CN106430313B - Treasure maesa herb bulk WO3Multilevel hierarchy gas sensitive, synthetic method and application - Google Patents
Treasure maesa herb bulk WO3Multilevel hierarchy gas sensitive, synthetic method and application Download PDFInfo
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- CN106430313B CN106430313B CN201610854196.XA CN201610854196A CN106430313B CN 106430313 B CN106430313 B CN 106430313B CN 201610854196 A CN201610854196 A CN 201610854196A CN 106430313 B CN106430313 B CN 106430313B
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- 241000612162 Maesa Species 0.000 title claims abstract description 22
- 238000010189 synthetic method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical class [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 5
- 239000001632 sodium acetate Substances 0.000 claims abstract description 5
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 5
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical group [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims 1
- 235000002906 tartaric acid Nutrition 0.000 claims 1
- 239000011975 tartaric acid Substances 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 25
- 230000035945 sensitivity Effects 0.000 abstract description 9
- 238000001035 drying Methods 0.000 abstract description 6
- NGPGDYLVALNKEG-UHFFFAOYSA-N azanium;azane;2,3,4-trihydroxy-4-oxobutanoate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)C(O)C([O-])=O NGPGDYLVALNKEG-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 51
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
- G01N33/004—CO or CO2
-
- 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
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- 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
- C01P2004/30—Particle morphology extending in three dimensions
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Food Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The present invention relates to a kind of treasure maesa herb bulk WO3The synthetic method of multilevel hierarchy gas sensitive, be specially：1）Soluble tungstate salt is dissolved under 60-80 DEG C of condition of water bath heating in deionized water and absolute ethyl alcohol mixed solution, multiple component structure directed agents are then added under stirring, aging is placed after being well mixed, solution A is obtained；Wherein, multiple component structure directed agents be by mass ratio be 1：0.5-1.3：The mixture that 0.9-1.9 polyvinylpyrrolidone, sodium acetate and ammonium tartrate is constituted；2）The pH value of solution A is adjusted to 1-2, ultrasonic disperse uniformly obtains mixed solution B；3）By mixed solution B in 120-160 DEG C of hydro-thermal reaction 12-24 hours, reaction terminates rear separation of solid and liquid, scrubbed, be drying to obtain.Gas sensitive of the present invention integrates hollow structure, multilevel hierarchy and particular exposed crystal face, and pattern is unique, novel；And, response high to CO sensitivity recovers rapid, selectivity is good, cyclical stability is protruded.
Description
Technical field
The invention belongs to new material technology field, and in particular to one kind is made up of hexagonal crystal phase nanometer rods, (001) crystal face is sudden and violent
The treasure maesa herb bulk WO of dew3The synthetic method of multilevel hierarchy gas sensitive and application.
Background technology
Carbon monoxide（CO）It is widely present in the living environment of the mankind, is a kind of toxicity very strong pollutant.The gas
The circulatory system can be entered by the respiratory system of human body, be combined with the hemoglobin in blood, so that reducing blood carries oxygen
Ability, causes body tissue downright bad because of anoxic, and threat to life.Therefore, the oxidation that Development response is rapid, sensitivity is protruded
Carbon sensor is significant.
Regulating microstructure is a kind of important means for developing high-performance gas sensitive.At present, three-dimensional multistage nanostructured
Especially application of the nano material with hollow feature in gas sensing field is in study hotspot., Lee summaries in 2009
Metal oxide hollow multilevel hierarchy influences on the prominent of its air-sensitive performance, it is believed that hollow multilevel hierarchy has larger surface
Product, easily gas transfer passage, the structural stability for being not easy reunion, are preferable gas sensitive structures, other researchers'
Numerous studies work also demonstrate that the conclusion.In addition, crystal face engineering is a new development of Crystal study in recent years.Research hair
It is existing：Metal oxide semiconductor gas sensitive with particular exposed crystal face, the metallic atom of its plane of crystal exposure and suspension
Key is more, just can adsorb more oxygen molecules and be ionized, so as to improve the susceptibility to detecting gas.Therefore, control
The nano material of system synthesis exposure particular crystal plane turns into the heat subject of Material Field, and by Hollow hierarchical and specific sudden and violent
It is a brand-new research direction that dew crystal face, which is combined, and it has had both the advantage of the two, can largely improve material
Gas-sensitive property, but this synthetic technology still faces the challenge.
Tungstic acid is a kind of important n-type semiconductor gas sensitive, and research shows that tungstic acid also has preferably to CO
Gas-sensitive property, but sensitivity, response speed and selectivity await further raising.The problems such as Nagarajan and Zhao
Group learns CO in hexagonal crystal phase WO by Density function theory technique study3's（001）Surface reaction can obtain higher
Energy of adsorption and the more reaction heat of release, are advantageous to improve WO3To CO sensitivity characteristic.But because plane of crystal controls to synthesize
Difficulty is high, and related experiment is rarely reported.
The content of the invention
Present invention aims to overcome that prior art defect there is provided one kind by hexagonal crystal phase WO3Nanometer rods are constituted, (001)
The treasure maesa herb bulk WO of crystal face exposure3Multilevel hierarchy gas sensitive.
Present invention also offers above-mentioned treasure maesa herb bulk WO3The synthetic method of multilevel hierarchy gas sensitive and its prepare CO
Application on gas sensor.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of treasure maesa herb bulk WO3The synthetic method of multilevel hierarchy gas sensitive, it comprises the following steps：
1）Soluble tungstate salt is dissolved in deionized water under 60-80 DEG C of condition of water bath heating and absolute ethyl alcohol is mixed
In solution, multiple component structure directed agents are then added under stirring, are well mixed（40-60 points of stirring need to typically be continued
Clock）After place aging（It is general to place 10-15 minutes）, obtain solution A；Wherein, multiple component structure directed agents are by quality
Than for 1：0.5-1.3：The mixture that 0.9-1.9 polyvinylpyrrolidone, sodium acetate and ammonium tartrate is constituted；
2）The acid adding into solution A（Such as can be hydrochloric acid, sulfuric acid or nitric acid）To adjust pH value to 1-2, ultrasonic disperse is equal
It is even（Typically about need 10-20 minutes）Obtain mixed solution B；
3）Mixed solution B is transferred in autoclave, and in 120-160 DEG C of hydrothermal synthesis reaction 12-24 hours,
Reaction terminates rear separation of solid and liquid, scrubbed, be drying to obtain.
Specifically, step 1）In, the soluble tungstate salt is sodium tungstate or ammonium tungstate, and the concentration of soluble tungstate salt
For 0.1-0.5mol.L-1；Deionized water and the volume ratio of absolute ethyl alcohol are 1：0.5-2.5.
Obtained treasure maesa herb bulk WO is synthesized using the above method3Multilevel hierarchy gas sensitive.
Above-mentioned treasure maesa herb bulk WO3Application of the multilevel hierarchy gas sensitive on CO gas sensors are prepared.
The present invention, using deionized water and absolute ethyl alcohol as solvent, utilizes multiple component structure using soluble tungstate salt as raw material
It is oriented to hollow hierarchy WO of the agent assisting alcohol-hydrothermal method synthesis with particular exposed crystal face3Gas sensitive.Compared to the prior art,
Beneficial effects of the present invention：
1）A kind of novel treasure maesa herb bulk WO is provided3The synthetic method of multilevel hierarchy gas sensitive, the flower is rolled into a ball by six sides
Crystalline phase WO3Nanometer rods are constituted, the exposure of (001) crystal face, and flower group is hollow, and surface porosity is porous.The synthetic method have low cost,
Speed is fast, technique is simple, non-environmental-pollution and be easy to large-scale production the advantages of；
2）Treasure maesa herb bulk WO3Multilevel hierarchy gas sensitive is effectively by hollow, multilevel hierarchy and special exposed crystal face phase
With reference to improving gas-sensitive property of the tungstic acid matrix material to CO gases well, made gas sensor has sensitive to CO
The features such as spending rapid high, response-recovery, selective protrusion, good stability, the material has well for the monitoring of CO in environment
Application prospect.
Brief description of the drawings
Fig. 1 is treasure maesa herb bulk WO3The XRD of multilevel hierarchy gas sensitive.By being contrasted with standard x RD spectrograms, the production
Thing belongs to hexagonal crystal phase WO3(JCPDS NO. 33-1387), pure phase exists without other impurity peaks；
Fig. 2 is treasure maesa herb bulk WO3The SEM figures of multilevel hierarchy gas sensitive, (a) low power figure, (b) high power figure.Can by Fig. 2
Know：Product morphology is colored bulk structure, a diameter of 450-600 nm of flower group, is made up of nano bar-shape crystal grain not of uniform size,
The a diameter of 30-95nm of nanometer rods crystal grain, flower group surface porosity is porous；
In Fig. 3, (a) is treasure maesa herb bulk WO3The TEM figures of multilevel hierarchy gas sensitive, as can be seen from the figure：Product shape
Looks are colored bulk structures, consistent with SEM conclusions, and internal to be hollow.(b) be hexagonal crystal phase nanometer rods crystal grain HRTEM figure, by
The lattice fringe data provided in HRTEM figures are understood：0.391nm corresponds to (001) interplanar distance, explanation（001）It is brilliant for exposure
Face, 0.365nm and 0.634nm are corresponded respectively to（110）With（010）Interplanar distance.(c) illustrated for hexagonal crystal phase crystal structure,
Readily appreciate content shown in Fig. 3 (b)；
Fig. 4 is sensitivity and the response-recovery the performance test results of the gas sensor made using gas sensitive of the present invention；
Fig. 5 is the selectivity test result of the gas sensor made using gas sensitive of the present invention；
Fig. 6 is the stability test result of the gas sensor made using gas sensitive of the present invention.
Embodiment
Technical scheme is further discussed in detail with reference to embodiments, but protection scope of the present invention
It is not limited thereto.
Embodiment 1
A kind of treasure maesa herb bulk WO3The synthetic method of multilevel hierarchy gas sensitive, it comprises the following steps：
1）Sodium tungstate is dissolved in deionized water and absolute ethyl alcohol mixed solution under 80 DEG C of condition of water bath heating（Sodium tungstate
Concentration is 0.4mol.L-1；Deionized water and the volume ratio of absolute ethyl alcohol are 1：2）In, then add multicomponent under stirring
Structure directing agent, persistently stirs after being well mixed within 60 minutes, places aging 15 minutes, obtain solution A；Wherein, multiple component structure
Directed agents be by mass ratio be 1：1：The mixture that 1.2 polyvinylpyrrolidone, sodium acetate and ammonium tartrate is constituted；
2）Appropriate hydrochloric acid is added into solution A（6 mol.L-1）To adjust pH value to 1-2, ultrasonic disperse is obtained for 20 minutes
Mixed solution B；
3）Mixed solution B is transferred in autoclave, and in 150 DEG C of hydrothermal synthesis reactions 17 hours, reaction terminated
Centrifuge separation of solid and liquid is used afterwards, and solid product is washed with deionized water, absolute ethyl alcohol, is subsequently placed in 80 in drying box respectively
DEG C drying produce gas sensitive within 2 hours.
Gained gas sensitive X-ray powder diffraction instrument（XRD）Its phase structure is detected, using SEM
（SEM）And transmission electron microscope（TEM）Determine the pattern and size of product；Using high power transmission electron microscope（HRTEM）It is determined that brilliant
The exposure crystal face of body.As a result see Fig. 1 to 3.
Embodiment 2
A kind of treasure maesa herb bulk WO3The synthetic method of multilevel hierarchy gas sensitive, it comprises the following steps：
1）Ammonium tungstate is dissolved in deionized water and absolute ethyl alcohol mixed solution under 60 DEG C of condition of water bath heating（Ammonium tungstate
Concentration is 0.2mol.L-1；Deionized water and the volume ratio of absolute ethyl alcohol are 1：0.8）In, then added under stirring multigroup
Separation structure directed agents, persistently stir after being well mixed within 40 minutes, place aging 15 minutes, obtain solution A；Wherein, multicomponent knot
Structure directed agents be by mass ratio be 1：0.6：The mixture that 1.8 polyvinylpyrrolidone, sodium acetate and ammonium tartrate is constituted；
2）Appropriate hydrochloric acid is added into solution A（6 mol.L-1）To adjust pH value to 1-2, ultrasonic disperse is obtained for 15 minutes
Mixed solution B；
3）Mixed solution B is transferred in autoclave, and in 130 DEG C of hydrothermal synthesis reactions 24 hours, reaction terminated
Centrifuge separation of solid and liquid is used afterwards, and solid product is washed with deionized water, absolute ethyl alcohol, is subsequently placed in 80 in drying box respectively
DEG C drying produce gas sensitive within 2 hours.
Application test：CO air-sensitive performances are tested
The treasure maesa herb bulk WO that above-described embodiment 1 is prepared3Multilevel hierarchy gas sensitive is prepared into CO gas sensors,
It is specific as follows：It is 7 in mass ratio by gas sensitive and deionized water：2 are mixed into slurry, then are evenly coated in the oxygen with gold electrode
Change on aluminium earthenware, dried under the conditions of 60-120 DEG C, calcined under the conditions of 400-600 DEG C 1-2 hours, then weld, dispense,
Aging, is produced.Welding therein, packing, aging technique are carried out according to the preparation method of traditional heater-type gas sensor,
This is prior art, therefore is repeated no more in the application.
It is following list dry under the conditions of 80 DEG C, under the conditions of 450 DEG C calcining make within 2 hours obtained CO gas sensors
Results of property.
1）Sensitivity is high：Gas sensor is in 270 DEG C of operating temperatures to 10,20,50,100,200 and 300 ppm CO
Sensitivity be respectively 6.7,12.9,16.6,22.7,32.6 and 41.9.As shown in Figure 4.
2）Response-recovery is rapid：Gas sensor response time and recovery time of CO gases in the range of 300ppm exists
Within 15 s.As shown in Figure 4.
3）Selectivity is good：Relative to CO, the gas sensor is to some common gas such as formaldehyde（HCHO）, methane（CH4）,
Hydrogen（H2）And liquefied gas（LPG）Deng and it is insensitive.As shown in Figure 5.
4）Good stability：In the continuous firing of 60 days, the sensitivity drift of gas sensor is within 0.9%.Such as Fig. 6 institutes
Show.
It in summary it can be seen：Treasure maesa herb bulk WO of the present invention3Multilevel hierarchy gas sensitive collection hollow structure, multilevel hierarchy and
Particular exposed crystal face is in one, and pattern is unique, novel；And, response-recovery high to CO sensitivity is rapid, selectivity is good, circulation
Stability is protruded.
Claims (4)
1. a kind of treasure maesa herb bulk WO3The synthetic method of multilevel hierarchy gas sensitive, it is characterised in that comprise the following steps：
1）Soluble tungstate salt is dissolved in deionized water and absolute ethyl alcohol mixed solution under 60-80 DEG C of condition of water bath heating
In, multiple component structure directed agents are then added under stirring, aging is placed after being well mixed, solution A is obtained；Wherein, it is many
Component structure directed agents be by mass ratio be 1：0.5-1.3：0.9-1.9 polyvinylpyrrolidone, sodium acetate and tartaric acid
The mixture of ammonium composition；
2）The pH value of solution A is adjusted to 1-2, ultrasonic disperse uniformly obtains mixed solution B；
3）By mixed solution B in 120-160 DEG C of hydro-thermal reaction 12-24 hours, reaction terminates rear separation of solid and liquid, scrubbed, dry
It is dry to produce.
2. treasure maesa herb bulk WO as claimed in claim 13The synthetic method of multilevel hierarchy gas sensitive, it is characterised in that step 1）
In, the soluble tungstate salt is sodium tungstate or ammonium tungstate, and the concentration of soluble tungstate salt is 0.1-0.5mol.L-1；Go from
The volume ratio of sub- water and absolute ethyl alcohol is 1：0.5-2.5.
3. the treasure maesa herb bulk WO obtained using the synthesis of the methods described of claim 1 or 23Multilevel hierarchy gas sensitive.
4. treasure maesa herb bulk WO described in claim 33Application of the multilevel hierarchy gas sensitive on CO gas sensors are prepared.
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| CN106430313B true CN106430313B (en) | 2017-07-14 |
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