CN110510657A - Copper oxide micro-sphere structure, these hydrogen sulfide gas sensor and preparation method thereof - Google Patents
Copper oxide micro-sphere structure, these hydrogen sulfide gas sensor and preparation method thereof Download PDFInfo
- Publication number
- CN110510657A CN110510657A CN201910858424.4A CN201910858424A CN110510657A CN 110510657 A CN110510657 A CN 110510657A CN 201910858424 A CN201910858424 A CN 201910858424A CN 110510657 A CN110510657 A CN 110510657A
- Authority
- CN
- China
- Prior art keywords
- copper oxide
- copper
- sphere structure
- oxide micro
- sphere
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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 present invention provides a kind of copper oxide micro-sphere structures, H2S gas sensor and preparation method thereof, wherein the copper oxide micro-sphere structure, comprising: the multiple bar elements being self-assembly of；Wherein, the first side of each bar element extends along the radial radiation of same sphere, and forming overall outer profile is spherical integral structure；Second edge direction of at least partly bar element of quantity complies with same streamline；The first of the bar element while direction perpendicular to its second while direction；The cupric oxide nano structure is that monoclinic system aoxidizes copper material.It is can be improved through the above scheme to H2The selectivity and sensitivity of S.
Description
Technical field
The present invention relates to field of material technology more particularly to a kind of copper oxide micro-sphere structure, these hydrogen sulfide gas sensor and
Preparation method.
Background technique
H2S is widely present in industry manufacture and rural activity, is a kind of inflammable to have severe toxicity and corrosive colourless gas
, there are rotten egg smell, the H of high concentration in body, when low concentration2S, which can benumb olfactory nerves and instead result in people, can't smell smell.Therefore, if
A kind of low manufacture cost is counted, is produced conveniently, high sensitivity, the good H of selectivity2Sensor is very important.
Summary of the invention
The present invention provides a kind of copper oxide micro-sphere structures, these hydrogen sulfide gas sensor and preparation method thereof, with raising pair
H2The selectivity and sensitivity of S.
In order to achieve the above object, the present invention is realized using following scheme:
In a first aspect, providing a kind of copper oxide micro-sphere structure, comprising: the multiple bar elements being self-assembly of；Wherein,
First side of each bar element extends along the radial radiation of same sphere, and forming overall outer profile is spherical one knot
Structure；Second edge direction of at least partly bar element of quantity complies with same streamline；First side of the bar element
Direction perpendicular to its second side direction；The cupric oxide nano structure is that monoclinic system aoxidizes copper material.
In one embodiment, first side is long side, and second side is broadside；The long edge size of the bar element
Greater than its broadside size, broadside size is greater than its thickness.
In one embodiment, the second edge direction complies with the gap between the outer end of the two neighboring bar element of same streamline
Size is less than the size on the second side of the respective outer end of described two bar elements.
In one embodiment, the diameter range of the totality outer profile is 12~18 μm, the size range on first side
For 180nm~1 μm, the size range on second side is 70~440nm.
In one embodiment, the periphery of the copper oxide micro-sphere structure is made of the bar element.
Second aspect provides a kind of copper oxide preparation method, is used to prepare copper oxide microballoon described in above-described embodiment
Structure, which comprises prepare the copper salt solution with the first concentration；The copper salt solution and ammonium hydroxide of volume ratio will be set
It is mixed, obtains blue clear solution；Add sodium hydroxide into the blue clear solution, make wherein sodium ion reach the
Two concentration；Solution after making addition sodium hydroxide carries out hydro-thermal reaction in setting hydrothermal temperature and continues to set duration；Collect water
The product of thermal response obtains copper oxide micro-sphere structure.
In one embodiment, the range of first concentration is 0.2mol/L~0.5mol/L；Copper salt solution and ammonium hydroxide
Volume ratio is set as 5:1~1:1；The range of second concentration is 0.23mol/L~0.72mol/L；The setting hydro-thermal temperature
The range of degree is 165 DEG C~240 DEG C；The range for setting duration is 21h~36h.
In one embodiment, the copper salt solution with the first concentration is prepared, comprising: according to the first concentration into deionized water
The soluble copper salt of corresponding amount, and stirring and dissolving are added, the copper salt solution with the first concentration is obtained；The institute of volume ratio will be set
It states copper salt solution and ammonium hydroxide is mixed, obtain blue clear solution, comprising: slowly add in copper salt solution by setting volume ratio
Add ammonium hydroxide, and magnetic agitation, obtains blue clear solution；Solution after making addition sodium hydroxide carries out water in setting hydrothermal temperature
Thermal response simultaneously continues to set duration, comprising: the solution after addition sodium hydroxide is transferred to the hydro-thermal containing polytetrafluoroethyllining lining
In kettle, the hydrothermal temperature of the water heating kettle is set for setting hydrothermal temperature, and keep setting duration；Collect hydro-thermal reaction
Product obtains copper oxide micro-sphere structure, comprising: the liquid after hydro-thermal reaction is cooled to room temperature naturally, after hydro-thermal reaction
Liquid carries out centrifugal treating to collect product, wherein cleans and utilize dehydrated alcohol using deionized water during centrifugal treating
Cleaning；The product of collection is placed in drying box and is dried, copper oxide micro-sphere structure is obtained.
The third aspect provides a kind of these hydrogen sulfide gas sensor, includes electrode slice, the surface of the electrode slice is coated with
Powder comprising copper oxide micro-sphere structure described in above-described embodiment.
Fourth aspect provides a kind of gas sensor preparation method, comprising: will include copper oxide described in above-described embodiment
The powder and ethyl alcohol of micro-sphere structure are placed in mortar, and grinding is formed uniformly slurries；The slurries are coated uniformly on gas to pass
Sensor electrode slice surface spontaneously dries to electrode slice surface, obtains gas sensor.
Copper oxide micro-sphere structure, copper oxide preparation method, these hydrogen sulfide gas sensor and gas sensor system of the invention
Preparation Method can be greatlyd improve to H2The selectivity and sensitivity of S.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.In the accompanying drawings:
Fig. 1 is the scanning electron microscope image of the copper oxide micro-sphere structure of one embodiment of the invention；
Fig. 2 is the flow diagram of the copper oxide preparation method of one embodiment of the invention；
Fig. 3 is the scanning electron microscope image of the CuO microballoon of one embodiment of the invention；
Fig. 4 is the X-ray diffraction spectrogram of the CuO microballoon of one embodiment of the invention；
Fig. 5 is spirit of the sensor to gas with various made of the CuO microballoon based on hierarchical structure of one embodiment of the invention
Sensitivity figure.
Specific embodiment
Understand in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, with reference to the accompanying drawing to this hair
Bright embodiment is described in further details.Here, the illustrative embodiments of the present invention and their descriptions are used to explain the present invention, but simultaneously
It is not as a limitation of the invention.
Fig. 1 is the scanning electron microscope image of the copper oxide micro-sphere structure of one embodiment of the invention.It is some referring to Fig. 1
The copper oxide micro-sphere structure of embodiment, comprising: the multiple bar elements 101 being self-assembly of.Wherein, each bar element
101 the first side extends along radial 102 radiation of same sphere, forms the integral structure that overall outer profile is spherical shape 103；Extremely
Second edge direction of the bar element 101 of small part quantity complies with same streamline 104；The of the bar element 101
Direction of the direction on one side perpendicular to its second side；The cupric oxide nano structure is that monoclinic system aoxidizes copper material.
Wherein, the first Bian Kewei long side, then the second Bian Kewei broadside.The long side ruler of the bar element 101
Very little to be greater than its broadside size, broadside size is greater than its thickness.In other embodiments, first side may be width
Side, then second side may be long side.The outer end on first side, that is, the one end exposed, end face can be smooth rectangle,
The strip face formed perpendicular to long side and broadside.
The gap size that second edge direction is complied between the outer end of the two neighboring bar element 101 of same streamline 104 is small
Size in the second side of the respective outer end of described two bar elements 101.In other words, the adjacent of same streamline 104 is complied with
The second edge direction (such as broadside) less parallel of two bar elements 101, the clearance ruler between approximately parallel bar shaped face
It is very little smaller, the even less than size on the second side of the bar element.In the case, bar element distribution is more intensive.
Further, the gap size that the second edge direction is complied between the outer end of the two neighboring bar element 101 of same streamline 104 is small
Size in the third side (such as thickness) of the respective outer end of described two bar elements 101.In other embodiments, in bar element
In the case that distribution is less intensive, the gap between adjacent bar element is likely larger than the broadside size of bar element.
The diameter range of the totality outer profile can be 10~12 μm, 12~18 μm or 18~20 μm, for example, being 11 μ
M, 15 μm or 19 μm or so.The size range on first side can be 180nm~1 μm, for example, for 400nm, 500nm or
700nm or so.The size range on second side can be 70~440nm, for example, being 100nm, 200nm, 300nm or 400nm
Left and right.Wherein, the bar element in copper oxide micro-sphere structure not necessarily all has identical size, and long side, broadside, thickness can
It can at least one be different.So above-mentioned totality outer profile can refer to can include copper oxide micro-sphere structure substantially
Spheric profile, for example, the quantity for exposing the bar element outside the totality outer profile accounts for the 0.2%~5% of bar element total quantity.
In addition, bar element can be the chief component of copper oxide micro-sphere structure, but inevitably may include
The microstructure unit of individual other shapes.Certainly, under some cases, the condition of self assembly is more suitable for that can make the oxygen
The periphery for changing copper micro-sphere structure is made of the bar element.Wherein, the periphery of copper oxide micro-sphere structure can refer to microballoon
Entire spherical surface and these parts for going deep into certain length to the centre of sphere.In the case, copper oxide micro-sphere structure has more uniformly
Contour structures.
The embodiment of the invention also provides a kind of copper oxide preparation methods, are used to prepare oxidation described in the various embodiments described above
Copper micro-sphere structure.As shown in Fig. 2, the copper oxide preparation method of some embodiments, it may include following steps S210 to step S240.
The specific embodiment of copper oxide preparation method will be illustrated below.
Step S210: the copper salt solution with the first concentration is prepared.
Specifically, the soluble copper salt of corresponding amount, and stirring and dissolving can be added into deionized water according to the first concentration,
Obtain the copper salt solution with the first concentration.Wherein, which may range from 0.2mol/L~0.5mol/L, example
It such as, is 0.3mol/L, 0.35mol/L, 0.4mol/L or 0.45mol/L.Soluble copper salt can be copper nitrate, copper chloride, second
One or more of sour copper etc..The amount (such as quality) of soluble copper salt can according to the type of soluble copper salt, this first
The value and deionized water of concentration are calculated.After soluble copper salt is added in deionized water, can by hand operated mixing, or
Magnetic agitation can be carried out, stirring to all mantoquitas is dissolved.In other embodiments, soluble copper salt can be dissolved to other
In solution.
Step S220: the copper salt solution for setting volume ratio and ammonium hydroxide are mixed, blue clear solution is obtained.
Specifically, it can be slowly added ammonium hydroxide, and magnetic agitation in copper salt solution by setting volume ratio, it is clear obtains blue
Clear solution.Wherein the setting volume ratio can refer to the volume ratio of the copper salt solution and ammonium hydroxide that prepare.Copper salt solution and ammonium hydroxide
Volume ratio may range from 5:1~1:1, for example, for 5:2,5:3 or 5:4 or so.Wherein, it will mix with ammonium hydroxide
Copper salt solution, which can be, to be taken out a part by the copper salt solution prepared from above-mentioned steps S210 and obtains.It can be with by magnetic agitation
So that two kinds of liquid are sufficiently mixed.Can be and ammonium hydroxide is slowly added in copper salt solution, at the same can continuous magnetic agitation, or
Magnetic agitation can be added after ammonium hydroxide again for a period of time.Certainly, in other embodiments, copper salt solution can be added to ammonium hydroxide
In.
Step S230: adding sodium hydroxide into the blue clear solution, make wherein sodium ion reach the second concentration.
Specifically, the sodium hydroxide of certain mass can be added into blue clear solution, so that sodium ion reaches second
Concentration.Wherein, the amount of added sodium hydroxide can be determined according to the amount of blue clear solution and second concentration.This second
Concentration may range from 0.23mol/L~0.72mol/L, for example, for 0.25mol/L, 0.3mol/L, 0.35mol/L,
0.4mol/L, 0.45mol/L, 0.5mol/L, 0.6mol/L etc..
Step S240: the solution after making addition sodium hydroxide is when setting hydrothermal temperature progress hydro-thermal reaction and continuing setting
It is long.
Specifically, the solution after addition sodium hydroxide can be transferred in the water heating kettle containing polytetrafluoroethyllining lining, if
The hydrothermal temperature of the water heating kettle is set as setting hydrothermal temperature, and keeps setting duration.Wherein, the setting hydrothermal temperature
It may range from 165 DEG C~240 DEG C, for example, being 180 DEG C, 200 DEG C, 210 DEG C, 230 DEG C etc..The range of the setting duration can be with
For 21h~36h, for example, 22h, for 24 hours, 28h, 32h etc..
Step S250: collecting the product of hydro-thermal reaction, obtains copper oxide micro-sphere structure.
Specifically, can be cooled to room temperature naturally in the liquid after hydro-thermal reaction, to the liquid after hydro-thermal reaction carry out from
Heart processing is to collect product, wherein cleans and utilize washes of absolute alcohol using deionized water during centrifugal treating；Then,
The product of collection can be placed in drying box and be dried, obtain copper oxide micro-sphere structure.When collecting hydro-thermal reaction product,
It is cleaned using deionized water cleaning and dehydrated alcohol, residual liquid can be removed.
In addition, include electrode slice the embodiment of the invention also provides a kind of these hydrogen sulfide gas sensor, the electrode slice
Surface is coated with the powder comprising copper oxide micro-sphere structure described in the various embodiments described above.Wherein, above-mentioned copper oxide micro-sphere structure
For a single structure, and since the copper oxide micro-sphere structure is microscopic dimensions (such as micron order or nanometer
Grade), thus a large amount of copper oxide micro-sphere structure can be considered as from the point of view of macro-size together it is powdered.And this powder can be with
Gas sensing property materials'use is used as on electrode slice coated in existing gas sensor.This programme inventor has found the embodiment of the present invention
Copper oxide micro-sphere structure can bring good selectivity and sensitivity, it is subsequent to illustrate.
In addition, the embodiment of the invention also provides a kind of gas sensor preparation method, comprising steps of S310, will include
The powder of copper oxide micro-sphere structure and ethyl alcohol described in the various embodiments described above are placed in mortar, and grinding is formed uniformly slurries；S320,
The slurries are coated uniformly on gas sensors electrode piece surface, is spontaneously dried to electrode slice surface, obtains gas sensor.
Wherein, gas sensors electrode piece can be the electrode slice in existing gas sensor, the coating master of copper oxide micro-sphere structure
If playing the role of gas sensing property.
To make those skilled in the art be best understood from the present invention, it will illustrate implementation of the invention with specific embodiment below
Mode.
In one specific embodiment, copper oxide micro-sphere structure, or it can be particularly referred to as the CuO microballoon based on hierarchical structure,
Preparation method may include following steps (1.1)~step (1.5).
(1.1) soluble copper salt (such as one or more of copper nitrate, copper chloride or copper acetate) is dissolved in deionized water
In, the copper salt solution of 0.2mol/L~0.5mol/L is made in stirring and dissolving.
(1.2) suitable copper salt solution is taken, a certain amount of ammonium hydroxide (V is slowly added intoAmmonium hydroxide/VCopper salt solutionIt is 1/5~1/1), magnetic
Power stirs to get blue clear solution.
(1.3) sodium hydroxide of certain mass is added into blue clear solution, so that Na+Concentration be 0.23mol/L
~0.72mol/L, and magnetic agitation 15min~45min.
(1.4) acquired solution is transferred in the water heating kettle containing polytetrafluoroethyllining lining, in 165 DEG C~240 DEG C hydro-thermal temperature
The lower heat preservation 21h~36h of degree carries out hydro-thermal reaction.
(1.5) it is cooled to room temperature naturally, product is collected by centrifugation, during which several times with deionized water and washes of absolute alcohol, most
It is dry in drying box afterwards, obtain the CuO microballoon based on hierarchical structure.
More specifically, for example, the preparation method of the CuO microballoon based on hierarchical structure may include following steps (1)~step
(5)。
(1) with Cu (NO3)2·3H2O crystal is raw material, by Cu (NO3)2·3H2O is dissolved in deionized water, stirring and dissolving system
At the Cu (NO of 0.25mol/L3)2Solution.
(2) suitable copper nitrate solution is taken, a certain amount of ammonium hydroxide (V is slowly added intoAmmonium hydroxide/VCopper nitrate solutionFor 2/5), magnetic force stirs
It mixes to obtain blue clear solution.
(3) sodium hydroxide of certain mass is added into blue clear solution, so that Na+Concentration be 0.46mol/L, and
Magnetic agitation 15min.
(4) acquired solution is transferred in the water heating kettle containing polytetrafluoroethyllining lining, is kept the temperature under 200 DEG C of hydrothermal temperatures
22h carries out hydro-thermal reaction.
(5) it is cooled to room temperature naturally, product is collected by centrifugation, during which several times with deionized water and washes of absolute alcohol, finally
It is dry in drying box, obtain the CuO microballoon of hierarchical structure.
Fig. 3 is the scanning electron microscope image of the CuO microballoon of one embodiment of the invention, as shown in figure 3, it is micro- that CuO is made
Ball is that the CuO microballoon based on hierarchical structure includes a large amount of plate structures (strip element), and the diameter range of the CuO structure is about 12
~18 μm, long range is about 180nm~1 μm, and wide range is about 70~440nm.
Fig. 4 is the X-ray diffraction spectrogram of the CuO microballoon of one embodiment of the invention, wherein top half shows the present invention
The X-ray diffraction spectrum of the CuO microballoon of embodiment, wherein with diffraction maximum has separately been marked, lower half portion shows JCPDS Card
The diffraction maximum of monoclinic system copper oxide in No.48-1548.As shown in figure 4, CuO microballoon (the pattern such as Fig. 3 institute being prepared
Show) diffraction maximum matched well with JCPDS Card No.48-1548, it is possible to determine final products therefrom be monoclinic system
CuO.
In another specific embodiment, above-mentioned steps (4) in hydrothermal temperature can be adjusted to 180 DEG C by 200 DEG C, soaking time
26h can be adjusted to by 22h, other steps and condition can refer to above-described embodiment implementation.
Certainly, above-mentioned hydro-thermal method preparation CuO microballoon is a kind of example.It utilizes other methods (such as chemical vapour deposition technique)
Copper oxide micro-sphere structure described in the various embodiments described above being prepared is also within the scope of the present invention.In addition, above-mentioned each
Copper oxide micro-sphere structure described in embodiment is also likely to be present other purposes, the claim in this copper oxide micro-sphere structure
In limited range.
It further, may include following steps using the method that the CuO microballoon based on hierarchical structure prepares gas sensor
(2.1)~step (2.3).
(2.1) CuO micro-sphere material is put into addition ethyl alcohol grinding in mortar and is formed uniformly slurries.
(2.2) slurries are coated uniformly on ceramic electrode on piece with small brushes, spontaneously dried.
(2.3) using the gas sensing characteristic of CGS-4TPs air-sensitive analysis system test sensor, test temperature is 30 DEG C.
Specifically, for example, based on gas sensing is made with the CuO microballoon made from above-described embodiment based on hierarchical structure
Device, and using the method for above-mentioned specific embodiment to H2S gas carries out relevant air-sensitive performance test.Fig. 5 is that the present invention one is real
Sensor made of the CuO microballoon based on hierarchical structure of example is applied to the sensitivity map of gas with various, wherein item from top to bottom
Shape figure respectively illustrates, the C that gas sensor is 100ppm to concentration at 210 DEG C2H5The response of OH gas
(Response), the CH that gas sensor is 100ppm to concentration at 210 DEG C3The response of OH gas, gas sensor exist
The CH for being 100ppm to concentration at 240 DEG C3COCH3The response of gas, gas sensor are 5ppb to concentration at 30 DEG C
The H of (1ppm=1000ppb)2The response of S gas, the CH that gas sensor is 100ppm to concentration at 240 DEG C3COOH gas
The response of body, the NH that gas sensor is 100ppm to concentration at 150 DEG C3·H2The response of O gas.As shown in figure 5,
The gas sensor is at 30 DEG C to 5ppb H2It is right under high temperature (210 DEG C, 240 DEG C, 150 DEG C) that the response of S is significantly larger than
The response of 100ppm remaining gas, air-sensitive performance are excellent.Wherein, it should be noted that in the case where same air-sensitive sex expression,
Test temperature is lower, illustrates that air-sensitive performance is better；In the case where same air-sensitive sex expression, the lower (1ppm=of gas concentration
1000ppb), illustrate that air-sensitive performance is better.So test condition shown in fig. 5, the test of the CuO microballoon of the embodiment of the present invention
Temperature is than minimum, and the H tested2S concentration is also very low, so, the sensor made of the CuO microballoon, to H2The susceptibility of S
The susceptibility for comparing other gases is higher by several magnitudes, this explanation is not only to H2The susceptibility of S is high, moreover, to H2S gas
Selectivity is fabulous.
In the present embodiment, it is prepared for the CuO microballoon gas sensitive based on hierarchical structure with simple hydro-thermal method, there is production
It is at low cost, the advantages that preparation is simple, and controllability is good.The gas sensitive is coated to electrode surface, a kind of gas sensor is made,
The sensitivity of superelevation, good selectivity, stability and repeatability, tool are shown to the hydrogen sulfide of ppb grades of concentration at 30 DEG C
Have broad application prospects.CuO microballoon based on hierarchical structure made from the embodiment of the present invention has unique space structure, structure
Flourishing classification channel has been built, the specific surface area of material is increased, there is super excellent gas sensing property with the gas sensor of its preparation
Energy.
In conclusion the copper oxide micro-sphere structure of the embodiment of the present invention, copper oxide preparation method, these hydrogen sulfide gas sensor
And gas sensor preparation method, it can be greatlyd improve by unique micro-structure to H2The selectivity and sensitivity of S.
In the description of this specification, reference term " one embodiment ", " specific embodiment ", " some implementations
Example ", " such as ", the description of " example ", " specific example " or " some examples " etc. mean it is described in conjunction with this embodiment or example
Particular features, structures, materials, or characteristics are included at least one embodiment or example of the invention.In the present specification,
Schematic expression of the above terms may not refer to the same embodiment or example.Moreover, the specific features of description, knot
Structure, material or feature can be combined in any suitable manner in any one or more of the embodiments or examples.Each embodiment
Involved in the step of sequence be used to schematically illustrate implementation of the invention, sequence of steps therein is not construed as limiting, can be as needed
It appropriately adjusts.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
Describe in detail it is bright, it should be understood that the above is only a specific embodiment of the present invention, the guarantor being not intended to limit the present invention
Range is protected, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should be included in this
Within the protection scope of invention.
Claims (10)
1. a kind of copper oxide micro-sphere structure characterized by comprising the multiple bar elements being self-assembly of；
Wherein, the first side of each bar element extends along the radial radiation of same sphere, and forming overall outer profile is ball
The integral structure of shape；Second edge direction of at least partly bar element of quantity complies with same streamline；The strip list
Member first while direction perpendicular to its second while direction；The cupric oxide nano structure is that monoclinic system aoxidizes copper material.
2. copper oxide micro-sphere structure as described in claim 1, which is characterized in that first side is long side, second side
For broadside；The long edge size of the bar element is greater than its broadside size, and broadside size is greater than its thickness.
3. copper oxide micro-sphere structure as described in claim 1, which is characterized in that the second edge direction complies with the adjacent of same streamline
Gap size between the outer end of two bar elements is less than the size on the second side of the respective outer end of described two bar elements.
4. copper oxide micro-sphere structure as described in claim 1, which is characterized in that the diameter range of the totality outer profile is 12
~18 μm, the size range on first side is 180nm~1 μm, and the size range on second side is 70~440nm.
5. such as the described in any item copper oxide micro-sphere structures of Claims 1-4, which is characterized in that the copper oxide micro-sphere structure
Periphery be made of the bar element.
6. a kind of copper oxide preparation method, which is characterized in that be used to prepare such as copper oxide described in any one of claim 1 to 5
Micro-sphere structure, which comprises
Prepare the copper salt solution with the first concentration；
The copper salt solution for setting volume ratio and ammonium hydroxide are mixed, blue clear solution is obtained；
Add sodium hydroxide into the blue clear solution, make wherein sodium ion reach the second concentration；
Solution after making addition sodium hydroxide carries out hydro-thermal reaction in setting hydrothermal temperature and continues to set duration；
The product for collecting hydro-thermal reaction, obtains copper oxide micro-sphere structure.
7. copper oxide preparation method as claimed in claim 6, which is characterized in that
The range of first concentration is 0.2mol/L~0.5mol/L；
Copper salt solution and ammonium hydroxide set volume ratio as 5:1~1:1；
The range of second concentration is 0.23mol/L~0.72mol/L；
The range for setting hydrothermal temperature is 165 DEG C~240 DEG C；
The range for setting duration is 21h~36h.
8. copper oxide preparation method as claimed in claims 6 or 7, which is characterized in that
Prepare the copper salt solution with the first concentration, comprising:
The soluble copper salt of corresponding amount, and stirring and dissolving are added into deionized water according to the first concentration, is obtained dense with first
The copper salt solution of degree；
The copper salt solution for setting volume ratio and ammonium hydroxide are mixed, blue clear solution is obtained, comprising:
It is slowly added ammonium hydroxide, and magnetic agitation in copper salt solution by setting volume ratio, obtains blue clear solution；
Solution after making addition sodium hydroxide carries out hydro-thermal reaction in setting hydrothermal temperature and continues to set duration, comprising:
Solution after addition sodium hydroxide is transferred in the water heating kettle containing polytetrafluoroethyllining lining, the water of the water heating kettle is set
Thermal response temperature is setting hydrothermal temperature, and keeps setting duration；
The product for collecting hydro-thermal reaction, obtains copper oxide micro-sphere structure, comprising:
Liquid after hydro-thermal reaction is cooled to room temperature naturally, is carried out centrifugal treating to the liquid after hydro-thermal reaction and is produced with collecting
Object, wherein clean and utilize washes of absolute alcohol using deionized water during centrifugal treating；
The product of collection is placed in drying box and is dried, copper oxide micro-sphere structure is obtained.
9. a kind of H2S gas sensor includes electrode slice, which is characterized in that the surface of the electrode slice, which is coated with, includes such as right
It is required that the powder of any one of 1 to the 5 copper oxide micro-sphere structure.
10. a kind of gas sensor preparation method characterized by comprising
It will be placed in mortar, grind comprising the powder of copper oxide micro-sphere structure and ethyl alcohol as described in any one of claim 1 to 5
It is formed uniformly slurries；
The slurries are coated uniformly on gas sensors electrode piece surface, are spontaneously dried to electrode slice surface, gas biography is obtained
Sensor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910858424.4A CN110510657B (en) | 2019-09-11 | 2019-09-11 | Copper oxide microsphere structure, hydrogen sulfide gas sensor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910858424.4A CN110510657B (en) | 2019-09-11 | 2019-09-11 | Copper oxide microsphere structure, hydrogen sulfide gas sensor and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110510657A true CN110510657A (en) | 2019-11-29 |
| CN110510657B CN110510657B (en) | 2022-12-23 |
Family
ID=68631984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910858424.4A Active CN110510657B (en) | 2019-09-11 | 2019-09-11 | Copper oxide microsphere structure, hydrogen sulfide gas sensor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110510657B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111517358A (en) * | 2020-06-16 | 2020-08-11 | 盐城工学院 | Synthetic method and application of flower-shaped copper oxide nanospheres |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20140286846A1 (en) * | 2012-09-25 | 2014-09-25 | University Of Connecticut | Mesoporous metal oxides and processes for preparation thereof |
| US20160368047A1 (en) * | 2015-06-16 | 2016-12-22 | Lawrence Livermore National Security, Llc | Porous materials via freeze-casting of metal salt solutions |
-
2019
- 2019-09-11 CN CN201910858424.4A patent/CN110510657B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20140286846A1 (en) * | 2012-09-25 | 2014-09-25 | University Of Connecticut | Mesoporous metal oxides and processes for preparation 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 |
| US20160368047A1 (en) * | 2015-06-16 | 2016-12-22 | Lawrence Livermore National Security, Llc | Porous materials via freeze-casting of metal salt solutions |
Non-Patent Citations (1)
| Title |
|---|
| LI,ZHI JIE ET AL.: ""Hydrothermal synthesis of hierarchically flower-like CuO nanostructures with porous nanosheets for excellent H2S sensing"", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111517358A (en) * | 2020-06-16 | 2020-08-11 | 盐城工学院 | Synthetic method and application of flower-shaped copper oxide nanospheres |
| CN111517358B (en) * | 2020-06-16 | 2021-11-02 | 盐城工学院 | Synthetic method and application of flower-shaped copper oxide nanospheres |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110510657B (en) | 2022-12-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Danielsen et al. | Effects of physicochemical properties of TiO2 nanomaterials for pulmonary inflammation, acute phase response and alveolar proteinosis in intratracheally exposed mice | |
| Liu et al. | Bioavailability of nickel in single‐wall carbon nanotubes | |
| Chauhan et al. | Methodological advancements in green nanotechnology and their applications in biological synthesis of herbal nanoparticles | |
| Sanpo et al. | Influence of chelating agents on the microstructure and antibacterial property of cobalt ferrite nanopowders | |
| Yang et al. | Fabrication of Cu 2 O/Ag composite nanoframes as surface-enhanced Raman scattering substrates in a successive one-pot procedure | |
| Karuppaiah et al. | Hierarchical construction and characterization of lanthanum molybdate nanospheres as an unassailable electrode material for electrocatalytic sensing of the antibiotic drug nitrofurantoin | |
| CN106115805A (en) | The preparation method of nanometer hierarchy cobalt acid nickel/mos2 microsphere | |
| CN102253027A (en) | Surface-enhanced Raman scattering active substrate based on star-shaped gold nanoparticles and preparation method thereof | |
| CN107405614A (en) | Exhaust gas purification catalyst, its manufacture method and the method using its purification waste gas | |
| Mohammed et al. | Green-synthesis of Platinum Nanoparticles using Olive Leaves Extracts and its Effect on Aspartate Aminotransferase Activity | |
| CN107572579B (en) | A kind of spherical zinc oxide gas sensing material and preparation method thereof of bismuth doping | |
| Hofmann et al. | Comparative short-term inhalation toxicity of five organic diketopyrrolopyrrole pigments and two inorganic iron-oxide-based pigments | |
| CN110510657A (en) | Copper oxide micro-sphere structure, these hydrogen sulfide gas sensor and preparation method thereof | |
| CN108546118A (en) | A kind of yttria-stabilized zirconia powder and preparation method thereof and ceramics | |
| Bergamonti et al. | Photocatalytic self-cleaning TiO 2 coatings on carbonatic stones | |
| Balamurugan et al. | Co-precipitation synthesis and characterization of rare-earth pyrochlore Gadolinium stannate; A novel electrocatalyst for the determination of furazolidone in water samples | |
| CN102259935A (en) | Auxiliary hydro-thermal method for preparing bird-nest-shaped Co3O4 surfactant | |
| CN103553119A (en) | Preparation method of aluminum-doped tin dioxide flower-like micro-sphere/nano-rod gas sensitive material | |
| CN104388084B (en) | Nano titanium oxide fluorescent powder and preparation method thereof | |
| JP2000264639A (en) | Strontium iron oxide particle powder and its production | |
| CN109592713B (en) | Tungsten trioxide hollow nanosphere semiconductor material and preparation method thereof, gas sensor and preparation method and application thereof | |
| Chen et al. | ZnGa2O4 Nanorod Arrays Decorated with Ag Nanoparticles as Surface‐Enhanced Raman‐Scattering Substrates for Melamine Detection | |
| Zhang et al. | Electrical characterization of tumor-derived exosomes by conductive atomic force microscopy | |
| Huang et al. | A rapid and dual-mode visualization of latent and bloody fingermarks using Cr-and Sb-codoped titanium dioxide nanoparticles | |
| Slipenyuk et al. | ESR investigation of yttria stabilized zirconia powders with nanosize particles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |