CN114956179B - Cobalt and zinc diatomic doped molybdenum disulfide nanosheets based on atomic-level dispersion and preparation method and application thereof - Google Patents
Cobalt and zinc diatomic doped molybdenum disulfide nanosheets based on atomic-level dispersion and preparation method and application thereof Download PDFInfo
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 31
- 239000011701 zinc Substances 0.000 title claims abstract description 31
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 26
- 239000010941 cobalt Substances 0.000 title claims abstract description 26
- 239000002135 nanosheet Substances 0.000 title claims abstract description 22
- 239000006185 dispersion Substances 0.000 title claims abstract description 13
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000002064 nanoplatelet Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000012300 argon atmosphere Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- 238000000137 annealing Methods 0.000 claims description 6
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- FCEOGYWNOSBEPV-FDGPNNRMSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FCEOGYWNOSBEPV-FDGPNNRMSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- PRCNQQRRDGMPKS-UHFFFAOYSA-N pentane-2,4-dione;zinc Chemical compound [Zn].CC(=O)CC(C)=O.CC(=O)CC(C)=O PRCNQQRRDGMPKS-UHFFFAOYSA-N 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 230000004044 response Effects 0.000 abstract description 14
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- 239000007789 gas Substances 0.000 description 38
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 12
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 12
- 125000004429 atom Chemical group 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
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- -1 Transition metal sulfides Chemical class 0.000 description 2
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- 229910052723 transition metal Inorganic materials 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 238000005275 alloying Methods 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical group 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000004098 selected area electron diffraction Methods 0.000 description 1
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- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- 229910052721 tungsten Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a cobalt and zinc diatomic doped molybdenum disulfide nano-sheet based on atomic level dispersion, and a preparation method and application thereof, which are implemented in MoS 2 Atomic fraction on the nanoplatelet lattice anchors cobalt atoms and zinc atoms. The cobalt and zinc diatomic doped molybdenum disulfide nano-sheet prepared by the invention has NO at room temperature 2 The method has the characteristics of excellent gas sensitivity, quick response/recovery time, low detection limit of 6.2ppb, repeated use, simple operation, low price and the like, and is used for detecting low-concentration NO at room temperature 2 The gas provides a research platform.
Description
Technical Field
The invention belongs to the technical field of chemical sensing materials, and relates to a cobalt and zinc diatomic doped MoS based on atomic level dispersion 2 Nanoplatelets and their use as gas sensitive materials.
Background
With the rapid development of the economic society, the industrial production scale is growing, and the earth ecological circle is being damaged wantonly by the use of traditional energy, automobile exhaust and poisonous and harmful gas generated by industrial emission, thereby threatening the health and development of human society. Nitrogen dioxide (NO) 2 ) Is a notoriously poisonous and harmful gas, is one of important air pollution sources, and can cause acid rain and photochemical smog. According to the statistics of the world health organization, millions of people die each year due to air pollution. The U.S. environmental protection agency (U.S. EPA) and European Environmental Agency (EEA) specify that the average exposure limits for nitrogen dioxide should not exceed 53ppb and 40ppb, respectively, over a year. Thus, a one is developedThe device capable of carrying out real-time monitoring and early warning on toxic and harmful gases is particularly important. Over the past several decades, based on different sensitive layers and measurement methods, different types of gas sensors have been developed, including semiconductor oxides, electrochemistry, infrared absorption, catalytic combustion, etc. The traditional semiconductor Metal Oxide (MOS) gas sensor is widely applied to the fields of air quality detection, chemical production, food safety, biomedicine and the like due to the advantages of high sensitivity, quick response, simple structure, convenient integration and the like. However, MOS gas sensors still have two major bottleneck problems: the working temperature is high (generally 200-600 ℃); the selectivity is poor. How to reduce the operating temperature of the gas sensor and to enhance the selectivity is the main direction of current research.
Transition metal sulfides (TMDC) are a class of two-dimensional materials with a band gap, commonly known as MX 2 The compound exists in a form in which M represents a transition metal (Mo, W, pd, etc.), X represents a chalcogen (S, se, te, etc.), and the semiconductor property thereof changes with the change of the layered structure (indirect band gap becomes direct band gap). The atomic-level thickness and the surface volume ratio close to the theoretical extremum endow the TMDC surface with ultrahigh surface activity, so that the TMDC surface is very sensitive to external signal change, and the gas sensing at room temperature is realized. Monoatomic catalysis (SAC) is a catalyst in which a single atom is supported to improve catalytic activity, and after alloying of metal atoms, coordination atoms change the electronic structure of active center atoms. When the loaded monoatomic sensitive layer is exposed to the target gas, both reduce the adsorption capacity of the metal atoms to other gases, thereby improving selectivity. Constructing sensitive layer by using TMDC as platform to load corresponding single atom, developing NO with high selectivity and working at room temperature 2 Great potential is exerted in gas sensors.
Disclosure of Invention
Aiming at the defects of an MOS gas sensor, the invention provides a cobalt and zinc diatomic doped MoS based on atomic level dispersion 2 Nanosheets and preparation method thereof, aiming at doping MoS with cobalt and zinc diatomic atoms 2 The sensitive layer device prepared by the nano-sheet can realize the detection of low-concentration NO at room temperature 2 Gas, and exhibit higherAnd excellent selectivity.
The invention adopts the following technical scheme for realizing the purpose:
the cobalt and zinc diatomic doped molybdenum disulfide nanosheets based on atomic level dispersion are characterized in that: is in MoS 2 Atomic fraction on the nanoplatelet lattice anchors cobalt atoms and zinc atoms. Further, the total loading of cobalt atoms and zinc atoms is 0.4 to 1wt%, and no metal bond exists between cobalt atoms and cobalt atoms, and between zinc atoms and zinc atoms; the MoS 2 The diameter of the nano-sheet is 400-500nm.
The preparation method of the cobalt and zinc diatomic doped molybdenum disulfide nanosheets based on atomic-level dispersion comprises the following steps:
step 1, synthesizing atomically dispersed cobalt atoms
20g dicyandiamide was heated at 350℃for 1 hour under argon atmosphere, the powder obtained being denoted CHN-350; dispersing 10mg of cobalt (II) acetylacetonate and 1mL of citric acid in ethanol solution in an ultrasonic manner, then dripping the solution into CHN-350, uniformly ball-milling, and annealing the obtained mixture at 680 ℃ for 2 hours in an argon atmosphere to obtain powder which is atomically dispersed cobalt atoms;
step 2, synthesizing atomically dispersed zinc atoms
20g dicyandiamide was heated at 350℃under argon atmosphere for 1 hour, the powder obtained being denoted CHN-350; dispersing 10mg of zinc (II) acetylacetonate and 1mL of citric acid in ethanol solution in an ultrasonic manner, then dripping the solution into CHN-350, uniformly ball-milling, and annealing the obtained mixture at 680 ℃ for 2 hours in an argon atmosphere to obtain powder which is atomically dispersed zinc atoms;
step 3, synthesizing an atomically dispersed cobalt and zinc diatomic doped MoS 2 Nanosheets
1mL of a 50% strength by mass aqueous solution of polyethylenimine and 50mg of polyvinylpyrrolidone were dispersed in an ethanol solution, followed by addition of 20mg of MoS 2 Uniformly dispersing the powder, simultaneously adding 1mg of atomically dispersed cobalt atoms and 1mg of atomically dispersed zinc atoms, uniformly dispersing by ultrasonic, magnetically stirring, drying and ball milling to obtain mixture powder;
heating the obtained mixture powder at 680 deg.C under argon atmosphere for 2 hr to obtain powder which is atomically dispersed cobalt and zinc diatomic doped MoS 2 A nano-sheet.
The cobalt and zinc diatomic doped molybdenum disulfide nanosheets based on atomic-level dispersion can be used for detecting NO 2 A gas-sensitive material of an isopipe gas.
Compared with the prior art, the invention has the beneficial effects that:
the cobalt and zinc diatomic doped molybdenum disulfide nano-sheet prepared by the invention has NO at room temperature 2 Exhibits excellent gas-sensitive performance (response value of 5.2 corresponds to 5ppmNO 2 ) And fast response/recovery time (for 1ppm NO 2 120/310 s), the lower detection limit is as low as 6.2ppb, and the method has the characteristics of reusability, simple operation, low price and the like, and is used for detecting low-concentration NO at room temperature 2 The gas provides a research platform.
Drawings
FIG. 1 shows a cobalt and zinc diatomic doped MoS based on atomic scale dispersion according to the present invention 2 Schematic of the preparation method of the nanoplatelets.
FIG. 2 shows the diatomic doping of Co and Zn with MoS in example 1 2 Morphology characterization of nanoplatelets, wherein: (a) is a Scanning Electron Microscope (SEM); (b) is a Transmission Electron Micrograph (TEM); (c) a selected area electron diffraction SAED pattern of pattern (b); (d-f) is a high angle annular dark field scanning transmission electron microscope (HAADF-STEM); (g) A low resolution high angle annular dark field scanning transmission electron microscope (HAADF-TEM) image; (h-k) are Mo, S, CO, zn element maps, respectively; (i-m) is an Energy Dispersive Spectroscopy (EDS) analysis chart.
FIG. 3 shows the sensitive layer of example 1 for NO at room temperature at various concentrations 2 Wherein: (a) 0.05-5ppm NO 2 A gas dynamic response map; (b) fitting in response to vs concentration; (c) 1ppm NO 2 Gas response/recovery time plot; (d) 1ppm NO 2 Gas repeatability graph.
FIG. 4 is a graph showing the response of the sensitive layer to different types of gases in example 1.
Detailed Description
The technical scheme of the present invention is described in detail below by specific examples, which are implemented on the premise of the technical scheme of the present invention, and detailed implementation and specific operation processes are given, but the protection scope of the present invention is not limited to the following examples.
Example 1
As shown in fig. 1, the preparation method of the embodiment comprises the following steps of:
step 1, synthesizing atomically dispersed cobalt atoms
Placing 20g of dicyandiamide in a high-temperature furnace, heating to 350 ℃ at a heating rate of 7 ℃/min under argon atmosphere (the flow rate is set to 50 sccm), and preserving the temperature for 1 hour, wherein the obtained powder is CHN-350; 10mg of cobalt (II) acetylacetonate and 1mL of citric acid are added into 5mL of ethanol solution, uniformly stirred and high-power ultrasonic is carried out for 30 minutes, then the mixture is dripped into CHN-350, ball milling is carried out for 5 hours, the obtained mixture is placed into a high temperature furnace, the temperature is increased to 680 ℃ at the heating rate of 7 ℃/min in argon atmosphere (the flow rate is set to 50 sccm), and the heat preservation and annealing are carried out for 2 hours, thus obtaining the powder which is the cobalt atoms dispersed in atomic scale.
Step 2, synthesizing atomically dispersed zinc atoms
Placing 20g of dicyandiamide in a high-temperature furnace, heating to 350 ℃ at a heating rate of 7 ℃/min under argon atmosphere (the flow rate is set to 50 sccm), and preserving the temperature for 1 hour, wherein the obtained powder is CHN-350; 10mg of zinc (II) acetylacetonate and 1mL of citric acid are added into 5mL of ethanol solution, uniformly stirred and high-power ultrasonic is carried out for 30 minutes, then the mixture is dripped into CHN-350, ball milling is carried out for 5 hours, the obtained mixture is placed into a high temperature furnace, the temperature is increased to 680 ℃ at the heating rate of 7 ℃/min in argon atmosphere (the flow rate is set to 50 sccm), and the heat preservation and annealing are carried out for 2 hours, thus obtaining the powder which is the zinc atoms dispersed in atomic scale.
Step 3, synthesizing an atomically dispersed cobalt and zinc diatomic doped MoS 2 Nanosheets
1mL of a 50% strength by mass aqueous solution of polyethylenimine and 50mg of polyvinylpyrrolidone (PVP average molecular weight 58000) were dispersed in 10mL of an ethanol solution, followed by addition of20mg MoS 2 The powder (particle size 200 meshes) is uniformly dispersed, 1mg of atomically dispersed cobalt atoms and 1mg of atomically dispersed zinc atoms are simultaneously added, high-power ultrasonic treatment is carried out for 30 minutes, then magnetic stirring is carried out for 2 hours, drying is carried out at 250 ℃ for 10 minutes, and ball milling is carried out for 5 hours, thus obtaining the mixture powder.
Placing the obtained mixture powder in a high temperature furnace, setting heating rate at 5 deg.C/min, heating to 680 deg.C under argon atmosphere (flow rate at 50 sccm), and maintaining for 2 hr to obtain powder of atomically dispersed cobalt and zinc diatomic doped MoS 2 A nano-sheet.
As shown in FIG. 2, more related cobalt and zinc diatomic doping MoS was obtained by scanning electron microscopy (FESEM) and High Resolution Transmission Electron Microscopy (HRTEM) 2 The surface morphology and crystal structure information of the nanoplatelets. As shown in FIG. 2 (a), moS 2 The material exists mainly in a nano-sheet structure. The high resolution image (FIG. 2 (b)) shows lattice fringes and MoS at a spacing of 0.27nm 2 (100) crystal plane matching of (2) and its Fast Fourier Transform (FFT) (FIG. 2 (c)) shows 2H-MoS 2 Is a sharp reflection characteristic of (c). Furthermore, characterization by HAADF-STEM (fig. 2 (d)) shows that small white dots (white circles) with bright contrast represent cobalt and zinc dispersed in atomic scale in MoS 2 On the lattice, the corresponding intensity curve of the selected line in FIG. 2 (e) shows MoS 2 Spots having different intensities on the lattice correspond to Mo, S, co and Zn atoms, respectively, wherein the combination of Co-Mo and Zn-Mo atoms exhibits a higher intensity compared to Mo and S atoms. The corresponding elemental map of FIG. 2 (h-k) shows a uniform distribution of Mo, S, co and Zn elements, indicating the presence of small amounts of Co and Zn atoms in the composition, in a ratio of about 1:1. FIG. 2 (i-m) shows that the loading of Co and Zn elements was 0.28% and 0.21%, respectively.
The cobalt and zinc diatomic doping MoS prepared in this example was performed as follows 2 The nano-sheet is prepared into a sensitive layer:
taking a small amount of cobalt and zinc diatomic doped MoS prepared in the embodiment 2 Grinding the nano-sheet powder in a mortar for multiple times until the particle size is about 200 meshes, adding a small amount of ethanol, and fully and uniformly grinding to obtain a pasty mixture; taking a small amount of the pasteThe mixture was applied to the surface of Jin Cha finger electrode as shown in fig. 1 and dried in an oven at 60 ℃ for 10 minutes to produce a gas sensor device.
The room temperature gas sensing performance of the sensor is measured by an intelligent gas sensing platform (CGS-MT photoelectric comprehensive test platform), and the background gas is high-purity dry air. Prior to sensing measurements, the sensor is placed in a sensing chamber and purged with high purity air until a stable electrical resistance is obtained. During the measurement process, the target gas and the high purity air are mixed in the mixing chamber at the desired concentration and then passed into the sensing chamber for the reaction process. When the reaction reaches saturation, only high-purity air is introduced to perform the recovery process. Testing sensitive layer materials for NO with different concentration gradients at room temperature 2 The gas sensitivity of the gas, as shown in FIG. 3 (a), was set to a concentration gradient in the range of 0.05 to 5ppm. As the concentration is increased, the resistance value of the sensitive layer material is reduced, which indicates that the response of the sensing device is along with NO 2 The increase in gas concentration increases. As shown in fig. 3 (b), in the different concentration ranges of 0.05-0.3ppm and 0.3-5ppm, the response of the sensor and the gas concentration can be fitted into two straight lines with different slopes, which shows that the response of the sensor and the gas concentration are in a linear relationship in a certain range; in addition, the sensitive layer material is resistant to NO at room temperature 2 The lower detection limit of the gas is as low as 6.2ppb. FIG. 3 (c) shows that the sensing device was for 1ppmNO 2 The response and recovery times of (1) are 120 and 310 seconds, respectively. FIG. 3 (d) shows the sensitive layer material vs. NO 2 The gas exhibits excellent repeatability.
Testing sensitive layer vs. NO 2 、NO、NH 3 、H 2 Response of six gases, CO and ethane, as shown in FIG. 4, the sensor sensitive layer is sensitive to NO 2 The response of the gas is significantly higher than that of the other gases, indicating NO for the sensitive material 2 Excellent selectivity of the gas.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (2)
1. The preparation method of the cobalt and zinc diatomic doped molybdenum disulfide nanosheets based on atomic-level dispersion is characterized by comprising the following steps:
step 1, synthesizing atomically dispersed cobalt atoms
20g dicyandiamide is heated for 1 hour at 350 ℃ under argon atmosphere, and the obtained powder is denoted as CHN-350; dispersing 10mg cobalt (II) acetylacetonate and 1mL of citric acid in ethanol solution in an ultrasonic manner, then dripping the mixture into CHN-350, uniformly ball-milling, and annealing the obtained mixture at 680 ℃ for 2 hours in an argon atmosphere, wherein the obtained powder is atomically dispersed cobalt atoms;
step 2, synthesizing atomically dispersed zinc atoms
20g dicyandiamide is heated for 1 hour at 350 ℃ under argon atmosphere, and the obtained powder is denoted as CHN-350; dispersing 10mg zinc (II) acetylacetonate and 1mL of citric acid in ethanol solution in an ultrasonic manner, then dripping the mixture into CHN-350, uniformly ball-milling, and annealing the obtained mixture at 680 ℃ for 2 hours in an argon atmosphere, wherein the obtained powder is atomically dispersed zinc atoms;
step 3, synthesizing cobalt and zinc diatomic doping MoS based on atomic level dispersion 2 Nanosheets
Dispersing 1mL mass concentration 50% polyethylene imine water solution and 50mg polyvinylpyrrolidone in ethanol solution, and adding 20mg MoS 2 Uniformly dispersing the powder, simultaneously adding 1mg atomic-level dispersed cobalt atoms and 1mg atomic-level dispersed zinc atoms, uniformly dispersing by ultrasonic, magnetically stirring, drying and ball milling to obtain mixture powder;
heating the obtained mixture powder at 680 deg.C for 2 hr under argon atmosphere to obtain powder which is cobalt and zinc diatomic doped MoS based on atomic level dispersion 2 A nanosheet; the cobalt and zinc diatomic doping MoS based on atomic level dispersion 2 The nano-sheet is in MoS 2 Atomic fraction on the nanoplatelet lattice anchors cobalt atoms and zinc atoms.
2. The method of manufacturing according to claim 1, characterized in that: the total loading of cobalt atoms and zinc atoms is 0.4-1 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202210553518.2A CN114956179B (en) | 2022-05-20 | 2022-05-20 | Cobalt and zinc diatomic doped molybdenum disulfide nanosheets based on atomic-level dispersion and preparation method and application thereof |
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| CN111847513A (en) * | 2019-04-28 | 2020-10-30 | 中国科学院大连化学物理研究所 | Polyatomic co-doped molybdenum disulfide and preparation method and application thereof |
| CN113351230A (en) * | 2021-06-21 | 2021-09-07 | 华侨大学 | Isolated cobalt atom doped single-layer or few-layer MoS2Process for preparing catalyst |
| CN113603142A (en) * | 2021-08-19 | 2021-11-05 | 曹洋 | Diatomic boron modified molybdenum disulfide nano material and preparation method and application thereof |
| CN114405521A (en) * | 2020-10-12 | 2022-04-29 | 武汉理工大学 | Preparation method of zinc-doped molybdenum disulfide nanosheet hydrogen evolution electrocatalyst with rich defects |
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| US20200308719A1 (en) * | 2016-11-28 | 2020-10-01 | North Carolina State University | Catalysts for hydrogen evolution reaction including transition metal chalcogenide films and methods of forming the same |
| CN107262117B (en) * | 2017-07-25 | 2020-06-19 | 华中师范大学 | Single-atom metal-doped few-layer molybdenum disulfide electrocatalytic material, synthesis method and electrocatalytic nitrogen fixation method thereof |
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| CN111847513A (en) * | 2019-04-28 | 2020-10-30 | 中国科学院大连化学物理研究所 | Polyatomic co-doped molybdenum disulfide and preparation method and application thereof |
| CN114405521A (en) * | 2020-10-12 | 2022-04-29 | 武汉理工大学 | Preparation method of zinc-doped molybdenum disulfide nanosheet hydrogen evolution electrocatalyst with rich defects |
| CN113351230A (en) * | 2021-06-21 | 2021-09-07 | 华侨大学 | Isolated cobalt atom doped single-layer or few-layer MoS2Process for preparing catalyst |
| CN113603142A (en) * | 2021-08-19 | 2021-11-05 | 曹洋 | Diatomic boron modified molybdenum disulfide nano material and preparation method and application thereof |
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| Enabling selective, room-temperature gas detection using atomically dispersed Zn;Junwen Qiu et al.;Sensors & Actuators: B. Chemical;第329卷;1-9 * |
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