Sustainable Metal Oxide Materials for Sensing Applications

A topical collection in Chemosensors (ISSN 2227-9040). This collection belongs to the section "Materials for Chemical Sensing".

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Editors


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Collection Editor
i3N/CENIMAT, Department of Materials Science, NOVA School of Science and Technology and CEMOP/UNINOVA, NOVA University Lisbon, Campus de Caparica, 2829-516 Caparica, Portugal
Interests: multicomponent oxides; nanostructures; nanofabrication; nano-lithography (EBL); nanodevices; flexible and transparent technology; oxide thin film transistors; energy harvesting; multifunctionality; sustainability
Special Issues, Collections and Topics in MDPI journals

Topical Collection Information

Dear Colleagues,

In the last several decades, nanotechnology has advanced at an impressive rate, owing to a high level of development in both materials and processing routes. This impressive progress is contributing significantly to the growth of several areas, such as (opto)electronics, chemical sensors, medicine/biology, energy, and others.

Particularly, sensors are some of the key devices in smart surfaces and Internet of things (IoT) applications. To meet these concepts, sensing applications now require flexible, transparent, nanoscale devices and materials. In this context, metal oxides are particularly interesting due to their good optical and electrical properties and their capability for transparency, large area uniformity, and good mechanical flexibility. Concerning the environmental issues the world is facing, special attention should be given to materials and methods which are low-cost and sustainable, while still enabling high integration levels.

Thus, this Special Issue welcomes the submission of papers focused on the fabrication of sustainable metal oxide materials, in the form of thin films or nanostructures, and their application for sensors.

Dr. Ana Rovisco
Prof. Dr. Elisabetta Comini
Collection Editors

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Keywords

  • metal oxides
  • thin films
  • nanomaterials
  • pH sensors
  • optical sensors
  • gas sensors
  • biosensors
  • sustainability

Published Papers (19 papers)

2023

Jump to: 2022, 2021

15 pages, 4867 KiB  
Article
Flexible Bending Sensors Fabricated with Interdigitated Electrode Structures Cross-Linked by Transition Metal Doped ZnO Nanorods
by Waqar Muhammad and Sam-Dong Kim
Chemosensors 2023, 11(10), 529; https://doi.org/10.3390/chemosensors11100529 - 08 Oct 2023
Viewed by 1152
Abstract
Bending strain sensors based on one-dimensional ZnO nanorod (NR) arrays cross-linked with interdigitated electrodes were fabricated on polyethylene terephthalate (PET) substrates. ZnO NRs were grown using the hydrothermal method through the dopings with different transition metals, such as Co, Ni, or Co-plus-Ni, on [...] Read more.
Bending strain sensors based on one-dimensional ZnO nanorod (NR) arrays cross-linked with interdigitated electrodes were fabricated on polyethylene terephthalate (PET) substrates. ZnO NRs were grown using the hydrothermal method through the dopings with different transition metals, such as Co, Ni, or Co-plus-Ni, on PET substrates, and their microstructural morphology and crystalline properties were examined by a variety of surface analysis methods. Ultraviolet photoresponse and normalized resistance change were measured according to the bending strains to concave and convex directions, and the highest gauge factors of 175 and 83 were achieved in the convex and concave directions, respectively, at a bending strain of 1.75%, when Co-plus-Ni was doped to the NRs. Full article
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16 pages, 6379 KiB  
Article
Temperature Modulation of MOS Sensors for Enhanced Detection of Volatile Organic Compounds
by Andrea Rescalli, Davide Marzorati, Simone Gelosa, Francesco Cellesi and Pietro Cerveri
Chemosensors 2023, 11(9), 501; https://doi.org/10.3390/chemosensors11090501 - 15 Sep 2023
Cited by 1 | Viewed by 1371
Abstract
Disease diagnosis through biological fluids, particularly exhaled breath analysis, has gained increasing importance. Volatile organic compounds (VOCs) present in exhaled breath offer diagnostic potential as they reflect altered and disease-specific metabolic pathways. While gas chromatography–mass spectrometry (GC–MS) has been traditionally used for VOCs [...] Read more.
Disease diagnosis through biological fluids, particularly exhaled breath analysis, has gained increasing importance. Volatile organic compounds (VOCs) present in exhaled breath offer diagnostic potential as they reflect altered and disease-specific metabolic pathways. While gas chromatography–mass spectrometry (GC–MS) has been traditionally used for VOCs detection, electronic noses have emerged as a promising alternative for disease screening. Metal oxide semiconductor (MOS) sensors play an essential role in these devices due to their simplicity and cost-effectiveness. However, their limited specificity and sensitivity pose challenges for accurate diagnosis at lower VOCs concentrations, typical of exhaled breath. To address specificity and sensitivity issues, temperature modulation (TM) has been proposed in this paper, introducing a custom-developed electronic nose based on multiple and heterogeneous gas sensors located within an analysis chamber. Four different TM patterns (i.e., square, sine, triangular, and a combination of square and triangular) were applied to the gas sensors to test their response to three different analytes at three distinct concentrations. Data were analyzed by extracting meaningful features from the sensor raw data, and dimensionality reduction using principal component analysis (PCA) was performed. The results demonstrated distinct clusters for each experimental condition, indicating successful discrimination of analytes and concentrations. In addition, an analysis of which set of sensors and modulation pattern yielded the best results was performed. In particular, the most promising TM pattern proved to be the square and triangular combination, with optimal discrimination accuracy between both concentrations and analytes. One specific sensor, namely, TGS2600 from Figaro USA, Inc., provided the best performance. While preliminary results highlighted the potential of TM to improve the sensitivity of gas sensors in electronic nose devices, paving the way for further advancements in the field of exhaled breath analysis. Full article
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18 pages, 10180 KiB  
Article
Fabrication of Electrochemical Sensor for the Detection of Mg(II) Ions Using CeO2 Microcuboids as an Efficient Electrocatalyst
by Girdega Muruganandam, Noel Nesakumar, Arockia Jayalatha Kulandaisamy, John Bosco Balaguru Rayappan and Balu Mahendran Gunasekaran
Chemosensors 2023, 11(8), 442; https://doi.org/10.3390/chemosensors11080442 - 07 Aug 2023
Viewed by 1181
Abstract
In human blood serum, the concentration of magnesium ions typically ranges from 0.7 mM to 1.05 mM. However, exceeding the upper limit of 1.05 mM can lead to the condition known as hypermagnesemia. In this regard, a highly sensitive and selective electrochemical sensor [...] Read more.
In human blood serum, the concentration of magnesium ions typically ranges from 0.7 mM to 1.05 mM. However, exceeding the upper limit of 1.05 mM can lead to the condition known as hypermagnesemia. In this regard, a highly sensitive and selective electrochemical sensor for Mg(II) ion detection was successfully fabricated by immobilizing cerium oxide (CeO2) microcuboids, synthesized via microwave radiation method, onto the surface of glassy carbon electrode (GCE). Cyclic voltammetry studies revealed the exceptional electrocatalytic effect of CeO2 microcuboid-modified GC electrode, particularly in relation to the irreversible reduction signal of Mg(II). The microcuboid-like structure of CeO2 microparticles facilitated enhanced adsorption of Mg(II) ion (Γ=2.17×107mol cm−2) and electron transfer (ks=8.94 s−1) between the adsorbed Mg(II) ions and GCE. A comprehensive analysis comparing the performance characteristics of amperometry, differential pulse voltammetry, cyclic voltammetry, and square wave voltammetry was conducted. The square wave voltammetry-based Mg(II) sensor exhibited remarkable sensitivity of 2.856 μA mM−1, encompassing a broad linear detection range of 0–3 mM. The detection and quantification limits were impressively low, with values of 19.84 and 66.06 μM, respectively. Remarkably, the developed electrode showed a rapid response time of less than 140 s. Multiple linear regression and partial least squares regression models were employed to establish a mathematical relationship between magnesium ion levels and electrochemical parameters. Notably, the proposed sensor exhibited excellent anti-interferent ability, repeatability, stability, and reproducibility, enabling the fabricated electrode to be used effectively for Mg(II) ion sensing in real-world samples. Full article
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15 pages, 3849 KiB  
Article
High Sensitivity Low-Temperature Hydrogen Sensors Based on SnO2/κ(ε)-Ga2O3:Sn Heterostructure
by Aleksei Almaev, Nikita Yakovlev, Viktor Kopyev, Vladimir Nikolaev, Pavel Butenko, Jinxiang Deng, Aleksei Pechnikov, Petr Korusenko, Aleksandra Koroleva and Evgeniy Zhizhin
Chemosensors 2023, 11(6), 325; https://doi.org/10.3390/chemosensors11060325 - 01 Jun 2023
Cited by 4 | Viewed by 1393
Abstract
The structural and gas-sensitive properties of n-N SnO2/κ(ε)-Ga2O3:Sn heterostructures were investigated in detail for the first time. The κ(ε)-Ga2O3:Sn and SnO2 films were grown by the halide vapor phase epitaxy [...] Read more.
The structural and gas-sensitive properties of n-N SnO2/κ(ε)-Ga2O3:Sn heterostructures were investigated in detail for the first time. The κ(ε)-Ga2O3:Sn and SnO2 films were grown by the halide vapor phase epitaxy and the high-frequency magnetron sputtering, respectively. The gas sensor response and speed of operation of the structures under H2 exposure exceeded the corresponding values of single κ(ε)-Ga2O3:Sn and SnO2 films within the temperature range of 25–175 °C. Meanwhile, the investigated heterostructures demonstrated a low response to CO, NH3, and CH4 gases and a high response to NO2, even at low concentrations of 100 ppm. The current responses of the SnO2/κ(ε)-Ga2O3:Sn structure to 104 ppm of H2 and 100 ppm of NO2 were 30–47 arb. un. and 3.7 arb. un., correspondingly, at a temperature of 125 °C. The increase in the sensitivity of heterostructures at low temperatures is explained by a rise of the electron concentration and a change of a microrelief of the SnO2 film surface when depositing on κ(ε)-Ga2O3:Sn. The SnO2/κ(ε)-Ga2O3:Sn heterostructures, having high gas sensitivity over a wide operating temperature range, can find application in various fields. Full article
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30 pages, 2648 KiB  
Review
Effect of Nanoparticle Interaction on Structural, Conducting and Sensing Properties of Mixed Metal Oxides
by Leonid I. Trakhtenberg, Maria I. Ikim, Olusegun J. Ilegbusi, Vladimir F. Gromov and Genrikh N. Gerasimov
Chemosensors 2023, 11(6), 320; https://doi.org/10.3390/chemosensors11060320 - 26 May 2023
Cited by 2 | Viewed by 1391
Abstract
This review analyzes the studies published, mainly in the last 10–15 years, on the synthesis, structure, and sensor properties of semiconductor nanocomposites. Particular attention is paid to the interaction between nanoparticles of the sensitive layer, and its effect on the structure, sensitivity, and [...] Read more.
This review analyzes the studies published, mainly in the last 10–15 years, on the synthesis, structure, and sensor properties of semiconductor nanocomposites. Particular attention is paid to the interaction between nanoparticles of the sensitive layer, and its effect on the structure, sensitivity, and selectivity of semiconductor sensor systems. Various mechanisms of interaction between nanoparticles in metal oxide composites are considered, including the incorporation of metal ions of one component into the structure of another, heterocontacts between different nanoparticles, and core–shell systems, as well as their influence on the characteristics of gas sensors. The experimental data and studies on the modeling of charge distribution in semiconductor nanoparticles, which determine the conductivity and sensor effect in one- and two-component systems, are also discussed. It is shown that the model which considers the interactions of nanoparticles best describes the experimental results. Some mechanisms of detection selectivity are considered in the conclusion. Full article
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19 pages, 4159 KiB  
Article
Printable and Flexible Iridium Oxide-Based pH Sensor by a Roll-to-Roll Process
by Khengdauliu Chawang, Sen Bing and Jung-Chih Chiao
Chemosensors 2023, 11(5), 267; https://doi.org/10.3390/chemosensors11050267 - 30 Apr 2023
Cited by 3 | Viewed by 1952
Abstract
A flexible pH sensor based on using iridium oxide (IrOx) as the sensing film was developed by the roll-to-roll (R2R) process. The inert and biocompatible properties of IrOx make it a desired metal oxide for pH-sensing applications. The flexible substrates [...] Read more.
A flexible pH sensor based on using iridium oxide (IrOx) as the sensing film was developed by the roll-to-roll (R2R) process. The inert and biocompatible properties of IrOx make it a desired metal oxide for pH-sensing applications. The flexible substrates being continuously processed by the R2R technique provides the advantages of scalability, reconfigurability, resiliency, on-demand manufacturing, and high throughput, without the need for vacuum systems. Potential sweeps by cyclic voltammetry across the IrOx film against commercial and planar Ag/AgCl electrodes validated the reversible electrochemical mechanisms. Multiple IrOx electrodes showed similar output potentials when continuously tested in the pH range of 2–13, indicating good fabrication uniformity. For practical applications, planar IrOx/Ag-AgCl pairs developed on polyimide substrates were tested, with a good linear fit within pH 2–13, achieving Nernstian responses of around −60.6 mV/pH. The pH sensors showed good repeatability when analyzed with hysteresis, drift, fluctuation, and deviation as the stability factors. The selectivity of the interference ions and the effect of temperature were studied and compared with the reported values. The electrodes were further laminated in a process compatible with the R2R technique for packaging. The flexible sensors were tested under flat and curved surface conditions. Tests in artificial sweat and viscous solutions were analyzed in the Clarke error grid, showing reliable pH-sensing performance. The materials used during the manufacturing processes were sustainable, as the active materials were in small amounts and there was no waste during processing. No toxic chemicals were needed in the fabrication processes. The cost-effective and efficient materials and the fabrication process allow for rapid production that is necessary for disposable and point-of-care devices. Flexible electronics provide a platform for device and sensor integration and packaging, which enables Internet-of-things (IoT) network applications. Full article
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13 pages, 3282 KiB  
Article
Porous Copper Oxide Thin Film Electrodes for Non-Enzymatic Glucose Detection
by Soledad Carinelli, Pedro A. Salazar-Carballo, Julio Ernesto De la Rosa Melián and Francisco García-García
Chemosensors 2023, 11(5), 260; https://doi.org/10.3390/chemosensors11050260 - 25 Apr 2023
Viewed by 1593
Abstract
The present work describes novel copper oxide thin film-modified indium tin oxide electrodes prepared by magnetron sputtering and their application for glucose sensing. Copper oxide-modified sensors were characterized by electrochemical techniques, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The deposited thin [...] Read more.
The present work describes novel copper oxide thin film-modified indium tin oxide electrodes prepared by magnetron sputtering and their application for glucose sensing. Copper oxide-modified sensors were characterized by electrochemical techniques, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The deposited thin film (of about 400 nm of thickness) consisted of Cu2O/CuO nanocolumns of ca. 80 nm in diameter. After optimizing the main experimental parameters, the electrodes showed noteworthy electrocatalytic properties for glucose detection (sensitivity ca. 2.89 A M−1 cm−2 and limit of detection ca. 0.29 μM (S/N = 3)). The sensor showed negligible response against common electroactive species and other sugars. Finally, recovery experiments in commercial soda drinks and the determination of glucose content in different commercial drinks, such as soda, tea, fruit juices, and sports drinks, are described. Full article
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17 pages, 16596 KiB  
Article
Distinct Roles of Additives in the Improved Sensitivity to CO of Ag- and Pd-Modified Nanosized LaFeO3
by Valentina Chumakova, Artem Marikutsa, Vadim Platonov, Nikolay Khmelevsky and Marina Rumyantseva
Chemosensors 2023, 11(1), 60; https://doi.org/10.3390/chemosensors11010060 - 13 Jan 2023
Cited by 2 | Viewed by 1666
Abstract
Perovskite-type mixed-metal oxides are of particular interest as semiconductor gas sensors due to the variability in the material composition and the stability of sensing parameters. LaFeO3 is a p-type semiconductor with relatively high conductivity and gas sensitivity. However, less is known [...] Read more.
Perovskite-type mixed-metal oxides are of particular interest as semiconductor gas sensors due to the variability in the material composition and the stability of sensing parameters. LaFeO3 is a p-type semiconductor with relatively high conductivity and gas sensitivity. However, less is known about the sensitivity and sensing mechanisms of LaFeO3 modified by catalytic noble metals. In this work, we used a microwave-assisted sol–gel method to synthesize perovskite LaFeO3 nanoparticles with an average size of 20–30 nm and a specific surface area of 6–8 m2/g. LaFeO3 was modified by 2–5 wt.% Ag and Pd nanoparticles via the impregnation route. Using X-ray photoelectron spectroscopy, the additives were observed in the partially oxidized states Ag2O/Ag and PdO/Pd, respectively. Electric conduction and sensitivity to noxious gases were characterized by electrophysical measurements. It was shown that LaFeO3 modified by Ag and Pd had improved sensitivity and selectivity to CO, and the sensing behavior persisted in a wide range of relative humidity. Pristine and Ag-modified LaFeO3 had the maximum sensitivity to CO at a temperature of 200 °C, while modification with Pd resulted in a decreased optimal operating temperature of 150 °C. In situ infrared spectroscopy revealed that supported Pd nanoparticles specifically catalyzed CO oxidation at the surface of LaFeO3 at room temperature, which was the likely reason for the improved sensitivity and decreased optimal operating temperature of LaFeO3/Pd sensors. On the other hand, Ag nanoparticles were deduced to activate CO oxidation by lattice oxygen at the surface of LaFeO3, providing enhanced CO sensitivity at a higher temperature. Full article
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14 pages, 3284 KiB  
Article
Effects of Addition of CuxO to Porous SnO2 Microspheres Prepared by Ultrasonic Spray Pyrolysis on Sensing Properties to Volatile Organic Compounds
by Soichiro Torai, Taro Ueda, Kai Kamada, Takeo Hyodo and Yasuhiro Shimizu
Chemosensors 2023, 11(1), 59; https://doi.org/10.3390/chemosensors11010059 - 11 Jan 2023
Cited by 6 | Viewed by 1534
Abstract
Porous (pr-)SnO2-based powders were synthesized by ultrasonic spray pyrolysis employing home-made polymethylmethacrylate (PMMA) microspheres (typical particle size: 70 nm in diameter), and effects of the CuxO addition to the pr-SnO2 powder on the acetone and toluene sensing properties [...] Read more.
Porous (pr-)SnO2-based powders were synthesized by ultrasonic spray pyrolysis employing home-made polymethylmethacrylate (PMMA) microspheres (typical particle size: 70 nm in diameter), and effects of the CuxO addition to the pr-SnO2 powder on the acetone and toluene sensing properties were investigated. Well-developed spherical pores reflecting the morphology of the PMMA microsphere templates were formed in the SnO2-based powders, which were quite effective in enhancing the acetone and toluene responses. The 0.8 wt% Cu-added pr-SnO2 sensor showed the largest acetone response at 350 °C among all the sensors. Furthermore, we clarified that the addition of CuxO onto the pr-SnO2 decreased the concentration of carrier electrons and the acetone-oxidation activity, leading to the improvement of the acetone-sensing properties of the pr-SnO2 sensor. Full article
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2022

Jump to: 2023, 2021

36 pages, 10219 KiB  
Article
Optimization of Aluminum Dopant Amalgamation Immersion Time on Structural, Electrical, and Humidity-Sensing Attributes of Pristine ZnO for Flexible Humidity Sensor Application
by A Shamsul Rahimi A Subki, Mohamad Hafiz Mamat, Musa Mohamed Zahidi, Mohd Hanapiah Abdullah, I. B. Shameem Banu, Nagamalai Vasimalai, Mohd Khairul Ahmad, Nafarizal Nayan, Suriani Abu Bakar, Azmi Mohamed, Muhammad Danang Birowosuto and Mohamad Rusop Mahmood
Chemosensors 2022, 10(11), 489; https://doi.org/10.3390/chemosensors10110489 - 17 Nov 2022
Cited by 8 | Viewed by 2633
Abstract
This study synthesized pristine and aluminum (Al)-doped zinc oxide (Al:ZnO) nanostructures through a simplistic low-temperature ultrasonicated solution immersion method. Al:ZnO nanostructures were synthesized as a sensing material using different immersion times varying from two to five hours. The Al:ZnO nanostructured-based flexible humidity sensor [...] Read more.
This study synthesized pristine and aluminum (Al)-doped zinc oxide (Al:ZnO) nanostructures through a simplistic low-temperature ultrasonicated solution immersion method. Al:ZnO nanostructures were synthesized as a sensing material using different immersion times varying from two to five hours. The Al:ZnO nanostructured-based flexible humidity sensor was fabricated by employing cellulose filter paper as a substrate and transparent paper glue as a binder through a simplistic brush printing technique. XRD, FESEM, HRTEM, EDS, XPS, a two-probe I–V measurement system, and a humidity measurement system were employed to investigate the structural, morphological, chemical, electrical, and humidity-sensing properties of the pristine ZnO and Al:ZnO nanostructures. The structural and morphological analysis confirmed that Al cations successfully occupied the Zn lattice or integrated into interstitial sites of the ZnO lattice matrix. Humidity-sensing performance analysis indicated that the resistance of the Al:ZnO nanostructure samples decreased almost linearly as the humidity level increased, leading to better sensitivity and sensing response. The Al:ZnO-4 h nanostructured-based flexible humidity sensor had a maximum sensing response and demonstrated the highest sensitivity towards humidity changes, which was noticeably superior to the other tested samples. Finally, this study explained the Al:ZnO nanostructures-based flexible humidity sensor sensing mechanism in terms of chemical adsorption, physical adsorption, and capillary condensation mechanisms. Full article
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13 pages, 3206 KiB  
Article
An Electrochemical Sensor Based on Reduced Graphene Oxide and Copper Nanoparticles for Monitoring Estriol Levels in Water Samples after Bioremediation
by Francisco Contini Barreto, Martin Kassio Leme Silva and Ivana Cesarino
Chemosensors 2022, 10(10), 395; https://doi.org/10.3390/chemosensors10100395 - 28 Sep 2022
Cited by 6 | Viewed by 1706
Abstract
Water contamination from endocrine disruptors has become a major problem for health issues. Estriol is a hormone often detected in several aquatic matrices, due to the inefficient removal of such compounds through conventional water treatment methods. Therefore, there is a continuous need to [...] Read more.
Water contamination from endocrine disruptors has become a major problem for health issues. Estriol is a hormone often detected in several aquatic matrices, due to the inefficient removal of such compounds through conventional water treatment methods. Therefore, there is a continuous need to develop new, efficient, and low-cost treatment methods for this hormone removal, as well as analytical devices able to detect estriol at low concentrations. In this present study, we report the use of the Eichhornia crassipes (water hyacinth) as a phytoremediation agent for estriol removal from aqueous matrices, in addition to a newly developed electrochemical sensor based on reduced graphene oxide and copper nanoparticles as a quantification and monitoring tool of the hormone. The developed sensor presented a linear detection region from 0.5 to 3.0 μmol L−1, with detection and quantification limits of 0.17 μmol L−1 and 0.56 μmol L−1, respectively. Phytoremediation experiments were conducted in 2 L beakers and the reducing levels of the hormone were studied. Water hyacinth was able to reduce contaminant levels by approximately 80.5% in 7 days and below detection limits in less than 9 days, which is a good alternative for water decontamination with this endocrine disruptor. Due to the hydrophobicity of estriol, the probable mechanism involved in the bioremediation process is rhizodegradation, and the decrease in pH in the beakers that contained the plants indicated a possible formation of biofilms on the roots. Full article
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2021

Jump to: 2023, 2022

13 pages, 46820 KiB  
Article
Controlled Growth of WO3 Pyramidal Thin Film via Hot-Filament Chemical Vapor Deposition: Electrochemical Detection of Ethylenediamine
by Mohammad Imran, Eun-Bi Kim, Dong-Heui Kwak, Mohammad Shaheer Akhtar and Sadia Ameen
Chemosensors 2021, 9(9), 257; https://doi.org/10.3390/chemosensors9090257 - 08 Sep 2021
Cited by 4 | Viewed by 2171
Abstract
In this work, the structural, optical, morphological, and sensing features of tungsten oxide (WO3) thin film deposited on a silicon substrate via hot-filament chemical vapor deposition (HFCVD) are described. The experimental characterization tools, such as X-ray diffraction (XRD), field emission scanning [...] Read more.
In this work, the structural, optical, morphological, and sensing features of tungsten oxide (WO3) thin film deposited on a silicon substrate via hot-filament chemical vapor deposition (HFCVD) are described. The experimental characterization tools, such as X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), ultraviolet-visible (UV-Vis), and Fourier transform infra-red (FTIR) spectroscopies, etc., were used to determine the properties of WO3 NPys thin films. The grown WO3 thin film illustrated closely packed porous pyramidal nanostructures (NPys) of improved grain size properties. The diffraction analysis revealed (100) and (200) of WO3 phases, suggesting the classic monoclinic crystal WO3 structure. HFCVD grown WO3 NPys thin film was employed as electro-active electrode for detecting ethylenediamine in 10 mL of 0.1 M phosphate buffer solution (PBS) by varying the ethylenediamine concentrations from 10 μM to 200 μM at room temperature. With a detection of limit (LOD) of ~9.56 μM, and a quick reaction time (10 s), the constructed chemical sensor achieved a high sensitivity of ~161.33 μA μM−1 cm−2. The durability test displayed an excellent stability of electrochemical sensor by maintaining over 90% sensitivity after 4 weeks of operation. This work provides a strategy for a facile preparation of WO3 NPys thin film electrode for sensor applications. Full article
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10 pages, 3879 KiB  
Article
Nickel-Oxide Based Thick-Film Gas Sensors for Volatile Organic Compound Detection
by Sai Kiran Ayyala and James A. Covington
Chemosensors 2021, 9(9), 247; https://doi.org/10.3390/chemosensors9090247 - 03 Sep 2021
Cited by 17 | Viewed by 2799
Abstract
In this paper, we report on the development of a highly sensitive and humidity-tolerant metal-oxide-based volatile organic compound (VOC) sensor, capable of rapidly detecting low concentrations of VOCs. For this, we successfully fabricated two different thicknesses of nickel oxide (NiO) sensors using a [...] Read more.
In this paper, we report on the development of a highly sensitive and humidity-tolerant metal-oxide-based volatile organic compound (VOC) sensor, capable of rapidly detecting low concentrations of VOCs. For this, we successfully fabricated two different thicknesses of nickel oxide (NiO) sensors using a spin-coating technique and tested them with seven different common VOCs at 40% r.h. The measured film thickness of the spin-coated NiO was ~5 μm (S-5) and ~10 μm (S-10). The fastest response and recovery times for all VOCs were less than 80 s and 120 s, respectively. The highest response (Rg/Ra = 1.5 for 5 ppm ethanol) was observed at 350 °C for both sensors. Sensors were also tested in two different humidity conditions (40% and 90% r.h.). The humidity did not significantly influence the observed sensitivity of the films. Furthermore, S-10 NiO showed only a 3% drift in the baseline resistance between the two humidity conditions, making our sensor humidity-tolerant compared to traditional n-type sensors. Thus, we propose thick-film NiO (10 μm) sensing material as an interesting alternative VOC sensor that is fast and humidity-tolerant. Full article
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13 pages, 4098 KiB  
Article
Nickel Manganite-Sodium Alginate Nano-Biocomposite for Temperature Sensing
by Milena P. Dojcinovic, Zorka Z. Vasiljevic, Janez Kovac, Nenad B. Tadic and Maria Vesna Nikolic
Chemosensors 2021, 9(9), 241; https://doi.org/10.3390/chemosensors9090241 - 27 Aug 2021
Cited by 7 | Viewed by 2433
Abstract
Nanocrystalline nickel manganite (NiMn2O4) powder with a pure cubic spinel phase structure was synthesized via sol-gel combustion and characterized with XRD, FT-IR, XPS and SEM. The powder was mixed with sodium alginate gel to form a nano-biocomposite gel, dried [...] Read more.
Nanocrystalline nickel manganite (NiMn2O4) powder with a pure cubic spinel phase structure was synthesized via sol-gel combustion and characterized with XRD, FT-IR, XPS and SEM. The powder was mixed with sodium alginate gel to form a nano-biocomposite gel, dried at room temperature to form a thick film and characterized with FT-IR and SEM. DC resistance and AC impedance of sensor test structures obtained by drop casting the nano-biocomposite gel onto test interdigitated PdAg electrodes on an alumina substrate were measured in the temperature range of 20–50 °C at a constant relative humidity (RH) of 50% and at room temperature (25 °C) in the RH range of 40–90%. The material constant obtained from the measured decrease in resistance with temperature was determined to be 4523 K, while the temperature sensitivity at room temperature (25 °C) was −5.09%/K. Analysis of the complex impedance plots showed a dominant influence of grains. The decrease in complex impedance with increase in temperature confirmed the negative temperature coefficient effect. The grain resistance and grain relaxation frequency were determined using an equivalent circuit. The activation energy for conduction was determined as 0.45 eV from the temperature dependence of the grain resistance according to the small polaron hopping model, while the activation energy for relaxation was 0.43 eV determined from the Arrhenius dependence of the grain relaxation frequency on temperature. Full article
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14 pages, 3593 KiB  
Article
UV-Responsive Screen-Printed Porous ZnO Nanostructures on Office Paper for Sustainable and Foldable Electronics
by Sofia Henriques Ferreira, Inês Cunha, Joana Vaz Pinto, Joana Pereira Neto, Luís Pereira, Elvira Fortunato and Rodrigo Martins
Chemosensors 2021, 9(8), 192; https://doi.org/10.3390/chemosensors9080192 - 24 Jul 2021
Cited by 10 | Viewed by 3639
Abstract
The fabrication of low-cost, flexible, and recyclable electronic devices has been the focus of many research groups, particularly for integration in wearable technology and the Internet of Things (IoT). In this work, porous zinc oxide (ZnO) nanostructures are incorporated as a UV sensing [...] Read more.
The fabrication of low-cost, flexible, and recyclable electronic devices has been the focus of many research groups, particularly for integration in wearable technology and the Internet of Things (IoT). In this work, porous zinc oxide (ZnO) nanostructures are incorporated as a UV sensing material into the composition of a sustainable water-based screen-printable ink composed of carboxymethyl cellulose (CMC). The formulated ink is used to fabricate flexible and foldable UV sensors on ubiquitous office paper. The screen-printed CMC/ZnO UV sensors operate under low voltage (≤2 V) and reveal a stable response over several on/off cycles of UV light exposure. The devices reach a response current of 1.34 ± 0.15 mA and a rise and fall time of 8.2 ± 1.0 and 22.0 ± 2.3 s, respectively. The responsivity of the sensor is 432 ± 48 mA W−1, which is the highest value reported in the literature for ZnO-based UV sensors on paper substrates. The UV-responsive devices display impressive mechanical endurance under folding, showing a decrease in responsivity of only 21% after being folded 1000 times. Their low-voltage operation and extreme folding stability indicate a bright future for low-cost and sustainable flexible electronics, showing potential for low-power wearable applications and smart packaging. Full article
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15 pages, 18747 KiB  
Article
A Magnetic Nanocomposite Modifier for Improved Ultrasensitive Detection of Hexavalent Chromium in Water Samples
by Nuša Hojnik, Olivija Plohl and Matjaž Finšgar
Chemosensors 2021, 9(8), 189; https://doi.org/10.3390/chemosensors9080189 - 22 Jul 2021
Cited by 1 | Viewed by 2585
Abstract
In this work, different electrodes were employed for the determination of Cr(VI) by the cathodic square-wave voltammetry (SWV) technique and the square-wave adsorptive stripping voltammetry (SWAdSV) technique in combination with diethylenetriaminepentaacetic acid. Using SWV, a comparison of the analytical performance of the bare [...] Read more.
In this work, different electrodes were employed for the determination of Cr(VI) by the cathodic square-wave voltammetry (SWV) technique and the square-wave adsorptive stripping voltammetry (SWAdSV) technique in combination with diethylenetriaminepentaacetic acid. Using SWV, a comparison of the analytical performance of the bare glassy carbon electrode (GCE), ex situ electrodes (antimony-film—SbFE, copper-film—CuFE, and bismuth-film—BiFE), and the GCE modified with a new magnetic nanocomposite (MNC) material was performed. First, the MNC material was synthesized, i.e., MNPs@SiO2@Lys, where MNPs stands for magnetic maghemite nanoparticles, coated with a thin amorphous silica (SiO2) layer, which was additionally functionalized with derived lysine (Lys). The crystal structure of the prepared MNCs was confirmed by X-ray powder diffraction (XRD), while the morphology and nano-size of the MNCs were investigated by field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM), where TEM was additionally used to observe the MNP core and silica layer thickness. The presence of functional groups of the MNCs was investigated by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and surface analysis was performed by X-ray photoelectron spectroscopy (XPS). The hydrophilicity of the modified electrodes was also tested by static contact angle measurements. Then, MNPs@SiO2@Lys was applied onto the electrodes and used with the SWV and SWAdSV techniques. All electrodes tested with the SWV technique were effective for Cr(VI) trace determination. On the other hand, the SWAdSV technique was required for ultra-trace determination of Cr(VI). Using the SWAdSV technique, it was shown that a combination of ex situ BiFE with the deposited MNPs@SiO2@Lys resulted in excellent analytical performance (LOQ = 0.1 µg/L, a linear concentration range of 0.2–2.0 µg/L, significantly higher sensitivity compared to the SWV technique, an RSD representing reproducibility of 9.0%, and an average recovery of 98.5%). The applicability of the latter system was also demonstrated for the analysis of a real sample. Full article
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16 pages, 4402 KiB  
Article
Sensing Properties of NiO Loaded SnO2 Nanoparticles—Specific Selectivity to H2S
by Adelina Stanoiu, Andrei C. Kuncser, Daniela Ghica, Ovidiu G. Florea, Simona Somacescu and Cristian E. Simion
Chemosensors 2021, 9(6), 125; https://doi.org/10.3390/chemosensors9060125 - 01 Jun 2021
Cited by 4 | Viewed by 2906
Abstract
NiO-loaded SnO2 powders were prepared involving two chemical procedures. The mesoporous SnO2 support was synthesized by a hydrothermal route using Brij 35 non-ionic surfactant as a template. The nickel loadings of 1 and 10 wt.%. NiO were deposited by the wet [...] Read more.
NiO-loaded SnO2 powders were prepared involving two chemical procedures. The mesoporous SnO2 support was synthesized by a hydrothermal route using Brij 35 non-ionic surfactant as a template. The nickel loadings of 1 and 10 wt.%. NiO were deposited by the wet impregnation method. The H2S sensing properties of xNiO-(1-x)SnO2 (x = 0, 1, 10%) thick layers deposited onto commercial substrates have been investigated with respect to different potential interfering gases (NO2, CO, CO2, CH4, NH3 and SO2) over a wide range of operating temperatures and relative humidity specific for in-field conditions. Following the correlation of the sensing results with the morphological ones, 1wt.% NiO/SnO2 was selected for simultaneous electrical resistance and work function investigations. The purpose was to depict the sensing mechanism by splitting between specific changes over the electron affinity induced by the surface coverage with hydroxyl dipoles and over the band bending induced by the variable surface charge under H2S exposure. Thus, it was found that different gas-interaction partners are dependent upon the amount of H2S, mirrored through the threshold value of 5 ppm H2S, which from an applicative point of view, represents the lower limit of health effects, an eight-hour TWA. Full article
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16 pages, 4477 KiB  
Article
Synthesis, Characterization and Gas Sensing Study of ZnO-SnO2 Nanocomposite Thin Films
by Victor V. Petrov, Victor V. Sysoev, Aleksandra P. Starnikova, Maria G. Volkova, Zamir Kh. Kalazhokov, Viktoriya Yu. Storozhenko, Soslan A. Khubezhov and Ekaterina M. Bayan
Chemosensors 2021, 9(6), 124; https://doi.org/10.3390/chemosensors9060124 - 30 May 2021
Cited by 22 | Viewed by 4204
Abstract
Thin nanocomposite films composed of ZnO and SnO2 at 0.5–5 mol.% concentrations were synthesized by a new solid-phase low-temperature pyrolysis under the developed protocols. This hetero-oxide material was thoroughly studied by X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy [...] Read more.
Thin nanocomposite films composed of ZnO and SnO2 at 0.5–5 mol.% concentrations were synthesized by a new solid-phase low-temperature pyrolysis under the developed protocols. This hetero-oxide material was thoroughly studied by X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) techniques to be compared with electrical and gas-sensing properties. We have found that the films have a poly-nanocrystal structure of ZnO and SnO2 crystals with characteristic grain sizes at 10–15 nm range. When comparing the chemiresistive response of the films with varied tin dioxide content, the sample of Sn:Zn optimum ratio taken as 1:99 yields 1.5-fold improvement upon to 5–50 ppm NO2 exposure at 200 °C. We argue that these remarkable changes have matured from both a reducing the intergrain potential barrier down to 0.58 eV and increasing the concentration of anionic vacancies at this rational composite. The results demonstrate that solid-phase low-temperature pyrolysis is a powerful technique for adjusting the functional gas-sensing properties of hetero-oxide film via modifying the ratio of the oxide components. Full article
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29 pages, 5926 KiB  
Article
Dual Transduction of H2O2 Detection Using ZnO/Laser-Induced Graphene Composites
by Julia Zanoni, Jorge P. Moura, Nuno F. Santos, Alexandre F. Carvalho, António J. S. Fernandes, Teresa Monteiro, Florinda M. Costa, Sónia O. Pereira and Joana Rodrigues
Chemosensors 2021, 9(5), 102; https://doi.org/10.3390/chemosensors9050102 - 05 May 2021
Cited by 12 | Viewed by 3651
Abstract
Zinc oxide (ZnO)/laser-induced graphene (LIG) composites were prepared by mixing ZnO, grown by laser-assisted flow deposition, with LIG produced by laser irradiation of a polyimide, both in ambient conditions. Different ZnO:LIG ratios were used to infer the effect of this combination on the [...] Read more.
Zinc oxide (ZnO)/laser-induced graphene (LIG) composites were prepared by mixing ZnO, grown by laser-assisted flow deposition, with LIG produced by laser irradiation of a polyimide, both in ambient conditions. Different ZnO:LIG ratios were used to infer the effect of this combination on the overall composite behavior. The optical properties, assessed by photoluminescence (PL), showed an intensity increase of the excitonic-related recombination with increasing LIG amounts, along with a reduction in the visible emission band. Charge-transfer processes between the two materials are proposed to justify these variations. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy evidenced increased electron transfer kinetics and an electrochemically active area with the amount of LIG incorporated in the composites. As the composites were designed to be used as transducer platforms in biosensing devices, their ability to detect and quantify hydrogen peroxide (H2O2) was assessed by both PL and CV analysis. The results demonstrated that both methods can be employed for sensing, displaying slightly distinct operation ranges that allow extending the detection range by combining both transduction approaches. Moreover, limits of detection as low as 0.11 mM were calculated in a tested concentration range from 0.8 to 32.7 mM, in line with the values required for their potential application in biosensors. Full article
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