of relative error) and a low limit of detection of 491 ppb were obtained, together with excellent long-term stability. Besides, an extensive material characterization was conducted, and vibration bands obtained via Raman spectroscopy confirmed the formation of PPy NPs, while X-ray spectroscopy (XPS) revealed the relative abundance of the different species, as polarons and bipolarons. Additionally, XPS analyses were conducted before and after NH3 exposure to assess the PPy aging and the changes induced in their physicochemical and electronic properties. Specifically, the gas sensor was tested during a 5-month period, demonstrating significant stability over time, since just a slight decrease (11%) in the responses was registered. In summary, the present work reports for the first time the use of PPy NPs decorating graphene for gas-sensing purposes, revealing promising properties for the development of unattended gas-sensing networks for monitoring air quality.

On the Use of Pulsed UV or Visible Light Activated Gas Sensing of Reducing and Oxidising Species with WO3 and WS2 Nanomaterials.

This paper presents a methodology to quantify oxidizing and reducing gases using n-type and p-type chemiresistive sensors, respectively. Low temperature sensor heating with pulsed UV or visible light modulation is used together with the application of the fast Fourier transform (FFT) to extract sensor response features. These features are further processed via principal component analysis (PCA) and principal component regression (PCR) for achieving gas discrimination and building concentration prediction models with R2 values up to 98% and RMSE values as low as 5% for the total gas concentration range studied. UV and visible light were used to study the influence of the light wavelength in the prediction model performance. We demonstrate that n-type and p-type sensors need to be used together for achieving good quantification of oxidizing and reducing species, respectively, since the semiconductor type defines the prediction model's effectiveness towards an oxidizing or reducing gas. The presented method reduces considerably the total time needed to quantify the gas concentration compared with the results obtained in a previous work. The use of visible light LEDs for performing pulsed light modulation enhances system performance and considerably reduces cost in comparison to previously reported UV light-based approaches.

LoRa Sensor Network Development for Air Quality Monitoring or Detecting Gas Leakage Events.

During the few last years, indoor and outdoor Air Quality Monitoring (AQM) has gained a lot of interest among the scientific community due to its direct relation with human health. The Internet of Things (IoT) and, especially, Wireless Sensor Networks (WSN) have given rise to the development of wireless AQM portable systems. This paper presents the development of a LoRa (short for long-range) based sensor network for AQM and gas leakage events detection. The combination of both a commercial gas sensor and a resistance measurement channel for graphene chemoresistive sensors allows both the calculation of an Air Quality Index based on the concentration of reducing species such as volatile organic compounds (VOCs) and CO, and it also makes possible the detection of NO2, which is an important air pollutant. The graphene sensor tested with the LoRa nodes developed allows the detection of NO2 pollution in just 5 min as well as enables monitoring sudden changes in the background level of this pollutant in the atmosphere. The capability of the system of detecting both reducing and oxidizing pollutant agents, alongside its low-cost, low-power, and real-time monitoring features, makes this a solution suitable to be used in wireless AQM and early warning systems.

The role of anions and cations in the gas sensing mechanisms of graphene decorated with lead halide perovskite nanocrystals.

We report the effects of both anions and cations in lead halide perovskite-graphene hybrids applied to gas sensing. Ultra-fast sensors that can work at room temperature are developed and studied to elucidate the role in the gas sensing mechanisms of different ions in perovskite nanocrystals.

Metal Oxide Nanoparticle-Decorated Few Layer Graphene Nanoflake Chemoresistors for the Detection of Aromatic Volatile Organic Compounds.

Benzene, toluene, and xylene, commonly known as BTX, are hazardous aromatic organic vapors with high toxicity towards living organisms. Many techniques are being developed to provide the community with portable, cost effective, and high performance BTX sensing devices in order to effectively monitor the quality of air. In this paper, we study the effect of decorating graphene with tin oxide (SnO2) or tungsten oxide (WO3) nanoparticles on its performance as a chemoresistive material for detecting BTX vapors. Transmission electron microscopy and environmental scanning electron microscopy are used as morphological characterization techniques. SnO2-decorated graphene displayed high sensitivity towards benzene, toluene, and xylene with the lowest tested concentrations of 2 ppm, 1.5 ppm, and 0.2 ppm, respectively. In addition, we found that, by employing these nanomaterials, the observed response could provide a unique double signal confirmation to identify the presence of benzene vapors for monitoring occupational exposure in the textiles, painting, and adhesives industries or in fuel stations.

Multiwalled carbon nanotube based aromatic volatile organic compound sensor: sensitivity enhancement through 1-hexadecanethiol functionalisation.

Aromatic volatile organic compound (VOC) sensors are attracting growing interest as a response to the pressing market need for sensitive, fast response, low power consumption and stable sensors. Benzene and toluene detection is subject to several potential applications such as air monitoring in chemical industries or even biosensing of human breath. In this work, we report the fabrication of a room temperature toluene and benzene sensor based on multiwall carbon nanotubes (MWCNTs) decorated with gold nanoparticles and functionalised with a long-chain thiol self-assembled monolayer, 1-hexadecanethiol (HDT). High-resolution transmission electron microscopy (HRTEM) and Fourier transform infrared spectroscopy (FTIR) were performed to characterize the gold nanoparticle decoration and to examine the thiol monolayer bonding to the MWCNTs. The detection of aromatic vapours using Au-MWCNT and HDT/Au-MWCNT sensors down to the ppm range shows that the presence of the self-assembled layer increases the sensitivity (up to 17 times), selectivity and improves the response dynamics of the sensors.

Gas Sensing Properties of Perovskite Decorated Graphene at Room Temperature.

This paper explores the gas sensing properties of graphene nanolayers decorated with lead halide perovskite (CH3NH3PbBr3) nanocrystals to detect toxic gases such as ammonia (NH3) and nitrogen dioxide (NO2). A chemical-sensitive semiconductor film based on graphene has been achieved, being decorated with CH3NH3PbBr3 perovskite (MAPbBr3) nanocrystals (NCs) synthesized, and characterized by several techniques, such as field emission scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy. Reversible responses were obtained towards NO2 and NH3 at room temperature, demonstrating an enhanced sensitivity when the graphene is decorated by MAPbBr3 NCs. Furthermore, the effect of ambient moisture was extensively studied, showing that the use of perovskite NCs in gas sensors can become a promising alternative to other gas sensitive materials, due to the protective character of graphene, resulting from its high hydrophobicity. Besides, a gas sensing mechanism is proposed to understand the effects of MAPbBr3 sensing properties.

Diamondoid Nanostructures as sp3 -Carbon-Based Gas Sensors.

Diamondoids, sp3 -hybridized nanometer-sized diamond-like hydrocarbons (nanodiamonds), difunctionalized with hydroxy and primary phosphine oxide groups, enable the assembly of the first sp3 -C-based chemical sensors by vapor deposition. Both pristine nanodiamonds and palladium nanolayered composites can be used to detect toxic NO2 and NH3 gases. This carbon-based gas sensor technology allows reversible NO2 detection down to 50 ppb and NH3 detection at 25-100 ppm concentration with fast response and recovery processes at 100 °C. Reversible gas adsorption and detection is compatible with 50 % humidity conditions. Semiconducting p-type sensing properties are achieved from devices based on primary phosphine-diamantanol, in which high specific area (ca. 140 m2 g-1 ) and channel nanoporosity derive from H-bonding.

Hydrophilicity and carbon chain length effects on the gas sensing properties of chemoresistive, self-assembled monolayer carbon nanotube sensors.

Here we describe the development of chemoresistive sensors employing oxygen-plasma-treated, Au-decorated multiwall carbon nanotubes (MWCNTs) functionalized with self-assembled monolayers (SAMs) of thiols. For the first time, the effects of the length of the carbon chain and its hydrophilicity on the gas sensing properties of SAMs formed on carbon nanotubes are studied, and additionally, the gas sensing mechanisms are discussed. Four thiols differing in the length of the carbon chain and in the hydrophobic or hydrophilic nature of the head functional group are studied. Transmission electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy are used to analyze the resulting gas-sensitive hybrid films. Among the different nanomaterials tested, short-chain thiols having a hydrophilic head group, self-assembled onto Au-decorated carbon nanotubes were most responsive to nitrogen dioxide and ethanol vapors, even in the presence of ambient humidity. In particular, this nanomaterial was about eight times more sensitive to nitrogen dioxide than bare Au-decorated carbon nanotubes when operated at room temperature. This response enhancement is attributed to the interaction, via strong hydrogen bonding, of the polar molecules tested to the polar surface of hydrophilic thiols. The approach discussed here could be extended further by combining hydrophilic and hydrophobic thiol SAMs in Au-MWCNT sensor arrays as a helpful strategy for tuning sensor response and selectivity. This would make the detection of polar and nonpolar gas species employing low-power gas sensors easier, even under fluctuating ambient moisture conditions.

Wet chemistry route for the decoration of carbon nanotubes with iron oxide nanoparticles for gas sensing.

In this work, we investigated the parameters for decorating multiwalled carbon nanotubes with iron oxide nanoparticles using a new, inexpensive approach based on wet chemistry. The effect of process parameters such as the solvent used, the amount of iron salt or the calcination time on the morphology, decoration density and nanocluster size were studied. With the proposed approach, the decoration density can be adjusted by selecting the appropriate ratio of carbon nanotubes/iron salt, while nanoparticle size can be modulated by controlling the calcination period. Pristine and iron-decorated carbon nanotubes were deposited on silicon substrates to investigate their gas sensing properties. It was found that loading with iron oxide nanoparticles substantially ameliorated the response towards nitrogen dioxide.

Gas Sensing with Iridium Oxide Nanoparticle Decorated Carbon Nanotubes.

The properties of multi-wall carbon nanotubes decorated with iridium oxide nanoparticles (IrOx-MWCNTs) are studied to detect harmful gases such as nitrogen dioxide and ammonia. IrOx nanoparticles were synthetized using a two-step method, based on a hydrolysis and acid condensation growth mechanism. The metal oxide nanoparticles obtained were employed for decorating the sidewalls of carbon nanotubes. Iridium-oxide nanoparticle decorated carbon nanotube material showed higher and more stable responses towards NH3 and NO2 than bare carbon nanotubes under different experimental conditions, establishing the optimal operating temperatures and estimating the limits of detection and quantification. Furthermore, the nanomaterials employed were studied using different morphological and compositional characterization techniques and a gas sensing mechanism is proposed.