Metal Oxide-based Gas Sensors Research Articles

Defect-enabled room-temperature acetone gas sensors based on Zn-doped cauliflower-like bismuth oxide

Metal oxide-based gas sensors have promising advantages, such as low cost and high sensitivities, but the high working temperature (150°C–300 °C) hinders their practical applications. Herein, this study demonstrated a Zinc (Zn)-doped approach to achieve defect-enabled room-temperature acetone gas sensors based on bismuth oxide (Bi2O3) thin film. Through a simple chemical bath deposition method, the varying substitutional doping of zinc (2 wt% to 8 wt%) can induce the morphological transformation of Bi2O3 nanosheets to a cauliflower-like nanostructure, leading to enhanced surface area and active sites. The incorporation of Zn ions can result in oxygen vacancies in the Bi2O3 lattice and the rising of the depletion layer, facilitating the interaction toward acetone molecules at ambient temperatures, leading to an increment of response ∼6. The Zn-doped cauliflower-like Bi2O3 electrode exhibits a superior sensing performance of acetone gas with a low detection limit of 1 ppm and high stability over 90 days. This work underscores the potential of controlled doping of Zn for oxygen vacancy-riched Bi2O3 thin film as a promising room-temperature acetone gas sensor, offering new avenues for the detection of hazardous gases with improved sensitivity.

Advances in Synthesis and Applications of Single-Atom Catalysts for Metal Oxide-Based Gas Sensors.

As a stable, low-cost, environment-friendly, and gas-sensitive material, semiconductor metal oxides have been widely used for gas sensing. In the past few years, single-atom catalysts (SACs) have gained increasing attention in the field of gas sensing with the advantages of maximized atomic utilization and unique electronic and chemical properties and have successfully been applied to enhance the detection sensitivity and selectivity of metal oxide gas sensors. However, the application of SACs in gas sensors is still in its infancy. Herein, we critically review the recent advances and current status of single-atom catalysts in metal oxide gas sensors, providing some suggestions for the development of this field. The synthesis methods and characterization techniques of SAC-modified metal oxides are summarized. The interactions between SACs and metal oxides are crucial for the stable loading of single-atom catalysts and for improving gas-sensitive performance. Then, the current application progress of various SACs (Au, Pt, Cu, Ni, etc.) in metal oxide gas sensors is introduced. Finally, the challenges and perspectives of SACs in metal oxide gas sensors are presented.

Metal oxide-based gas sensor array for VOCs determination in complex mixtures using machine learning

Detection of volatile organic compounds (VOCs) from the breath is becoming a viable route for the early detection of diseases non-invasively. This paper presents a sensor array of 3 component metal oxides that give maximal cross-sensitivity and can successfully use machine learning methods to identify four distinct VOCs in a mixture. The metal oxide sensor array comprises NiO-Au (ohmic), CuO-Au (Schottky), and ZnO–Au (Schottky) sensors made by the DC reactive sputtering method and having a film thickness of 80–100 nm. The NiO and CuO films have ultrafine particle sizes of < 50 nm and rough surface texture, while ZnO films consist of nanoscale platelets. This array was subjected to various VOC concentrations, including ethanol, acetone, toluene, and chloroform, one by one and in a pair/mix of gases. Thus, the response values show severe interference and departure from commonly observed power law behavior. The dataset obtained from individual gases and their mixtures were analyzed using multiple machine learning algorithms, such as Random Forest (RF), K-Nearest Neighbor (KNN), Decision Tree, Linear Regression, Logistic Regression, Naive Bayes, Linear Discriminant Analysis, Artificial Neural Network, and Support Vector Machine. KNN and RF have shown more than 99% accuracy in classifying different varying chemicals in the gas mixtures. In regression analysis, KNN has delivered the best results with an R2 value of more than 0.99 and LOD of 0.012 ppm, 0.015 ppm, 0.014 ppm, and 0.025 ppm for predicting the concentrations of acetone, toluene, ethanol, and chloroform, respectively, in complex mixtures. Therefore, it is demonstrated that the array utilizing the provided algorithms can classify and predict the concentrations of the four gases simultaneously for disease diagnosis and treatment monitoring.Graphical

Enhanced hydrogen gas sensing characteristics of CuO/ZnO heterojunction for thickness-dependence and its application

In this study, we experimentally verified the synthesis of ZnO and CuO thin films using a droplet-based hydrothermal method and their hydrogen sensing performance. The hydrogen gas detection performance of the fabricated heterostructured gas sensor was evaluated based on the results of an experiment conducted while controlling the temperature and hydrogen concentration in the gas chamber. According to the responses of single metal oxide sensors made of each ZnO and CuO and their heterojunction sensors, CuO deposited with 7 cycles on 5 cycles of ZnO had a resistance change rate of about 164 % and the change of the resistance took 3 s in the environment of 4 % hydrogen at 300 °C. This sensor showed the highest response rate and fastest reaction time out of all. CuO/ZnO showed the highest reaction at 300 °C, confirming its selective reaction to hydrogen. To solve the problem of metal oxide-based gas sensors with low selectivity, the operating principle of the heterojunction between metal oxide that has selective gas reactivity was analyzed and experimentally verified. Additionally, the fabricated sensor was confirmed to have selective responsiveness to different gases at various temperatures. Using these characteristics, it was confirmed that this heterostructure based sensor can be used as a sensor array for electronic nose that could classify unknown gases using the same sensor at various temperatures.

Lacunary polyoxometalates-induced controllable synthesis of Fe2O3/Si-FeWO4 heterostructure nanotubes for selective sensing of m-xylene

Metal oxide-based gas sensors encounter challenges in effectively detecting hazardous benzenes due to their stability and structural similarities. Here we report an innovative in situ growth method for synthesizing Fe2O3/Si-FeWO4 heterostructure nanotubes (NTs) using highly negatively charged multivacant lacunary TBA4H6[SiW9O34]·2H2O (α-SiW9) and Fe3+ as precursors. A two-step process involving electrospinning followed by a thermal oxidation method was employed to synthesize a series of the uniform Si-FeWO4 decorated Fe2O3 heterostructure NTs. Considering the rich Fe2O3/Si-FeWO4 active interfaces, rapid electron transfer, and high specific surface area, the optimal Fe2O3/Si-FeWO4 based sensors demonstrate significantly higher sensitivity (S = 27.5) towards 50 ppm m-xylene in comparison to pristine Fe2O3 (S = 1.8). Furthermore, the Fe2O3/Si-FeWO4 exhibits excellent stability, humidity resistance, and high selectivity for m-xylene. This work offers an efficient, cost-effective strategy to synthesize Fe2O3/Si-FeWO4 heterostructure NTs, with prospects for synthesizing other advanced sensing heterostructure nanomaterials with lacunary polyoxometalates as precursors.

Facile preparation of Au-loaded mesoporous In2O3 nanoparticles with improved ethanol sensing performance.

The in situ monitoring of toxic volatile organic compound gases using metal oxide-based gas sensors is still challenging. Herein, mesoporous In2O3 nanoparticles, assembled using smaller nanoparticles, were synthesized via a facile solvothermal method and used to load Au nanoparticles to prepare mesoporous Au/In2O3 for ethanol detection. The obtained In2O3 and Au/In2O3 were meticulously analysed by XRD, SEM, BET, TEM and XPS techniques. It was revealed that Au nanoparticles were uniformly distributed on mesoporous In2O3 nanoparticles. Notably, the obtained mesoporous 1% Au/In2O3 is highly sensitive to ethanol gas at an optimal working temperature of 180 °C, showing a response of 55 to 50 ppm of ethanol, which is considerably higher compared to that of In2O3 nanoparticles. The significantly enhanced sensitivity results from the electronic and chemical sensitization effects of Au nanoparticles. Moreover, the mesoporous Au/In2O3 nanoparticles also showed eminent selectivity, short response/recovery time, low detection limit, good linear relationship, superb repeatability, and wonderful long-term stability, suggesting that Au/In2O3 nanoparticles have great potential application for in situ monitoring of ethanol gas.

Study of the response behavior of a CdS-SnO2 thick film for high selectivity towards propanol gas.

Gas monitoring devices are in demand for a rapidly growing range of applications. Metal oxide-based gas sensors have been extensively used for the detection of toxic pollutant gases, combustible gases, and hydrocarbon vapors. The sensitivity for a low concentration and observed response and the recovery times of the reported gas sensors are not satisfactory, and it needs further detailed studies. In the present work, undoped SnO2 and cadmium sulfide (CdS)-doped SnO2 thick films were fabricated using the screen-printing method to study their sensing behavior towards tested organic vapors such as acetone, propanol, and ethanol. The sensing properties of fabricated sensors were investigated for the test gases, i.e. acetone, propanol, and ethanol, at an elevated temperature of 473 K. It was observed that the 2 wt% CdS-doped SnO2 sensor showed a maximum response (78%) and was highly selective (44.6%) to propanol over acetone and ethanol. The results showed that the diminution of the SnO2 crystallite size with the CdS content leads to an improvement in the response of the SnO2 sensor for the tested gases. The microstructural properties are also correlated to the sensing behavior. The measurement showed that the CdS-SnO2 thick film sensor is highly sensitive. At the same time, it is more selective to propanol than the other test gases, ethanol and acetone.

Low-Power Consumption IGZO Memristor-Based Gas Sensor Embedded in an Internet of Things Monitoring System for Isopropanol Alcohol Gas.

Low-power-consumption gas sensors are crucial for diverse applications, including environmental monitoring and portable Internet of Things (IoT) systems. However, the desorption and adsorption characteristics of conventional metal oxide-based gas sensors require supplementary equipment, such as heaters, which is not optimal for low-power IoT monitoring systems. Memristor-based sensors (gasistors) have been investigated as innovative gas sensors owing to their advantages, including high response, low power consumption, and room-temperature (RT) operation. Based on IGZO, the proposed isopropanol alcohol (IPA) gas sensor demonstrates a detection speed of 105 s and a high response of 55.15 for 50 ppm of IPA gas at RT. Moreover, rapid recovery to the initial state was achievable in 50 μs using pulsed voltage and without gas purging. Finally, a low-power circuit module was integrated for wireless signal transmission and processing to ensure IoT compatibility. The stability of sensing results from gasistors based on IGZO has been demonstrated, even when integrated into IoT systems. This enables energy-efficient gas analysis and real-time monitoring at ~0.34 mW, supporting recovery via pulse bias. This research offers practical insights into IoT gas detection, presenting a wireless sensing system for sensitive, low-powered sensors.

High-Sensitivity Hydrogen Sulfide Electrochemical Gas Sensor Based on CNT/Pt Cluster Electrode

Recently, due to the development of industrial technology, harmful gases discharged from industrial sites are gradually increasing, and as a result, inconvenience and civil complaints due to odor in the community are rapidly increasing. Among several types of harmful gases, hydrogen sulfide (H2S) is a colorless representative harmful gas that can cause pain through irritation of the mucous membranes of the eyes and respiratory tract, and can cause central nerve paralysis and suffocation at the same time when exposed to high concentrations. In addition, H2S is not only harmful to the human body, but also can create an unpleasant feeling by causing an odor even in a very small amount. Therefore, in order to manage H2S, research on a gas sensor capable of quickly and stably detecting H2S has been actively conducted. Most of the sensors that have been studied in the past are metal oxide-based semiconductor H2S gas sensors, which have high sensitivity, but have disadvantages in that low selectivity and high-temperature operating conditions are required. On the other hand, the electrochemical gas sensor can measure H2S gas with high selectivity because a chemical reaction occurs with respect to a specific gas depending on the type of electrolyte and electrode, and a potential difference due to electrons generated thereby is measured. Therefore, in this study, a CNT/Pt-based electrochemical H2S gas sensor capable of detecting at room temperature with high selectivity for H2S was developed. After forming a CNT thin film on a PTFE membrane, Pt was deposited through an E-beam to fabricate a working electrode capable of selectively detecting only H2S, and applied to an electrochemical H2S gas sensor using sulfuric acid (H2SO4) electrolyte. H2S was measured at a concentration of 100 to 10 ppm in units of 10 ppm using the manufactured CNT/Pt-based electrochemical H2S gas sensor. As a result, the amount of current change was confirmed to be 100uA at a concentration of 100 ppm, and the response time and recovery time were confirmed to be about 10 seconds.This work was supported by the Korea Innovation Foundation(INNOPOLIS) grant funded by the Korea government(MSIT) (2020-DD-UP-0348). This study has been conducted with the support of the Korea Institute of Industrial Technology as "Development of a thermal convection-type flow sensor with high-sensitivity for emergency patients breathing monitoring in real-time" (Kitech UI-23-0012).

MOF-derived flower-like Fe-doped Co3O4 porous hollow structures with enhanced n-butanol sensing properties at low temperature

Metal oxide-based gas sensors are widely used in the detection of toxic and harmful gases due to their advantages of high precision, convenient use and stable performance, but their application range is limited due to the high working temperature. In this work, MOF-derived flower-like Fe-doped Co3O4 porous hollow structures are obtained using a simple solvothermal method. The obtained samples are characterized in terms of their crystalline structure, morphology, chemical composition, optical properties and specific surface area. This study systematically investigates the sensing performance of pristine and Fe-doped Co3O4 samples. The results show that the 2 at% Fe-Co3O4 sample has the best n-butanol sensing properties. This sample exhibits high response and rapid response/recovery speed at a low working temperature of 110 °C, as well as good repeatability and anti-humidity features. The enhanced sensing properties can be attributed to several factors, including the adjustment of baseline resistance, increase in oxygen vacancies, decrease in bandgap, and the formation of unique hollow and porous structures. Overall, this work provides valuable insights into the potential applications of Fe-doped Co3O4 materials in sensing technologies.

Nano Hotplate Fabrication for Metal Oxide-Based Gas Sensors by Combining Electron Beam and Focused Ion Beam Lithography.

Metal oxide semiconductor (MOS) gas sensors are widely used for gas detection. Typically, the hotplate element is the key component in MOS gas sensors which provide a proper and tunable operation temperature. However, the low power efficiency of the standard hotplates greatly limits the portable application of MOS gas sensors. The miniaturization of the hotplate geometry is one of the most effective methods used to reduce its power consumption. In this work, a new method is presented, combining electron beam lithography (EBL) and focused ion beam (FIB) technologies to obtain low power consumption. EBL is used to define the low-resolution section of the electrode, and FIB technology is utilized to pattern the high-resolution part. Different Au++ ion fluences in FIBs are tested in different milling strategies. The resulting devices are characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), and secondary ion mass spectrometry (SIMS). Furthermore, the electrical resistance of the hotplate is measured at different voltages, and the operational temperature is calculated based on the Pt temperature coefficient of resistance value. In addition, the thermal heater and electrical stability is studied at different temperatures for 110 h. Finally, the implementation of the fabricated hotplate in ZnO gas sensors is investigated using ethanol at 250 °C.

Epitaxial growth of Co3O4/In2O3 p-n heterostructure with rich oxygen vacancies for ultrahigh triethylamine sensing

Although metal oxides based gas sensors have been researched extensively in previous works, there are enormous challenges on improving the deficiencies in poor selectivity, sensitivity, humidity resistance and so on. Hence, we developed an epitaxial growth method to prepare dendritic Co3O4/In2O3-(1−3) heterostructures of distinct Co/In mass ratios through perfect lattice matching between the two crystal domains at the interface, along with introducing large amounts of oxygen vacancies. As a result, the Co3O4/In2O3-2 heterostructure based gas sensor showed enhanced sensing properties towards triethylamine (TEA, 100 ppm) with a high response value of Ra/Rg = 576.1 at an optimal working temperature of 200 °C, which is 93 times higher than that of pristine In2O3. Moreover, the Co3O4/In2O3-2 sensor exhibited excellent gas selectivity, quick recovery time, repeatable cycling, long-term stability, as well as outstanding humidity resistance. The improved TEA gas sensing performance can be attributed to the integration of interfacial synergies in Co3O4/In2O3 p-n heterostructure and generation of rich oxygen vacancies, exposing more active sites to facilitate the adsorption/desorption of gas molecules. This work provides a feasible pathway to regulate TEA sensing performance of metal oxide semiconductor (MOS) gas sensors by capitalizing on self-sacrificial template strategy and reconstruction of novel metal oxide heterostructure.

Application of Semiconductor Metal Oxide in Chemiresistive Methane Gas Sensor: Recent Developments and Future Perspectives.

The application of semiconductor metal oxides in chemiresistive methane gas sensors has seen significant progress in recent years, driven by their promising sensitivity, miniaturization potential, and cost-effectiveness. This paper presents a comprehensive review of recent developments and future perspectives in this field. The main findings highlight the advancements in material science, sensor fabrication techniques, and integration methods that have led to enhanced methane-sensing capabilities. Notably, the incorporation of noble metal dopants, nanostructuring, and hybrid materials has significantly improved sensitivity and selectivity. Furthermore, innovative sensor fabrication techniques, such as thin-film deposition and screen printing, have enabled cost-effective and scalable production. The challenges and limitations facing metal oxide-based methane sensors were identified, including issues with sensitivity, selectivity, operating temperature, long-term stability, and response times. To address these challenges, advanced material science techniques were explored, leading to novel metal oxide materials with unique properties. Design improvements, such as integrated heating elements for precise temperature control, were investigated to enhance sensor stability. Additionally, data processing algorithms and machine learning methods were employed to improve selectivity and mitigate baseline drift. The recent developments in semiconductor metal oxide-based chemiresistive methane gas sensors show promising potential for practical applications. The improvements in sensitivity, selectivity, and stability achieved through material innovations and design modifications pave the way for real-world deployment. The integration of machine learning and data processing techniques further enhances the reliability and accuracy of methane detection. However, challenges remain, and future research should focus on overcoming the limitations to fully unlock the capabilities of these sensors. Green manufacturing practices should also be explored to align with increasing environmental consciousness. Overall, the advances in this field open up new opportunities for efficient methane monitoring, leak prevention, and environmental protection.

Highly sensitive and stable room-temperature gas sensors based on the photochemically activated p-type CuAlO2 thin films

Activating metal oxide-based gas sensors using UV-LED is a promising approach to operating them at low temperatures. This method preserves the film characteristics, thereby ensuring the stability of the devices. In this report, we present a remarkably sensitive and stable gas sensor based on solution-processed p-type copper aluminum oxide (CuAlO2), which can sense O3 gas at room temperature. Moreover, the sensitivity is further improved through exposure to ultraviolet (UV) radiation. The optimal gas response of 12.32 can be achieved under UV illumination of 20 mW/cm2 at room temperature. More importantly, the CuAlO2 sensor exhibits outstanding stability, with a deterioration of only ∼10% over a period of 3 months. These findings suggest that CuAlO2 is a promising material for gas sensing at room temperature.

Ultrasensitive gas sensor developed from SnS/TiO2-based memristor for dilute methanol detection at room temperature

Metal oxide-based gas sensors are widely studied and applied due to simple operation principle, small size and high stability. However, numerous gas sensors based on metals oxides usually exhibit high optimal operating temperatures and show poor response/recovery performance at room temperature (RT). To overcome the above problems, innovative device forms should be explored. Herein, we developed a memristor-based gas sensor (gasistor) for the detection of dilute methanol vapor at RT, and the resistive layer material was SnS-modified TiO2. Compared with the general film-based gas sensors, the gasistor exhibits unique resistive switching function, and the baseline resistance in the high resistance state is reduced by about 3 × 104 times, demonstrating the construction of gasistor is an effective way to solve the high resistance of metal oxides at RT. Meanwhile, the SnS/TiO2-based gasistor showed a high response of 85.2 for 1 ppm methanol, a fast response/recovery within 1.2 s for rarefied methanol (< 5 ppm), and remarkable selectivity towards methanol at RT. This indicates that the SnS/TiO2-based gasistor is a competitive candidate for methanol detection. Besides, the mechanisms of resistive switching and gas sensing were further discussed. The present work brings new inspiration to the future research of gas sensors.

Accelerating the Gas-Solid Interactions for Conductometric Gas Sensors: Impacting Factors and Improvement Strategies.

Metal oxide-based conductometric gas sensors (CGS) have showcased a vast application potential in the fields of environmental protection and medical diagnosis due to their unique advantages of high cost-effectiveness, expedient miniaturization, and noninvasive and convenient operation. Of multiple parameters to assess the sensor performance, the reaction speeds, including response and recovery times during the gas-solid interactions, are directly correlated to a timely recognition of the target molecule prior to scheduling the relevant processing solutions and an instant restoration aimed for subsequent repeated exposure tests. In this review, we first take metal oxide semiconductors (MOSs) as the case study and conclude the impact of the semiconducting type as well as the grain size and morphology of MOSs on the reaction speeds of related gas sensors. Second, various improvement strategies, primarily including external stimulus (heat and photons), morphological and structural regulation, element doping, and composite engineering, are successively introduced in detail. Finally, challenges and perspectives are proposed so as to provide the design references for future high-performance CGS featuring swift detection and regeneration.

Gas sensing performance of In2O3 nanostructures: A mini review.

Effective detection of toxic and hazardous gases is crucial for ensuring human safety, and high-performance metal oxide-based gas sensors play an important role in achieving this goal. In2O3 is a widely used n-type metal oxide in gas sensors, and various In2O3 nanostructures have been synthesized for detecting small gas molecules. In this review, we provide a brief summary of current research on In2O3-based gas sensors. We discuss methods for synthesizing In2O3 nanostructures with various morphologies, and mainly review the sensing behaviors of these structures in order to better understand their potential in gas sensors. Additionally, the sensing mechanism of In2O3 nanostructures is discussed. Our review further indicates that In2O3-based nanomaterials hold great promise for assembling high-performance gas sensors.

Recent Advances and Trends in Metal Oxide-based Semiconductor Gas Sensors

With rapid industrial development, a large amount of waste gases has been produced, causing severe industrial disasters and human health problems. In order to avoid gas-related accidents and prevent potential health issues, the detection and monitoring of hazardous gases is essential. In order to effectively detect harmful gases, semiconductor gas sensors have gained increasing attention due to their high sensitivity, small size, cost-effectiveness and ease of manufacturing. This article reviews metal oxide-based semiconductor gas sensors. Firstly, features of metal oxide-based semiconductor gas sensors including major advantages and limitations are discussed. Then, the operating mechanism of semiconductor gas sensors are discussed with a list of widely studied metal oxides. Finally, the semiconductor gas sensors made of four different metal oxides – i) tin oxide (SnO&lt;sub&gt;2&lt;/sub&gt;), ii) indium oxide (In&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;3&lt;/sub&gt;), iii) zinc oxide (ZnO), and iv) tungsten trioxide (WO&lt;sub&gt;3&lt;/sub&gt;) – are discussed from the aspects of current challenges, recent research strategies and future perspectives.

Improved NO2 gas sensing performance of nanoporous conjugated polymer (CP) thin films by incorporating preformed CP nanowires

Conjugated polymer (CP)-based organic field-effect transistor (OFET) gas sensors can detect gas molecules at room temperature with high sensitivity and selectivity. However, their performance, particularly when detecting oxidizing gases, has fallen behind that of their metal oxide counterparts. Hence, improving their sensing performance as well as understanding the correlation between it and the structural and electrical properties of the sensing materials is necessary. Herein, we demonstrate that gas sensing performance of an OFET sensor based on nanoporous poly(3-hexylthiophene) (P3HT) films can be improved simply by incorporating preformed P3HT nanowires (NWs), which act as an efficient charge transport pathway. It detects nitrogen dioxide (NO2) molecules with high sensitivity due to the efficient charge transport pathway as well as ultrathin nanoporous structure of the P3HT films. Upon exposure to 10 ppm NO2 at room temperature, the OFET gas sensor based on the P3HT-NW embedded nanoporous P3HT film exhibits excellent responsivity (34%), fast response and recovery times (∼69 and ∼133 s, respectively), and a low limit of detection of under 0.1 ppm, which are comparable to those of conventional metal oxide-based gas sensors. Based on the correlation study between the morphology, charge transport ability, and sensing performance of the P3HT-NWs embedded nanoporous P3HT films, it is revealed that the efficient charge transport ability is an important factor for realizing high-performance CP-based OFET gas sensors, along with excellent morphological features such as thinness and high pore density.

Comparative study of CuO/Co3O4 external and CuO-Co3O4 internal heterojunctions: Do these factors always enhance gas-sensing performance?

The nanoscale heterojunctions in the nanofiber (NF) structure have been widely utilized in semiconductor metal oxide-based gas sensors to optimize the sensing characteristics. In this study, the CuO-Co3O4 composite and CuO/Co3O4 mixed-NFs were synthesized to compare the influence level of internal- and external- junctions within NF on the gas sensing characteristics. The gas-sensing properties of four kinds of sensors based on NFs (CuO-Co3O4 composite, CuO/Co3O4 mixed, pristine CuO, and pristine Co3O4 NFs) were investigated in the concentration ranges of 0.1–1 ppm H2S reducing gas and 1–10 ppm NO2 oxidizing gas at different working temperatures from 250 °C to 450 °C. In addition, the response/recovery times, and the detection limits of NF sensors toward the target gases were explored. The evidence confirmed that both the internal and external junctions influenced the gas sensing performances for the reducing and oxidizing gases in two opposite trends. The response of hetero-junction NF sensors was increased to H2S gas while reduced to NO2 gas. Thermal fingerprint analysis using the machine learning algorithm was applied to strengthen the selection of the gases. The results confirmed the internal junction existing within NFs was mainly governing the gas sensing performance.