Enhanced NO2 gas sensor device based on supramolecularly assembled polyaniline/silver oxide/graphene oxide composites

Herein, we report a successful synthesis of supramolecularly assembled polyaniline/silver oxide/graphene oxide composite (PANI/Ag₂O/GO) for enhanced NO₂ gas sensing application. The PANI/Ag₂O/GO composite was synthesized by facile stirring followed by an ultrasonication process. The prepared material was characterized by different techniques such as x-ray diffraction, field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy and Raman-scattering spectroscopy. The detailed analysis revealed that the average crystallite sizes of PANI/Ag₂O and PANI/Ag₂O/GO composites were found to be 37.37 nm and 41.55 nm, respectively. FESEM and TEM analysis showed coral-like rough-surfaced and extensively agglomerated morphology for PANI and ultrathin flexible sheet-like morphology for GO. Ag₂O nanoparticles with diameters 20–30 nm were well incorporated in the GO sheets and PANI matrix in the case of PANI/Ag₂O/GO composites. The synthesized materials were used to make resistive sensor devices that had a high response to NO₂ gas. The fabricated sensors were examined at various temperatures to obtain the optimal sensing temperature. The fabricated NO₂ gas sensor device based on PANI/Ag₂O/GO composite exhibited a highest sensitivity of 5.85 for 25 ppm at an optimized temperature (100 °C) as compared to the pure PANI (2.5) and PANI/Ag₂O composite (3.25). Further, the fabricated sensor device based on PANI/Ag₂O/GO composite was also examined at different NO₂ gas concentrations.     

Review of recent progress on graphene-based composite gas sensors

Development of gas sensors for detecting toxic, harmful, flammable, and explosive gases has always been very popular research direction. Graphene is considered potential chemi-resistive gas sensing material owing to its high specific surface area and good conductivity. Recent studies have shown that graphene-based gas sensors doped with metals, polymers, and metal oxides have good sensitivity, selectivity, and repeatability. Moreover, they are superior to traditional gas sensors. In this review, sensing mechanism of such composite sensors is introduced. In addition, research status on various sensors is discussed, and their advantages and disadvantages are summarized. Possible improvement methods are proposed as well. Finally, several common problems characteristic of graphene-based gas sensors are described, together with some critical ideas for improving their performance.     

Low concentration ethanol sensor based on graphene/ZnO nanowires

Metal-oxide based gas sensors are widely used as the gas sensing elements in industrial and residential areas. Many efforts have been made to increase sensitivity and reduce the working temperature of metal-oxide based gas sensors. In this paper, ZnO nanowires (NWs) were successfully grown on graphene (Gr) nanosheets by the hydrothermal method. The synthesized Gr/ZnO NWs nanocomposite were investigated as the sensing material. Not only is the sensor response much higher, it also works in a lower working temperature toward a low concentration of ethanol in comparison with pure ZnO NWs. The optimum working temperature is reduced from 200 °C in pure ZnO NWs to 125 in Gr/ZnO NWs sensor. The maximum response of the Gr/ZnO NWs sensor is 26, which is approximately enhanced twice as much as the pure ZnO NWs sensor. The lower limit of detection (LLOD) of the proposed sensor is as low as 1 ppm ethanol vapor. The sensor was shown a high response, good selectivity, fast response toward ethanol vapor, excellent repeatability, and low sensitivity toward a high relative humidity, as well as remarkable long-term stability.     

Easy preparation of ultrathin reduced graphene oxide sheets at a high stirring speed

This work explored the synthesis of rGO sheets from graphene oxide (GO) using hydrazine solvent as reducing agent through chemical reduction. Meanwhile, GO films with a 2D structure were prepared from graphite flakes (starting material with an average flake size of 150 nm) by an Improved Hummer׳s method. Results showed that the chemical oxidation of graphite flakes carried out at room temperature could be used to prepare GO sheets in the initial stage. The conversion of GO into large-area rGO sheets with ~85% of carbon content could then be achieved by chemical reduction. RGO sheets with a lateral dimension of up to ~45 nm were obtained, which indicated the formation of an extremely thin layer of rGO sheets. A high degree of GO reduction was also realized using a high stirring speed (1200 rpm) for 72 h in a mixture of acids and potassium permanganate, resulting in a high carbon content of rGO with a large lateral dimension and area. Overall, our Improved Hummer׳s method with a high stirring speed (1200 rpm) for 72 h provided an easy approach to the preparation of large-area and ultrathin rGO sheets.     

NO2 gas sensing responses of In2O3 nanoparticles decorated on GO nanosheets

Nanomaterials offer a wide range of applications in environmental nanotechnology. Hazardous pollutants in the environment are needed to be detected and controlled effectively to avoid human health risks. In this paper, we described the fine-controlled growth of In₂O₃ nanoparticles embedded on GO nanosheets by a facile precipitation method. The In₂O₃@GO nanocomposites exhibited outstanding gas sensing performance as compared with pure In₂O₃ nanoparticles towards NO₂. At 225 °C, the sensor displayed high selectivity, best response (78) to 40 ppm NO₂, quick response, and recovery times of 106s/42s. The improved sensing performances of the nanocomposite were attributed to large surface area, high gas adsorption-desorption capability, and the formation of p-n heterojunctions between In₂O₃ nanoparticles and GO nanosheets. The excellent gas detecting activities validate In₂O₃@GO nanocomposites as a promising candidate in the NO₂ gas sensor industry.     

Effects of graphene oxide and chemically reduced graphene oxide on the curing kinetics of epoxy amine composites

The curing kinetics of epoxy nanocomposites prepared by incorporating graphene oxide (GO) and chemically reduced graphene oxide (rGO) have been studied using isothermal and nonisothermal differential scanning calorimetry. The kinetic parameters of the curing processes in these systems have been determined by a Kamal and Sourour phenomenological model expanded by a diffusion factor. The predicted curves determined using the kinetic parameters fit well with the isothermal DSC thermograms revealing the proposed kinetic equation clearly explains the curing kinetics of the prepared epoxy amine nanocomposites. Experimental and modeling results demonstrate the presence of an accelerating effect of the GO on the cure of the resin matrix. The use of rGO instead of GO resulted in a slight acceleration reaction rate due to the reduced presence of oxidation groups in rGO. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44803.     

Photo-induced selective gas detection based on reduced graphene oxide/Si Schottky diode

Reduced graphene oxide (RGO)/Si Schottky diode has been fabricated by a simple drop-casting/annealing process. Common combustible and/or toxic gases including CH₄, O₂, CO, NO₂, NO, and SO₂ were employed to evaluate the detection performance of such device. The relationship between current response and gas flow rate, concentration, bias voltage as well as operating time has been systematically studied, and the results indicated that the RGO/Si-based device is selective to gases like NO₂ and NO. In some cases (i.e. flow rate detection), however, the current response for one gas is completely contrary to others, presumably due to the oxygen functional groups (OFGs) presiding on the surface of reduced graphene oxide. Finally, the effects of OFGs on the gas detection performance of RGO/Si-based devices were thoroughly discussed.     

Flow-injection amperometric glucose biosensors based on graphene/Nafion hybrid electrodes

In this research, we demonstrated the fabrication of flow-injection amperometric glucose biosensors based on RGO/Nafion hybrids. The nanohybridization of the reduced graphene oxide (RGO) by Nafion provided the fast electron transfer (ET) for the sensitive amperometric biosensor platforms. The ET rate (k_s) and the charge transfer resistance (R_CT) of GOx-RGO/Nafion hybrids were evaluated to verify the accelerated ET. Moreover, hybrid biosensors revealed a quasi-reversible and surface controlled process, as confirmed by the low peak-to-peak (ΔE_p) and linear relations between I_p and scan rate (ν). Hybrid biosensors showed the fast response time of ∼3 s, the sensitivity of 3.8 μA mM⁻¹ cm⁻², the limit of detection of 170 μM, and the linear detection range of 2–20 mM for the flow-injection amperometric detection of glucose. Furthermore, interference effect of oxidizable species such as ascorbic acid (AA) and uric acid (UA) on the performance of hybrid biosensors was prevented at the operating potential of −0.20 V even under the flow injection mode. Therefore, the fast, sensitive, and stable amperometric responses of hybrid biosensors in the flow injection system make it highly suitable for automatically monitoring glucose.     

Effect of UV irradiation on magnetic behavior of reduced graphene oxide decorated with nickel nanostructure

Reduced graphene oxide (RGO) decorated with nickel has been synthesized via an in-situ reduction of graphene oxide (GO) and nickel nitrate using NaOH and hydrazine. The starting materials Ni (NO₃)₂ and GO were taken in two different ratios and the products formed were designated as RGNi₂ and RGNi₁. The formation of the composite was confirmed by the appearance of X-ray diffraction peaks at 44.5°, 51.9°, 76.5° corresponding to Ni and at 24.8°and 43.2° for RGO. The RGNi₂ was irradiated with UV light (λ=254 nm) for different durations (2, 6, 12, 24 and 48 h). Intensity ratio of d and g-bands (I_d/I_g) of Raman spectra increases from 1.18 to 1.47 over the duration of irradiation period (2–48 h). The magnetization measurements using the vibrating sample magnetometer (VSM) of these samples reveal their ferromagnetic behavior. The calculated saturation magnetization (M_S) value of Ni, RGNi₁and RGNi₂ is 47.86, 30.56 and 8.25 emu/g respectively and the corresponding coercivity (H_C) value is found to be 181, 227 and 296 Oe. The M_S of RGNi₂ is found to increase to 10.65 emu/g after 48 h of irradiation. This enhancement in the M_S(~23%) with irradiation may be due to defect formation by the UV light.     

The additive-free electrode based on the layered MnO2 nanoflowers/reduced,graphene oxide film for high performance supercapacitor

The MnO₂ nanoflowers/reduced graphene oxide composite is coated on a nickel foam substrate (denoted as MnO₂ NF/RGO @ Ni foam) via the layer by layer (LBL) self-assembly technology without any polymer additive, following the soft chemical reduction. The layered MnO₂ NF/RGO composite is uniformly anchored on the Ni foam skeleton to form the 3D porous framework, and the interlayers have access to lots of ions channels to improve the electron transfer and diffusion. This special construction of 3D porous structure is beneficial to the enhancement of electrochemical property. The specific capacitance is up to 246 F g⁻¹ under the current density of 0.5 A g⁻¹. After 1000 cycles, it can retain about 93%, exhibiting excellent cycle stability. The electrochemical impedance spectroscopy measurements confirm that MnO₂ NF/RGO @ Ni foam electrode has lower R_ESR and R_CT values when compared to MnO₂ @ Ni foam and RGO @ Ni foam. This study opens a new door to the preparation of composite electrodes for high performance supercapacitor.     

Influence of the synthesis conditions on the microstructural,compositional and morphological properties of graphene oxide sheets

In this paper we report about the synthesis and characterization of graphene oxide (GO). We monitor the effects of the different synthetic processes on the morphological and structural properties of the materials. A modified Hummers' method is adopted to obtain GO powder; H₂SO₄ is employed as intercalating agent, to increase the distance between graphitic layers, while KMnO₄ is used as oxidizing reagent for introducing the oxygen functionalities in the graphitic structure. The oxidized graphite powder is treated in acid solution; different washing cycles are applied. The recovered powders are dispersed in aqueous solution and sonicated for 30 min or 60 min, respectively. Subsequently, these solutions are deposited on Si and SiO₂(317 nm)/Si substrates by means of dip coating. GO powders, GO solutions and GO on substrate are characterized through several analytical and spectroscopic techniques. These analyses reveal that the sonication time and the washing procedure of the samples can influence the structure and the morphology of the graphene oxide flakes. Moreover, when KOH is employed as alkaline agent in a chemical reducing treatment of the GO powder before sonication, a considerable alteration of the native structure of graphene oxide is observed. The detailed characterization indicates that the properties of the GO samples are strongly influenced by the chemical and physical treatments to which it is subjected.     

Synthesis and optical properties of ZnSe micro-grasses and microspheres grown on graphene oxide sheets by the hydrothermal method

Zinc selenide (ZnSe) micro-grasses and microspheres have been successfully grown on graphene oxide sheets by the hydrothermal method. The morphologies, structures, chemical compositions and optical properties of the as-synthesized graphene oxide (GO)/ZnSe microstructures have been characterized by X-ray power diffraction (XRD), scanning electron microscope (SEM), energy dispersive spectrometer (EDS), ultraviolet-visible (UV–vis) absorption spectroscopy and photoluminescence (PL) spectroscopy. By adjusting the concentration of NaOH and EDTA, needle-like, coral grass-like, orchid-like, and spherical ZnSe microstructures have been synthesized.     

Synthesis of manganese (IV) oxide at activated carbon on reduced graphene oxide sheets via laser irradiation technique for organic binder-free electrodes in flexible supercapacitors

We report a novel, green, scalable technique to synthesize binder-free, high-purity conductive composite comprising activated carbon (AC), manganese dioxide nanorods (MnO₂), and reduced graphene oxide sheets (rGO) for flexible supercapacitors with outstanding electrochemical performance. UV pulsed laser irradiation of GO-based composite dispersion (AC/GO or MnO₂@AC/GO) in ethanol aqueous medium was used to induce a photocatalytic reduction of GO and simultaneous anchor AC particles or AC loaded MnO₂ nanorods (MnO₂@AC) on the reduced GO sheets (rGO) at room temperature and atmospheric pressure. rGO sheets serve as a large surface area, conductive binder to enhance the ion adsorption, electrical conductivity, and mechanical flexibility of supercapacitor electrodes. This laser-induced photocatalytic reduction method was used to prepare two different rGO-based colloidal composites AC/rGO (CG) and MnO₂@AC/rGO (MCG). The prepared rGO-based colloidal composites were used to fabricate symmetric supercapacitors (CG//CG and MCG//MCG) and asymmetric supercapacitors (MCG//CG) in which MCG is the positive electrode and CG is the negative one. All prepared rGO-based supercapacitors demonstrated significant improvement in their electrochemical performance compared with rGO-free AC based supercapacitors. The enhancement in the electrochemical properties of rGO-based supercapacitors could be attributed to the intrinsic characteristics of rGO, such as high surface area, excellent electrical conductivity, and super mechanical flexibility. Our approach is a one-step, scalable, cost-effective synthesis technique to produce all binder-free AC/rGO based composites for flexible energy-storage devices.     

Effects of dopants on percolation behaviors and gas sensing characteristics of polyaniline film

Effects of dopants on the correlation between the polyaniline (PAn) film resistance (R) and the reduction charge (Q) injected to the PAn film was investigated in dry acetonitrile solutions during electrochemical reduction by using the double potential step method. The R-Q correlation behaves as S-type curves, leading to the determination of the critical reduction charge (Q_c). The latter represents the reduction charge required for the formation of a continuous partially reduced phase in the PAn film. It was observed that the PAn film doped with sodium dodecylbenzene sulphate (SDBS) yielded a smaller Q_c than that doped with perchlorate, when the PAn films were electrochemically reduced under given conditions. The resistance of the pre-doped PAn film will increase significantly when the film is injected with reduction charge more than Q_c. Hence, a smaller Q_c means that the film can respond to very light reduction (or dedoping), being indicative of better sensing ability toward alkaline and reducing gases. This was confirmed by the increased sensitivity of the PAn/SDBS sensor toward 100 ppm NH₃ vapor, compared with the PAn/ClO₄⁻ sensor.     

金属氧化物半导体基三乙胺传感器研究进展

三乙胺是一种应用广泛但对人体有毒副作用的挥发性有机物,需要长期有效的监测,开发一种性能稳定、安全可靠的三乙胺气敏传感器,实现对环境中三乙胺气体浓度实时检测,对于三乙胺的安全储存、运输和使用等环节是至关重要的。金属氧化物半导体基气敏传感器具有制备简单、价格低廉、响应值高等优点,在三乙胺气体的检测中具有不可替代的作用。重点介绍了基于金属氧化物半导体的三乙胺传感器最新研究进展。综述了近年来包括掺杂、异质结、有机金属骨架和氧化还原石墨烯在内的关于金属氧化物半导体基三乙胺气敏材料的制备和性能等方面的研究成果。论述了金属氧化物半导体基复合材料对三乙胺气敏性能的机理。展望了金属氧化物基三乙胺气敏材料的未来研究方向。     

Electrochemical sensing based on graphene oxide/Prussian blue hybrid film modified electrode

A novel graphene oxide (GO)/Prussian blue (PB) hybrid film was constructed by electropolymerizing Prussian blue onto the GO modified glassy carbon electrode, and its electrochemical behaviors were studied. Raman spectra were used to investigate the successful formation of the GO/PB hybrid film. Electrochemical experiments showed that the graphene oxide greatly enhanced electrochemical reactivity of the PB. Moreover, a much higher Prussian blue (PB) loading (6.388 × 10⁻⁸ mol cm⁻²) is obtained as compared to the bare glass carbon surface (3.204 × 10⁻⁹ mol cm⁻²). The GO/PB hybrid film modified electrode was used for the sensitive detection of hydrogen peroxide. The sensor exhibited a wide linearity range from 5.0 × 10⁻⁶ to 1.2 × 10⁻³ M with a detection limit of 1.22 × 10⁻⁷ M (S/N = 3), high sensitivity of 408.7 μA mM⁻¹ cm⁻² and good reproducibility. Furthermore, with glucose oxidase (GOD) as a model, the GO/PB/GOD/chitosan composite-modified electrode was also constructed.The resulting biosensor exhibited good amperometric response to glucose with linear range from 0.1 to 13.5 mM at 0.1 V, good reproducibility and detection limit of 3.43 × 10⁻⁷ M (S/N = 3). In addition, the biosensor presented high selectivity and long-term stability. Therefore, the PB/GO hybrid films-based modified electrode may hold great promise for electrochemical sensing and biosensing applications.     

Room temperature NH3 gas sensor based on PMMA/RGO/ZnO nanocomposite films fabricated by in-situ solution polymerization

Effective detection of ammonia gas is of great importance due to its detrimental effects on human health, environment, and ecosystem. High-performance composite gas sensors are vital in accomplishing this goal. Herein, we investigate the performance of an ammonia (NH₃) gas sensor fabricated via dip-coating the silver interdigitated electrode for PMMA/RGO/ZnO (PRZ) nanocomposite solution with acetone as a solvent. The PRZ ternary nanocomposite was synthesized using the in-situ solution polymerization method and the resistive properties of the films assembled on the interdigitated electrode were analyzed, with respect to the fixed and varying ammonia gas concentrations, using LCR meter. When the sensor is operated in the controlled chamber containing ammonia gas at room temperature, the sensor responds rapidly to ammonia with a fast recovery of 13.02 s at a gas concentration of 350 ppm. The PRZ sensor exhibits high sensing percentage response (527%), excellent repeatability (four times), high sensitivity at low concentrations (less than 10 ppm), swift response and recovery times (1.94 s/13.02 s), and long-term stability (up to 90 days) with fluctuation of 3.2%, which signifies PRZ composite as a potential material for ammonia gas sensor. Aspects such as simplicity of the synthesis process and fabrication, excellent sensing performance, as well as fast response-recovery time at a particular gas concentration are noteworthy in this study. These features can be utilized for the detection of ammonia gas in chemical and biological fields.     

Highly sensitive and selective acetylene sensors based on p-n heterojunction of NiO nanoparticles on flower-like ZnO structures

Acetylene (C₂H₂) gas concentration is a key parameter in transformer monitoring. In current work, the selective acetylene sensors which based on flower-like ZnO structures with NiO nanoparticles were successfully fabricated. The NiO–ZnO composites were synthesized by two-step hydrothermal method. And various of characterization analyses had been applied to the exploration of crystal structure and the p-n heterojunction. According to the systematic gas sensitivity tests, the response of NiO–ZnO (5%) to 50 ppm C₂H₂ was 15.23 at 200 °C whereas the response of pure ZnO was 4.1 in the same condition. In addition, the response value of NiO–ZnO (5%) to 50 ppm C₂H₂ was 3.6 times to 50 ppm H₂. Such a good gas-sensing property of NiO–ZnO composites is due to p-n heterojunction and high catalytic activity of NiO.     

Laser-induced anchoring of WO3 nanoparticles on reduced graphene oxide sheets for photocatalytic water decontamination and energy storage

In this work, the synthesis of tungsten oxide/reduced graphene oxide (WO₃-rGO) nanocomposite, using a simple method of pulsed laser ablation in liquids (PLAL) is reported. The pulsed laser beam of 355 nm wavelength carries out two simultaneous processes: the reduction of graphene oxide and at the same time the anchoring of nanostructured WO₃ on reduced graphene oxide. In the photo-catalytic application, WO₃-rGO shows much better visible light absorption and less photo-generated charge recombination than pure WO₃, as indicated by optical absorption and photoluminescence spectra. These improved features in WO₃-rGO significantly enhanced the photo-catalytic decontamination of methylene blue (MB) dye in the water, compared to the use of pure WO₃ as a photocatalyst. A Poly 2-acrylamido-2-methyl-1-propanesulfonic acid (PAMPS) based electrolyte together with the high electrical conductance and porosity of rGO which were produced after anchoring WO₃ on the graphene oxide, were harnessed for the energy storage application using this material for a supercapacitor. The specific capacitance for WO₃-rGO based device is achieved to be 577 F g⁻¹ measured by the galvanostatic charge-discharge (GCD) method. Also, at a power density of 1000 W kg⁻¹, the as-synthesized WO₃-rGO demonstrated a large energy density value of 76.3 Wh Kg⁻¹ that is much larger than obtained, using WO₃ alone. Besides these photocatalytic and energy storage performance evaluation of WO₃-rGO, the optical, morphological and elemental characteristics of synthesized WO₃-rGO were also investigated to study the improved performance of the nanocomposite in these two applications.