CN111470480A - Molybdenum diselenide gas-sensitive sensing material and preparation and application thereof - Google Patents
Molybdenum diselenide gas-sensitive sensing material and preparation and application thereof Download PDFInfo
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Abstract
The invention provides a molybdenum diselenide nano material which has a nanoflower structure formed by assembling molybdenum diselenide nanosheets. MoSe with a hierarchical porous structure with a specific morphology obtained by the invention2The nanometer material has nanometer flower with hierarchical porous structure, unique two-dimensional plane structure and three-dimensional porous structure, greatly enhances the chemical adsorption between the material and target molecules, and accelerates the electronic exchange between the substrate and the gas molecules to be measured. The gas-sensitive detection of the gas to be detected has high selectivity and stability even if there are many gas to be detectedFor example, when formaldehyde, chlorobenzene, ethanol, acetone, toluene and other impurity gases coexist, the gas to be detected can still be detected with high selectivity and high sensitivity, and the result repeatability is high during continuous cycle detection. And the preparation method is simple, mild in condition and controllable in process, is beneficial to industrial realization, and has wide practical prospect.
Description
Technical Field
The invention relates to the technical field of preparation of two-dimensional transition metal sulfide gas-sensitive sensing materials, and relates to a molybdenum diselenide nano material, a preparation method and application thereof, in particular to a molybdenum diselenide gas-sensitive sensing material, and preparation and application thereof.
Background
Since graphene was successfully stripped by two scientists at the university of manchester, uk in 2004, graphene is favored for its excellent electrical, optical, mechanical and electrochemical properties. However, intrinsic graphene does not have a band gap, which severely limits its application in electronic and optoelectronic devices, and thus, transition metal dichalcogenide TMD (MoS)2、WSe2、TiS2、TaS2Etc.) the research of nanomaterials is in progress. In recent years, it has been found that when bulk transition metal dichalcogenides are converted to two-dimensional nanosheets, the nanosheets have a controlled morphology and size due to the two-dimensional confinement effect. The electronic band structure of the material can often generate some singular transformation, such as the indirect band gap is changed into the direct band gap, or the band gap width is changed, the forbidden band width is different along with the different layers of the material, so that the performances of TMDs such as light (mainly shown in the aspects of photoluminescence/electroluminescence, absorption spectrum, vibration spectrum, photovoltaic effect and the like), electricity (mainly shown in the aspects of semiconductor characteristics, dynamic and static storage, superconduction and the like) are greatly changed, and the material is even better than graphene in some fields, especially the application in the aspect of electronic devices. In addition, the graphene has a wide application prospect in the aspects of transistors, lithium ion batteries, sensors and photocatalysis, and is known as graphene in the semiconductor industry.
The detection technology is an important technical tool for human to know the world and transform the world, and the sensor plays an important role in scientific experiments, chemical production research and development, acquisition, transmission, information resource processing and the like. Among them, the gas sensor is an electronic component extremely sensitive to some gases having oxidation/reduction properties or organic solvent vapors in the environment, can detect specific gas molecules, and is widely applied to places such as detection, alarm, monitoring and the like of combustible gases and toxic gases. At present, a series of regulations and policies are formulated in China, the investment is increased for monitoring the environmental quality, the full coverage of the environmental quality, the serious pollution source and the ecological condition monitoring network is promoted, various policies are intensively released, and the atmospheric pollution detection and treatment become one of the key contents of the current environment-friendly work. The gas sensitive detection technology is vigorously developed, and the method has important scientific significance for national health and production safety. Common gas sensor types include semiconductor gas sensors, contact combustion gas sensors and electrochemical gas sensors, among which the most widely used is the semiconductor gas sensor, and the principle involved is to detect target gas molecules by utilizing physical property changes such as electrical conductivity and the like generated when the gas molecules to be detected contact with the surface of a semiconductor. A qualified gas sensor must meet the following requirements: the gas concentration of the allowable concentration and other standard values of the alarm gas can be detected, the gas can stably work for a long time, the repeatability is high, the response speed is high, and the influence of coexisting substances on the detection is small.
Ammonia (NH)3) Is widely used in food processing, chemical industry, agriculture and medical diagnosis, is flammable and explosive, and is a toxic gas. With the improvement of the living standard of modern society and the increasing attention to environmental protection, the real-time monitoring of air quality and pollution, especially NH3Gas sensors are placing higher demands. In industry, NH3The gas sensor is widely applied to various cold rooms, laboratories containing ammonia and ammonia storage warehouses and other related industrial places, and can effectively prevent ammonia poisoning and explosion accidents, thereby ensuring the safety of lives and property. In agriculture, statistics show that livestock and poultry industry breeding is a main source for emission of ammonia gas, mainly comes from fermentation of excrement such as livestock and poultry manure, can react with oxidation products of sulfur dioxide and nitrogen oxides to generate ammonium salts such as ammonium nitrate and ammonium sulfate, and is also an important source of PM 2.5. At present, livestock and poultryNH in house3The content is generally 10ppm to 30ppm when the content is small, and is more than 100ppm when the content is large, and NH is arranged in the piggery according to the regulation of Chinese pollution-free breeding standard3Concentration of<25mg/m3(about 33 ppm). Therefore, NH in the livestock and poultry house3The concentration of (b) has become a key index parameter for profitability of the breeding industry. Currently, NH based on semiconductor materials3Gas sensing technology also suffers from several challenges, including higher operating temperatures (typically > 200 ℃), which results in high power consumption and complex sensor design and manufacture. Some studies have indicated that surface modification using noble metals is considered to be an effective strategy to enhance the detection performance of semiconductor-based gas sensors. Noble metal nanoparticles such as gold, silver and platinum are a class of nanoparticles having unique chemical and physical properties and are widely used in gas sensors because the noble metal loading can improve the adsorption of gas molecules on the surface of the semiconductor material and accelerate the electronic exchange between the sensor and the test gas, but the extreme high price and storage of noble metals limit their wide application in gas sensors.
Therefore, how to find a more suitable gas sensitive material, solve the existing problems, save more energy, reduce the working temperature and improve the gas detection efficiency has become one of the problems to be solved urgently by the prospective scientific researchers.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a molybdenum diselenide nanomaterial, a preparation method thereof, and an application thereof, and in particular, to a molybdenum diselenide gas-sensitive sensing material, the molybdenum diselenide nanomaterial prepared by the present invention has a unique two-dimensional planar structure and a three-dimensional porous structure, has high selectivity for gas-sensitive detection of ammonia, and can perform high-selectivity and high-sensitivity detection on ammonia even when impurity gases such as formaldehyde, chlorobenzene, ethanol, acetone, toluene, and the like coexist in a gas to be detected, and the result repeatability is high during continuous cycle detection, and the preparation method is simple, mild in conditions, controllable in process, beneficial to industrial implementation, and has a wide practical prospect.
The invention provides a molybdenum diselenide nano material which has a nanoflower structure formed by assembling molybdenum diselenide nanosheets.
Preferably, the size of the nanoflower is 100-200 nm;
the thickness of the molybdenum diselenide nanosheet is 2-4 nm;
the diameter of the molybdenum diselenide nanosheet is 100-200 nm;
the molybdenum diselenide nano material is a 2H-phase molybdenum diselenide nano material.
Preferably, the manner of assembly comprises stacking;
the stacked part of the molybdenum diselenide nanosheets has an extrusion collapsing shape;
the extrusion collapse shape has a defect structure generated by lattice distortion;
the molybdenum diselenide nano material is a molybdenum diselenide nano gas-sensitive material.
Preferably, in the nanoflower structure, the molybdenum diselenide nanosheets have an extruded and collapsed shape in the radial direction;
the extrusion collapse shape has a defect structure generated by lattice distortion;
the nanoflower structure comprises a porous nanoflower structure;
the molybdenum diselenide nano material comprises porous MoSe2A nanomaterial;
the detection bottom limit of the molybdenum diselenide nano gas-sensitive material to ammonia in single ammonia gas or mixed gas is less than or equal to 5 ppm.
The invention relates to a preparation method of a molybdenum diselenide nano material, which comprises the following steps:
A) mixing molybdenyl acetylacetonate and oleylamine to obtain a solution A;
mixing dibenzyl diselenide and oleylamine to obtain a solution B;
B) and mixing the solution A and the solution B obtained in the step again, and reacting in a protective atmosphere to obtain the molybdenum diselenide nano material.
Preferably, in the solution A, the molar concentration of the molybdenum acetylacetonate is 0.1-0.3 mol/L;
in the solution B, the molar concentration of the dibenzyl diselenide is 0.1-0.3 mol/L;
the molar ratio of the molybdenum acetylacetonate to the dibenzyl diselenide is 1: 1;
the mixing is dissolution.
Preferably, the means of mixing comprises ultrasonic mixing;
the mixing time is more than or equal to 15 min;
the remixing mode comprises high-temperature magneton stirring and mixing;
the step of removing air by protective gas is also included when the mixture is mixed again;
the time for removing the dissolved air is more than or equal to 20 min.
Preferably, the reaction also comprises a step of impurity removal before the reaction;
the temperature for removing the impurities is 130-150 ℃;
the time for removing the impurities is more than or equal to 30 min;
the impurities removed include water and/or low boiling impurities.
Preferably, the temperature rise rate during the reaction is 10-15 ℃/min;
the reaction temperature is 240-260 ℃;
the reaction time is 20-30 min.
The invention also provides the application of the molybdenum diselenide nano material prepared by the preparation method in any one of the technical schemes or the molybdenum diselenide nano material prepared by the preparation method in the field of gas sensors.
The invention provides a molybdenum diselenide nano material which has a nanoflower structure formed by assembling molybdenum diselenide nanosheets. Compared with the prior art, the invention aims at the problems of insufficient detection limit, poor selectivity, higher working temperature (generally more than 200 ℃), requirement of loading of noble metals (gold, silver, platinum … …) and the like of the existing gas-sensitive detection material. The gas-sensitive material containing noble metal material has high priceAnd difficult to be popularized in large area. The invention creatively obtains MoSe with a graded porous structure with a specific morphology2Nanomaterial of the MoSe2The nano material is assembled by ultrathin molybdenum diselenide nanosheets, has a nanoflower with a hierarchical porous structure, and has a unique two-dimensional planar structure and a unique three-dimensional porous structure, so that the chemical adsorption between the material and target molecules is greatly enhanced, and the electronic exchange between a substrate and gas molecules to be detected is accelerated. The gas-sensitive detection of the gas to be detected has high selectivity and stability, even if impurity gases such as formaldehyde, chlorobenzene, ethanol, acetone, toluene and the like coexist in the gas to be detected, the gas to be detected can still be detected with high selectivity and high sensitivity, and the result repeatability is high during continuous cycle detection.
In addition, the preparation method provided by the invention only takes the molybdenum acetylacetonate and the dibenzyl diselenide as raw materials, adopts simple oil bath reaction, and prepares the porous MoSe assembled by the ultrathin nanosheets2And (4) nano flowers. The preparation method is simple, mild in condition and controllable in process, is beneficial to industrial realization, and has wide practical prospect.
The experimental result shows that the molybdenum diselenide nano material prepared by the invention is applied to NH3The detection realizes the high-sensitivity detection of the ammonia gas under the room temperature condition (about 25 ℃) for the first time, and the detection limit can be as low as 5 ppm. While the porous MoSe2The material has high selectivity on the gas-sensitive detection of ammonia gas, the detection effect is still not influenced even if the gas to be detected coexists such as formaldehyde, chlorobenzene, ethanol, acetone and toluene, the ammonia gas can be detected with high selectivity and high sensitivity, and continuous cycle measurement also shows that the detection effect of the material has high repeatability, the performance of the material is obviously superior to that of the prior pure semiconductor metal oxide and other two-dimensional gas-sensitive sensing materials, and the material does not contain noble metal, so the material has wide practical prospect.
Drawings
FIG. 1 shows MoSe prepared in example 1 of the present invention2The appearance of the nanometer material is a real object photo;
FIG. 2 shows an embodiment of the present invention1 prepared MoSe2SEM scanning electron microscope image of the nanometer material;
FIG. 3 shows MoSe prepared according to example 1 of the present invention2HRTEM high magnification transmission electron microscope image of the nano material;
FIG. 4 shows MoSe prepared according to example 1 of the present invention2XRD diffraction pattern of the nano material;
FIG. 5 shows MoSe prepared according to example 1 of the present invention2Raman spectrum of the nanometer material;
FIG. 6 shows the MoSe test of the present invention2A schematic diagram of a gas sensor assembled by nano materials;
FIG. 7 shows the MoSe test of the present invention2A schematic diagram of a gas-sensitive detection system assembled by nano materials;
FIG. 8 shows MoSe test in example 1 of the present invention2Response graphs of the gas sensor assembled by the nano materials to ammonia gas with different concentrations;
FIG. 9 shows MoSe test in example 1 of the present invention2The sensitivity of the gas sensor assembled by the nano material to ammonia gas with different concentrations;
FIG. 10 shows MoSe test in example 1 of the present invention2The selectivity of the gas sensor assembled by the nano material to ammonia gas detection (at the concentration of 50 ppm);
FIG. 11 shows MoSe test in example 1 of the present invention2The gas sensor assembled by the nano material detects the stability of ammonia with the concentration of 50 ppm;
FIG. 12 shows MoSe prepared according to example 2 of the present invention2TEM transmission electron microscope images of the nanomaterials;
FIG. 13 shows MoSe prepared according to example 2 of the present invention2HRTEM high magnification transmission electron microscope image of the nano material.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are included merely to further illustrate the features and advantages of the invention and are not intended to limit the invention to the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
The raw materials used in the present invention are not particularly limited in purity, and the present invention is preferably analytically pure or in a purity conventional in the field of gas sensitive material preparation.
All the raw materials, the marks and the acronyms thereof belong to the conventional marks and acronyms in the field, each mark and acronym is clear and definite in the field of related application, and the raw materials can be purchased from the market or prepared by a conventional method by the technical staff in the field according to the marks, the acronyms and the corresponding application.
All the processes of the invention, the abbreviations thereof belong to the common abbreviations in the art, each abbreviation is clear and definite in the field of its associated use, and the ordinary process steps thereof can be understood by those skilled in the art from the abbreviations.
The invention provides a molybdenum diselenide nano material which has a nanoflower structure formed by assembling molybdenum diselenide nanosheets.
The definition of the molybdenum diselenide nanomaterial in the present invention is not particularly limited, and may be defined as the definition of the molybdenum diselenide nanomaterial well known to those skilled in the art, and the general formula or chemical formula of the molybdenum diselenide in the present invention is specifically MoSe2。
The specific parameters of the nanoflower structure are not particularly limited in principle, and a person skilled in the art can select and adjust the nanoflower structure according to actual conditions, raw material conditions and product requirements.
The thickness of the molybdenum diselenide nanosheet is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual conditions, raw material conditions and product requirements, in order to ensure the specific morphology of a nano material and enhance the selectivity, sensitivity and stable repeatability of subsequent application, the thickness of the molybdenum diselenide nanosheet is preferably 2-4 nm, more preferably 2.3-3.7 nm, more preferably 2.6-3.4 nm, and more preferably 2.8-3.1 nm.
The invention has no particular limitation on the sheet diameter of the molybdenum diselenide nanosheet in principle, and a person skilled in the art can select and adjust the molybdenum diselenide nanosheet according to actual conditions, raw material conditions and product requirements.
The invention is not particularly limited in principle to the assembly mode of the molybdenum diselenide nanosheets, and a person skilled in the art can select and adjust the molybdenum diselenide nanosheets according to actual conditions, raw material conditions and product requirements.
In order to ensure the specific morphology of the nano material and enhance the selectivity, sensitivity and stable repeatability of subsequent applications, the part of the stacked molybdenum diselenide nanosheets preferably has an extrusion collapse morphology, and more specifically, the extrusion collapse morphology (in the thickness direction) of the part of the stacked molybdenum diselenide nanosheets preferably has a defect structure generated by lattice distortion, that is, the molybdenum diselenide nanosheets have a wrinkled morphology in the thickness direction. Meanwhile, in the nanoflower structure, the molybdenum diselenide nanosheets preferably have an extrusion collapsing shape in the sheet diameter direction. More specifically, the molybdenum diselenide nanosheets preferably also have a defect structure caused by lattice distortion in an extrusion collapsed morphology in the radial direction of the sheet, that is, the molybdenum diselenide nanosheets have a wrinkled morphology in the radial direction of the sheet.
The structure of the nanoflower is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual conditions, raw material conditions and product requirements. In the invention, the nanoflower has both small pores and large pores, for example, the defects of the nanosheets can form pores of several nanometers or even smaller, the nanosheets are stacked to form a flower-like structure, and the pores formed in the nanoflower have gaps of hundreds of nanometers. The hierarchical structure of the present invention is simple in that the distribution of pores is from several nanometers to several hundred nanometers.
The specific crystal phase of the molybdenum diselenide nanosheet is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual conditions, raw material conditions and product requirements.
The invention has no particular limitation on the overall structure of the molybdenum diselenide nano material in principle, and a person skilled in the art can select and adjust the molybdenum diselenide nano material according to the actual conditions, the raw material conditions and the product requirements2And (3) nano materials.
In order to ensure the specific morphology of the nano material and enhance the selectivity, sensitivity and stable repeatability of subsequent application, the molybdenum diselenide nano material is preferably a molybdenum diselenide nano gas-sensitive material, and more particularly, the detection bottom limit of the molybdenum diselenide nano gas-sensitive material on ammonia in single ammonia gas or mixed gas is preferably less than or equal to 5ppm, also can be less than or equal to 10ppm, and also can be less than or equal to 20 ppm. The mixed gas of the present invention preferably includes one or more of formaldehyde, chlorobenzene, ethanol, acetone, and toluene, and more preferably, a plurality of formaldehyde, chlorobenzene, ethanol, acetone, and toluene.
The invention also provides a preparation method of the molybdenum diselenide nano material, which comprises the following steps:
A) mixing molybdenyl acetylacetonate and oleylamine to obtain a solution A;
mixing dibenzyl diselenide and oleylamine to obtain a solution B;
B) and mixing the solution A and the solution B obtained in the step again, and reacting in a protective atmosphere to obtain the molybdenum diselenide nano material.
In the preparation method of the molybdenum diselenide nanomaterial, the structures, selections and appearances of the products or the raw materials, and the optimization principles thereof, preferably the structures, selections and appearances of the products or the raw materials corresponding to the molybdenum diselenide nanomaterial, and the optimization principles thereof, may correspond to each other, and are not described in detail herein.
Firstly, mixing molybdenyl acetylacetonate and oleylamine to obtain a solution A; and mixing dibenzyl diselenide and oleylamine to obtain a solution B.
In the solution a, the molar concentration of the molybdenum oxide acetylacetonate is preferably 0.1 to 0.3 mol/L, more preferably 0.13 to 0.27 mol/L, more preferably 0.16 to 0.24 mol/L, and more preferably 0.19 to 0.21 mol/L, and the present invention is directed to ensure the specific morphology of the nanomaterial and enhance the selectivity, sensitivity, and stable repeatability of the subsequent application.
In the solution B, the molar concentration of the dibenzyl diselenide is preferably 0.1 to 0.3 mol/L, more preferably 0.13 to 0.27 mol/L, more preferably 0.16 to 0.24 mol/L, and more preferably 0.19 to 0.21 mol/L, in order to ensure the specific morphology of the nanomaterial and enhance the selectivity, sensitivity, and stable repeatability of subsequent applications.
In the invention, the molar ratio of the molybdenum oxide acetylacetonate to the dibenzyl diselenide is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual conditions, raw material conditions and product requirements, and in order to ensure the specific morphology of a nano material and enhance the selectivity, sensitivity and stable repeatability of subsequent application, the molar ratio of the molybdenum oxide acetylacetonate to the dibenzyl diselenide is preferably 1: 1.
The definition of the mixing is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual conditions, raw material conditions and product requirements.
The mixing mode is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual conditions, raw material conditions and product requirements.
The mixing time is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual conditions, raw material conditions and product requirements, and in order to ensure the specific morphology of the nano material and enhance the selectivity, sensitivity and stable repeatability of subsequent applications, the mixing time is preferably greater than or equal to 15min, more preferably greater than or equal to 30min, and more preferably greater than or equal to 60 min.
Finally, the solution A and the solution B obtained in the step are mixed again and react in a protective atmosphere to obtain the molybdenum diselenide nano material.
The remixing mode is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual conditions, raw material conditions and product requirements.
The invention is a complete and refined preparation scheme, better ensures the specific morphology of the nano material, enhances the selectivity, the sensitivity and the stable repeatability of subsequent application, and preferably further comprises a protective gas air removal step during remixing.
The specific selection of the protective gas or protective atmosphere is not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to actual conditions, raw material conditions and product requirements.
The time for removing the dissolved air is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual conditions, raw material conditions and product requirements, and in order to ensure the specific morphology of the nanomaterial and enhance the selectivity, sensitivity and stable repeatability of subsequent applications, the time for removing the dissolved air is preferably greater than or equal to 20min, more preferably greater than or equal to 40min, and more preferably greater than or equal to 60 min.
The invention is a complete and refined preparation scheme, better ensures the specific morphology of the nano material, enhances the selectivity, the sensitivity and the stable repeatability of subsequent application, and preferably also comprises an impurity removal step before the reaction.
The temperature for impurity removal is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual conditions, raw material conditions and product requirements, and in order to ensure the specific morphology of the nano material and enhance the selectivity, sensitivity and stable repeatability of subsequent application, the temperature for impurity removal is preferably 130-150 ℃, more preferably 133-147 ℃, more preferably 136-144 ℃, and more preferably 139-141 ℃.
In the invention, the time for removing the impurities is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual conditions, raw material conditions and product requirements, and in order to ensure the specific morphology of the nano material and enhance the selectivity, sensitivity and stable repeatability of subsequent application, the time for removing the impurities is preferably greater than or equal to 30min, more preferably greater than or equal to 45min, and more preferably greater than or equal to 60 min.
The impurities to be removed are not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual conditions, raw material conditions and product requirements.
The temperature rise rate during the reaction is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual conditions, raw material conditions and product requirements, in order to ensure the specific morphology of the nano material and enhance the selectivity, sensitivity and stable repeatability of subsequent application, the temperature rise rate during the reaction is preferably 10-15 ℃/min, more preferably 11-14 ℃/min, and more preferably 12-13 ℃/min.
The reaction temperature is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual conditions, raw material conditions and product requirements, in order to ensure the specific morphology of the nano material and enhance the selectivity, sensitivity and stable repeatability of subsequent application, the reaction temperature is preferably 240-260 ℃, more preferably 243-257 ℃, more preferably 246-254 ℃, and more preferably 249-251 ℃.
The reaction time is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual conditions, raw material conditions and product requirements, in order to ensure the specific morphology of the nano material and enhance the selectivity, sensitivity and stable repeatability of subsequent application, the reaction time is preferably 20-30 min, more preferably 22-28 min and even more preferably 24-26 min.
The invention is a complete and refined integral preparation scheme, better ensures the specific morphology of the nano material, enhances the selectivity, the sensitivity and the stable repeatability of subsequent application, and preferably also comprises the post-treatment steps of washing and the like after the reaction. Wherein the washing is organic solvent washing.
The invention is a complete and refined integral preparation scheme, better ensures the specific morphology of the nano material, enhances the selectivity, the sensitivity and the stable repeatability of subsequent application, and the preparation method specifically comprises the following steps:
1) the preparation method of the precursor material liquid comprises the following steps: weighing acetylacetonato molybdenum oxide [ MoO ]2(acac)2]Dissolving in oleylamine, and marking as feed liquid A after ultrasonic treatment and complete dissolution; weighing dibenzyl diselenide [ (PhCH)2)2Se2]Dissolved in oleylamine, and labeled as feed liquid B after being completely dissolved by ultrasonic treatment.
2) Preparation of self-assembled MoSe2And nano flower, mixing the A and B liquid, carefully transferring the mixture to the bottom of a three-neck flask, adding high-temperature magnetons, stirring, introducing argon to exhaust air, heating the reactant, keeping for a period of time, and removing water and other impurities with low boiling points. The temperature is controlled by a program and is increased to the reaction temperature at a certain temperature-rising rate for reaction. And after the reaction is finished, naturally cooling to room temperature, washing the obtained product for many times by using normal hexane and toluene, dispersing the product into the toluene, testing for later use, and drying in vacuum to obtain the molybdenum diselenide nano material.
The invention also provides the application of the molybdenum diselenide nano material in any one of the technical schemes or the molybdenum diselenide nano material prepared by the preparation method in any one of the technical schemes in the field of gas sensors.
The invention provides a molybdenum diselenide gas-sensitive sensing material, and preparation and application thereof. MoSe with hierarchical porous structure with specific morphology prepared by the invention2The nanometer material is assembled by ultrathin molybdenum diselenide nanosheets and has the componentsThe nanoflower with the hierarchical porous structure has the unique two-dimensional plane structure and three-dimensional porous structure, greatly enhances the chemical adsorption between the material and target molecules, accelerates the electronic exchange between the substrate and gas molecules to be detected, and due to the introduction of defects in the three-dimensional structure, the adsorption capacity of the material to the gas molecules is effectively improved, the charge exchange between the molecules and the substrate is enhanced, the sensitivity of gas-sensitive detection is improved, and the material can keep extremely high stability and selectivity when being recycled. The gas-sensitive sensing device is simple to manufacture, has high selectivity and stability for gas-sensitive detection of ammonia gas at working temperature, has low detection limit at room temperature, can reach 5ppm, can not influence the gas-sensitive detection effect of the ammonia gas even if the gas-sensitive sensing device is interfered by impurity gases such as formaldehyde, chlorobenzene, ethanol, acetone, methylbenzene and the like, can still carry out high-selectivity and high-sensitivity detection on the ammonia gas, and has high repeatability of results during continuous cycle detection.
In addition, the preparation method provided by the invention only takes the molybdenum acetylacetonate and the dibenzyl diselenide as raw materials, adopts simple oil bath reaction, and prepares the porous MoSe assembled by the ultrathin nanosheets2The nanometer flower has simple production process and flow, the used oil bath heating reaction is a modern mature synthesis means, the condition is mild, the process is controllable, and the prepared MoSe2The material has high yield, stable structure and pure crystal phase, is beneficial to the realization of industrialization and has wide practical prospect. Meanwhile, the working principle of the sensor is based on physical change, and no relative motion part exists, so that the sensor is simple in structure, small in size, easy to integrate and intelligentize, low in power consumption, safe and reliable.
The experimental result shows that the molybdenum diselenide nano material prepared by the invention is applied to NH3The detection realizes the high-sensitivity detection of the ammonia gas under the room temperature condition (about 25 ℃) for the first time, and the detection limit can be as low as 5 ppm. While the porous MoSe2The material has high selectivity on the gas-sensitive detection of ammonia gas, even if the gas to be detected coexists with formaldehyde, chlorobenzene, ethanol, acetone and toluene, the detection effect is still not influenced, and the material can carry out high selectivity on the ammonia gasAnd high-sensitivity detection, and continuous cycle measurement also shows that the detection effect of the material has high repeatability, the performance of the material is obviously superior to that of the prior pure semiconductor metal oxide and other two-dimensional gas-sensitive sensing materials, and the material does not contain noble metal, so the material has wide practical prospect.
For further illustration of the present invention, the molybdenum diselenide nanomaterial provided by the present invention, the preparation method and the application thereof are described in detail below with reference to the following examples, but it should be understood that the examples are implemented on the premise of the technical solution of the present invention, and the detailed embodiments and the specific operation procedures are given, only for further illustration of the features and advantages of the present invention, but not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
0.6520g (2mmol) of molybdenum acetylacetonate [ MoO ] were weighed2(acac)2]Dissolving in oleylamine (10 m L), ultrasonic treating for 15min, marking as solution A, weighing 0.6800g (2mmol) dibenzyl diselenide [ (PhCH)2)2Se2]Dissolved in oleylamine with a volume of 10m L, and after being completely dissolved by ultrasonic treatment for 15 minutes, it was labeled as feed liquid B.
Mixing the feed liquid A and the feed liquid B, carefully transferring the feed liquid A and the feed liquid B to the bottom of a three-neck flask with the diameter of 50m L, adding high-temperature magnetons, stirring, introducing argon for 20 minutes, exhausting air, heating the reactants to 130 ℃, keeping the temperature for 30 minutes, removing moisture and other impurities with low boiling points, controlling the temperature by a program, heating to 240 ℃ at the heating rate of 10 ℃ per minute, reacting for 20 minutes, naturally cooling to room temperature after the reaction is finished, washing the obtained product for multiple times by using normal hexane and toluene, dispersing the product into the toluene, and testing for later use.
The molybdenum diselenide nanomaterial prepared in example 1 of the present invention was characterized.
Referring to FIG. 1, FIG. 1 shows MoSe prepared according to example 1 of the present invention2And (3) an appearance physical photograph of the nanometer material.
Referring to FIG. 2, FIG. 2 shows MoSe prepared according to example 1 of the present invention2SEM scanning electron microscope image of the nanometer material. Fig. 2 includes fig. 2(a) and 2 (b).
As can be seen from FIG. 2, the MoSe prepared by the invention2The sample has a nanoflower structure and a width of about 100-200 nm.
Referring to FIG. 3, FIG. 3 shows MoSe prepared according to example 1 of the present invention2HRTEM high magnification transmission electron microscope image of the nano material.
As can be seen from FIG. 3, MoSe2The appearance of the sample is nanoflower formed by assembling ultrathin nanosheets, the thickness of the nanoflower is about 2-4 nanometers, the stacked parts of the nanosheets are extruded and collapsed, lattice distortion occurs to generate a defect structure, and the nanoflower also has the appearance in the radial direction of the nanosheets, so that the adsorption of the substrate to gas molecules is enhanced.
Referring to FIG. 4, FIG. 4 shows MoSe prepared according to example 1 of the present invention2XRD diffraction pattern of the nano material.
As can be seen from FIG. 4, MoSe2The sample lattice structure was a pure phase 2H phase, consistent with standard cards in the database.
Referring to FIG. 5, FIG. 5 shows MoSe prepared according to example 1 of the present invention2Raman spectrum of the nanomaterial.
As can be seen from FIG. 5, MoSe2The lattice structure of the sample was a pure phase of 2H phase, consistent with the results reported in the prior literature.
For MoSe prepared in the invention example 12And (4) detecting the electrochemical performance of the nano material.
The gas sensor is composed of a ceramic tube, a heating electrode (Ni-Cr alloy) and MoSe2Gas sensitive material and signal electrode, and MoSe is used as gas sensitive material2The sensor is coated on a ceramic tube, a signal electrode is also linked with the ceramic tube, and the whole sensor is placed in a closed air chamber for testing.
Referring to FIG. 6, FIG. 6 shows a MoSe test according to the present invention2And (3) a schematic diagram of a gas sensor assembled by nano materials. The gas sensitive sensor for testing adopts an indirectly heated device structure.
Referring to FIG. 7, FIG. 7 shows a MoSe test according to the present invention2The gas-sensitive detection system assembled by the nanometer materials is schematically shown.
Referring to FIG. 8, FIG. 8 shows a MoSe test in example 1 of the present invention2Response graphs of the gas sensor assembled by the nano materials to ammonia gas with different concentrations.
As can be seen from FIG. 8, MoSe in the present invention2The sample has good gas-sensitive detection performance on ammonia gas, the lowest detection limit can reach 5ppm, and the method has good industrial practical prospect.
According to the thirty-second sanitation of the third workshop of the chapter III of the design and sanitation Standard of Industrial enterprises (TJ36-79) in China: the maximum allowable concentration of harmful substances in the air of the workshop is 30mg/m of ammonia3(about 39.53 ppm). According to the regulation of China related to the national emission standard in 'emission Standard of malodorous pollutants' GB14554-93, the corresponding standard values in the enterprise implementation three-level standard are respectively 5.0mg/m3(about 6.56 ppm).
Referring to FIG. 9, FIG. 9 shows a MoSe test performed in example 1 of the present invention2The sensitivity of the gas sensor assembled by the nano materials to ammonia with different concentrations.
As can be seen from FIG. 9, MoSe in the present invention2The sample has good sensitivity to ammonia gas, and the sensitivity S can reach 12.5% when the lowest detection limit is 5 ppm.
Referring to FIG. 10, FIG. 10 shows a MoSe test in example 1 of the present invention2The selectivity of the gas sensor assembled by the nano materials to the detection of ammonia gas (at the concentration of 50 ppm).
As can be seen from FIG. 10, MoSe in the present invention2The sample has good selectivity to ammonia gas, and has no influence on other impurity gas molecules, such as formaldehyde, chlorobenzene, ethanol, acetone and toluene (the concentration of the impurity gases is 50ppm) without affecting MoSe2Response of sample material to ammonia gas.
Referring to FIG. 11, FIG. 11 shows a MoSe test in example 1 of the present invention2And (3) testing the detection stability of the gas sensor assembled by the nano material on ammonia gas with the concentration of 50 ppm.
As can be seen from FIG. 11, MoSe in the present invention2The sample has good stability and repeatability for ammonia detection.
Example 2
1.3040g (4mmol) of ethyl are weighedMolybdenum oxo acetylacetonate [ MoO2(acac)2]Dissolving in 15m L m oleylamine, ultrasonic treating for 18 min, marking as solution A, weighing 1.3600g (4mmol) dibenzyl diselenide [ (PhCH)2)2Se2]Dissolved in oleylamine with a volume of 15m L, and after being completely dissolved by sonication for 18 minutes, it was labeled as feed liquid B.
Mixing the feed liquid A and the feed liquid B, carefully transferring the feed liquid A and the feed liquid B to the bottom of a three-neck flask with the diameter of 80m L, adding high-temperature magnetons, stirring, introducing argon for 25 minutes, exhausting air, heating the reactants to 140 ℃, keeping the temperature for 40 minutes, removing moisture and other impurities with low boiling points, controlling the temperature by a program, heating to 245 ℃ at the heating rate of 12 ℃ per minute, reacting for 25 minutes, naturally cooling to room temperature after the reaction is finished, washing the obtained product for multiple times by using normal hexane and toluene, dispersing the product into the toluene, and testing for later use.
The gas sensor is composed of a ceramic tube, a heating electrode (Ni-Cr alloy) and MoSe2Gas sensitive material and signal electrode, and MoSe is used as gas sensitive material2The sensor is coated on a ceramic tube, a signal electrode is also linked with the ceramic tube, and the whole sensor is placed in a closed air chamber for testing.
The molybdenum diselenide nanomaterial prepared in example 2 of the present invention was characterized.
Referring to FIG. 12, FIG. 12 shows MoSe prepared according to example 2 of the present invention2TEM transmission electron microscopy of nanomaterials.
Referring to FIG. 13, FIG. 13 shows MoSe prepared according to example 2 of the present invention2HRTEM high magnification transmission electron microscope image of the nano material.
As can be seen from FIGS. 12 and 13, MoSe2The appearance of the sample is nanoflower formed by assembling ultrathin nanosheets, the thickness of the nanoflower is about 2-4 nanometers, the stacked parts of the nanosheets are extruded and collapsed, lattice distortion occurs to generate a defect structure, and the nanoflower also has the appearance in the radial direction of the nanosheets, so that the adsorption of the substrate to gas molecules is enhanced.
Example 3
1.9560g (6mmol) of molybdenum acetylacetonate [ MoO ] were weighed2(acac)2]Dissolving in 25m L oleylamine, ultrasonic treating for 25 min, marking as solution A, weighing 2.0400g (6mmol) dibenzyl diselenide [ (PhCH)2)2Se2]Dissolved in 25m L volume of oleylamine, and after complete dissolution by sonication for 25 minutes, labeled as feed liquid B.
Mixing the feed liquid A and the feed liquid B, carefully transferring the feed liquid A and the feed liquid B to the bottom of a three-neck flask with the diameter of 100m L, adding high-temperature magnetons, stirring, introducing argon for 30 minutes, exhausting air, heating the reactants to 145 ℃, keeping the temperature for 28 minutes, removing moisture and other impurities with low boiling points, controlling the temperature by a program, heating to 250 ℃ at the heating rate of 10 ℃ per minute, reacting for 30 minutes, naturally cooling to room temperature after the reaction is finished, washing the obtained product for multiple times by using normal hexane and toluene, dispersing the product into the toluene, and testing for later use.
The gas sensor is composed of a ceramic tube, a heating electrode (Ni-Cr alloy) and MoSe2Gas sensitive material and signal electrode, and MoSe is used as gas sensitive material2The sensor is coated on a ceramic tube, a signal electrode is also linked with the ceramic tube, and the whole sensor is placed in a closed air chamber for testing.
Example 4
0.3260g (1mmol) of molybdenum acetylacetonate [ MoO ] were weighed2(acac)2]Dissolving in oleylamine (8 m L), ultrasonic treating for 20min, marking as solution A, weighing 0.3400g (1mmol) dibenzyl diselenide [ (PhCH)2)2Se2]Dissolved in oleylamine with a volume of 8m L, and after being completely dissolved by sonication for 20 minutes, it was labeled as feed liquid B.
Mixing the feed liquid A and the feed liquid B, carefully transferring the feed liquid A and the feed liquid B to the bottom of a three-neck flask with the diameter of 25m L, adding high-temperature magnetons, stirring, introducing nitrogen for 20 minutes, exhausting air, heating the reactants to 150 ℃, keeping the temperature for 40 minutes, removing moisture and other impurities with low boiling points, controlling the temperature by a program, heating to 240 ℃ at the heating rate of 14 ℃ per minute, reacting for 25 minutes, naturally cooling to room temperature after the reaction is finished, washing the obtained product for multiple times by using normal hexane and toluene, dispersing the product into the toluene, and testing for later use.
The gas sensor is composed of a ceramic tube, a heating electrode (Ni-Cr alloy) and MoSe2Gas sensitive material and signal electrode, and MoSe is used as gas sensitive material2The sensor is coated on a ceramic tube, a signal electrode is also linked with the ceramic tube, and the whole sensor is placed in a closed air chamber for testing.
Example 5
0.4890g (1.5mmol) of molybdenum acetylacetonate [ MoO ] were weighed2(acac)2]Dissolving in oleylamine (10 m L), ultrasonic treating for 15min, marking as solution A, weighing 0.5100g (1.5mmol) dibenzyl diselenide [ (PhCH)2)2Se2]Dissolved in oleylamine with a volume of 10m L, and after being completely dissolved by ultrasonic treatment for 15 minutes, it was labeled as feed liquid B.
Mixing the feed liquid A and the feed liquid B, carefully transferring the feed liquid A and the feed liquid B to the bottom of a three-neck flask with the diameter of 30m L, adding high-temperature magnetons, stirring, introducing nitrogen for 28 minutes, exhausting air, heating the reactants to 140 ℃, keeping the temperature for 35 minutes, removing moisture and other impurities with low boiling points, controlling the temperature by a program, heating to 260 ℃ at the heating rate of 15 ℃ per minute, reacting for 20 minutes, naturally cooling to room temperature after the reaction is finished, washing the obtained product for multiple times by using normal hexane and toluene, dispersing the product into the toluene, and testing for later use.
The gas sensor is composed of a ceramic tube, a heating electrode (Ni-Cr alloy) and MoSe2Gas sensitive material and signal electrode, and MoSe is used as gas sensitive material2The sensor is coated on a ceramic tube, a signal electrode is also linked with the ceramic tube, and the whole sensor is placed in a closed air chamber for testing.
While the molybdenum diselenide gas-sensitive sensing material provided by the present invention and the preparation and use thereof have been described in detail, the principles and embodiments of the present invention are described herein with reference to specific examples, which are intended to serve only as an aid in understanding the methods and their underlying concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. The molybdenum diselenide nanomaterial is characterized in that the molybdenum diselenide nanomaterial has a nanoflower structure formed by assembling molybdenum diselenide nanosheets.
2. The molybdenum diselenide nanomaterial according to claim 1, wherein the nanoflower is 100-200 nm in size;
the thickness of the molybdenum diselenide nanosheet is 2-4 nm;
the diameter of the molybdenum diselenide nanosheet is 100-200 nm;
the molybdenum diselenide nano material is a 2H-phase molybdenum diselenide nano material.
3. The molybdenum diselenide nanomaterial according to claim 1, wherein the manner of assembly comprises stacking;
the stacked part of the molybdenum diselenide nanosheets has an extrusion collapsing shape;
the extrusion collapse shape has a defect structure generated by lattice distortion;
the molybdenum diselenide nano material is a molybdenum diselenide nano gas-sensitive material.
4. The molybdenum diselenide nanomaterial according to claim 3, wherein in the nanoflower structure, the molybdenum diselenide nanosheets have an extruded collapsed morphology in the radial direction;
the extrusion collapse shape has a defect structure generated by lattice distortion;
the nanoflower structure comprises a porous nanoflower structure;
the molybdenum diselenide nano material comprises porous MoSe2A nanomaterial;
the detection bottom limit of the molybdenum diselenide nano gas-sensitive material to ammonia in single ammonia gas or mixed gas is less than or equal to 5 ppm.
5. A preparation method of a molybdenum diselenide nano material is characterized by comprising the following steps:
A) mixing molybdenyl acetylacetonate and oleylamine to obtain a solution A;
mixing dibenzyl diselenide and oleylamine to obtain a solution B;
B) and mixing the solution A and the solution B obtained in the step again, and reacting in a protective atmosphere to obtain the molybdenum diselenide nano material.
6. The method according to claim 5, wherein the molar concentration of the molybdenum acetylacetonate in the solution A is 0.1-0.3 mol/L;
in the solution B, the molar concentration of the dibenzyl diselenide is 0.1-0.3 mol/L;
the molar ratio of the molybdenum acetylacetonate to the dibenzyl diselenide is 1: 1;
the mixing is dissolution.
7. The method of claim 5, wherein the manner of mixing comprises ultrasonic mixing;
the mixing time is more than or equal to 15 min;
the remixing mode comprises high-temperature magneton stirring and mixing;
the step of removing air by protective gas is also included when the mixture is mixed again;
the time for removing the dissolved air is more than or equal to 20 min.
8. The preparation method according to claim 5, characterized by further comprising a step of removing impurities before the reaction;
the temperature for removing the impurities is 130-150 ℃;
the time for removing the impurities is more than or equal to 30 min;
the impurities removed include water and/or low boiling impurities.
9. The production method according to any one of claims 5 to 8, wherein the temperature rise rate during the reaction is 10 to 15 ℃/min;
the reaction temperature is 240-260 ℃;
the reaction time is 20-30 min.
10. The molybdenum diselenide nanomaterial according to any one of claims 1 to 4 or the molybdenum diselenide nanomaterial prepared by the preparation method according to any one of claims 5 to 9, and the application thereof in the field of gas sensors.
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