CN105731523B - Preparation method of zinc oxide/zinc sulfide heterojunction nonstandard explosive sensing material - Google Patents
Preparation method of zinc oxide/zinc sulfide heterojunction nonstandard explosive sensing material Download PDFInfo
- Publication number
- CN105731523B CN105731523B CN201610049048.0A CN201610049048A CN105731523B CN 105731523 B CN105731523 B CN 105731523B CN 201610049048 A CN201610049048 A CN 201610049048A CN 105731523 B CN105731523 B CN 105731523B
- Authority
- CN
- China
- Prior art keywords
- zinc oxide
- sensing material
- mouth bottle
- explosive
- junctions
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/08—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- 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
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- 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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a preparation method of a zinc oxide/zinc sulfide heterojunction nonstandard explosive sensing material. The method comprises the following steps: preparing zinc oxide nanosheets by a sol-gel process, and carrying out hydrothermal vulcanization reaction to obtain the zinc oxide/zinc sulfide heterojunction sensing material. The formation of the zinc oxide/zinc sulfide heterojunction can regulate the energy band structure of the sensing material and regulate the surface defects of the material, thereby improving the gas sensitivity of the material. The zinc oxide/zinc sulfide heterojunction sensing material can implement sensitive and quick detection on standard raw materials ammonium nitrate and urea and various nonstandard explosives potassium permanganate, potassium chlorate, sulfur and black powder atmospheres within the room temperature range of 20-30 DEG C.
Description
Technical field
The present invention relates to functional material scientific domain and gas sensing materials field, more particularly to a kind of efficient detection is non-
The preparation method of the zinc oxide/sulfide hetero-junctions sensing material of standard explosive atmosphere.
Background technology
Explosive is divided into two classes:Standard explosive and non-standard explosive.Standard explosive:Such as with trinitrotoluene
(TNT), dinitrotoluene (DNT) (DNT), para-nitrotoluene (PNT), picric acid (PA), hexogen (RDX) etc. for representative nitro class
Explosive, can be using accomplished in many ways early warning and detections such as fluorescence, surface-enhanced Raman, Photoelectric Detections.But, with state
Family is gradually improved for the management and control system of standard explosive, and the acquisition channel of standard explosive is limited, and some lawless persons attempt
Non- standard blast is made using the easy blast raw material (such as ammonium nitrate, urea, potassium permanganate, potassium chlorate, black powder, sulphur) for obtaining
Thing, and carry out destroying the illegal activity of public safety.So, development is directed to the efficient sensing of the non-standard explosive detection of trace
Material is one of research tendency of current functional material exploitation.
By taking ammonium nitrate and urea as an example, powder ammonium nitrate explosive is mixed by oxidant, fuel agent and sensitizer, and nitre
Sour ammonium is the primary oxidizers of powder ammonium nitrate explosive.Urea nitrate is a kind of explosive material, while being also the centre for preparing explosive
Body and raw material, can mix with organic matter, reducing agent, sulphur powder, phosphorus etc., form explosive mixture, and urea can and nitric acid
Reaction generates urea nitrate.Therefore, the detection of ammonium nitrate and urea can be realized to the blast based on powder ammonium nitrate and urea nitrate
The raw material detection of thing.
Nano zine oxide (ZnO) and zinc sulphide (ZnS) are two kinds of semiconductors being most widely used in gas sensitive field
Material.Zinc oxide has larger energy gap width (3.37eV), the advantages of good stability, cheap and easy to get, pattern are easily controlled, extensively
It is general to be applied to the fields such as Photoelectric Detection, luminescent material, gas sensing.Zinc sulphide is equally a kind of broad-spectrum typical II-VI
Race's wide bandgap semiconductor materials, energy gap is 3.67eV under room temperature, is passed in light emitting diode, photocatalysis, fluorescent illumination, gas
The application of the fields such as sense is universal.However, because the performance of nano material depends mainly on the structure of its intrinsic material, with single crystalline substance
The nanostructured of state its application will be very restricted.To realize the multifunction of nano material, integrated zinc oxide and sulfuration
The approximate semi-conducting material of both physical indexs of zinc so as to suitable for the air-sensitive detection under low-temperature and low-concentration, and then the company of realization
Continue the indexs such as adjustable, electric conductivity is good, chemical stability is good, this is for the range of application and gas of pioneering and inventing of extension bi-material
Quick performance is significant.At present, in known method prepare zinc oxide/sulfide hetero-junctions mostly be core-shell type nano-wire and
Nanobelt.
Patent of invention, Shanghai Communications University " aligns the preparation side of zinc sulphide-zinc oxide nano cable composite
Nano-cable prepared by method " (200410015984.7) can realize that highdensity zinc oxide nano array turns to zinc sulphide array
Change.The patent of invention prepares nanometic zinc oxide rod array using wet chemistry method, and under the conditions of 130 DEG C of temperature vulcanization reaction is carried out,
Zinc sulphide-the zinc oxide nano array that aligns of gained is mainly used in nano-device, does not probe into its concrete application.
The present invention prepares ultra-thin Zinc oxide nano sheet, and the cryogenic vulcanization for carrying out at lower temperatures using sol-gal process
Reaction;The present invention is applied to gas sensing field, mainly for the detection of the raw material trace steam that explodes in non-standard;The present invention
Compared with prior art:There is difference in preparation method, appearance structure, application.
The content of the invention
It is an object of the present invention to provide a kind of system of the non-standard explosive sensing material of zinc oxide/sulfide hetero-junctions
Preparation Method, the method prepares Zinc oxide nano sheet initially with sol-gal process, is then obtained by low-temperature hydrothermal vulcanization reaction
Zinc oxide/sulfide hetero-junctions sensing material, the formation of zinc oxide/sulfide hetero-junctions can adjust the energy band knot of sensing material
The surface defect of structure, controlled material, and then improve the air-sensitive performance of material.The zinc oxide/sulfide that the present invention is obtained is heterogeneous
Knot sensing material can be realized quick-fried to easily making quick-fried raw material ammonium nitrate, urea and all kinds of non-standards in room temperature scope (20 DEG C -30 DEG C)
Fried thing potassium permanganate, potassium chlorate, sulphur, the sensitive quick detection of black powder atmosphere.
The non-standard explosive sensing material of zinc oxide/sulfide hetero-junctions of the present invention, the sensing material is nanometer
Particle, average grain diameter is 20-30nm, and concrete operations follow these steps to carry out:
Prepare Zinc oxide nano sheet:
A, zinc nitrate hexahydrate is dissolved in the blue mouth bottle A containing absolute ethyl alcohol;
B, Lithium hydroxide monohydrate, NaOH or potassium hydroxide are dissolved in the blue mouth bottle B containing absolute ethyl alcohol, magnetic force
Stir to being completely dissolved, then the blue mouth bottle B of the blue mouth bottle A of step a and step b is transferred in refrigerator, freeze 12 hours;
C, the solution in blue mouth bottle B is added in blue mouth bottle A, solution is placed in water-bath by magnetic agitation to being well mixed
Or in ice bath, the temperature for controlling water or ice bath pot is 0-60 DEG C, stirs 0.5-24h, obtains opaque colloid;
D, the opaque colloidal dispersions for obtaining step c in normal heptane or n-hexane, centrifugation, by centrifugal sediment
In being dispersed in absolute ethyl alcohol, centrifugation again, will centrifugation twice as a washing cycle, the repeated washing cycle 3 times,
Sediment after washing is transferred in surface plate, in temperature is for 50-80 DEG C of baking oven 10-20h is dried, filled with agate mortar
Divide grinding, obtain ultra-thin Zinc oxide nano sheet;
Prepare zinc oxide/sulfide hetero-junctions explosive sensing material:
E, the Zinc oxide nano sheet that step d is obtained is dispersed in the reaction vessel containing 10ml deionized waters, magnetic agitation
To being uniformly dispersed, sulphur source is subsequently adding for thioacetamide, thiocarbamide, ATS (Ammonium thiosulphate), sodium thiosulfate or vulcanized sodium within 30 minutes,
After stirring, temperature 60-120 DEG C, hydro-thermal reaction 2-6h obtains faint yellow turbid solution, the wherein mol ratio of zinc oxide and sulphur source
Example is 1:0.01-4;
F, faint yellow turbid solution is disperseed in deionized water, to be centrifugally separating to obtain pale yellow precipitate, then faint yellow will be sunk
Shallow lake is transferred in porcelain boat, controls temperature for 50-80 DEG C, is dried 4-12h, is fully ground, that is, obtain zinc oxide/sulfide hetero-junctions
Explosive sensing material.
The non-standard explosive sensing material of zinc oxide/sulfide hetero-junctions that methods described is obtained contains nitric acid in detection
Purposes in the non-standard explosive atmosphere of ammonium, urea, potassium permanganate, potassium chlorate, sulphur and black powder.
The preparation method of the non-standard explosive sensing material of zinc oxide/sulfide hetero-junctions of the present invention, the method
Middle Zinc oxide nano sheet is prepared using method in patent of invention 2015104008765.3, and the method is the early stage work of the present invention
Make, the method for the invention is the research for being further directed to the non-standard explosive of quick detection on this basis.
The preparation method of the non-standard explosive sensing material of zinc oxide/sulfide hetero-junctions of the present invention, the method
Nano particle of the material of preparation with multiple average grain diameters as 20-30nm clusters round presentation, shows good electric signal transmission energy
Power.(see accompanying drawing 12/13/14) by taking black powder as an example, compared with pure phase zinc oxide and zinc sulphide prepared by this experiment, air-sensitive performance
Significantly improve.The method of the invention firstly the need of prepare pure phase Zinc oxide nano sheet as crystal seed, by different degrees of sulphur
Change reaction and realize constructing for zinc oxide/sulfide hetero-junctions.
The present invention has the advantage that and good effect compared with known technology:
The non-standard explosive sensing material of zinc oxide/sulfide hetero-junctions of the present invention, first by collosol and gel
Method prepares ultra-thin Zinc oxide nano sheet, and then hydro-thermal vulcanizing treatment obtains zinc oxide/sulfide hetero-junctions nano particle under low temperature,
The method is a kind of simple to operate, low cost, the chemical method of efficiency high.By the molar ratio for adjusting sulphur source and zinc oxide,
The heterojunction structure of composite can be adjusted, regulates and controls the surface defect state of gas sensitive, finally improve the air-sensitive response of material
Performance.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the present invention;
Fig. 2 is the transmission electron microscope picture of the present invention;
Fig. 3 is the EDS spectrograms of the present invention, wherein-△-for the characteristic peak positions of oxygen element ,-▽-for element sulphur
Characteristic peak positions ,-◇-for Zn-ef ficiency characteristic peak positions;
Fig. 4 is the X-ray diffractogram of the present invention;
Fig. 5 is the photoelectron spectroscopy figure of the present invention, wherein --- for the feature locations of element sulphur,For oxygen element
Feature locations;
Fig. 6 is the electron paramagnetic resonance strength test figure of the present invention;Show that material surface contains Lacking oxygen;
Fig. 7 is response curve of the present invention to the raw material ammonium nitrate that explodes;
Fig. 8 is response curve of the present invention to the raw material urea that explodes;
Fig. 9 is response curve of the present invention to non-standard explosive sulphur;
Figure 10 is response curve of the present invention to non-standard explosive potassium chlorate;
Figure 11 is response curve of the present invention to non-standard explosive potassium permanganate;
Figure 12 is response curve of the present invention to non-standard explosive black powder;
Figure 13 is response curve of the pure phase zinc oxide of the present invention to non-standard explosive black powder;
Figure 14 is response curve of the pure phase zinc sulphide of the present invention to non-standard explosive black powder.
Specific embodiment
The flesh and blood of the present invention is further illustrated below in conjunction with accompanying drawing, but is not limited only to following examples.
Embodiment 1
Prepare Zinc oxide nano sheet:
1.4875 grams of zinc nitrate hexahydrates are dissolved in the blue mouth bottle A containing 50ml absolute ethyl alcohols;
0.4208 gram of potassium hydroxide is dissolved in the blue mouth bottle B containing 50ml absolute ethyl alcohols, magnetic agitation is to completely molten
Solution, then blue mouth bottle A and indigo plant mouth bottle B are transferred in refrigerator, freeze 12 hours;
Solution in blue mouth bottle B is added in blue mouth bottle A, magnetic agitation is placed in solution in ice bath to being well mixed, is controlled
The temperature of ice making bath is 0 DEG C, stirs 2h, obtains opaque colloid;
By the opaque colloidal dispersions for obtaining in normal heptane, centrifugal sediment is dispersed in absolute ethyl alcohol by centrifugation
In, centrifugation again will be washed twice as a washing cycle, repeated washing cycle 3 times, and the sediment after washing is turned
In moving to surface plate, 12h is dried in the baking oven that temperature is 60 DEG C, is fully ground with agate mortar, obtain ultra-thin zinc oxide nano
Rice piece;
Prepare zinc oxide/sulfide hetero-junctions explosive sensing material:
The Zinc oxide nano sheet 0.08g for obtaining is dispersed in the reaction vessel containing 10ml deionized waters, magnetic agitation 30
Minute, to being uniformly dispersed, adds 0.02g thioacetamides, and after stirring, 90 DEG C of temperature, hydro-thermal reaction 4h obtains faint yellow muddy
Turbid liquid;
Faint yellow turbid solution is disperseed in deionized water, to be centrifugally separating to obtain pale yellow precipitate, then by pale yellow precipitate
In being transferred to porcelain boat, temperature is controlled for 60 DEG C, be dried 8h, be fully ground, that is, obtain zinc oxide/sulfide hetero-junctions explosive biography
Sense material.
Embodiment 2
Prepare Zinc oxide nano sheet:
1.4875 grams of zinc nitrate hexahydrates are dissolved in the blue mouth bottle A containing 50ml absolute ethyl alcohols;
0.3000 gram of NaOH is dissolved in the blue mouth bottle B containing 50ml absolute ethyl alcohols, magnetic agitation is to completely molten
Solution, then blue mouth bottle A and indigo plant mouth bottle B are transferred in refrigerator, freeze 12 hours;
Solution in blue mouth bottle B is added in blue mouth bottle A, magnetic agitation is placed in solution in water-bath to being well mixed, is controlled
The temperature of water-bath processed is 60 DEG C, stirs 24h, obtains opaque colloid;
By the opaque colloidal dispersions for obtaining in normal heptane, centrifugal sediment is dispersed in absolute ethyl alcohol by centrifugation
In, centrifugation again will be washed twice as a washing cycle, repeated washing cycle 3 times, and the sediment after washing is turned
In moving to surface plate, 12h is dried in the baking oven that temperature is 80 DEG C, is fully ground with agate mortar, obtain ultra-thin zinc oxide nano
Rice piece;
Prepare zinc oxide/sulfide hetero-junctions explosive sensing material:
The Zinc oxide nano sheet 0.08g for obtaining is dispersed in the reaction vessel containing 10ml deionized waters, magnetic agitation 30
Minute, to being uniformly dispersed, adds 0.04g thiocarbamides, and after stirring, temperature 60 C, hydro-thermal reaction 2h obtains faint yellow turbid solution;
Faint yellow turbid solution is disperseed in deionized water, to be centrifugally separating to obtain pale yellow precipitate, then by pale yellow precipitate
In being transferred to porcelain boat, temperature is controlled for 50 DEG C, be dried 4h, be fully ground, that is, obtain zinc oxide/sulfide hetero-junctions explosive biography
Sense material.
Embodiment 3
Prepare Zinc oxide nano sheet:
1.4875 grams of zinc nitrate hexahydrates are dissolved in the blue mouth bottle A containing 50ml absolute ethyl alcohols;
0.3000 gram of NaOH is dissolved in the blue mouth bottle B containing 50ml absolute ethyl alcohols, magnetic agitation is to completely molten
Solution, then blue mouth bottle A and indigo plant mouth bottle B are transferred in refrigerator, freeze 12 hours;
Solution in blue mouth bottle B is added in blue mouth bottle A, magnetic agitation is placed in solution in water-bath to being well mixed, is controlled
The temperature of water-bath processed is 25 DEG C, stirs 0.5h, obtains opaque colloid;
By the opaque colloidal dispersions for obtaining in n-hexane, centrifugal sediment is dispersed in absolute ethyl alcohol by centrifugation
In, centrifugation again will be washed twice as a washing cycle, repeated washing cycle 3 times, and the sediment after washing is turned
In moving to surface plate, 10h is dried in the baking oven that temperature is 60 DEG C, is fully ground with agate mortar, obtain the ultra-thin of nickel doping
Zinc oxide nano sheet;
Prepare zinc oxide/sulfide hetero-junctions explosive sensing material:
The Zinc oxide nano sheet 0.08g for obtaining is dispersed in the reaction vessel containing 10ml deionized waters, magnetic agitation 30
Minute, to being uniformly dispersed, adds 0.08g ATS (Ammonium thiosulphate), and after stirring, 120 DEG C of temperature, hydro-thermal reaction 6h obtains faint yellow muddy
Turbid liquid;
Faint yellow turbid solution is disperseed in deionized water, to be centrifugally separating to obtain pale yellow precipitate, then by pale yellow precipitate
In being transferred to porcelain boat, temperature is controlled for 80 DEG C, be dried 6h, be fully ground, that is, obtain zinc oxide/sulfide hetero-junctions explosive biography
Sense material.
Embodiment 4
Prepare Zinc oxide nano sheet:
1.4875 grams of zinc nitrate hexahydrates are dissolved in the blue mouth bottle A containing 50ml absolute ethyl alcohols;
0.3150 gram of Lithium hydroxide monohydrate is dissolved in the blue mouth bottle B containing 50ml absolute ethyl alcohols, magnetic agitation is to complete
CL, then blue mouth bottle A and indigo plant mouth bottle B are transferred in refrigerator, freeze 12 hours;
Solution in blue mouth bottle B is added in blue mouth bottle A, magnetic agitation is placed in solution in ice bath to being well mixed, is controlled
The temperature of ice making bath is 0 DEG C, stirs 0.5h, obtains opaque colloid;
By the opaque colloidal dispersions for obtaining in normal heptane, centrifugal sediment is dispersed in absolute ethyl alcohol by centrifugation
In, centrifugation again will be washed twice as a washing cycle, repeated washing cycle 3 times, and the sediment after washing is turned
In moving to surface plate, 24h is dried in the baking oven that temperature is 60 DEG C, is fully ground with agate mortar, obtain ultra-thin zinc oxide nano
Rice piece;
Prepare zinc oxide/sulfide hetero-junctions explosive sensing material:
The Zinc oxide nano sheet 0.08g for obtaining is dispersed in the reaction vessel containing 10ml deionized waters, magnetic agitation 30
Minute, to being uniformly dispersed, adds 0.15g vulcanized sodium, and after stirring, temperature 60 C, hydro-thermal reaction 2h obtains faint yellow turbid solution;
Faint yellow turbid solution is disperseed in deionized water, to be centrifugally separating to obtain pale yellow precipitate, then by pale yellow precipitate
In being transferred to porcelain boat, temperature is controlled for 60 DEG C, be dried 12h, be fully ground, that is, obtain zinc oxide/sulfide hetero-junctions explosive
Sensing material.
Embodiment 5
Prepare Zinc oxide nano sheet:
1.4875 grams of zinc nitrate hexahydrates are dissolved in the blue mouth bottle A containing 50ml absolute ethyl alcohols;
0.3150 gram of Lithium hydroxide monohydrate is dissolved in the blue mouth bottle B containing 50ml absolute ethyl alcohols, magnetic agitation is to complete
CL, then blue mouth bottle A and indigo plant mouth bottle B are transferred in refrigerator, freeze 12 hours;
Solution in blue mouth bottle B is added in blue mouth bottle A, magnetic agitation is placed in solution in water-bath to being well mixed, is controlled
The temperature of water-bath processed is 15 DEG C, stirs 4h, obtains opaque colloid;
By the opaque colloidal dispersions for obtaining in n-hexane, centrifugal sediment is dispersed in absolute ethyl alcohol by centrifugation
In, centrifugation again will be washed twice as a washing cycle, repeated washing cycle 4 times, and the sediment after washing is turned
In moving to surface plate, 10h is dried in the baking oven that temperature is 50 DEG C, is fully ground with agate mortar, obtain ultra-thin zinc-oxide nano
Piece;
Prepare zinc oxide/sulfide hetero-junctions explosive sensing material:
The Zinc oxide nano sheet 0.08g for obtaining is dispersed in the reaction vessel containing 10ml deionized waters, magnetic agitation 30
Minute, to being uniformly dispersed, adds 0.04g sodium thiosulfate, and after stirring, 120 DEG C of temperature, hydro-thermal reaction 4h obtains faint yellow muddy
Turbid liquid;
Faint yellow turbid solution is disperseed in deionized water, to be centrifugally separating to obtain pale yellow precipitate, pale yellow precipitate is turned
In moving to porcelain boat, temperature is controlled for 70 DEG C, be dried 6h, be fully ground, that is, obtain zinc oxide/sulfide hetero-junctions explosive sensing
Material.
Embodiment 6
Prepare Zinc oxide nano sheet:
1.4875 grams of zinc nitrate hexahydrates are dissolved in the blue mouth bottle A containing 50ml absolute ethyl alcohols;
0.3000 gram of NaOH is dissolved in the blue mouth bottle B containing 50ml absolute ethyl alcohols, magnetic agitation is to completely molten
Solution, then blue mouth bottle A and indigo plant mouth bottle B are transferred in refrigerator, freeze 12 hours;
Solution in blue mouth bottle B is added in blue mouth bottle A, magnetic agitation is placed in solution in water-bath to being well mixed, is controlled
The temperature of water-bath processed is 50 DEG C, stirs 24h, obtains opaque colloid;
By the opaque colloidal dispersions for obtaining in n-hexane, centrifugal sediment is dispersed in absolute ethyl alcohol by centrifugation
In, centrifugation again will be washed twice as a washing cycle, repeated washing cycle 4 times, and the sediment after washing is turned
In moving to surface plate, 10h is dried in the baking oven that temperature is 60 DEG C, is fully ground with agate mortar, obtain ultra-thin zinc-oxide nano
Piece;
Prepare zinc oxide/sulfide hetero-junctions explosive sensing material:
The Zinc oxide nano sheet 0.08g for obtaining is dispersed in the reaction vessel containing 10ml deionized waters, magnetic agitation 30
Minute, to being uniformly dispersed, adds 0.02g thioacetamides, and after stirring, 90 DEG C of temperature, hydro-thermal reaction 6h obtains faint yellow muddy
Turbid liquid;
Faint yellow turbid solution is disperseed in deionized water, to be centrifugally separating to obtain pale yellow precipitate, then by pale yellow precipitate
In being transferred to porcelain boat, temperature is controlled for 80 DEG C, be dried 4h, be fully ground, that is, obtain zinc oxide/sulfide hetero-junctions explosive biography
Sense material.
Embodiment 7
Embodiment 1-6 is detected:
Any one the zinc oxide/sulfide hetero-junctions explosive sensing material obtained by 0.05 gram of embodiment 1-6 is taken in agate
In Nao mortars, 2-3 drop absolute ethyl alcohols are added, wear into pasty state, pastel is applied on the electrode slice of comb electrode with fine, soft fur pen, used
Catherine's ammeter test containing zinc oxide/sulfide hetero-junctions explosive sensing material in atmosphere with explosive atmosphere in electricity
Resistance, the response curve of gained is as shown in accompanying drawing 7 to 14.
Claims (2)
1. a kind of preparation method of the non-standard explosive sensing material of zinc oxide/sulfide hetero-junctions, it is characterised in that the sensing
Material is nano particle, and average grain diameter is 20-30 nm, and concrete operations follow these steps to carry out:
Prepare Zinc oxide nano sheet:
A, zinc nitrate hexahydrate is dissolved in the blue mouth bottle A containing absolute ethyl alcohol;
B, Lithium hydroxide monohydrate is dissolved in the blue mouth bottle B containing absolute ethyl alcohol, magnetic agitation to being completely dissolved, then by step
The blue mouth bottle A of a and the blue mouth bottle B of step b are transferred in refrigerator, are freezed 12 hours;
C, the solution in blue mouth bottle B is added in blue mouth bottle A, solution is placed in water-bath or ice by magnetic agitation to being well mixed
In bath, the temperature for controlling water or ice bath pot is 0-60 DEG C, stirs 0.5-24 h, obtains opaque colloid;
In normal heptane or n-hexane, centrifugation disperses centrifugal sediment for d, the opaque colloidal dispersions for obtaining step c
In absolute ethyl alcohol, centrifugation again, will centrifugation twice as a washing cycle, the repeated washing cycle 3 times, will wash
Sediment after washing is transferred in surface plate, and in temperature is for 50-80 DEG C of baking oven 10-20 h are dried, abundant with agate mortar
Grinding, obtains ultra-thin Zinc oxide nano sheet;
Prepare zinc oxide/sulfide hetero-junctions explosive sensing material:
E, the Zinc oxide nano sheet that step d is obtained is dispersed in the reaction vessel containing 10 ml deionized waters, 30 points of magnetic agitation
Clock is subsequently adding sulphur source for thioacetamide, thiocarbamide, ATS (Ammonium thiosulphate), sodium thiosulfate or vulcanized sodium, stirring to being uniformly dispersed
After uniform, temperature 60-120 DEG C, hydro-thermal reaction 2-6 h obtains faint yellow turbid solution, and wherein zinc oxide is with the molar ratio of sulphur source
1:0.01-4;
F, faint yellow turbid solution is disperseed in deionized water, to be centrifugally separating to obtain pale yellow precipitate, then pale yellow precipitate is turned
In moving to porcelain boat, temperature is controlled for 50-80 DEG C, be dried 4-12 h, be fully ground, that is, obtain zinc oxide/sulfide hetero-junctions quick-fried
Fried thing sensing material.
2. the non-standard explosive sensing material of zinc oxide/sulfide hetero-junctions that according to claim 1 method is obtained is in inspection
Survey containing the purposes in the non-standard explosive atmosphere of ammonium nitrate, urea, potassium permanganate, potassium chlorate, sulphur and black powder.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610049048.0A CN105731523B (en) | 2016-01-25 | 2016-01-25 | Preparation method of zinc oxide/zinc sulfide heterojunction nonstandard explosive sensing material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610049048.0A CN105731523B (en) | 2016-01-25 | 2016-01-25 | Preparation method of zinc oxide/zinc sulfide heterojunction nonstandard explosive sensing material |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105731523A CN105731523A (en) | 2016-07-06 |
CN105731523B true CN105731523B (en) | 2017-05-17 |
Family
ID=56247622
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610049048.0A Active CN105731523B (en) | 2016-01-25 | 2016-01-25 | Preparation method of zinc oxide/zinc sulfide heterojunction nonstandard explosive sensing material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105731523B (en) |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101607689B (en) * | 2008-06-17 | 2010-12-22 | 国家纳米科学中心 | Zinc oxide and zinc sulfide nano-belt composite heterogenous junction material and preparation method |
CN102345162B (en) * | 2011-04-19 | 2014-04-09 | 中国科学院合肥物质科学研究院 | One-dimensional axial type nano zinc oxide / zinc sulfide heterojunction and preparation method thereof |
CN103599738A (en) * | 2013-11-22 | 2014-02-26 | 天津大学 | Method of synthesizing zinc oxide/cadmium sulfide heterojunction nanorod array by virtue of two-step ion exchange in liquid phase |
CN104944463B (en) * | 2015-07-13 | 2016-08-24 | 中国科学院新疆理化技术研究所 | The quickly preparation method of the Zinc oxide nanoparticle of detection explosive atmosphere |
-
2016
- 2016-01-25 CN CN201610049048.0A patent/CN105731523B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN105731523A (en) | 2016-07-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Li et al. | High piezocatalytic capability in CuS/MoS2 nanocomposites using mechanical energy for degrading pollutants | |
Kole et al. | Morphology controlled synthesis of wurtzite ZnS nanostructures through simple hydrothermal method and observation of white light emission from ZnO obtained by annealing the synthesized ZnS nanostructures | |
CN101913600A (en) | Method for preparing graphene/semiconductor quantum dot composite material | |
CN104944463B (en) | The quickly preparation method of the Zinc oxide nanoparticle of detection explosive atmosphere | |
Fan et al. | Direct synthesis of sulfide capped CdS and CdS/ZnS colloidal nanocrystals for efficient hydrogen evolution under visible light irradiation | |
CN106745322A (en) | A kind of iron disulfide microspheres and preparation method thereof | |
CN105879884A (en) | One-dimensional ZnS (zinc sulfide)/CdS-C nanocomposite material and preparation method thereof | |
CN109809491A (en) | A kind of micron of flower ball-shaped mangano-manganic oxide and its preparation and application | |
CN103965866A (en) | Preparation method of carboxyl modified CdSe-ZnS quantum dot adopting core-shell structure | |
Li et al. | Gas sensing properties of flower-like ZnO prepared by a microwave-assisted technique | |
CN105731523B (en) | Preparation method of zinc oxide/zinc sulfide heterojunction nonstandard explosive sensing material | |
Zhu et al. | Selective processing, structural characterization, and photoluminescence behaviors of single crystalline (Gd1-xEux) 2O3 nanorods and nanotubes | |
Jasrotia et al. | Nanocrystalline Co/Ga substituted CuFe2O4 magnetic nanoferrites for green hydrogen generation | |
Maroufi et al. | Waste-cleaning waste: Synthesis of ZnO porous nano-sheets from batteries for dye degradation | |
CN111111699A (en) | Nickel-cobalt disulfide composite material and preparation method and application thereof | |
CN101152957A (en) | Method for producing nano zinc peroxide and zinc oxide by using solar | |
CN101941677A (en) | Method for preparing manganese oxide surface modified zinc oxide nano rod | |
Wang et al. | Enhanced photoelectric properties by the coordinating role of doping and modification | |
Tashi et al. | A down converting serine-functionalised NaYF 4: Ce 3+/Gd 3+/Eu 3+@ NaGdF 4: Tb 3+ photoluminescent probe for chemical sensing of explosive nitroaromatic compounds | |
Pathan et al. | Improved photocatalytic properties of NiS nanocomposites prepared by displacement method for removal of rose bengal dye | |
CN107805495A (en) | The preparation method of high brightness zinc-manganese sulfide nano-phosphor | |
CN113860357A (en) | Preparation method of out-of-phase junction CdS nanowire | |
CN105692720A (en) | Preparation method of spinous yttrium cobaltate microballs | |
Li et al. | Structural, optical, photocurrent and mechanism-induced photocatalytic properties of surface-modified ZnS thin films by chemical bath deposition | |
KR101498227B1 (en) | Methods for preparing te(0) from te(iv) using metal-reducing bacteria and iron ion |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |