CN116253361B - WS (WS)2/SnSe2Nano heterogeneous material and nitrogen dioxide gas sensor as well as preparation methods and applications thereof - Google Patents
WS (WS)2/SnSe2Nano heterogeneous material and nitrogen dioxide gas sensor as well as preparation methods and applications thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of nanomaterial gas sensors, and particularly relates to a WS 2/SnSe2 heterogeneous gas-sensitive material based on first sex principle research, a preparation method and application thereof. WS 2 used in the invention is of a nano sheet structure, and SnSe 2 is of a nano flower structure. WS 2 nano-sheets are uniformly adhered to the surface of flower-shaped SnSe 2, so that a heterostructure is formed between nano-materials, the gas adsorption capacity is enhanced, and meanwhile, the flower-shaped structure provides rich reaction sites for gas adsorption. The method is characterized in that a solution of WS 2/SnSe2 heterogeneous material is spin-coated on an interdigital electrode to form a nano film with uniform thickness, and the nano film is combined with a density functional first principle, so that theory and data are combined, and the improvement of the gas-sensitive performance of the nano heterogeneous material is systematically analyzed and verified. The invention is used for detecting nitrogen dioxide gas at room temperature, realizes low detection limit, high sensitivity, quick response/recovery time and excellent stability, and the gas sensor has simple preparation method and is suitable for mass production.
Description
Technical Field
The invention belongs to the technical field of gas sensors, and particularly relates to a WS 2/SnSe2 nanometer heterogeneous material, a nitrogen dioxide gas sensor, and a preparation method and application thereof.
Background
Nitrogen dioxide (NO 2) is a colorless gas that is long-term in everyday life and is also a toxic and harmful pollutant, mainly originating from manufacturing production, vehicle emissions and fuel combustion production, which is not completely contained. The World Health Organization (WHO) believes that the allowable contact concentration value is 1ppm when exposed to NO 2 for a long period of time. Meanwhile, long-time contact of high-concentration NO 2 can generate stimulation effect on human respiratory tissues and eyes, and even cause irreparable harm to other important parts of the human body. Importantly, when in contact with other contaminants or water, reactions can occur, which in turn can lead to smoke, acid rain natural disasters, etc., causing unavoidable damage to the living environment. Therefore, it is urgent to study a high-sensitivity nitrogen dioxide gas sensor with a low detection limit.
In recent years, gas detection techniques mainly include gas chromatography, infrared absorption spectroscopy, mass spectrometry, semiconductor sensor methods, and the like, however, in view of practical operational problems, semiconductor material-based gas sensors have been rapidly developed due to low cost, low power consumption, simple manufacturing, high sensitivity, and rapid response. For semiconductor sensors, the selection of materials that are sensitive to the target gas is a critical step in the fabrication of high performance gas sensors. Currently, many two-dimensional materials with excellent properties are developed for application in various fields. Studies have shown that two-dimensional (2D) transition metal chalcogenide (TMDs) nanomaterials are considered to be excellent sensing materials for room temperature gas sensors, which can reduce the detection limit of the sensor. Taking SnSe 2 as an example, the material has excellent electrical property and larger specific surface area, can provide more adsorption sites, and has wide development prospect in the field of gas sensitivity as an n-type TMD material. As a typical p-type TMD material, WS 2 receives great attention because it has smaller conductivity and higher stability, so that mobility of carriers is increased. Therefore, two nano materials with different morphologies and performance advantages are doped, and the gas sensing performance can be effectively improved.
The Density Functional Theory (DFT) first principle calculation method plays an increasingly important role in the field of gas sensing. The first principle research can be used as a supplement to gas detection experiments, because the adsorption system can be constructed to simulate and train the electronic structural characteristics, and meanwhile, the experiments can be more effectively performed under the guidance of theoretical calculation. Importantly, DFT calculations can theoretically predict the gas-sensitive properties of the new materials, and therefore, combining first principles of research with gas sensor detection would have long been developed. Therefore, there is an urgent need for a nano heterogeneous thin film sensor having good responsiveness and ultra-low detection limit to nitrogen dioxide gas, and simultaneously having excellent repeatability, fast response/recovery time and long-term stability, and a preparation method and application thereof.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a WS 2/SnSe2 nanometer heterogeneous material and a gas sensor as well as a preparation method and application thereof, so as to solve the problems related to the background technology.
In order to achieve the above purpose, the present invention adopts the following technical scheme: WS 2/SnSe2 nanometer heterogeneous material, WS 2 is nanometer sheet structure, and SnSe 2 is nanometer flower structure, provides abundant reaction site for gas adsorption, and WS 2 nanometer sheet evenly adheres on flower-like SnSe 2's surface, makes the heterostructure between the nano material.
The preparation method of the WS 2/SnSe2 nanometer heterogeneous material comprises the following steps:
①WS2 Synthesis of nanosheets:
dissolving Na 2WO4·2H2 O and TAA in deionized water, stirring to fully dissolve, adding oxalic acid under continuous stirring, carrying out ultrasonic treatment after fully stirring, transferring the solution into an autoclave for heating and maintaining, after the reaction is finished and cooled to room temperature, alternately cleaning with deionized water and absolute ethyl alcohol to remove impurities, and drying to obtain WS 2 powder;
②SnSe2 Synthesis of nanoflower:
Dissolving SnCl 2·2H2 O and Se powder in ethylene glycol, stirring at room temperature for dissolution, adding ethylenediamine solution to form suspension, continuously stirring until the suspension is fully mixed, transferring into an autoclave for hydrothermal treatment, cooling to room temperature, washing the solution with deionized water and absolute ethyl alcohol to remove impurities, and finally carrying out vacuum drying to obtain SnSe 2 powder;
③WS2/SnSe2 Synthesis of heterogeneous materials:
WS 2 powder is uniformly dispersed in deionized water to prepare WS 2 solution, snSe 2 powder is uniformly dispersed in deionized water to prepare SnSe 2 solution, and the two solutions are mixed according to different volume ratios and subjected to ultrasonic treatment to obtain WS 2/SnSe2 heterogeneous materials with different doping ratios.
Further, the method comprises the steps of,
In the step ①, the reaction temperature time in the autoclave is 200 ℃ for 24 hours; the drying temperature time is 60 ℃ and 5 hours; ultrasonic treatment for 30min;
In the step ②, the reaction temperature time in the autoclave is 180 ℃ for 5 hours; the vacuum drying temperature time is 60 ℃ and 12 hours;
In the step ③, the concentration of WS 2 and SnSe 2 is 0.1g/mL; WS 2/SnSe2 volume ratio is 3:1, 2:1, 1:1, 1:2, or 1:3.
Further, the specific preparation steps comprise:
①WS2 Synthesis of nanosheets:
dissolving 1.2g of Na 2WO4·2H2 O and 1.6g of TAA in 80mL of deionized water, stirring until the solution is fully dissolved, adding 0.6g of oxalic acid into the solution under continuous stirring, carrying out ultrasonic treatment for 30min after the full stirring, transferring the solution into an autoclave, heating for 24h, maintaining 180 ℃, cooling to room temperature after the reaction is finished, alternately cleaning the obtained product with deionized water and absolute ethyl alcohol to remove impurities, and drying for 5h at 60 ℃ to obtain WS 2 powder;
②SnSe2 Synthesis of nanoflower:
Dissolving 0.452g of SnCl 2·2H2 O and 0.158g of Se powder in 38mL of ethylene glycol, stirring at room temperature for dissolution, adding 1.5mL of ethylenediamine solution to form suspension, continuously stirring until the mixture is fully mixed, transferring into an autoclave for hydrothermal treatment, maintaining at 180 ℃ for 5 hours, cooling to room temperature, washing the solution with deionized water and absolute ethyl alcohol to remove impurities, and finally performing vacuum drying at 60 ℃ for 12 hours to obtain SnSe 2 powder;
③WS2/SnSe2 Synthesis of heterogeneous materials:
For WS 2/SnSe2 heterogeneous materials, the same ratio was maintained for SnSe 2 by dissolving 0.1g WS 2 powder in 1mL deionized water to prepare the desired WS 2 solution; mixing WS 2 solution and SnSe 2 solution according to volume ratio of 3:1, 2:1, 1:1, 1:2 and 1:3, and performing ultrasonic treatment for 30min to obtain WS 2/SnSe2 heterogeneous films with different doping ratios.
The WS 2/SnSe2 nanometer heterogeneous material gas sensor takes an epoxy resin substrate as a substrate, a gas sensor with a metal interdigital copper-nickel alloy electrode is prepared on the surface of the substrate, a solution of the heterogeneous material is spin-coated on the metal interdigital copper-nickel alloy electrode to form a nanometer film with uniform thickness, and the size of the metal interdigital copper-nickel alloy electrode is 1cm multiplied by 1cm.
Further, the principle of the sensor is as follows:
When two different sensing materials are contacted, electrons move from a fermi level to a low part until equilibrium is reached, a hole accumulation layer is formed at the SnSe 2 by the heterogeneous materials, when the WS 2/SnSe2 heterogeneous thin film sensor is contacted with oxidizing gas, namely NO 2 gas molecules react with O 2 - and consume part of electrons, so that the concentration of hole carriers at the SnSe 2 is increased, at the moment, the hole accumulation layer is widened, the resistance is reduced, the morphology and structure of the materials also influence the gas sensitivity, flower-like SnSe 2 and WS 2 nano-sheets have larger specific surface areas, more active centers can be provided for the gas molecules, the adsorption and desorption of gas are facilitated, and meanwhile, the structure consisting of nano-sheets is also favorable for the diffusion of NO 2 gas molecules; a p-n heterostructure is formed between the SnSe 2 and the WS 2, electrons flow from the SnSe 2 to the WS 2, and the heterostructure also improves the carrier transfer rate and the response value of the sensor.
The preparation method of the WS 2/SnSe2 nanometer heterogeneous material gas sensor comprises the following preparation steps:
And coating a solution of WS 2/SnSe2 heterogeneous material on the Cu/Ni interdigital electrode by adopting a spin coating method, forming a film with uniform thickness on the surface, and drying the prepared gas sensor in a vacuum environment at 60 ℃ for one day to ensure the stability of the gas sensor.
Application of WS 2/SnSe2 nanometer heterogeneous material gas sensor,
The sensor is used for detecting nitrogen dioxide at room temperature.
Further, the first principle is a theory that electron density distribution is used as a basic variable and applied to the research of the ground state properties of a multiparticulate system; when the space position of the atomic nucleus of each atom of the molecular system is determined, the distribution of the electron density outside the nucleus of the atom in space is also determined, and the functional of the electron density in space can be used for representing the energy of the substance system, so that the gas adsorption capacity of the system is indicated.
Further, first principle gas adsorption system construction:
The WS 2/SnSe2 heterogeneous gas-sensitive material is used for a substrate for adsorbing gas molecules, and the most stable adsorption model is obtained by calculation through adjusting the direction and the position relation between the WS 2/SnSe2 substrate and the surface NO 2 gas molecules, and the adsorption mechanism and the adsorption capacity are mainly analyzed through adsorption energy, bond energy, band gap change, electrostatic charge transfer and state density change parameters of an adsorption system.
The WS 2/SnSe2 nanometer heterogeneous material and the gas sensor as well as the preparation method and the application thereof have the advantages that:
the invention prepares a resistive semiconductor gas sensor based on WS 2/SnSe2 heterogeneous film, which is used for detecting nitrogen dioxide (NO 2) at room temperature, has high response (79%) at 30ppm NO 2 and has quick response/recovery time (15 s/14 s). It also exhibits good moisture resistance (11-87 RH%), excellent stability (1-50 days) and repeatability (error < 2%). Because NO 2 gas is colorless and has low concentration and NO obvious peculiar smell, the invention mainly detects the gas under low concentration. Meanwhile, the invention combines the first principle research to predict the gas-sensitive characteristic of the novel material in theory, so that different directions and position relations between the substrate (WS 2/SnSe2) and the gas molecule (NO 2) are constructed to calculate and obtain the most stable adsorption model, and theoretical guidance is provided for the experimental detection of the sensor. The gas sensor is expected to play a role in monitoring the NO 2 gas in the atmosphere.
Drawings
FIG. 1 is a process diagram of a WS 2/SnSe2 gas sensor according to an embodiment of the present invention;
FIG. 2 is a diagram of a test platform for a WS 2/SnSe2 gas sensor in accordance with an embodiment of the present invention;
FIGS. 3 (a-b) are SEM images of SnSe 2 films according to examples of the present invention;
FIG. 3 (c) is an SEM image of a WS 2 film according to an example of the invention;
FIG. 3 (d) is an SEM image of a WS 2/SnSe2 film according to an example of the invention;
FIG. 3 (e) is a TEM image of a WS 2/SnSe2 film according to an embodiment of the invention;
FIG. 3 (f) is a HRTEM image of a WS 2/SnSe2 film according to an embodiment of the invention;
FIG. 4 (a) is an XRD pattern of single WS 2, single SnSe 2 and WS 2/SnSe2 films of the examples of the invention;
FIG. 4 (b) is a measurement spectrum of a WS 2/SnSe2 film according to an example of the present invention;
FIG. 4 (c) is a W4 f spectrum of a WS 2/SnSe2 film according to an example of the invention;
FIG. 4 (d) is an S2 p spectrum of a WS 2/SnSe2 film according to an example of the present invention;
FIG. 4 (e) is a Sn 3d spectrum of a WS 2/SnSe2 film according to an example of the present invention;
FIG. 4 (f) is a Se 3d spectrum of a WS 2/SnSe2 film of the example of the invention;
FIG. 5 (a) is a graph showing the response of a heterogeneous thin film gas sensor of different proportions of WS 2/SnSe2 in accordance with an embodiment of the present invention at 10ppm NO 2;
FIG. 5 (b) is a graph showing the response of a single WS 2, single SnSe 2、WS2/SnSe2 thin film gas sensor at a concentration of 1-30ppm NO 2 in an embodiment of the invention;
FIG. 5 (c) is a graph showing the response of a WS 2/SnSe2 thin-film gas sensor according to an example of the present invention at various NO 2 concentrations;
FIG. 5 (d) is a graph showing a fit of the concentration of NO 2 to the response of a single WS 2, single SnSe 2、WS2/SnSe2 thin film gas sensor of the example of the invention at 1-30 ppm;
FIG. 6 (a) is a chart showing the repeatability of the WS 2/SnSe2 thin-film gas sensor of the example of the invention at1, 10, 30ppm NO 2;
FIG. 6 (b) is a diagram showing the selectivity of WS 2/SnSe2 film gas sensor to various interfering gases according to one embodiment of the present invention;
FIG. 6 (c) is a graph comparing response/recovery times of a WS 2、SnSe2、WS2/SnSe2 thin-film gas sensor of example of the invention at 30ppm NO 2;
FIG. 6 (d) is a graph showing the long-term stability test of WS 2/SnSe2 film gas sensor of example of this invention at 1, 10, 30ppm NO 2;
FIG. 7 is a graph showing the change in resistance and response of a WS 2/SnSe2 thin-film gas sensor according to an example of the present invention at different relative humidities (11-85% RH);
FIG. 8 is an I-V graph of a WS 2、SnSe2、WS2/SnSe2 thin film gas sensor according to an embodiment of the invention;
FIG. 9 (a) is a schematic diagram of a sensing mechanism and an energy band structure diagram of an embodiment of the present invention when WS 2、SnSe2 thin film is not in contact;
FIG. 9 (b) is a schematic diagram of a sensing mechanism and an energy band structure diagram of a WS 2/SnSe2 film exposed to air according to an embodiment of the present invention;
FIG. 9 (c) is a schematic diagram of a sensing mechanism and a band structure diagram of the WS 2/SnSe2 film exposed to NO 2 according to an embodiment of the present invention;
FIG. 10 (a) is a schematic diagram showing the structure of the SnSe 2 film in MATERIALS STUDIO (MS) according to an embodiment of the present invention;
FIG. 10 (b) is a schematic diagram showing the structure of a WS 2/SnSe2 film in a MS according to an embodiment of the present invention;
FIG. 10 (c) is a graph TDOS of the SnSe 2、WS2/SnSe2 film according to the example of the present invention calculated in MS;
FIG. 10 (d) is a PDOS image calculated in MS for the SnSe 2、WS2/SnSe2 film of the present invention;
FIG. 11 (a) is a schematic diagram showing the top structure of the SnSe 2-NO2 adsorption system in MS according to the embodiment of the present invention;
FIG. 11 (b) is a schematic diagram showing a side view of the SnSe 2-NO2 adsorption system in MS according to an embodiment of the present invention;
FIG. 11 (c) is an electron density diagram of an embodiment of the SnSe 2-NO2 adsorption system in MS;
FIG. 11 (d) is an electron density diagram of a WS 2/SnSe2-NO2 adsorption system in a MS according to an example of the present invention;
FIG. 11 (e) is a diagram TDOS calculated in MS using the WS 2/SnSe2、WS2/SnSe2-NO2 adsorption system of the example of the invention;
FIG. 11 (f) is a PDOS image calculated in MS by WS 2/SnSe2、WS2/SnSe2-NO2 adsorption system according to an embodiment of the present invention.
Detailed Description
The following description of the embodiments is provided in conjunction with the accompanying drawings.
The reagents and apparatus in the examples below were conventional experimental reagents and apparatus.
Example 1:
A nano heterogeneous thin film based on WS 2/SnSe2, wherein WS 2 is a nano sheet structure, and SnSe 2 is a nano flower structure. WS 2 nano-sheets are uniformly adhered to the surface of flower-shaped SnSe 2, so that a heterostructure is formed between nano-materials, the gas adsorption capacity is enhanced, and meanwhile, the flower-shaped structure provides rich reaction sites for gas adsorption.
A method for preparing nano heterogeneous thin film based on WS 2/SnSe2,
1.2G of Na 2WO4·2H2 O and 1.6g of TAA were dissolved in 80mL of deionized water and stirred until fully dissolved. To form an acidic environment, 0.6g of oxalic acid was added to the above solution under continuous stirring, and after sufficient stirring, ultrasonic treatment was performed for 30 minutes. Transferring the solution into an autoclave, heating for 24 hours, keeping 180 ℃, after the reaction is finished and the solution is cooled to room temperature, alternately cleaning the obtained product by deionized water and absolute ethyl alcohol to remove impurities, and drying at 60 ℃ for 5 hours to obtain WS 2 powder;
0.452g SnCl 2·2H2 O and 0.158g Se powder were dissolved in 38mL ethylene glycol and stirred at room temperature. 1.5mL of ethylenediamine solution was added to form a suspension, stirring was continued until sufficient mixing was achieved, the suspension was transferred to an autoclave for hydrothermal treatment, maintained at 180℃for 5 hours, cooled to room temperature, and the solution was rinsed with deionized water and absolute ethanol to remove impurities. Finally, vacuum drying is carried out at 60 ℃ for 12 hours to obtain SnSe 2 powder.
For WS 2/SnSe2 heterogeneous materials, the same ratio was maintained for SnSe 2 by dissolving 0.1g WS 2 powder in 1mL deionized water to prepare the desired WS 2 solution; mixing WS 2 solution and SnSe 2 solution according to volume ratio of 3:1, 2:1, 1:1, 1:2 and 1:3, and performing ultrasonic treatment for 30min to obtain WS 2/SnSe2 heterogeneous films with different doping ratios.
FIG. 1 is a diagram of a process for preparing WS 2/SnSe2 nanometer heterogeneous films.
Gas sensitive heterogeneous thin film characterization analysis:
Microstructure analysis was performed on WS 2/SnSe2 nm heterogeneous thin films using SEM, XRD, TEM and XPS characterization methods.
The surface morphology of the sensing material is characterized by scanning electron microscopy.
The flower-like structure of SnSe 2 can be clearly seen from fig. 3 (a-b), and it is uniformly dispersed in the solution. FIG. 3 (c) shows a typical lamellar WS 2 morphology. Fig. 3 (d) is an SEM image of WS 2/SnSe2 nm heterogeneous material, and it can be observed that WS 2 nm sheets uniformly adhere to SnSe 2, and the two materials contact each other, indicating successful preparation.
Fig. 3 (e) shows TEM of WS 2/SnSe2 heterogeneous material. It can be found that there is a contact surface between WS 2 NSs and SnSe 2 NFs, which gives a heterogeneous thin film sensor with suitable conductivity. FIG. 3 (f) is the HRTEM of WS 2/SnSe2 heterogeneous material, the lattices of different crystal planes SnSe 2(001)、SnSe2(011)、WS2 (100) and WS 2 (002) are 0.61, 0.29, 0.27 and 0.62nm, respectively.
Fig. 4 is an X-ray diffraction (XRD) pattern and an X-ray photoelectron spectroscopy (XPS) pattern of WS 2、SnSe2、WS2/SnSe2.
The XRD patterns of WS 2、SnSe2 and WS 2/SnSe2 samples are shown in FIG. 4 (a). The diffraction peaks at 2θ for SnSe 2 were 14.41, 23.64, 29.76, 30.73, 40.22, 43.60, 45.53, 47.79, 52.13, 56.15, 57.92, 65.17 and 78.50 °, corresponding to the (001), (100), (002), (011), (012), (003), (110), (111), (103), (201), (004), (113) and (121) crystal planes, respectively, demonstrating successful production of SnSe 2. The main characteristic peaks of WS 2 at 2θ=14.35, 32.77, 33.51, 43.91 and 59.77 ° correspond to the (002), (100), (101), (006) and (112) crystal planes, which are consistent with JCPDS No. 33-1387. Diffraction peaks for WS 2/SnSe2 heterogeneous films included all of the characteristic peaks described above, indicating successful preparation of WS 2/SnSe2 heterogeneous films. FIG. 4 (b) is a measurement spectrum of WS 2/SnSe2 sample, the constituent elements mainly including Sn, se, W, S, illustrating successful preparation of heterogeneous films. FIG. 4 (c) shows that the W atom has two electron states. The characteristic peaks of W 6+ consist of W 6+4f7/2 (35.78 eV) and W 6+4f1/2 (37.85 eV), and furthermore, the characteristic peaks of W 4+4f7/2 and W 4+4f1/2 can be observed at 32.68 and 34.78 eV. Fig. 4 (e) shows that two characteristic peaks of Sn 3d appear at 495.35 and 486.84eV, which are attributed to Sn 3d 3/2 and Sn 3d 5/2 in SnSe 2. Fig. 4 (f) shows XPS images of Se 3d, with characteristic peaks at 54.69eV and 55.69eV caused by Se 3d 5/2 and Se 3d 3/2.
Example 2:
WS 2/SnSe2 nm heterogeneous film based sensor: the WS 2/SnSe2 heterogeneous material solution is coated on the Cu/Ni interdigital electrode to prepare the gas-sensitive film with uniform thickness.
The preparation method of the sensor based on WS 2/SnSe2 nanometer heterogeneous film comprises the following steps: and coating a solution of WS 2/SnSe2 heterogeneous material on the Cu/Ni interdigital electrode by adopting a spin coating method, forming a film with uniform thickness on the surface, and drying the prepared gas sensor in a vacuum environment at 60 ℃ for one day to ensure the stability of the gas sensor.
The built experimental test platform of the gas sensor is shown in figure 2. The prepared gas sensor was placed in a standard conical flask for experiments, and NO 2 was mixed with dry air by a flow controller to obtain a test gas at a concentration of 1-30 ppm. The sensor was connected to Keysight 34470a and tested experimentally at 25 ℃.
Gas sensing mechanism of WS 2/SnSe2 heterogeneous thin film gas sensor:
The mechanism of the resistive semiconductor gas sensor can be attributed to the change in the resistance value of the sensing layer, i.e., the gas adsorption and desorption process. As shown in FIG. 8, a bias voltage of-5V-5V was applied at the time of the test, and an increase in current with an increase in voltage was observed. It can be derived that the I-V curve characteristic of WS 2/SnSe2 hetero-thin film sensor is nonlinear, indicating that p-n heterojunction is formed at its contact face and its forward turn-on voltage is 1.2V.
The materials have different work functions, follow an electron affinity model and drive electron flow. The work function of SnSe 2 is 4.3eV, while WS 2 is 6.2eV. When two different sensing materials are in contact, electrons will move from the portion of the fermi level to the lower portion until equilibrium is reached, and thus electrons will flow from SnSe 2 to WS 2. In air, a hole accumulation layer will form on the surface of SnSe 2. When WS 2/SnSe2 heterogeneous material gas sensor is contacted with oxidizing gas, i.e. NO 2 gas molecules react with O 2 - and consume part of electrons, resulting in an increase in hole carrier concentration, widening of hole accumulation layer and decrease in resistance. These reactions are as follows:
O2(gas)→O2(ads) (1)
O2(ads)+e-→O2 -(ads) (2)
NO2(gas)+e-→NO2 -(ads) (3)
NO2(gas)+O2 -(ads)+2e-→NO2 -(ads)+2O-(ads) (4)
The gas sensitivity of WS 2/SnSe2 heterogeneous thin film sensor to NO 2 is superior to that of single WS 2 and SnSe 2 gas sensors, which can be attributed to the following reasons. On one hand, the flower-shaped SnSe 2 and WS 2 nano-sheets have larger specific surface area due to the special structure, and can provide more active centers for gas molecules, thereby being beneficial to gas adsorption and desorption. Importantly, the structure consisting of the nanoplatelets also facilitates the diffusion of NO 2 gas molecules. On the other hand, the improvement in performance is the formation of a p-n heterostructure between SnSe 2 and WS 2, and electrons will flow from SnSe 2 to WS 2 until they reach the fermi level balance. Fig. 9 (a-c) depicts a schematic of the band structure changes of SnSe 2 NFs and WS 2 NSs before and after contact. When the WS 2/SnSe2 sensor is placed in NO 2 gas, NO 2 molecules can react with O 2 - on the heterogeneous thin film, resulting in a change in carrier concentration and a decrease in resistance, thereby enhancing the response of the gas sensor.
The nitrogen dioxide sensing characteristics of the WS 2/SnSe2 heterogeneous film gas sensor are as follows:
To demonstrate that heterogeneous materials are more advantageous than single materials, sensors based on WS 2、SnSe2 and WS 2/SnSe2 were developed. Wherein the response value is defined as:
Where Ra and Rg are the resistance of the sensor in air and NO 2. The response of WS 2/SnSe2 heterogeneous thin film sensors with different doping ratios to 10ppm NO 2 is shown in FIG. 5 (a). The performance of the doping ratio 1:1 gas sensor is best, and the response value can reach 36.68%, so the heterogeneous thin film sensor is selected for testing. FIG. 5 (b) is a graph showing that the response of WS 2、SnSe2、WS2/SnSe2 sensor was tested by placing it in different concentrations of NO 2, and it was not difficult to find that the WS 2/SnSe2 sensor maintained the optimal response at the same concentration. Furthermore, the sensor response increases with increasing concentration. FIG. 5 (c) is a diagram mainly depicting the typical response of WS 2/SnSe2 heterogeneous thin film sensor at different gas concentrations of 1ppm-30ppm, which has a reversible response to various concentrations of NO 2, which can be restored to baseline values when in the atmosphere. As can be seen from fig. 5 (d), for WS 2/SnSe2、SnSe2 and WS 2 sensors, the functional relationship between response (Y) and gas concentration (X) can be expressed as y= 127.86-122.791e -0031x,Y＝11507.7-11506.95e-0.0005x,Y＝-3.884+4.075e0.031x, and the corresponding correlation coefficients (R 2) can be determined as 0.9896, 0.9507 and 0.9529, respectively.
To verify whether WS 2/SnSe2 heterogeneous thin film gas sensors can be stably applied to practical detection for a long period of time, other properties of the sensor device, such as response time, selectivity, long-term stability, repeatability, etc., need to be tested.
FIG. 6 (a) is a graph showing the change in resistance of the sensor in 1, 5, 10ppm NO 2 several times. Repeatability of the WS 2/SnSe2 sensor was studied, and the response/recovery curve indicated that the sensor had good repeatability.
Fig. 6 (b) mainly illustrates the selectivity index test of the sensor. The response of the sensor to NO 2 is much higher than other interfering gases (e.g., CH 4、SO2、CO、NH3, ethanol), indicating good selectivity of the sensor.
Fig. 6 (c) mainly illustrates the test of response/recovery time of the sensor at 30ppm NO 2. The response/recovery times of the single WS 2、SnSe2 and WS 2/SnSe2 sensors are respectively 72s/56s, 64s/55s and 15s/14s, and the response/recovery time of the WS 2/SnSe2 sensor is obviously shortened, which proves that the WS 2/SnSe2 heterogeneous material is more suitable for NO 2 gas detection.
Fig. 6 (d) mainly illustrates the long-term stability of the sensor. During the test, performance test is carried out every seven days, and the sensor mainly aims at 2ppm, 15ppm and 30ppm NO 2, has small fluctuation of response values with time, has negligible change and has long-term working performance.
Furthermore, since the gas sensor is to be operated at room temperature, it is necessary to consider the influence of ambient humidity on its gas-sensitive performance. The effect of different relative humidity (11-85% RH) on sensor response was studied. As shown in fig. 7, as the relative humidity increases, the resistance and response have a slight decrease, possibly with water molecules reacting with lewis acid sites (metal sites) and lewis base sites (oxygen sites), resulting in a decrease in sensor resistance and response.
The WS 2/SnSe2 gas sensor has the characteristics of simple preparation process, low power consumption and sensitive response. Table 1 lists the gas sensing characteristics of WS 2/SnSe2 sensors, such as operating temperature, response/recovery time and response values, compared to reported sensors, based on the above analysis, NO 2 sensors based on WS 2/SnSe2 nanomaterials had better performance than conventional sensors. In addition, WS 2/SnSe2 thin film gas sensors have a higher response than single WS 2、SnSe2 -based gas sensors when detecting NO 2 at room temperature. This phenomenon is due to the unique morphology of WS 2/SnSe2 film and the heterostructure between WS 2 and SnSe 2.
TABLE 1 WS 2/SnSe2 comparison of the sensing Performance of gas sensors with existing sensors
Example 3:
A sensor based on WS 2/SnSe2 nanometer heterogeneous film combines the first sexual principle of density functional to predict the gas sensitivity of the novel material in theory, and experiments are more effectively carried out under the guidance of theoretical calculation.
A Density Functional Theory (DFT) simulation study was performed using a Material Studio (DMol). An NO 2 adsorption model based on SnSe 2 and WS 2/SnSe2 was constructed, and fig. 10 (a, b) is a molecular structure diagram of two systems. Partial state density (PDOS) and total state density (TDOS) plots were calculated for the system, as shown in fig. 10 (c, d), with a slight shift in TDOS electron density after doping WS 2. In addition, the W-5d and Se-3p orbitals have overlapping peaks at about-3.57 eV, -2.65eV and 1.42eV, indicating the presence of hybridization. Fig. 11 (a, b) illustrates the SnSe 2-NO2 adsorption structure, and fig. 11 (c, d) illustrates the charge density of the SnSe 2 and WS 2/SnSe2 systems after NO 2 adsorption, and the electron ratio between WS 2/SnSe2-NO2 is relatively large and the adsorption capacity is relatively strong. The adsorption energy (E ad) can be calculated in public:
Ead＝EA/gas-Egas-EA
e A and E A/gas represent the energy of the system A before and after gas adsorption, and E gas represents the energy of NO 2. Table 2 compares the DFT calculations for the adsorption system, and it can be seen that the NO 2 gas molecules are closer to the sensing layer of the WS 2/SnSe2 adsorption system. The adsorption energy of the WS 2/SnSe2 sensor system is-2.122 eV, the system is chemisorption, and the other two systems are physisorption. Thus, WS 2/SnSe2 heterogeneous films have better sensing performance for NO 2 gas.
TABLE 2 SnSe 2/WS2 parameters of pure SnSe 2、WS2 adsorption systems
FIG. 11 (e) illustrates that TDOS of WS 2/SnSe2-NO2 moves to the left and increases significantly around-13.28, -12.32, -1.28, and 1.49 eV.
FIG. 11 (f) is a PDOS diagram of a WS 2/SnSe2-NO2 adsorption system. W-5d, S-3p, se-3p, N-2p and O-2p orbitals have overlapping peaks at-7.19 eV, -4.55eV, -2.65eV, -0.70eV and 0.96eV, further illustrating the chemisorption characteristics of the WS 2/SnSe2 system.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the essence of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. WS 2/SnSe2 nanometer heterogeneous material for gas sensor, characterized in that: WS 2 is of a nano sheet structure, snSe 2 is of a nano flower-like structure, rich reaction sites are provided for gas adsorption, and WS 2 nano sheets are uniformly adhered to the surface of flower-like SnSe 2, so that a heterostructure is formed between nano materials.
2. The method for preparing the WS 2/SnSe2 nano heterogeneous material according to claim 1, wherein the preparing step comprises the following steps:
①WS2 Synthesis of nanosheets:
dissolving Na 2WO4·2H2 O and TAA in deionized water, stirring to fully dissolve, adding oxalic acid under continuous stirring, carrying out ultrasonic treatment after fully stirring, transferring the solution into an autoclave for heating and maintaining, after the reaction is finished and cooled to room temperature, alternately cleaning with deionized water and absolute ethyl alcohol to remove impurities, and drying to obtain WS 2 powder;
②SnSe2 Synthesis of nanoflower:
Dissolving SnCl 2·2H2 O and Se powder in ethylene glycol, stirring at room temperature for dissolution, adding ethylenediamine solution to form suspension, continuously stirring until the suspension is fully mixed, transferring into an autoclave for hydrothermal treatment, cooling to room temperature, washing the solution with deionized water and absolute ethyl alcohol to remove impurities, and finally carrying out vacuum drying to obtain SnSe 2 powder;
③WS2/SnSe2 Synthesis of heterogeneous materials:
WS 2 powder is uniformly dispersed in deionized water to prepare WS 2 solution, snSe 2 powder is uniformly dispersed in deionized water to prepare SnSe 2 solution, and the two solutions are mixed according to different volume ratios and subjected to ultrasonic treatment to obtain WS 2/SnSe2 heterogeneous materials with different doping ratios.
3. The method for preparing the WS 2/SnSe2 nanometer heterogeneous material according to claim 2, which is characterized in that:
In the step ①, the reaction temperature time in the autoclave is 200 ℃ for 24 hours; the drying temperature time is 60 ℃ and 5 hours; ultrasonic treatment for 30min;
In the step ②, the reaction temperature time in the autoclave is 180 ℃ for 5 hours; the vacuum drying temperature time is 60 ℃ and 12 hours;
In the step ③, the concentration of WS 2 and SnSe 2 is 0.1g/mL; WS 2/SnSe2 volume ratio is 3:1, 2:1, 1:1, 1:2, or 1:3.
4. The method for preparing the WS 2/SnSe2 nanometer heterogeneous material according to claim 2, wherein the specific preparation steps comprise:
①WS2 Synthesis of nanosheets:
dissolving 1.2g of Na 2WO4·2H2 O and 1.6g of TAA in 80mL of deionized water, stirring until the solution is fully dissolved, adding 0.6g of oxalic acid into the solution under continuous stirring, carrying out ultrasonic treatment for 30min after the full stirring, transferring the solution into an autoclave, heating for 24h, maintaining 180 ℃, cooling to room temperature after the reaction is finished, alternately cleaning the obtained product with deionized water and absolute ethyl alcohol to remove impurities, and drying for 5h at 60 ℃ to obtain WS 2 powder;
②SnSe2 Synthesis of nanoflower:
Dissolving 0.452g of SnCl 2·2H2 O and 0.158g of Se powder in 38mL of ethylene glycol, stirring at room temperature for dissolution, adding 1.5mL of ethylenediamine solution to form suspension, continuously stirring until the mixture is fully mixed, transferring into an autoclave for hydrothermal treatment, maintaining at 180 ℃ for 5 hours, cooling to room temperature, washing the solution with deionized water and absolute ethyl alcohol to remove impurities, and finally performing vacuum drying at 60 ℃ for 12 hours to obtain SnSe 2 powder;
③WS2/SnSe2 Synthesis of heterogeneous materials:
For WS 2/SnSe2 heterogeneous materials, the same ratio was maintained for SnSe 2 by dissolving 0.1g WS 2 powder in 1mL deionized water to prepare the desired WS 2 solution; mixing WS 2 solution and SnSe 2 solution according to volume ratio of 3:1, 2:1, 1:1, 1:2 and 1:3, and performing ultrasonic treatment for 30min to obtain WS 2/SnSe2 heterogeneous films with different doping ratios.
5. A gas sensor of WS 2/SnSe2 nm heterogeneous material, using the material according to claim 1 or prepared by the preparation method according to any one of claims 2-4 as raw material, characterized in that: the method comprises the steps of taking an epoxy resin substrate as a substrate, preparing a gas sensor with a metal interdigital copper-nickel alloy electrode on the surface of the substrate, and spin-coating a solution of a heterogeneous material on the metal interdigital copper-nickel alloy electrode to form a nano film with uniform thickness, wherein the size of the metal interdigital copper-nickel alloy electrode is 1cm multiplied by 1cm.
6. The method for preparing the WS 2/SnSe2 nano heterogeneous material gas sensor according to claim 5, wherein the preparing step comprises the following steps:
And coating a solution of WS 2/SnSe2 heterogeneous material on the Cu/Ni interdigital electrode by adopting a spin coating method, forming a film with uniform thickness on the surface, and drying the prepared gas sensor in a vacuum environment at 60 ℃ for one day to ensure the stability of the gas sensor.
7. The use of WS 2/SnSe2 nano-heterogeneous material gas sensor according to claim 5, characterized in that:
The sensor is used for detecting nitrogen dioxide at room temperature.
8. The use of WS 2/SnSe2 nm heterogeneous material gas sensor according to claim 7, characterized by the construction of first principles gas adsorption system:
The WS 2/SnSe2 heterogeneous gas-sensitive material is used for a substrate for adsorbing gas molecules, and the most stable adsorption model is obtained by calculation through adjusting the direction and the position relation between the WS 2/SnSe2 substrate and the surface NO 2 gas molecules, and the adsorption mechanism and the adsorption capacity are mainly analyzed through adsorption energy, bond energy, band gap change, electrostatic charge transfer and state density change parameters of an adsorption system.
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| CN109668936A (en) * | 2018-11-30 | 2019-04-23 | 大连理工大学 | One kind being based on flower-shaped SnSe2/SnO2Nitrogen dioxide gas sensor, preparation process and the application of hetero-junctions |
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| CN105858646A (en) * | 2016-04-19 | 2016-08-17 | 北京航空航天大学 | Preparation method of transparent thin film |
| CN107424911A (en) * | 2017-04-25 | 2017-12-01 | 郑州轻工业学院 | SnSe with vertical stratification2/MoSe2The preparation method and its field effect behavior method of modifying of novel heterojunction |
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