CN116893206A - Copper oxide/bismuth sulfide heterojunction material, gas sensor, gas detection device, preparation method and application - Google Patents
Copper oxide/bismuth sulfide heterojunction material, gas sensor, gas detection device, preparation method and application Download PDFInfo
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- CN116893206A CN116893206A CN202311162698.2A CN202311162698A CN116893206A CN 116893206 A CN116893206 A CN 116893206A CN 202311162698 A CN202311162698 A CN 202311162698A CN 116893206 A CN116893206 A CN 116893206A
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- bismuth sulfide
- copper oxide
- gas
- vacuum drying
- hydrothermal reaction
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- NNLOHLDVJGPUFR-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(=O)C([O-])=O.OCC(O)C(O)C(O)C(=O)C([O-])=O NNLOHLDVJGPUFR-UHFFFAOYSA-L 0.000 title claims abstract description 131
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 104
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 104
- 239000000463 material Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 238000001514 detection method Methods 0.000 title claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 114
- 239000002135 nanosheet Substances 0.000 claims abstract description 39
- 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 claims abstract description 36
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002105 nanoparticle Substances 0.000 claims abstract description 24
- 239000013078 crystal Substances 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 40
- 238000001291 vacuum drying Methods 0.000 claims description 35
- 239000000758 substrate Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 28
- 239000006185 dispersion Substances 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 25
- 239000007790 solid phase Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 239000007795 chemical reaction product Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920000307 polymer substrate Polymers 0.000 claims description 3
- 229910052594 sapphire Inorganic materials 0.000 claims description 3
- 239000010980 sapphire Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 230000004044 response Effects 0.000 abstract description 49
- 230000035945 sensitivity Effects 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 8
- 239000007791 liquid phase Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 21
- 239000002064 nanoplatelet Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 3
- 238000005459 micromachining Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- -1 transition metal chalcogenides Chemical class 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pathology (AREA)
- Electrochemistry (AREA)
- Immunology (AREA)
- Biochemistry (AREA)
- Analytical Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Molecular Biology (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention relates to a copper oxide/bismuth sulfide heterojunction material, a gas sensor, a gas detection device, a preparation method and application. The copper oxide/bismuth sulfide heterojunction material comprises copper oxide and bismuth sulfide, wherein the mass ratio of the copper oxide to the bismuth sulfide is 0.05-0.5, at least one part of the copper oxide is copper oxide nano particles with the average particle size of 200-400 nm, and at least one part of the bismuth sulfide is bismuth sulfide nano sheets with the average particle size of 10-20 nm. The copper oxide/bismuth sulfide heterojunction material has good gas sensitivity characteristics, and can be well applied to gas detection of nitrogen dioxide and the like; the bismuth sulfide crystal is stripped into a nano sheet structure by adopting a liquid phase stripping method, and the bismuth sulfide crystal is prepared by a hydrothermal methodThe heterojunction material is obtained, the process is simple and convenient, and the controllability is strong; the material can also be used for a simple and reliable method to form a gas sensor and realize the low concentration NO 2 The high sensitivity response of the method is faster, and the selectivity and the stability are better.
Description
Technical Field
The application relates to the technical field of gas sensors, in particular to a copper oxide/bismuth sulfide heterojunction material, a gas sensor, a gas detection device, a preparation method and application.
Background
NO 2 Is an important source of environmental pollution, which seriously jeopardizes human health and hinders the sustainable development of society, and develops a reagent capable of detecting NO 2 The sensor of the sensor has important significance for environmental monitoring and human health protection. For detecting NO in conventional techniques 2 The detection equipment has the problems of high working temperature, low response signal, low response speed, poor stability of detection signals and the like, and cannot meet the requirements of the market on NO 2 The requirement of reliable detection is realized.
Disclosure of Invention
Based on the above, the application aims to provide the copper oxide/bismuth sulfide heterojunction material and the sensor using the copper oxide/bismuth sulfide heterojunction material as the gas-sensitive layer material, which can realize rapid and sensitive response to low-concentration nitrogen dioxide and have better selectivity and stability.
In a first aspect of the present application, there is provided a copper oxide/bismuth sulfide heterojunction material comprising copper oxide and bismuth sulfide, wherein a mass ratio of the copper oxide to the bismuth sulfide is 0.05 to 0.5, wherein at least a part of the copper oxide is copper oxide nano-particles having an average particle diameter of 200nm to 400nm, at least a part of the bismuth sulfide is bismuth sulfide nano-sheets having an average particle diameter of 10nm to 20nm, and at least a part of the copper oxide nano-particles and at least a part of the bismuth sulfide nano-sheets constitute a heterojunction structure.
A second aspect of the present application provides a method for preparing the copper oxide/bismuth sulfide heterojunction material according to the first aspect, comprising the following steps:
grinding bismuth sulfide crystals in the presence of a first solvent, drying, performing ultrasonic dispersion in a second solvent, performing solid-liquid separation on bismuth sulfide dispersion liquid obtained by ultrasonic dispersion, and performing vacuum drying treatment on the collected bismuth sulfide solid phase substance to prepare bismuth sulfide nanosheets;
mixing the bismuth sulfide nanosheets and a copper source in a third solvent, and adding a pH regulator under the stirring condition for regulating to prepare a precursor dispersion;
and carrying out hydrothermal reaction on the precursor dispersion liquid, carrying out solid-liquid separation on a hydrothermal reaction system after the reaction is finished, washing a collected solid-phase hydrothermal reaction product, and carrying out vacuum drying treatment on the washed solid-phase hydrothermal reaction product to prepare the copper oxide/bismuth sulfide heterojunction material.
In some embodiments, the methods of preparation meet one or more of the following characteristics:
the first solvent is at least one selected from acetonitrile, isopropanol and N-methyl pyrrolidone;
the second solvent is at least one selected from deionized water, N-dimethylformamide, methanol, ethanol and acetone;
The third solvent is at least one selected from deionized water, N-dimethylformamide, methanol, ethanol and acetone;
the mass concentration of the copper oxide nano particles in the precursor dispersion liquid is 1 mg/L-10 mg/L;
the ratio of the molar amount of copper atoms to the molar amount of bismuth sulfide in the precursor dispersion is 0.1 to 1.
In some embodiments, the methods of preparation meet one or more of the following characteristics:
the ultrasonic dispersion frequency is 50 kHz-100 kHz;
the ultrasonic dispersion time is 10-20 min;
in the step of carrying out vacuum drying treatment on the collected bismuth sulfide solid phase, the temperature of the vacuum drying treatment is 50-80 ℃;
in the step of carrying out vacuum drying treatment on the collected bismuth sulfide solid phase substance, the time of the vacuum drying treatment is 10-15 hours;
in the step of adding the pH regulator under the stirring condition, the stirring rotating speed is 100 rpm-500 rpm;
in the step of adding the pH regulator under the stirring condition, the stirring time is 1-3 h; the temperature of the hydrothermal reaction is 70-100 ℃;
the time of the hydrothermal reaction is 15-20 hours;
in the step of separating the solid and liquid of the hydrothermal reaction system after the reaction is finished, the solid and liquid separation adopts a centrifugal mode, the centrifugal speed is 5000 rpm-8000 rpm, and the centrifugal time is 5 min-30 min;
In the step of washing the collected solid-phase hydrothermal reaction product, a solvent used for washing is at least one selected from deionized water and ethanol;
in the step of carrying out vacuum drying treatment on the washed solid-phase hydrothermal reaction product, the temperature of the vacuum drying treatment is 40-80 ℃;
and in the step of carrying out vacuum drying treatment on the washed solid-phase hydrothermal reaction product, the time of the vacuum drying treatment is 20-25 h.
According to a third aspect of the application, a gas sensor is provided, which comprises a gas-sensitive layer, wherein the gas-sensitive layer comprises the copper oxide/bismuth sulfide heterojunction material in the first aspect or the copper oxide/bismuth sulfide heterojunction material prepared by the preparation method in the second aspect.
In some embodiments, the gas sensor further comprises a substrate and an interdigital electrode disposed on at least one side of the substrate, the gas sensitive layer being disposed on a surface of the interdigital electrode on a side remote from the substrate.
In some embodiments, the gas sensor satisfies one or more of the following characteristics:
the substrate is selected from one or more of a silicon substrate, a polymer substrate, a ceramic substrate and a sapphire substrate;
The interval between the positive electrode and the negative electrode of the interdigital electrode is 200-900 mu m;
the number of the interdigital electrodes is one or more, and when the number of the interdigital electrodes is a plurality of interdigital electrodes, the distance between two adjacent interdigital electrodes is 50-500 mu m;
the thickness of the gas-sensitive layer is 1-2 mu m.
In a fourth aspect of the present application, there is provided a method for manufacturing a gas sensor according to the third aspect, comprising the steps of:
arranging interdigital electrodes on a substrate;
preparing a gas-sensitive material into a gas-sensitive layer dispersion liquid, coating the gas-sensitive layer dispersion liquid on the surface of one side of the interdigital electrode far away from the substrate, and drying to form a gas-sensitive layer to prepare the gas sensor.
In a fifth aspect of the present application, there is provided a gas detection device comprising the gas sensor according to the third aspect or the gas sensor produced by the production method according to the fourth aspect.
According to a sixth aspect of the application, there is provided an application of the copper oxide/bismuth sulfide heterojunction material according to the first aspect or the copper oxide/bismuth sulfide heterojunction material prepared by the preparation method according to the second aspect in nitrogen dioxide detection or in preparation of a nitrogen dioxide gas detection device or a nitrogen dioxide gas detection apparatus.
The copper oxide/bismuth sulfide heterojunction material provided by the application has the characteristics of nano particles, the bismuth sulfide has the characteristics of nano sheets, and the copper oxide/bismuth sulfide heterojunction material has good gas sensitivity and can be well applied to gas detection of nitrogen dioxide and the like.
In the preparation method of the copper oxide/bismuth sulfide heterojunction material, a liquid phase stripping method is adopted to strip bismuth sulfide crystals into a nano-sheet structure, and then a hydrothermal method is utilized to prepare the copper oxide/bismuth sulfide heterojunction material.
The gas sensor provided by the application can realize NO 2 The high sensitivity response of (2) is faster, and in addition, the low concentration NO can be realized 2 Is detected.
The preparation method of the gas sensor provided by the application adopts a micro-machining method to machine and prepare the interdigital electrode on the substrate, and then coats a layer of nano composite material on the surface of the interdigital electrode as a gas-sensitive coating to prepare the gas sensor.
The gas detection device provided by the application can realize high-sensitivity response to nitrogen dioxide gas, and has short response time and better selectivity and stability.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 shows the gas sensor structure of the present invention with the gas sensitive layer vs. NO 2 Schematic diagram of the principle of response.
Fig. 2 is an SEM image of the copper oxide nanoparticle-bismuth sulfide nanomaterial in example 3.
FIG. 3 is a TEM image of copper oxide nanoparticle-bismuth sulfide nanomaterial in example 3; wherein CuO particles are in the dashed circles.
Fig. 4 is an XRD pattern of the bismuth sulfide nanosheet material and the copper oxide nanoparticle-bismuth sulfide nanosheet material prepared in example 3 and an XRD standard card of copper oxide and bismuth sulfide.
FIG. 5 shows XPS spectra of the copper oxide nanoparticle-bismuth sulfide nanoplatelet material of example 3, where (a) is XPS fine spectrum of O1s and (b) is XPS full spectrum of the sample.
FIG. 6 is a graph of the response of sensor CB-10 of example 3 to 10ppm nitrogen dioxide at room temperature; the rectangular area of the gray frame line is that the sensor is in nitrogen dioxide of 10ppm of the atmosphere to be measured, and the rest white area is that the sensor is in air atmosphere.
FIG. 7 shows the sensor CB-10 of example 3 for 10ppm NH at room temperature 3 、H 2 、H 2 S and SO 2 Wherein (a), (b), (c) and (d) are respectively NH of 10ppm of the gas to be measured 3 、H 2 、H 2 S and SO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the rectangular area of the gray frame line is NH of 10ppm of the sensor in the atmosphere to be measured 3 、H 2 、H 2 S or SO 2 The rest area is that the sensor is in the air atmosphere.
FIG. 8 (a) is a graph showing the response of sensor CB-10 of example 3 to 0.5ppm, 1ppm, 2.5ppm, 5ppm, 10ppm, 25ppm, 50ppm and 100ppm of nitrogen dioxide at room temperature; (b) Is a graph of repeated response to 10ppm nitrogen dioxide at room temperature.
FIGS. 9 (a), (b), (c), (d), (e), (f), (g), (h) and (i) are the sensors Bulk Bi in examples 1 to 6, respectively 2 S 3 、Bi 2 S 3 Graphs of NSs, CB-5, CB-7.5, CB-10, CB-15, CB-25, CB-50 and CuO responses to 10ppm nitrogen dioxide at room temperature; the rectangular area of the gray frame line is that the sensor is in nitrogen dioxide of 10ppm of the atmosphere to be measured, and the rest areas are that the sensor is in air atmosphere.
Fig. 10 (a) is an SEM image of commercial bismuth sulfide bulk crystal powder in comparative example 1, and (b) is an SEM image of bismuth sulfide nanoplatelets in comparative example 2.
Fig. 11 (a) and (b) are SEM images and XRD patterns of CuO in comparative example 3, respectively, in comparison with standard cards.
Detailed Description
In order that the invention may be understood more fully, a more particular description of the invention will be rendered by reference to preferred embodiments thereof. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
The invention is described in detail below with reference to the accompanying drawings. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are provided, but the protection scope of the present invention is not limited to the following embodiments.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Terminology
Unless otherwise indicated or contradicted, terms or phrases used herein have the following meanings:
In the present invention, the terms "plurality", and the like relate to, but are not particularly limited to, 2 or more in number. For example, "one or more" means one kind or two or more kinds.
In the present invention, "further," "particularly," etc. are used for descriptive purposes and are not to be construed as limiting the scope of the invention.
In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
In the present invention, a numerical range (i.e., a numerical range) is referred to, and, unless otherwise indicated, a distribution of optional values within the numerical range is considered to be continuous and includes two numerical endpoints (i.e., a minimum value and a maximum value) of the numerical range, and each numerical value between the two numerical endpoints. When a numerical range merely points to integers within the numerical range, unless expressly stated otherwise, both endpoints of the numerical range are inclusive of the integer between the two endpoints, and each integer between the two endpoints is equivalent to the integer directly recited. When multiple numerical ranges are provided to describe a feature or characteristic, the numerical ranges may be combined. In other words, unless otherwise indicated, the numerical ranges disclosed herein are to be understood as including any and all subranges subsumed therein. The "numerical value" in the numerical interval may be any quantitative value, such as a number, a percentage, a proportion, or the like. "numerical intervals" allows for the broad inclusion of numerical interval types such as percentage intervals, proportion intervals, ratio intervals, and the like.
In the present invention, the term "room temperature" generally means 4℃to 35℃and preferably 20.+ -. 5 ℃. In some embodiments of the invention, room temperature refers to 20 ℃ to 30 ℃.
In the present invention, the temperature parameter is allowed to be constant temperature processing, and also allowed to vary within a certain temperature range, unless otherwise specified. It should be appreciated that the constant temperature process described allows the temperature to fluctuate within the accuracy of the instrument control. Allows for fluctuations within a range such as + -5 ℃, + -4 ℃, + -3 ℃, + -2 ℃, + -1 ℃.
In the present invention, referring to a unit of a data range, if a unit is only carried behind a right end point, the units indicating the left and right end points are the same. For example, 2 to 5h means that the units of the left end point "2" and the right end point "5" are both h (hours).
In recent years, environmental pollution caused by nitrogen dioxide gas is receiving more and more attention, and has become an important problem for harming human health and preventing sustainable development of society. The development of a high-performance nitrogen dioxide gas sensor is significant for solving the environmental monitoring and human health protection.
Two-dimensional metal materials, particularly transition metal chalcogenides, have received attention in the fields of electrocatalysis, semiconductors, and secondary batteries because of their advantages of high specific surface area, excellent physicochemical properties, good conductivity, and the like. Bismuth sulfide is taken as a typical n-type two-dimensional transition metal chalcogenide, has high carrier mobility and excellent environment-friendly characteristic, and is expected to be used in the field of gas detection; however, the conventional technology using bismuth sulfide as a sensor still faces difficulties including low sensitivity and poor selectivity.
The inventors of the present application developed a material in which bismuth sulfide is compounded with other materials to significantly improve the gas sensitivity characteristics thereof, while a high sensitivity response to a specific gas can be achieved by using a copper oxide/bismuth sulfide heterojunction material of copper oxide nanoparticles having p-type semiconductor characteristics and a bismuth sulfide member.
In a first aspect of the present application, there is provided a copper oxide/bismuth sulfide heterojunction material comprising copper oxide and bismuth sulfide, wherein a mass ratio of the copper oxide to the bismuth sulfide is 0.05 to 0.5, wherein at least a part of the copper oxide is copper oxide nano-particles having an average particle diameter of 200nm to 400nm, at least a part of the bismuth sulfide is bismuth sulfide nano-sheets having an average particle diameter of 10nm to 20nm, and at least a part of the copper oxide nano-particles and at least a part of the bismuth sulfide nano-sheets constitute a heterojunction structure.
The copper oxide/bismuth sulfide heterojunction material provided by the application has the characteristics of nano particles, the bismuth sulfide has the characteristics of nano sheets, and the copper oxide/bismuth sulfide heterojunction material has good gas sensitivity and can be well applied to gas detection of nitrogen dioxide and the like.
In some embodiments, in the copper oxide/bismuth sulfide heterojunction material, the mass ratio of the copper oxide to the bismuth sulfide is 0.05-0.5, and may be selected from any one or any two of the following ranges: 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, etc. The more proper mass ratio of the copper oxide to the bismuth sulfide is more beneficial to improving the gas-sensitive characteristic of the copper oxide/bismuth sulfide heterojunction material; if the mass ratio is too large, i.e. the content of copper oxide in the copper oxide/bismuth sulfide heterojunction material is high, although the increase of the copper oxide content means more sensitive sites, the high copper oxide content leads to the intrinsic resistance of the sensitive layer I.e. the conductivity of the material is increased, which leads to NO being obtained 2 The change in resistance due to molecular adsorption is more difficult to observe, and is manifested as a decrease in response speed. If the mass ratio is too small, namely the content of bismuth sulfide in the copper oxide/bismuth sulfide heterojunction material is high, the sensitive sites of the gas sensitive layer are less when the content of copper oxide is low, and the sensitivity of the gas sensitive layer is small.
A second aspect of the present application provides a method for preparing the copper oxide/bismuth sulfide heterojunction material according to the first aspect, comprising the following steps:
s100: grinding bismuth sulfide crystals in the presence of a first solvent, drying, performing ultrasonic dispersion in a second solvent, performing solid-liquid separation on bismuth sulfide dispersion liquid obtained by ultrasonic dispersion, and performing vacuum drying treatment on the collected bismuth sulfide solid phase substance to prepare bismuth sulfide nanosheets;
s200: mixing the bismuth sulfide nanosheets and a copper source in a third solvent, and adding a pH regulator under the stirring condition to prepare a precursor dispersion;
s300: and carrying out hydrothermal reaction on the precursor dispersion liquid, carrying out solid-liquid separation on a hydrothermal reaction system after the reaction is finished, washing a collected solid-phase hydrothermal reaction product, and carrying out vacuum drying treatment on the washed solid-phase hydrothermal reaction product to prepare the copper oxide/bismuth sulfide heterojunction material.
In the preparation method of the copper oxide/bismuth sulfide heterojunction material, a liquid phase stripping method is adopted to strip bismuth sulfide crystals into a nano-sheet structure, and then a hydrothermal method is utilized to prepare the copper oxide/bismuth sulfide heterojunction material.
In some embodiments, in step S100 of the preparation method, the first solvent is selected from at least one of acetonitrile, isopropanol, and N-methylpyrrolidone. The adoption of a proper solvent and grinding are performed, and the separation of the blocky bismuth oxide in a centrifugal mode is beneficial to obtaining the thin bismuth sulfide nano-sheet, so that the atomic utilization rate of materials is increased, and the performance of the sensor is improved.
In some embodiments, in step S100 of the preparation method, the second solvent is selected from at least one of deionized water, N-dimethylformamide, methanol, ethanol, or acetone.
In some embodiments, in step S100 of the preparation method, the frequency of the ultrasonic dispersion is 50kHz to 100kHz, and may be selected from any one frequency or any two frequency intervals: 50kHz, 60kHz, 70kHz, 80kHz, 90kHz and 100kHz.
In some embodiments, in step S100 of the preparation method, the time of ultrasonic dispersion is 10min to 20min, and may be selected from any one time or any two time interval of the following: 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min, 20min, etc.
In some embodiments, in the step S100 of the preparation method, in the step of performing vacuum drying treatment on the collected bismuth sulfide solid phase, the temperature of the vacuum drying treatment is 50-80 ℃, and the vacuum drying treatment may be selected from any one temperature or any two temperature intervals: 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ and the like. The proper temperature of vacuum drying treatment is more favorable for drying and curing the bismuth sulfide material, improves the drying efficiency and obtains the bismuth sulfide material with excellent performance. If the temperature is too high, the structure of the bismuth sulfide material can be changed, and the property of the material can be changed; if the temperature is too low, the solvent in the material cannot be completely removed, and the drying effect and quality of the material are affected.
In some embodiments, in the step S100 of the preparation method, in the step of performing vacuum drying treatment on the collected bismuth sulfide solid phase, the time of the vacuum drying treatment is 10h to 15h, and may be selected from any one time or any two time interval of the following: 10h, 11h, 12h, 13h, 14h, 15h, etc. The proper vacuum drying treatment time is more favorable for keeping the material sufficiently dried, and the condition of uneven drying or excessive drying is avoided; if the time is too long, the material is excessively dried, and cracking, deformation, cracking and the like occur; if this time is too short, incomplete or uneven drying of the material may result.
In some embodiments, in step S200 of the preparation method, the third solvent is selected from at least one of deionized water, N-dimethylformamide, methanol, ethanol, and acetone.
In some embodiments, in step S200 of the preparation method, the mass concentration of the copper oxide nanoparticles in the precursor dispersion is 1mg/L to 10mg/L. The mass concentration of the copper oxide nano particles in the precursor dispersion is more favorable for loading the copper oxide nano particles on the bismuth sulfide nano sheet; if the concentration is too high, the copper oxide nano particles are excessively loaded on the bismuth sulfide nano particles, so that the response time of the material is increased; if the concentration is too low, the copper oxide nanoparticles are too little loaded on the bismuth sulfide nanoparticles, which may reduce the sensitivity of the material.
In some embodiments, in step S200 of the preparation method, the ratio of the molar amount of copper atoms in the precursor dispersion to the molar amount of bismuth sulfide is 0.1 to 1, and may be selected from a range consisting of any one ratio or any two ratios of: 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 1, etc.
In some embodiments, in the step S200 of the preparation method, in the step of adding the pH adjuster under stirring, the rotation speed of the stirring treatment is 100rpm to 500rpm, and may be selected from any one rotation speed or any two rotation speeds as follows: 100rpm, 200rpm, 300rpm, 400rpm, 500rpm, etc.
In some embodiments, in the step S200 of the preparation method, in the step of adding the pH adjuster under stirring, the stirring treatment time is 1h to 3h, and may be selected from any one time or any two time intervals as follows: 1h, 2h, 3h, etc.
In some embodiments, in step S300 of the preparation method, the temperature of the hydrothermal reaction is 70 ℃ to 100 ℃, and may be selected from any one temperature or any two temperature intervals: 70 ℃, 75 ℃, 80 ℃, 90 ℃, 95 ℃, 100 ℃, etc. The proper temperature of the hydrothermal reaction is more favorable for the synthesis and growth of materials, because the hydrothermal reaction needs to be carried out at a certain temperature, the proper temperature can promote the reaction, the reaction efficiency is improved, and the problems of crystallization, precipitation and the like can be avoided. If the temperature is too high, the crystal may grow too fast, so that tiny particles or clusters are generated, and the quality and gas-sensitive performance of the product are affected; if the temperature is too low, incomplete reaction and incomplete product growth can result, affecting the gas-sensitive properties of the material.
In some embodiments, in step S300 of the preparation method, the hydrothermal reaction time is 15h to 20h, and may be selected from any one time or any two time interval of the following: 15h, 16h, 17h, 18h, 20h, etc.
The proper hydrothermal reaction time is more favorable for crystal growth and reaction, because the proper time can ensure that reactants are fully reacted and the crystal growth is complete, thereby improving the reaction efficiency and the product quality. If the hydrothermal reaction time is too long, excessive reaction or by-products may occur, which affects the quality and performance of the product. If the hydrothermal reaction time is too short, the reaction may not proceed sufficiently, the crystal growth may not be complete, and the structure and properties of the product may be affected.
In some embodiments, in the step S300 of the preparation method, in the step of separating the solid and liquid of the hydrothermal reaction system after the reaction is completed, the solid and liquid separation is performed by a centrifugal method, and the centrifugal speed of the centrifugal treatment is 5000rpm to 8000rpm, and may be selected from any one or any two of the following rotation speeds: 5000rpm, 6000rpm, 7000rpm, 8000rpm, etc.
In some embodiments, in step S300 of the preparation method, the centrifugation time is 5min to 30min, and may be selected from any one time or any two time interval of the following: 5min, 10min, 15min, 20min, 25min, 30min, etc.
In some embodiments, in the step S300 of the preparation method, the washing of the collected solid-phase hydrothermal reaction product is performed using a solvent selected from at least one of deionized water and ethanol.
In some embodiments, in the step S300 of the preparation method, in the step of performing vacuum drying treatment on the washed solid phase hydrothermal reaction product, the temperature of the vacuum drying treatment is 40-80 ℃, and the vacuum drying treatment may be selected from any one temperature or any two temperature intervals: 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ and the like. If the temperature is too high, the crystal may grow too fast, so that tiny particles or clusters are generated, and the quality and gas-sensitive performance of the product are affected; if the temperature is too low, incomplete reaction and incomplete product growth can result, affecting the gas-sensitive properties of the material.
In some embodiments, in the step S300 of the preparation method, in the step of performing vacuum drying treatment on the washed solid-phase hydrothermal reaction product, the time of the vacuum drying treatment is 20h to 25h, and may be selected from any one time or any two time interval of the following: 20h, 21h, 22h, 23h, 24h, 25h, etc.
According to a third aspect of the application, a gas sensor is provided, which comprises a gas-sensitive layer, wherein the gas-sensitive layer comprises the copper oxide/bismuth sulfide heterojunction material in the first aspect or the copper oxide/bismuth sulfide heterojunction material prepared by the preparation method in the second aspect.
The gas sensor provided by the application can realize NO 2 The high sensitivity response of (2) is faster, and in addition, the low concentration NO can be realized 2 Is detected.
In some embodiments, the gas sensor further comprises a substrate and an interdigital electrode disposed on at least one side of the substrate, the gas sensitive layer being disposed on a surface of the interdigital electrode on a side remote from the substrate.
In some embodiments, the gas sensor is one or more selected from the group consisting of a silicon substrate, a polymer substrate, a ceramic substrate, and a sapphire substrate.
In some embodiments, in the gas sensor, the inter-digital electrode has a positive-negative electrode spacing of 200 μm to 900 μm.
In some embodiments, in the gas sensor, the number of the interdigital electrodes is one or more, and when the number of the interdigital electrodes is a plurality of interdigital electrodes, the distance between two adjacent interdigital electrodes is 50 μm to 500 μm.
In some embodiments, in the gas sensor, the thickness of the gas-sensitive layer is 1 μm to 2 μm.
In a fourth aspect of the present application, there is provided a method for manufacturing a gas sensor according to the third aspect, comprising the steps of:
p100: arranging interdigital electrodes on a substrate;
p200: preparing a gas-sensitive material into a gas-sensitive layer dispersion liquid, coating the gas-sensitive layer dispersion liquid on the surface of one side of the interdigital electrode far away from the substrate, and drying to form a gas-sensitive layer to prepare the gas sensor.
The preparation method of the gas sensor provided by the application adopts a micro-machining method to machine and prepare the interdigital electrode on the substrate, and then coats a layer of nano composite material on the surface of the interdigital electrode as a gas-sensitive coating to prepare the gas sensor.
In a fifth aspect of the present application, there is provided a gas detection device comprising the gas sensor according to the third aspect or the gas sensor produced by the production method according to the fourth aspect.
The gas detection device provided by the application can realize high-sensitivity response to nitrogen dioxide gas, and has short response time and better selectivity and stability.
According to a sixth aspect of the application, there is provided an application of the copper oxide/bismuth sulfide heterojunction material according to the first aspect or the copper oxide/bismuth sulfide heterojunction material prepared by the preparation method according to the second aspect in nitrogen dioxide detection or in preparation of a nitrogen dioxide gas detection device or a nitrogen dioxide gas detection apparatus.
FIG. 1 shows the gas sensor structure of the present application with the gas sensitive layer vs. NO 2 Schematic diagram of the principle of response. CuO nano-particles as target gas molecules NO 2 Is identical to NO in the adsorption capture site of (2) 2 Charge transfer is performed. The Bi2S3 nano-sheet is used as a charge transmission channel, and the two interact to realize an efficient gas sensing process, and the sensing process has higher sensitivity and higher response speed.
In order that the application may be more readily understood and put into practical effect, the following more particular examples and comparative examples are provided as reference.
The conception, specific examples and technical effects of the present application will be further described with reference to the drawings to fully understand the present application. These descriptions are provided only to help explain the present application and should not be used to limit the scope of the claims of the present application.
Unless otherwise specified, the raw materials used in each of the following experiments are commercially available.
Example 1
100mg of commercial bismuth sulfide bulk crystal powder was put into an agate mortar for manual grinding for 2 hours, and during this process, an appropriate amount of acetonitrile (equivalent to the first solvent) was added for auxiliary grinding. The milled powder was dried in a vacuum oven at 60 ℃ overnight to evaporate residual solvent, which was then dispersed in 50mL of 70vol% aqueous ethanol (equivalent to the second solvent). After the above dispersion was treated with 200W ultrasonic waves for 3 hours (corresponding to the bismuth sulfide dispersion obtained by ultrasonic dispersion), the mixture was centrifuged at 1500rpm for 20 minutes, and the supernatant was collected to obtain bismuth sulfide nanoplatelets.
After dispersing 25mg of bismuth sulfide nanoplatelets and 1.2mg of copper nitrate trihydrate (copper source) in 10mL of deionized water, stirring with magnetic force for 30 minutes, 0.2mL of aqueous ammonia (pH adjuster) was added to the above solution and stirring was continued for 2 hours. The resulting solution (corresponding to the precursor dispersion, wherein the weight ratio of copper oxide to bismuth sulfide is about 5%) was hydrothermally treated in an environment at 85 ℃ for 16 hours. Finally, the precipitated sample of the product from the above procedure was collected by centrifugation and washed alternately 3 times with ethanol and deionized water to ensure complete removal of the reactants. And (3) drying the product in a vacuum oven at 50 ℃ for 24 hours to obtain the copper oxide nano-particle-bismuth sulfide nano-sheet material (copper oxide/bismuth sulfide heterojunction material).
Adding the copper oxide nano particles-bismuth sulfide nano sheets into deionized water at the concentration of 1mg/L, and carrying out ultrasonic treatment for 10 minutes at 40KHz to uniformly disperse the composite material in the deionized water, thereby obtaining the dispersion liquid of the copper oxide nano particles-bismuth sulfide nano sheets.
The gold electrode is prepared by adopting a micromachining process, the spacing between the positive electrode and the negative electrode is controlled to be 800 mu m, and the spacing between the adjacent electrodes is controlled to be 300 mu m. Dripping 1 μL of copper oxide nano particle-bismuth sulfide nano sheet dispersion liquid onto the surface of an electrode, and vacuum drying at 60 ℃ for 1h to obtain the copper oxide nano particle-bismuth sulfide nano sheet gas sensor (CuONPs/Bi) 2 O 3 NSs0D/2D heterostructure sensor, i.e. CuO nanoparticle/Bi 2 O 3 Nanoplatelets/electrodes), the sensor is denoted CB-5.
Examples 2 to 6
The method for preparing copper oxide nanoparticle-bismuth sulfide nanoplatelets of examples 2 to 6 was basically the same as that of example 1, except that the addition amounts of copper nitrate trihydrate in the steps of dispersing bismuth sulfide nanoplatelets and copper nitrate trihydrate (copper source) in deionized water were different, and 2.4mg of copper nitrate trihydrate added in example 1 was changed to 1.8mg, 2.4mg, 3.6mg, 6mg and 12mg, respectively.
The gas sensors were prepared by the same method as in example 1 using copper oxide nanoparticle-bismuth sulfide nanosheet material as a raw material of the gas sensitive layer, and the sensors constructed in examples 2 to 6 were denoted as CB-7.5, CB-10, CB-15, CB-25 and CB-50, respectively.
TABLE 1 sensor CB-10 of example 3 for 10ppm NO at room temperature 2 、NH 3 、H 2 、H 2 S and SO 2 Is a response value of (a).
TABLE 2 the sensors of examples 1-6 and comparative examples 1-3 at room temperature for 10ppm NO 2 A response value.
Characterization tests were performed on the copper oxide nanoparticle-bismuth sulfide nanoplatelet material (copper oxide to bismuth sulfide weight ratio of about 10%) prepared in example 3. Fig. 2 is an SEM image of the copper oxide nanoparticle-bismuth sulfide nanosheet material of example 3, and it can be seen that the copper oxide nanoparticles are uniformly and tightly compounded on the bismuth sulfide nanosheets, and the average size of the bismuth sulfide nanosheets is about 200nm to 300nm. FIG. 3 is a TEM image of copper oxide nanoparticle-bismuth sulfide nanosheet material of example 3, with CuO particles in the dashed circle; it can be seen that the copper oxide nanoparticles were uniformly and tightly compounded on the bismuth sulfide nanoplatelets, and the average particle diameter of the copper oxide nanoparticles was about 15nm. FIG. 4 is an XRD pattern of bismuth sulfide nanosheet material and copper oxide nanoparticle-bismuth sulfide nanosheet material obtained in example 3, cuO and Bi 2 S 3 XRD standard card of (b); the bismuth sulfide nano-sheet material prepared by the technical scheme is matched with the standard card of bismuth oxide, and the copper oxide nano-particle-bismuth sulfide nano-sheet material is matched with the standard card of bismuth oxide and copper oxide, so that the bismuth sulfide nano-sheet material and the copper oxide nano-particle-bismuth sulfide nano-sheet material are successfully synthesized. FIG. 5 is an XPS spectrum of the copper oxide nanoparticle-bismuth sulfide nanoplatelet material of example 3, where (a) is XPS fine spectrum of O1s and (b) is XPS full spectrum of the sample; the former gives XPS of O1s orbitals indicating lattice Oxygen (OL), oxygen Vacancies (OV), and chemisorbed Oxygen (OC), and FIG. 4 shows successful synthesis of bismuth sulfide nanoplatelet materials and copper oxide nanoparticle-bismuth sulfide nanoplatelet materials.
A series of performance tests were performed on sensor CB-10 of example 3. In the present application, unless otherwise specified, the response test refers to the test of the resistance value R of the sensor in the atmosphere to be measured g And in the air ringResistance value R in environment a By R a /R g As a response value of the sensor; the response time is calculated from the time when the atmosphere in which the sensor is positioned is changed from the air atmosphere to the atmosphere to be measured, and the resistance value of the sensor changes to |R a -R g Time elapsed of 90%.
FIG. 6 is a graph of the response of sensor CB-10 in example 3 to 10ppm nitrogen dioxide at room temperature, wherein the rectangular area of the gray box indicates that the sensor CB-10 is in the atmosphere to be measured of 10ppm nitrogen dioxide and the remaining white area is that the sensor is in the air atmosphere; the response value of the sensor CB-10 to 10ppm of nitrogen dioxide is calculated to be 9.6, and the response time is 20s; specific response values can also be seen in table 1.
FIG. 7 shows the sensor CB-10 of example 3 for 10ppm NH at room temperature 3 、H 2 、H 2 S and SO 2 Wherein (a), (b), (c) and (d) are respectively NH of 10ppm of the gas to be measured 3 、H 2 、H 2 S and SO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the rectangular area of the gray frame line is NH of 10ppm of the sensor in the atmosphere to be measured 3 、H 2 、H 2 S or SO 2 The rest areas are the sensor in the air atmosphere; it can be seen that the sensor pair NH 3 、H 2 、H 2 S and SO 2 The response speed of the gas is slow and the resistance value in these atmospheres is unstable; specific response values can also be seen in table 1. FIG. 8 (a) is a graph showing the continuous response of sensor CB-10 of example 3 to 0.5ppm, 1ppm, 2.5ppm, 5ppm, 10ppm, 25ppm, 50ppm and 100ppm nitrogen dioxide at room temperature, wherein FIG. 8 (b) is a graph showing the repeated response to 10ppm nitrogen dioxide at room temperature; as can be seen from fig. 8 (a), as the response value of the gas sensor gradually increases with the increase of the nitrogen dioxide concentration in the atmosphere to be measured, the minimum response concentration can reach 0.5ppm; from fig. 8 (b), it can be derived that the repeated response test result of the sensor is good, the baseline of the sensor in the air atmosphere is stable, and the repeated response value and response speed to 10ppm of nitrogen dioxide are basically inconvenient. In FIG. 9(c) (d), (e), (f), (g) and (h) are graphs of the response of the sensors CB-5, CB-7.5, CB-10, CB-15, CB-25 and CB-50 in examples 1 to 6, respectively, to 10ppm nitrogen dioxide at room temperature (the response values can be seen in Table 2); it can be seen that CB-10 performs best, showing a response value to 10ppmno29.6, and shows a faster recovery rate without any auxiliary means.
Comparative example 1
In comparative example 1, commercial bismuth sulfide bulk crystal powder was directly used as a raw material of the gas sensitive layer; a gas sensor was prepared in the same manner as in example 1, and the sensor constructed in comparative example 1 was designated Bulk Bi 2 S 3 。
Comparative example 2
In comparative example 2, commercial bismuth sulfide bulk crystal powder was prepared as bismuth sulfide nanoplatelets and used as a raw material for a gas sensitive layer (no addition of copper source and hydrothermal reaction process was performed); a gas sensor was prepared in the same manner as in example 1, and the sensors constructed in comparative example 2 were respectively designated as Bi 2 S 3 NSs。
Comparative example 3
In comparative example 3, copper nitrate trihydrate is directly dispersed in deionized water, magnetically stirred, ammonia water is added, and the same hydrothermal reaction is carried out to prepare CuO which is used as a raw material of a gas sensitive layer; a gas sensor was prepared in the same manner as in example 1, and the sensor constructed in comparative example 3 was designated CuO.
The sensors Bulk Bi in comparative examples 1 to 3 are shown in FIG. 9 as (a), (b) and (i), respectively 2 S 3 、Bi 2 S 3 Response plots of NSs and CuO for 10ppm nitrogen dioxide at room temperature (response values can be seen in Table 2); it can be seen that example 3 has a significantly improved response to both the platy copper oxide and copper oxide compared to the bulk bismuth sulfide. Fig. 10 (a) is an SEM image of the commercial bismuth sulfide bulk crystal powder of comparative example 1, and it can be seen that the morphology is a structure in which a plurality of layers are stacked together; FIG. 10 (b) is an SEM image of the commercial bismuth sulfide bulk crystal powder prepared as bismuth sulfide nanoplatelets in comparative example 2, it can be seen The liquid phase stripping is adopted to make the film structure. Fig. 11 (a) and (b) are SEM images and XRD patterns of CuO in comparative example 3, respectively, in comparison with standard cards; it can be seen that Bi is not added 2 S 3 In the case of nanoplatelets, pure phase CuO grows into disordered nanoplatelets during hydrothermal processes due to the lack of a two-dimensional lamellar substrate to provide growth sites.
The sensor of comparative example 1 (noted Bulk Bi 2 S 3 ) The response to 10ppm of nitrogen dioxide is low (R a /R g =3.1), the sensor in comparative example 2 (noted Bi 2 S 3 NSs) has a lower response value to 10ppm nitrogen dioxide (R a /R g =3.2), probably due to the insufficient surface active centers of bulk bismuth sulfide, reduces its response to nitrogen dioxide. The sensor of comparative example 3 (noted CuO) has a low response value to 10ppm of nitrogen dioxide (R a /R g =3.1), probably due to the good conductivity of pure copper oxide, leading to NO 2 After the effect, the concentration change of the current carrier is not obvious, and the response value is low.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention by one of ordinary skill in the art without undue burden. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the application, which are described in detail and are not to be construed as limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. The scope of the application is therefore indicated by the appended claims, and the description and drawings may be used to interpret the contents of the claims.
Claims (10)
1. A copper oxide/bismuth sulfide heterojunction material, characterized in that it comprises copper oxide and bismuth sulfide, the mass ratio of the copper oxide to the bismuth sulfide is 0.05-0.5, wherein at least a part of the copper oxide is copper oxide nano-particles with average particle size of 200-400 nm, at least a part of the bismuth sulfide is bismuth sulfide nano-sheets with average particle size of 10-20 nm, and at least a part of the copper oxide nano-particles and at least a part of the bismuth sulfide nano-sheets form a heterojunction structure.
2. The method for preparing the copper oxide/bismuth sulfide heterojunction material as claimed in claim 1, comprising the following steps:
grinding bismuth sulfide crystals in the presence of a first solvent, drying, performing ultrasonic dispersion in a second solvent, performing solid-liquid separation on bismuth sulfide dispersion liquid obtained by ultrasonic dispersion, and performing vacuum drying treatment on the collected bismuth sulfide solid phase substance to prepare bismuth sulfide nanosheets;
mixing the bismuth sulfide nanosheets and a copper source in a third solvent, and adding a pH regulator under the stirring condition to prepare a precursor dispersion;
and carrying out hydrothermal reaction on the precursor dispersion liquid, carrying out solid-liquid separation on a hydrothermal reaction system after the reaction is finished, washing a collected solid-phase hydrothermal reaction product, and carrying out vacuum drying treatment on the washed solid-phase hydrothermal reaction product to prepare the copper oxide/bismuth sulfide heterojunction material.
3. The method of manufacturing according to claim 2, characterized in that one or more of the following characteristics are fulfilled:
the first solvent is at least one selected from acetonitrile, isopropanol and N-methyl pyrrolidone;
the second solvent is at least one selected from deionized water, N-dimethylformamide, methanol, ethanol and acetone;
The third solvent is at least one selected from deionized water, N-dimethylformamide, methanol, ethanol and acetone;
the mass concentration of the copper oxide nano particles in the precursor dispersion liquid is 1 mg/L-10 mg/L;
the ratio of the molar amount of copper atoms to the molar amount of bismuth sulfide in the precursor dispersion is 0.1 to 1.
4. The method of manufacturing according to claim 2, characterized in that one or more of the following characteristics are fulfilled:
the ultrasonic dispersion frequency is 50 kHz-100 kHz;
the ultrasonic dispersion time is 10-20 min;
in the step of carrying out vacuum drying treatment on the collected bismuth sulfide solid phase, the temperature of the vacuum drying treatment is 50-80 ℃;
in the step of carrying out vacuum drying treatment on the collected bismuth sulfide solid phase substance, the time of the vacuum drying treatment is 10-15 hours;
in the step of adding the pH regulator under the stirring condition, the stirring rotating speed is 100 rpm-500 rpm;
in the step of adding the pH regulator under the stirring condition, the stirring time is 1-3 h;
the temperature of the hydrothermal reaction is 70-100 ℃;
the time of the hydrothermal reaction is 15-20 hours;
in the step of separating the solid and liquid of the hydrothermal reaction system after the reaction is finished, the solid and liquid separation adopts a centrifugal mode, the centrifugal speed is 5000 rpm-8000 rpm, and the centrifugal time is 5 min-30 min;
In the step of washing the collected solid-phase hydrothermal reaction product, a solvent used for washing is at least one selected from deionized water and ethanol;
in the step of carrying out vacuum drying treatment on the washed solid-phase hydrothermal reaction product, the temperature of the vacuum drying treatment is 40-80 ℃;
and in the step of carrying out vacuum drying treatment on the washed solid-phase hydrothermal reaction product, the time of the vacuum drying treatment is 20-25 h.
5. A gas sensor comprising a gas sensitive layer comprising the copper oxide/bismuth sulfide heterojunction material of claim 1 or prepared by the preparation method of any one of claims 2 to 4.
6. The gas sensor of claim 5, further comprising a substrate and an interdigital electrode disposed on at least one side of the substrate, the gas sensitive layer being disposed on a surface of the interdigital electrode on a side remote from the substrate.
7. The gas sensor of claim 6, wherein one or more of the following characteristics are satisfied:
The substrate is selected from one or more of a silicon substrate, a polymer substrate, a ceramic substrate and a sapphire substrate;
the interval between the positive electrode and the negative electrode of the interdigital electrode is 200-900 mu m;
the number of the interdigital electrodes is one or more, and when the number of the interdigital electrodes is a plurality of interdigital electrodes, the distance between two adjacent interdigital electrodes is 50-500 mu m;
the thickness of the gas-sensitive layer is 1-2 mu m.
8. A method of manufacturing a gas sensor according to any one of claims 5 to 7, comprising the steps of:
arranging interdigital electrodes on a substrate;
preparing a gas-sensitive material into a gas-sensitive layer dispersion liquid, coating the gas-sensitive layer dispersion liquid on the surface of one side of the interdigital electrode far away from the substrate, and drying to form a gas-sensitive layer to prepare the gas sensor.
9. A gas detection apparatus comprising the gas sensor according to any one of claims 5 to 7 or the gas sensor produced by the production method according to claim 8.
10. The copper oxide/bismuth sulfide heterojunction material as defined in claim 1 or the copper oxide/bismuth sulfide heterojunction material prepared by the preparation method as defined in any one of claims 2 to 4, or the application thereof in nitrogen dioxide detection or in preparation of a nitrogen dioxide gas detection device or a nitrogen dioxide gas detection apparatus.
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