CN110510657B - Copper oxide microsphere structure, hydrogen sulfide gas sensor and preparation method thereof - Google Patents
Copper oxide microsphere structure, hydrogen sulfide gas sensor and preparation method thereof Download PDFInfo
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- CN110510657B CN110510657B CN201910858424.4A CN201910858424A CN110510657B CN 110510657 B CN110510657 B CN 110510657B CN 201910858424 A CN201910858424 A CN 201910858424A CN 110510657 B CN110510657 B CN 110510657B
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- C01G3/02—Oxides; Hydroxides
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- G—PHYSICS
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- 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
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
Abstract
The invention provides a copper oxide microsphere structure and H 2 The S gas sensor and the preparation method thereof, wherein the copper oxide microsphere structure comprises: a plurality of strip-shaped units formed by self-assembly; the first edge of each strip-shaped unit radially extends along the radial direction of the same sphere to form an integral structure with a spherical overall outer contour; the directions of the second edges of at least part of the strip-shaped units conform to the same streamline; the direction of the first edge of the strip-shaped unit is vertical to the direction of the second edge of the strip-shaped unit; the copper oxide nano structure is monoclinic system copper oxide. By adopting the scheme, H can be improved 2 Selectivity and sensitivity of S.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a copper oxide microsphere structure, a hydrogen sulfide gas sensor and a preparation method thereof.
Background
H 2 S is widely existed in industrial production and agricultural activities, is a flammable, extremely toxic and corrosive colorless gas, has a stinky egg smell at a low concentration, and has a high concentration of H 2 S can paralyze olfactory nerves and cause people to smell nothing. Therefore, the design of the H with low manufacturing cost, convenient preparation, high sensitivity and good selectivity 2 The S sensor is very important.
Disclosure of Invention
The invention provides a copper oxide microsphere structure, a hydrogen sulfide gas sensor and a preparation method thereof, which aim to improve H-pair 2 Selectivity and sensitivity of S.
In order to achieve the purpose, the invention adopts the following scheme:
in a first aspect, there is provided a copper oxide microsphere structure comprising: a plurality of strip-shaped units formed by self-assembly; the first edge of each strip-shaped unit radially extends along the radial direction of the same sphere to form an integral structure with a spherical overall outer contour; the directions of the second edges of at least part of the strip-shaped units conform to the same streamline; the direction of the first edge of the strip-shaped unit is vertical to the direction of the second edge of the strip-shaped unit; the copper oxide nano structure is monoclinic system copper oxide.
In one embodiment, the first edge is a long edge and the second edge is a wide edge; the long side size of the strip-shaped unit is larger than the wide side size of the strip-shaped unit, and the wide side size of the strip-shaped unit is larger than the thickness size of the strip-shaped unit.
In one embodiment, the size of the gap between the outer ends of two adjacent strip-shaped units, the second edges of which are oriented to follow the same streamline, is smaller than the size of the second edge of each outer end of the two strip-shaped units.
In one embodiment, the overall outer contour has a diameter in the range of 12 to 18 μm, the first side has a size in the range of 180nm to 1 μm, and the second side has a size in the range of 70 to 440nm.
In one embodiment, the periphery of the copper oxide microsphere structure is formed by the strip-shaped units.
In a second aspect, a method for preparing copper oxide is provided, which is used to prepare the copper oxide microsphere structure according to the above embodiment, and the method includes: preparing a copper salt solution having a first concentration; mixing the copper salt solution and ammonia water in a set volume ratio to obtain a blue clear solution; adding sodium hydroxide to the blue clear solution to bring sodium ions therein to a second concentration; carrying out hydrothermal reaction on the solution added with the sodium hydroxide at a set hydrothermal temperature for a set duration; and collecting a product of the hydrothermal reaction to obtain the copper oxide microsphere structure.
In one embodiment, the first concentration is in a range of 0.2mol/L to 0.5mol/L; the set volume ratio of the copper salt solution to the ammonia water is 5:1-1:1; the range of the second concentration is 0.23 mol/L-0.72 mol/L; the range of the set hydrothermal temperature is 165-240 ℃; the set duration ranges from 21h to 36h.
In one embodiment, preparing a copper salt solution having a first concentration comprises: adding a corresponding amount of soluble copper salt into deionized water according to the first concentration, and stirring for dissolving to obtain a copper salt solution with the first concentration; mixing the copper salt solution and ammonia water in a set volume ratio to obtain a blue clear solution, wherein the blue clear solution comprises: slowly adding ammonia water into the copper salt solution according to a set volume ratio, and magnetically stirring to obtain a blue clear solution; and (2) carrying out hydrothermal reaction on the solution added with the sodium hydroxide at a set hydrothermal temperature for a set time length, wherein the hydrothermal reaction comprises the following steps: transferring the solution added with the sodium hydroxide into a hydrothermal kettle containing a polytetrafluoroethylene lining, setting the hydrothermal reaction temperature of the hydrothermal kettle to be a set hydrothermal temperature, and keeping the hydrothermal kettle for a set time; collecting the product of the hydrothermal reaction to obtain a copper oxide microsphere structure, wherein the method comprises the following steps: after the liquid after the hydrothermal reaction is naturally cooled to room temperature, carrying out centrifugal treatment on the liquid after the hydrothermal reaction to collect a product, wherein deionized water is used for cleaning and absolute ethyl alcohol is used for cleaning during the centrifugal treatment; and (4) drying the collected product in a drying box to obtain the copper oxide microsphere structure.
In a third aspect, a hydrogen sulfide gas sensor is provided, which comprises an electrode sheet, wherein the surface of the electrode sheet is coated with powder containing the copper oxide microsphere structure of the embodiment.
In a fourth aspect, a method for preparing a gas sensor is provided, which includes: placing powder containing the copper oxide microsphere structure in the embodiment and ethanol in a mortar, and uniformly grinding to form slurry; and uniformly coating the slurry on the surface of the electrode plate of the gas sensor, and naturally drying the surface of the electrode plate to obtain the gas sensor.
The copper oxide microsphere structure, the copper oxide preparation method, the hydrogen sulfide gas sensor and the gas sensor preparation method can greatly improve H pair 2 Selectivity and sensitivity of S.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts. In the drawings:
FIG. 1 is a scanning electron microscope image of a copper oxide microsphere structure according to an embodiment of the present invention;
FIG. 2 is a schematic flow chart illustrating a method for preparing copper oxide according to an embodiment of the present invention;
fig. 3 is a scanning electron microscope image of CuO microspheres according to an embodiment of the present invention;
fig. 4 is an X-ray diffraction pattern of CuO microspheres according to an embodiment of the present invention;
fig. 5 is a graph showing the sensitivity of a sensor made of CuO microspheres based on a hierarchical structure to different gases according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the embodiments of the present invention are further described in detail below with reference to the accompanying drawings. The exemplary embodiments and descriptions of the present invention are provided to explain the present invention, but not to limit the present invention.
FIG. 1 is a scanning electron microscope image of the structure of copper oxide microspheres according to an embodiment of the present invention. Referring to fig. 1, some embodiments of a copper oxide microsphere structure include: a plurality of stripe units 101 formed by self-assembly. The first edge of each strip-shaped unit 101 extends radially along the radial direction 102 of the same sphere to form an integral structure with a spherical outer contour 103; at least the second side directions of a part of the strip-shaped units 101 all conform to the same streamline 104; the direction of the first edge of the strip-shaped unit 101 is perpendicular to the direction of the second edge; the copper oxide nano structure is monoclinic system copper oxide.
Wherein, the first side can be a long side, and then the second side can be a wide side. The long side of the strip-shaped unit 101 is larger than the wide side thereof, and the wide side thereof is larger than the thickness thereof. In other embodiments, the first side may be a wide side, and the second side may be a long side. The outer end of the first side, i.e. the exposed end, may have a smooth rectangular end surface perpendicular to the strip-shaped surfaces formed by the long sides and the wide sides.
The size of the gap between the outer ends of two adjacent strip-shaped units 101, the second edge of which conforms to the same streamline 104, is smaller than the size of the second edge of the outer end of each of the two strip-shaped units 101. In other words, the directions of the second sides (e.g., the directions of the wide sides) of two adjacent stripe units 101 following the same streamline 104 are approximately parallel, and the size of the gap between the approximately parallel stripe surfaces is smaller, even smaller than the size of the second sides of the stripe units. In this case, the stripe units are distributed more densely. Further, the size of the gap between the outer ends of two adjacent stripe units 101 whose second side direction follows the same streamline 104 is smaller than the size of the third side (e.g. thickness) of the outer end of each of the two stripe units 101. In other embodiments, in the case that the stripe units are distributed less densely, the gap between adjacent stripe units may be larger than the width dimension of the stripe units.
The overall outer profile may have a diameter in the range 10 to 12 μm, 12 to 18 μm or 18 to 20 μm, for example around 11 μm, 15 μm or 19 μm. The first side may have a size in the range of 180nm to 1 μm, for example, about 400nm, 500nm or 700 nm. The second side may have a size in the range of 70 to 440nm, for example, around 100nm, 200nm, 300nm or 400 nm. The strip-shaped units in the copper oxide microsphere structure do not necessarily have the same size, and at least one of the long sides, the wide sides and the thickness of the strip-shaped units may be different from one another. Therefore, the overall outline may refer to a spherical outline capable of substantially enclosing the copper oxide microsphere structure, for example, the number of the bar-shaped units exposed outside the overall outline is 0.2% to 5% of the total number of the bar-shaped units.
In addition, the stripe-shaped unit may be a main component of the copper oxide microsphere structure, but inevitably may contain individual microstructure units of other shapes. Of course, in some cases, the self-assembly condition is suitable, so that the periphery of the copper oxide microsphere structure is formed by the strip-shaped units. Wherein, the periphery of the copper oxide microsphere structure can refer to the whole spherical surface of the microsphere and the parts which go deep into the center of the sphere for a certain length. In this case, the copper oxide microsphere structure has a relatively uniform profile structure.
The embodiment of the invention also provides a preparation method of copper oxide, which is used for preparing the copper oxide microsphere structure in each embodiment. As shown in fig. 2, the method for preparing copper oxide according to some embodiments may include the following steps S210 to S240.
The following will describe a specific embodiment of the method for producing copper oxide.
Step S210: a copper salt solution having a first concentration is prepared.
Specifically, a corresponding amount of a soluble copper salt may be added to deionized water according to a first concentration and dissolved with stirring to obtain a copper salt solution having a first concentration. The first concentration may be in the range of 0.2mol/L to 0.5mol/L, for example, 0.3mol/L, 0.35mol/L, 0.4mol/L, or 0.45mol/L. The soluble copper salt can be one or more of copper nitrate, copper chloride, copper acetate and the like. The amount (e.g., mass) of the soluble copper salt can be calculated according to the type of the soluble copper salt, the value of the first concentration, and the deionized water. After adding the soluble copper salt to the deionized water, stirring may be performed by hand or by magnetic stirring until all the copper salt is dissolved. In other embodiments, the soluble copper salt may be dissolved into other solutions.
Step S220: and mixing the copper salt solution and ammonia water in a set volume ratio to obtain a blue clear solution.
Specifically, ammonia water can be slowly added into the copper salt solution according to a set volume ratio, and magnetic stirring is carried out, so as to obtain a blue clear solution. Wherein the set volume ratio can refer to the volume ratio of the prepared copper salt solution and the ammonia water. The volume ratio of the copper salt solution to the aqueous ammonia may be 5:1 to 1:1, for example, about 5:2, 5:3, or 5:4. Here, the copper salt solution to be mixed with the aqueous ammonia may be obtained by taking out a part of the copper salt solution prepared in the above step S210. The two liquids can be mixed well by magnetic stirring. Ammonia water can be slowly added into the copper salt solution, and magnetic stirring can be continuously carried out, or ammonia water can be added and then magnetic stirring is carried out for a period of time. Of course, in other embodiments, the copper salt solution may be added to aqueous ammonia.
Step S230: adding sodium hydroxide to the blue clear solution to bring the sodium ions therein to a second concentration.
In particular, a mass of sodium hydroxide may be added to the blue clear solution such that the sodium ions reach a second concentration. Wherein the amount of sodium hydroxide added may be determined based on the amount of blue clear solution and the second concentration. The second concentration may range from 0.23mol/L to 0.72mol/L, for example, 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.4mol/L, 0.45mol/L, 0.5mol/L, 0.6mol/L, and the like.
Step S240: and carrying out hydrothermal reaction on the solution added with the sodium hydroxide at a set hydrothermal temperature for a set time.
Specifically, the solution after the sodium hydroxide is added can be transferred to a hydrothermal kettle containing a polytetrafluoroethylene lining, the hydrothermal reaction temperature of the hydrothermal kettle is set to be a set hydrothermal temperature, and the hydrothermal kettle is kept for a set time. The set hydrothermal temperature may be in the range of 165 to 240 ℃, for example, 180 ℃, 200 ℃, 210 ℃, 230 ℃, or the like. The set time period may range from 21h to 36h, for example, 22h, 24h, 28h, 32h, and the like.
Step S250: and collecting a product of the hydrothermal reaction to obtain the copper oxide microsphere structure.
Specifically, after the liquid after the hydrothermal reaction naturally drops to room temperature, the liquid after the hydrothermal reaction may be subjected to a centrifugal treatment to collect a product, wherein the liquid is washed with deionized water and washed with absolute ethyl alcohol during the centrifugal treatment; the collected product may then be dried in a drying oven to obtain a copper oxide microsphere structure. When the hydrothermal reaction product is collected, the residual liquid can be removed by washing with deionized water and absolute ethyl alcohol.
In addition, the embodiment of the invention also provides a hydrogen sulfide gas sensor which comprises an electrode plate, wherein the surface of the electrode plate is coated with powder containing the copper oxide microsphere structure in each embodiment. The copper oxide microsphere structure is mainly directed at a single structure, and since the copper oxide microsphere structure is in a microscopic size (such as a micron-scale or a nanometer-scale), a large number of copper oxide microsphere structures can be regarded as powder together in a macroscopic size. The powder can be coated on the electrode sheet of the existing gas sensor to be used as a gas sensitive material. The inventor of the present invention finds that the copper oxide microsphere structure of the embodiment of the present invention can provide good selectivity and sensitivity, and will be illustrated in the following.
In addition, the embodiment of the invention also provides a preparation method of the gas sensor, which comprises the following steps: s310, placing powder containing the copper oxide microsphere structure in each embodiment and ethanol in a mortar, and grinding uniformly to form slurry; and S320, uniformly coating the slurry on the surface of the electrode plate of the gas sensor, and naturally drying the surface of the electrode plate to obtain the gas sensor. The electrode plate of the gas sensor can be an electrode plate in the existing gas sensor, and the coating of the copper oxide microsphere structure mainly plays a role in gas sensitivity.
In order that those skilled in the art will better understand the present invention, embodiments of the present invention will be described below with reference to specific examples.
In one embodiment, the copper oxide microsphere structure, or more specifically referred to as CuO microsphere based hierarchical structure, may be prepared by a method comprising the following steps (1.1) to (1.5).
(1.1) dissolving soluble copper salt (such as one or more of copper nitrate, copper chloride or copper acetate) in deionized water, and stirring to dissolve to prepare 0.2-0.5 mol/L copper salt solution.
(1.2) taking a proper amount of copper salt solution, and slowly adding a certain amount of ammonia water (V) Aqueous ammonia /V Copper salt solution 1/5-1/1), and magnetically stirring to obtain a blue clear solution.
(1.3) adding a certain mass of sodium hydroxide to the blue clear solution so that Na is formed + The concentration of (A) is 0.23-0.72 mol/L, and the magnetic stirring is carried out for 15-45 min.
(1.4) transferring the obtained solution into a hydrothermal kettle containing a polytetrafluoroethylene lining, and carrying out hydrothermal reaction at the hydrothermal temperature of 165-240 ℃ for 21-36 h.
(1.5) naturally cooling to room temperature, centrifuging to collect the product, washing the product with deionized water and absolute ethyl alcohol for several times, and finally drying the product in a drying box to obtain the CuO microspheres based on the hierarchical structure.
More specifically, for example, the preparation method of the CuO microspheres based on a hierarchical structure may include the following steps (1) to (5).
(1) With Cu (NO) 3 ) 2 ·3H 2 O crystal as raw material, cu (NO) 3 ) 2 ·3H 2 Dissolving O in deionized water, stirring to obtain 0.25mol/L Cu (NO) 3 ) 2 And (3) solution.
(2) Taking a proper amount of copper nitrate solution, slowly adding a certain amount of ammonia water (V) Ammonia water /V Copper nitrate solution 2/5) magnetically stirred to give a blue clear solution.
(3) Adding sodium hydroxide into the blue clear solution to make Na + Was 0.46mol/L and was magnetically stirred for 15min.
(4) Transferring the obtained solution into a hydrothermal kettle containing a polytetrafluoroethylene lining, and carrying out hydrothermal reaction at 200 ℃ for 22 h.
(5) And naturally cooling to room temperature, centrifuging to collect the product, washing the product for several times by using deionized water and absolute ethyl alcohol, and finally drying the product in a drying box to obtain the CuO microspheres with the hierarchical structure.
Fig. 3 is a scanning electron microscope image of CuO microspheres according to an embodiment of the present invention, and as shown in fig. 3, cuO microspheres are prepared as a hierarchical structure-based CuO microspheres comprising a plurality of plate-shaped structures (stripe units), the diameter of the CuO structure ranges from about 12 to 18 μm, the length ranges from about 180nm to about 1 μm, and the width ranges from about 70 to about 440nm.
Fig. 4 is an X-ray diffraction pattern of CuO microspheres according to an embodiment of the present invention, wherein the upper half shows the X-ray diffraction pattern of CuO microspheres according to an embodiment of the present invention, wherein diffraction peaks are additionally indicated, and the lower half shows the diffraction peaks of monoclinic copper oxide in JCPDS Card No. 48-1548. As shown in FIG. 4, the diffraction peak of the prepared CuO microsphere (the morphology is shown in FIG. 3) is well matched with JCPDS Card No.48-1548, so that the finally obtained product can be determined to be monoclinic CuO.
In another specific embodiment, the hydrothermal temperature in step four may be adjusted from 200 ℃ to 180 ℃, the soaking time may be adjusted from 22h to 26h, and other steps and conditions may be implemented with reference to the above embodiment.
Of course, the hydrothermal preparation of CuO microspheres described above is only an example. The copper oxide microsphere structures prepared by other methods (such as chemical vapor deposition) and described in the above embodiments are also within the scope of the present invention. In addition, other applications of the copper oxide microsphere structure described in the above embodiments are possible, and all are within the scope of the present copper oxide microsphere structure defined in the claims.
Further, the method for preparing a gas sensor using the CuO microspheres based on the hierarchical structure may include the following steps (2.1) to (2.3).
(2.1) putting the CuO microsphere material into a mortar, adding ethanol, and grinding uniformly to form slurry.
And (2.2) uniformly coating the slurry on a ceramic electrode plate by using a small hairbrush, and naturally drying.
And (2.3) testing the gas sensing characteristics of the sensor by using a CGS-4TPs gas-sensitive analysis system, wherein the testing temperature is 30 ℃.
Specifically, for example, a gas sensor was made based on the CuO microspheres based on the hierarchical structure prepared in the above-described examples, and the method of the above-described specific example was used for H 2 And (5) carrying out related gas-sensitive performance test on the S gas. FIG. 5 is a graph showing the sensitivity of a sensor made of CuO microspheres based on a hierarchical structure to different gases according to an embodiment of the present invention, wherein bar graphs from top to bottom respectively show that the gas sensor has a C concentration of 100ppm at 210 deg.C 2 H 5 Response value (Response) of OH gas, gas sensor at 210 ℃ to CH concentration of 100ppm 3 Response value of OH gas, gas sensor to CH concentration of 100ppm at 240 ℃ 3 COCH 3 Response value of gas sensor to H concentration of 5ppb (1ppm = 1000ppb) at 30 DEG C 2 Response value of S gas, gas sensor to CH concentration of 100ppm at 240 deg.C 3 Response value of COOH gas, gas sensor at 150 ℃ to NH concentration of 100ppm 3 ·H 2 Response value of O gas. As shown in FIG. 5, the gas sensor is operated at 30 ℃ for 5ppb H 2 The response value of S is much higher than that of the gas at high temperature (210 ℃, 240 ℃, 150 ℃) to 100ppm of the rest gasThe strain value and the gas-sensitive property are excellent. Wherein, it is to be noted that, under the condition of the same gas sensitivity performance, the lower the test temperature is, the better the gas sensitivity performance is; in the case of the same gas sensitivity expression, the lower the gas concentration (1ppm = 1000ppb), the better the gas sensitivity performance. Therefore, under the test conditions shown in FIG. 5, the test temperature ratio of the CuO microspheres of the examples of the present invention was the lowest, and the H value was tested 2 The S concentration is also very low, so that the sensor made of the CuO microspheres has high sensitivity to H 2 S sensitivity is several orders of magnitude higher than that of other gases, which indicates that it is not only sensitive to H 2 S has high sensitivity to H 2 The selectivity of S gas is excellent.
In the embodiment, the CuO microsphere gas-sensitive material based on the hierarchical structure is prepared by a simple hydrothermal method, and the CuO microsphere gas-sensitive material has the advantages of low manufacturing cost, simplicity in preparation, good controllability and the like. The gas sensitive material is coated on the surface of an electrode to prepare a gas sensor, and the gas sensor has ultrahigh sensitivity to ppb level concentration hydrogen sulfide at 30 ℃, good selectivity, stability and repeatability, and wide application prospect. The CuO microsphere based on the hierarchical structure prepared by the embodiment of the invention has a unique spatial structure, a developed hierarchical channel is constructed, the specific surface area of the material is increased, and the gas sensor prepared by the CuO microsphere has super-excellent gas-sensitive performance.
In summary, the copper oxide microsphere structure, the copper oxide preparation method, the hydrogen sulfide gas sensor and the gas sensor preparation method of the embodiments of the present invention can greatly improve the H pair ratio by the unique microstructure 2 Selectivity and sensitivity of S.
In the description herein, reference to the description of the terms "one embodiment," "a particular embodiment," "some embodiments," "for example," "an example," "a particular example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. The sequence of steps involved in the various embodiments is provided to schematically illustrate the practice of the invention, and the sequence of steps is not limited and can be suitably adjusted as desired.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (6)
1. A copper oxide microsphere structure, comprising: the copper oxide microsphere structure comprises a plurality of strip-shaped units formed by self-assembly, wherein the periphery of the copper oxide microsphere structure is formed by the strip-shaped units;
the first edge of each strip-shaped unit radially extends along the radial direction of the same sphere to form an integral structure with a spherical overall outer contour; the directions of the second edges of at least part of the strip-shaped units are all compliant with the same streamline; the direction of the first edge of the strip-shaped unit is vertical to the direction of the second edge of the strip-shaped unit; the copper oxide nano structure is monoclinic system copper oxide; the size of a gap between the outer ends of two adjacent strip-shaped units, of which the second edge direction conforms to the same streamline, is smaller than the thickness of the outer ends of the two strip-shaped units; the first edge is a long edge, and the second edge is a wide edge; the long side size of the strip-shaped unit is larger than the wide side size of the strip-shaped unit, and the wide side size of the strip-shaped unit is larger than the thickness size of the strip-shaped unit; the size of a gap between the outer ends of two adjacent strip-shaped units, of which the second edge direction conforms to the same streamline, is smaller than the size of the second edge of the outer end of each of the two strip-shaped units;
the preparation method of the copper oxide microsphere structure comprises the following steps: preparing a copper salt solution having a first concentration; mixing the copper salt solution and ammonia water in a set volume ratio to obtain a blue clear solution; adding sodium hydroxide to the blue clear solution to bring sodium ions therein to a second concentration; carrying out hydrothermal reaction on the solution added with the sodium hydroxide at a set hydrothermal temperature for a set duration; collecting a product of the hydrothermal reaction to obtain a copper oxide microsphere structure; wherein, the step of collecting the product of the hydrothermal reaction to obtain the copper oxide microsphere structure specifically comprises: after the liquid after the hydrothermal reaction is naturally cooled to room temperature, carrying out centrifugal treatment on the liquid after the hydrothermal reaction to collect a product, wherein deionized water is used for cleaning and absolute ethyl alcohol is used for cleaning during the centrifugal treatment; putting the collected product in a drying box for drying to obtain a copper oxide microsphere structure;
wherein the first concentration is in a range of 0.35mol/L, 0.4mol/L, or 0.45mol/L; the set volume ratio of the copper salt solution to the ammonia water is 5: 2. 5:3 or 5:4; the second concentration ranges from 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.4mol/L, 0.45mol/L, 0.5mol/L and 0.6mol/L; the set hydrothermal temperature is 200 ℃, 210 ℃ or 230 ℃; the set time period is 22h, 28h or 32h.
2. The copper oxide microsphere structure of claim 1, wherein the overall outer contour has a diameter in the range of 12 to 18 μm, the first side has a size in the range of 180nm to 1 μm, and the second side has a size in the range of 70 to 440nm.
3. A method for preparing copper oxide, which is used for preparing the copper oxide microsphere structure according to any one of claims 1 to 2, and comprises the following steps:
preparing a copper salt solution having a first concentration;
mixing the copper salt solution and ammonia water in a set volume ratio to obtain a blue clear solution;
adding sodium hydroxide to the blue clear solution to bring sodium ions therein to a second concentration;
carrying out hydrothermal reaction on the solution added with the sodium hydroxide at a set hydrothermal temperature for a set duration;
collecting the product of the hydrothermal reaction to obtain a copper oxide microsphere structure, which comprises the following steps: after the liquid after the hydrothermal reaction is naturally cooled to room temperature, carrying out centrifugal treatment on the liquid after the hydrothermal reaction to collect a product, wherein deionized water is used for cleaning and absolute ethyl alcohol is used for cleaning during the centrifugal treatment; drying the collected product in a drying box to obtain a copper oxide microsphere structure;
wherein the first concentration is in a range of 0.35mol/L, 0.4mol/L, or 0.45mol/L; the set volume ratio of the copper salt solution to the ammonia water is 5: 2. 5:3 or 5:4; the second concentration ranges are 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.4mol/L, 0.45mol/L, 0.5mol/L and 0.6mol/L; the set hydrothermal temperature is 180 ℃, 200 ℃, 210 ℃ or 230 ℃; the set time period is 22h, 28h or 32h.
4. The method for preparing copper oxide according to claim 3,
preparing a copper salt solution having a first concentration, comprising:
adding a corresponding amount of soluble copper salt into deionized water according to the first concentration, and stirring for dissolving to obtain a copper salt solution with the first concentration;
mixing the copper salt solution and ammonia water in a set volume ratio to obtain a blue clear solution, wherein the blue clear solution comprises:
slowly adding ammonia water into the copper salt solution according to a set volume ratio, and magnetically stirring to obtain a blue clear solution;
and (2) carrying out hydrothermal reaction on the solution added with the sodium hydroxide at a set hydrothermal temperature for a set time length, wherein the hydrothermal reaction comprises the following steps:
and transferring the solution added with the sodium hydroxide into a hydrothermal kettle containing a polytetrafluoroethylene lining, setting the hydrothermal reaction temperature of the hydrothermal kettle to be a set hydrothermal temperature, and keeping the hydrothermal kettle for a set time.
5. H 2 An S gas sensor comprising an electrode sheet, wherein the surface of the electrode sheet is coated with a powder comprising the copper oxide microsphere structure according to any one of claims 1 to 2.
6. A method for preparing a gas sensor is characterized by comprising the following steps:
placing powder containing the copper oxide microsphere structure according to any one of claims 1 to 2 and ethanol in a mortar, and grinding the mixture uniformly to form slurry;
and uniformly coating the slurry on the surface of the electrode plate of the gas sensor, and naturally drying the surface of the electrode plate to obtain the gas sensor.
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| CN101279758A (en) * | 2008-05-16 | 2008-10-08 | 西北师范大学 | Preparation of nano-cupric oxide powder |
| CN102491404A (en) * | 2011-12-19 | 2012-06-13 | 天津理工大学 | Copper oxide micro-nano composite structural material and preparation method thereof |
| CN102502770A (en) * | 2011-10-21 | 2012-06-20 | 中国科学院过程工程研究所 | Flower-like copper oxide catalyst and preparation method and application thereof |
| CN103303963A (en) * | 2013-06-14 | 2013-09-18 | 同济大学 | Preparation method of copper oxide material with high sensitivity response property to hydrogen sulfide |
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| CN101279758A (en) * | 2008-05-16 | 2008-10-08 | 西北师范大学 | Preparation of nano-cupric oxide powder |
| CN102502770A (en) * | 2011-10-21 | 2012-06-20 | 中国科学院过程工程研究所 | Flower-like copper oxide catalyst and preparation method and application thereof |
| CN102491404A (en) * | 2011-12-19 | 2012-06-13 | 天津理工大学 | Copper oxide micro-nano composite structural material and preparation method thereof |
| CN103303963A (en) * | 2013-06-14 | 2013-09-18 | 同济大学 | Preparation method of copper oxide material with high sensitivity response property to hydrogen sulfide |
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