skip to main content


Title: Recent Advances in Electrochemical Sensors for Detecting Toxic Gases: NO2, SO2 and H2S
Toxic gases, such as NOx, SOx, H2S and other S-containing gases, cause numerous harmful effects on human health even at very low gas concentrations. Reliable detection of various gases in low concentration is mandatory in the fields such as industrial plants, environmental monitoring, air quality assurance, automotive technologies and so on. In this paper, the recent advances in electrochemical sensors for toxic gas detections were reviewed and summarized with a focus on NO2, SO2 and H2S gas sensors. The recent progress of the detection of each of these toxic gases was categorized by the highly explored sensing materials over the past few decades. The important sensing performance parameters like sensitivity/response, response and recovery times at certain gas concentration and operating temperature for different sensor materials and structures have been summarized and tabulated to provide a thorough performance comparison. A novel metric, sensitivity per ppm/response time ratio has been calculated for each sensor in order to compare the overall sensing performance on the same reference. It is found that hybrid materials-based sensors exhibit the highest average ratio for NO2 gas sensing, whereas GaN and metal-oxide based sensors possess the highest ratio for SO2 and H2S gas sensing, respectively. Recently, significant research efforts have been made exploring new sensor materials, such as graphene and its derivatives, transition metal dichalcogenides (TMDs), GaN, metal-metal oxide nanostructures, solid electrolytes and organic materials to detect the above-mentioned toxic gases. In addition, the contemporary progress in SO2 gas sensors based on zeolite and paper and H2S gas sensors based on colorimetric and metal-organic framework (MOF) structures have also been reviewed. Finally, this work reviewed the recent first principle studies on the interaction between gas molecules and novel promising materials like arsenene, borophene, blue phosphorene, GeSe monolayer and germanene. The goal is to understand the surface interaction mechanism.  more » « less
Award ID(s):
1840712
NSF-PAR ID:
10210677
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
Sensors
Volume:
19
Issue:
4
ISSN:
1424-8220
Page Range / eLocation ID:
905
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. null (Ed.)
    In the last two decades, GaN nanostructures of various forms like nanowires (NWs), nanotubes (NTs), nanofibers (NFs), nanoparticles (NPs) and nanonetworks (NNs) have been reported for gas sensing applications. In this paper, we have reviewed our group’s work and the works published by other groups on the advances in GaN nanostructures-based sensors for detection of gases such as hydrogen (H2), alcohols (R-OH), methane (CH4), benzene and its derivatives, nitric oxide (NO), nitrogen dioxide (NO2), sulfur-dioxide (SO2), ammonia (NH3), hydrogen sulfide (H2S) and carbon dioxide (CO2). The important sensing performance parameters like limit of detection, response/recovery time and operating temperature for different type of sensors have been summarized and tabulated to provide a thorough performance comparison. A novel metric, the product of response time and limit of detection, has been established, to quantify and compare the overall sensing performance of GaN nanostructure-based devices reported so far. According to this metric, it was found that the InGaN/GaN NW-based sensor exhibits superior overall sensing performance for H2 gas sensing, whereas the GaN/(TiO2–Pt) nanowire-nanoclusters (NWNCs)-based sensor is better for ethanol sensing. The GaN/TiO2 NWNC-based sensor is also well suited for TNT sensing. This paper has also reviewed density-functional theory (DFT)-based first principle studies on the interaction between gas molecules and GaN. The implementation of machine learning algorithms on GaN nanostructured sensors and sensor array has been analyzed as well. Finally, gas sensing mechanism on GaN nanostructure-based sensors at room temperature has been discussed. 
    more » « less
  2. Liquid crystals (LCs), when supported on reactive surfaces, undergo changes in ordering that can propagate over distances of micrometers, thus providing a general and facile mechanism to amplify atomic-scale transformations on surfaces into the optical scale. While reactions on organic and metal substrates have been coupled to LC ordering transitions, metal oxide substrates, which offer unique catalytic activities for reactions involving atmospherically important chemical species such as oxidized sulfur species, have not been explored. Here we investigate this opportunity by designing LCs that contain 4′-cyanobiphenyl-4-carboxylic acid (CBCA) and respond to surface reactions triggered by parts-per-billion concentrations of SO2 gas on anatase (101) substrates. We used electronic structure calculations to predict that the carboxylic acid group of CBCA binds strongly to anatase (101) in a perpendicular orientation, a prediction that we validated in experiments in which CBCA (0.005 mol%) was doped into a LC (4’-n-pentyl-4-biphenylcarbonitrile). Both experiment and computational modeling further demonstrated that SO3-like species, produced by a surface-catalyzed reaction of SO2 with H2O on anatase (101), displace CBCA from the anatase surface, resulting in an orientational transition of the LC. Experiments also reveal the LC response to be highly selective to SO2 over other atmospheric chemical species (including H2O, NH3, H2S, and NO2), in agreement with our computational predictions for anatase (101) surfaces. Overall, we establish that the catalytic activities of metal oxide surfaces offer the basis of a new class of substrates that trigger LCs to undergo ordering transitions in response to chemical species of relevance to atmospheric chemistry. 
    more » « less
  3. null (Ed.)
    The spread of the COVID-19 pandemic and consequent lockdowns all over the world have had various impacts on atmospheric quality. This study aimed to investigate the impact of the lockdown on the air quality of Nanjing, China. The off-axis measurements from state-of-the-art remote-sensing Multi-Axis Differential Optical Absorption Spectroscope (MAX-DOAS) were used to observe the trace gases, i.e., Formaldehyde (HCHO), Nitrogen Dioxide (NO2), and Sulfur Dioxide (SO2), along with the in-situ time series of NO2, SO2 and Ozone (O3). The total dataset covers the span of five months, from 1 December 2019, to 10 May 2020, which comprises of four phases, i.e., the pre lockdown phase (1 December 2019, to 23 January 2020), Phase-1 lockdown (24 January 2020, to 26 February 2020), Phase-2 lockdown (27 February 2020, to 31 March 2020), and post lockdown (1 April 2020, to 10 May 2020). The observed results clearly showed that the concentrations of selected pollutants were lower along with improved air quality during the lockdown periods (Phase-1 and Phase-2) with only the exception of O3, which showed an increasing trend during lockdown. The study concluded that limited anthropogenic activities during the spring festival and lockdown phases improved air quality with a significant reduction of selected trace gases, i.e., NO2 59%, HCHO 38%, and SO2 33%. We also compared our results with 2019 data for available gases. Our results imply that the air pollutants concentration reduction in 2019 during Phase-2 was insignificant, which was due to the business as usual conditions after the Spring Festival (Phase-1) in 2019. In contrast, a significant contamination reduction was observed during Phase-2 in 2020 with the enforcement of a Level-II response in lockdown conditions i.e., the easing of the lockdown situation in some sectors during a specific interval of time. The observed ratio of HCHO to NO2 showed that tropospheric ozone production involved Volatile Organic Compounds (VOC) limited scenarios. 
    more » « less
  4. Sensors are routinely developed for specific applications, but multipurpose sensors are challenging, due to stability and poor functional design. We report organic materials that operate in solution and gas phase. They show a strong response behaviour to at least three types of environmental changes: pH, amine and metal ion binding/detection. We have confirmed and validated our findings using various analytical and computational methods. We found that the changes in polarity of the solvent and pH not only red shift the tail of the absorption spectra, but also extend the peak optical absorption of these structures by up to 100 nm, with consequential effects on the optical gap and colour changes of the materials. Acid–base response has been studied by spectrophotometric titrations with trifluoroacetic acid (TFA) and triethyl amine (TEA). The experiments show excellent reversibility with greater sensitivity to base than acid for all compounds. Analysis into metal sensing using Zn( ii ) and Cu( ii ) ions as analytes show that the materials can successfully bind the cations forming stable complexes. Moreover, a strong suppression of signal with copper gives an operative modality to detect the copper ion as low as 2.5 × 10 −6 M. The formation of the metal complexes was also confirmed by growing crystals using a slow diffusion method; subsequent single crystal X-ray analysis reveals the ratio of ligand to metal to be 2 to 1. To test sensitivity towards various amine vapours, paper-based sensors have been fabricated. The sensors show a detection capability at 1 ppm of amine concentration. We have employed CIE L * a * b * colour space as the evaluation method, this provides numeric comparison of the samples from different series and allows comparison of small colour differences, which are generally undetectable by the human-eye. It shows that the CIE L * a * b * method can assess both sensitivity to a particular class of analytes and a specificity response to individual amines in this subclass offering an inexpensive and versatile methodology. 
    more » « less
  5. Abstract

    In this study, the hydrogen gas (H2) sensing mechanism of suspended graphene (Gr)/ Poly(3,4‐ethylene dioxythiophene): Poly(styrene sulfonate) – Polyethylene oxide (PEDOT: PSS‐PEO) composite nanoscale channels precisely patterned with near‐field electrospinning is investigated. Suspended Gr/PEDOT: PSS‐PEO nanoscale channels not only have a higher surface‐to‐volume ratio for easy diffusion in/out of the composite but also show enhanced response due to effective charge transfer at the interface of suspended graphene and PEDOT: PSS‐PEO nanofiber. A sensing response of 2% for 1 ppm of H2concentration with good linearity over a wide dynamic range is achieved. Arrays of nanoscale channels for enhanced sensitivity are also implemented and microheaters for effective and fast device recovery are integrated. Moreover, the sensor response is also characterized at various conditions such as channel materials and sizes, temperatures, and gas concentrations. The demonstrated performance, with low power consumption and small form factor, promises a facile and low‐cost suspended graphene/PEDOT: PSS‐PEO sensor solution with enhanced sensitivity.

     
    more » « less