CN109607621A - A kind of multilevel structure α-Fe2O3/α-MoO3Hollow Sphere Composites and preparation method thereof - Google Patents
A kind of multilevel structure α-Fe2O3/α-MoO3Hollow Sphere Composites and preparation method thereof Download PDFInfo
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- CN109607621A CN109607621A CN201811599812.7A CN201811599812A CN109607621A CN 109607621 A CN109607621 A CN 109607621A CN 201811599812 A CN201811599812 A CN 201811599812A CN 109607621 A CN109607621 A CN 109607621A
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- multilevel structure
- hollow sphere
- acetylacetone
- sphere composites
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- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 229910003145 α-Fe2O3 Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 96
- 229910003149 α-MoO3 Inorganic materials 0.000 claims abstract description 63
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 32
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002055 nanoplate Substances 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 69
- 239000007789 gas Substances 0.000 abstract description 44
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract description 16
- 229910000476 molybdenum oxide Inorganic materials 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
- 241000251468 Actinopterygii Species 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012544 monitoring process Methods 0.000 abstract description 2
- 238000011897 real-time detection Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- 238000001354 calcination Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 239000002127 nanobelt Substances 0.000 description 6
- 238000010276 construction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- -1 Acyl acetone iron Chemical compound 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910018487 Ni—Cr Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 208000021017 Weight Gain Diseases 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 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
- 238000010438 heat treatment Methods 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/02—Oxides; Hydroxides
-
- 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
-
- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compounds Of Iron (AREA)
Abstract
A kind of multilevel structure α-Fe2O3/α‑MoO3Hollow Sphere Composites and preparation method thereof, the present invention relates to MoO3Composite material and preparation method.The present invention is to solve multilevel structure molybdenum oxide multilevel structure is difficult to keep in doping and the modifications such as compound the technical issues of.Multilevel structure α-Fe of the invention2O3/α‑MoO3Hollow Sphere Composites are a kind of microballoons of hollow structure, and the shell of microballoon is by α-Fe2O3/α‑MoO3Composite Nano sheetpile is folded to be formed.Preparation method: one, acetylacetone,2,4-pentanedione oxygen molybdenum solution is prepared；Two, the pH value of acetylacetone,2,4-pentanedione oxygen molybdenum solution is adjusted；Three, ferric acetyl acetonade is added and obtains mixed solution；Four, solvent thermal reaction；Five, calcine to get.The composite material is 10ppb to the minimum detectability of Triethylamine gas, can be used for industrial production, in fish processing and complex environment Triethylamine gas real-time detection and monitoring field.
Description
Technical field
The present invention relates to MoO3Composite material and preparation method.
Background technique
MoO3It is a kind of environmental-friendly n-type semiconductor metal oxide, has obtained answering extensively in gas sensor domain
With.Currently, the composite metal oxide material of three-dimensional multilevel structure is one of the research hotspot of gas sensor sensitive material, because
More active surfaces can be provided for the composite material with this structure, are more advantageous to transmission and gas of the electronics on surface
Absorption and desorption of the body molecule on surface are improving the property such as electrochemistry, gas sensing and the photocatalysis of metal oxide semiconductor
Energy aspect shows great potentiality.Compared with the complex technique of the low-dimensional alkaline metal oxide of current comparative maturity, to oxygen
Change molybdenum and carry out compound relative difficult because molybdenum oxide is acidic metal oxide, in recombination process, when with before basic anhydride
Drive liquid solution is soluble when being blended, and the especially original multilevel structure of molybdenum oxide is difficult to keep, so that current multilevel structure oxygen
Changing molybdenum composite material, development is restricted in nano-sensor field.
Currently, the preparation method of oxidation molybdenum composite material mainly takes secondary or multistep hydrothermal/solvent thermal method.2015
" RSC progress " (the RSC Advances) page 39442-39448 of 5th phase, which is reported, a kind of prepares MoO3/Fe2O3The side of nanometer rods
Method, this method is first soluble in water by Ammonium Molybdate Tetrahydrate, and instills HNO dropwise3, above-mentioned mixed solution hydro-thermal reaction 36h will give birth to
At presoma calcine 2h at 300 DEG C after obtain MoO3Nanobelt；By the MoO of preparation3Nanobelt is soluble in water, instills dropwise
The FeCl centainly matched3·6H2O and Na2SO4·10H2O mixed solution, through secondary hydro-thermal reaction 10h, the presoma of generation exists
MoO is obtained after calcining 2h at 500 DEG C3/Fe2O3Nanometer rods, this method need to carry out hydro-thermal reaction twice, final product one
The nanometer rod composite material of dimension, material are applied to catalytic field." environmental science and technology " of 52nd phase in 2018
(Environ.Sci.Technol) 11796-11802 pages, which reports, a kind of prepares MoO3/Fe2O3The method of nanobelt, the party
Method is first by Fe (NO3)3·9H2O and polyvinylpyrrolidone (PVP) are dissolved in dimethylformamide (DMF) reagent, to solvent heat
After 30h, Fe is obtained2O3Material；In preparation MoO3When, molybdenum powder is dissolved in water first, then H is slowly added2O2Solution, hydro-thermal reaction
4h is calcined after 48h at 400 DEG C and obtains MoO3Nanobelt；Finally, by the Fe of preparation2O3It is dissolved in water, is poured into containing MoO3Nanobelt
Solution in, 80 DEG C drying, 105 DEG C are dried overnight, at 300 DEG C calcine 4h obtain MoO3/Fe2O3Composite material, in preparation process
In will use organic solvent and pass through multiple hydro-thermal and high-temperature process, preparation process is cumbersome, and composite material does not have multistage knot
Structure, pattern are one-dimensional nanobelt.When the composite material is applied to the test of dimethylbenzene, optimum working temperature is relatively high to be
206 DEG C, lower to the response of 100ppm dimethylbenzene is 6.8, and response speed is 87s more slowly.
Summary of the invention
The present invention is aoxidized in reaction system to solve multilevel structure molybdenum oxide in doping and the modifications such as compound
The problem of self assembly of molybdenum construction unit and the mode of constructing are highly vulnerable to breakage, are difficult to keep multilevel structure, and a kind of multistage is provided
Structure α-Fe2O3/α-MoO3Hollow Sphere Composites and preparation method thereof.
Multilevel structure α-Fe of the invention2O3/α-MoO3Hollow Sphere Composites are a kind of microballoon of hollow structure, microballoon
Shell by α-Fe2O3/α-MoO3Composite Nano sheetpile is folded to be formed.
Above-mentioned multilevel structure α-Fe2O3/α-MoO3The preparation method of Hollow Sphere Composites, sequentially includes the following steps:
One, it is 0.005~0.018mol/L by the concentration of acetylacetone,2,4-pentanedione oxygen molybdenum, n-butanol is added in acetylacetone,2,4-pentanedione oxygen molybdenum
In, ultrasonic disperse is uniform, obtains acetylacetone,2,4-pentanedione oxygen molybdenum solution；
Two, HNO under agitation, is added dropwise dropwise into acetylacetone,2,4-pentanedione oxygen molybdenum solution3, make the pH value 1.0 of solution~
2.0；
Three, it is Fe/Mo=(4~8) by the atomic ratio of the iron of ferric acetyl acetonade and the molybdenum of acetylacetone,2,4-pentanedione oxygen molybdenum: 100, by second
Acyl acetone iron is added in the solution of step 2, is stirred evenly, is obtained mixed solution；
Four, the mixed liquor of step 3 is transferred in the reaction kettle with polytetrafluoroethyllining lining, after sealing, 200~
Solvent thermal reaction 6 under conditions of 230 DEG C~for 24 hours, is cooled to room temperature, then successively with distilled water and ethyl alcohol by the washing of precipitate of generation
Completely, it then dries, obtains presoma；
Five, presoma is placed in roaster, in air atmosphere temperature be 410~460 DEG C under conditions of calcining 1~
2h obtains multilevel structure α-Fe2O3/α-MoO3Hollow Sphere Composites.
Multilevel structure α-Fe of the invention2O3/α-MoO3Hollow Sphere Composites pattern is uniform, is by α-Fe2O3With α-
MoO3Shaggy hollow sphere made of compound nano-plates stack, stable structure.Regulated and controled first by inorganic acid when preparation
Then the critical acidity range that pH value of reaction system coexists to molybdenum oxide and iron oxide presoma passes through a step solvent-thermal method and passes through
Subsequent calcination processing, obtains α-Fe2O3/α-MoO3Hollow Sphere Composites, preparation process do not use template and surfactant,
At low cost, post-processing simply, is easy to be mass produced.
Multilevel structure α-Fe of the invention2O3/α-MoO3Hollow Sphere Composites have the triethylamine (TEA) of low concentration
Good sensitivity, minimum detectability is up to 10ppb, the reality that can be used in industrial production, fish processing and complex environment to TEA
When detection and monitoring field.
Detailed description of the invention
Fig. 1 is multilevel structure α-Fe prepared by embodiment 12O3/α-MoO3The XRD diagram of Hollow Sphere Composites；
The low range scanning electron microscope (SEM) photograph of presoma in the step of Fig. 2 is embodiment 1 four；
The high magnification scanning electron microscope (SEM) photograph of presoma in the step of Fig. 3 is embodiment 1 four；
Fig. 4 is multilevel structure α-Fe prepared by embodiment 12O3/α-MoO3The high magnification scanning electron microscope of Hollow Sphere Composites
Figure；
Fig. 5 is multilevel structure α-Fe prepared by embodiment 12O3/α-MoO3The low range transmission electron microscope of Hollow Sphere Composites
Figure；
Fig. 6 is multilevel structure α-Fe prepared by embodiment 12O3/α-MoO3The high magnification transmission electron microscope of Hollow Sphere Composites
Figure；
Fig. 7 is α-Fe in embodiment 12O3/α-MoO3Hollow sphere gas sensor is when operating temperature is 170 DEG C to 100ppm
The selective figure of gas with various；
Multilevel structure α-Fe when Fig. 8 is 170 DEG C of test temperatures in embodiment 12O3/α-MoO3Hollow Sphere Composites gas
Response diagram of the sensing element to 10ppb~100ppm triethylamine (TEA) gas.
Fig. 9 is multilevel structure α-Fe in embodiment 12O3/α-MoO3Hollow Sphere Composites gas detecting element is to 10ppb
The response-recovery curve of~100ppm triethylamine (TEA) gas.
Figure 10 is the stereoscan photograph of product prepared by embodiment 2；
The hot weight curve for the presoma that the step of Figure 11 is embodiment 3 four obtains；
Figure 12 is the stereoscan photograph for the product that embodiment 4 obtains；
Figure 13 is the multilevel structure α-Fe that embodiment 5 obtains2O3/α-MoO3The stereoscan photograph of Hollow Sphere Composites.
Specific embodiment
Specific embodiment 1: the multilevel structure α-Fe of present embodiment2O3/α-MoO3Hollow Sphere Composites are a kind of
The microballoon of hollow structure, the shell of microballoon is by α-Fe2O3/α-MoO3Composite Nano sheetpile is folded to be formed.
The shell of the microballoon of present embodiment is stacked by nano-plates, rough surface.
Specific embodiment 2: the present embodiment is different from the first embodiment in that: the outer diameter of microballoon be 400~
800nm, shell with a thickness of 80~120nm.It is other same as the specific embodiment one.
Specific embodiment 3: the present embodiment is different from the first and the second embodiment in that: the α-Fe2O3/α-
MoO3Composite Nano plate, width is 30~90nm, with a thickness of 20~40nm.It is other the same as one or two specific embodiments.
α-the Fe of the present embodiment2O3/α-MoO3Composite Nano plate stacks mutually, and a part is grown inside spherical shell, can only survey
Measure its width and thickness.
Specific embodiment 4: multilevel structure α-Fe described in specific embodiment one2O3/α-MoO3Hollow sphere composite wood
The preparation method of material, sequentially includes the following steps:
One, it is 0.005~0.018mol/L by the concentration of acetylacetone,2,4-pentanedione oxygen molybdenum, n-butanol is added in acetylacetone,2,4-pentanedione oxygen molybdenum
In, ultrasonic disperse is uniform, obtains acetylacetone,2,4-pentanedione oxygen molybdenum solution；
Two, HNO under agitation, is added dropwise dropwise into acetylacetone,2,4-pentanedione oxygen molybdenum solution3, make the pH value 1.0 of solution~
2.0；
Three, it is Fe/Mo=(4~8) by the atomic ratio of the iron of ferric acetyl acetonade and the molybdenum of acetylacetone,2,4-pentanedione oxygen molybdenum: 100, by second
Acyl acetone iron is added in the solution of step 2, is stirred evenly, is obtained mixed solution；
Four, the mixed liquor of step 3 is transferred in the reaction kettle with polytetrafluoroethyllining lining, after sealing, 200~
Solvent thermal reaction 6 under conditions of 230 DEG C~for 24 hours, is cooled to room temperature, then successively with distilled water and ethyl alcohol by the washing of precipitate of generation
Completely, it then dries, obtains presoma；
Five, presoma is placed in roaster, in air atmosphere temperature be 410~460 DEG C under conditions of calcining 1~
2h obtains multilevel structure α-Fe2O3/α-MoO3Hollow Sphere Composites.
Specific embodiment 5: present embodiment and ultrasonic disperse time in step 1 unlike specific embodiment four
For 10~30min.It is other identical as specific embodiment four.
Specific embodiment 6: present embodiment HNO in step 2 unlike specific embodiment four or five3It is dense
Degree is 0.8~2.0mol/L.It is other identical as specific embodiment four or five.
Specific embodiment 7: dry in step 4 unlike one of present embodiment and specific embodiment four to six
Dry, drying temperature is 60~80 DEG C, and drying time is 8~10h.It is other identical as one of specific embodiment four to six.
Beneficial effects of the present invention are proved with the following examples:
Embodiment 1: the multilevel structure α-Fe of the present embodiment2O3/α-MoO3The preparation method of Hollow Sphere Composites, by with
Lower step carries out:
One, acetylacetone,2,4-pentanedione oxygen molybdenum 3.49 × 10 is added in 50mL weighing bottle-4Mol adds n-butanol 30mL, ultrasound point
10min is dissipated, acetylacetone,2,4-pentanedione oxygen molybdenum solution is obtained；
Two, by the acetylacetone,2,4-pentanedione oxygen molybdenum solution magnetic agitation 10min of step 1, and it is 1mol/L that 5mL concentration is added dropwise dropwise
HNO3, the pH value of solution reaches 1.3；
Three, by 2.10 × 10-5The ferric acetyl acetonade of mol is added in the solution of step 2, is continued to stir 30min, be obtained
Mixed solution；The atomic ratio in the mixed solution being Fe/Mo is 6.0:100；
Four, the mixed liquor of step 3 is transferred to volume is 50mL in the reaction kettle of polytetrafluoroethyllining lining, is sealed
Solvent thermal reaction 12h under conditions of 220 DEG C afterwards；It is cooled to room temperature, the black precipitate of generation is first washed with distilled water 3 times,
It uses again ethanol washing 3 times, then dry 8h under the conditions of 80 DEG C, obtains presoma；
Five, presoma is placed in roaster, calcines 2h under conditions of temperature is 450 DEG C in air atmosphere, obtains more
Level structure α-Fe2O3/α-MoO3Hollow Sphere Composites.
Multilevel structure α-Fe manufactured in the present embodiment2O3/α-MoO3The XRD diagram of Hollow Sphere Composites will be as shown in Figure 1, will
33.1,35.6 ° of two diffraction maximums (being marked in Fig. 1 with black dot) in figure, with picture library standard card (JCPDSNo.33-
0664) compare, discovery respectively with bloodstone α-Fe2O3(104), the diffraction maximum of (110) crystal face is consistent；And other diffraction maximums and figure
Library Plays card (JCPDS No.05-0508) comparison, with α-MoO3It coincide, and diffraction maximum is very strong and sharp, illustrates in α-
MoO3In material, α-Fe is successfully introduced2O3, obtained α-Fe2O3/α-MoO3Composite material.
Low range scanning electron microscope (SEM) figure of presoma in the step of the present embodiment four as shown in Fig. 2, from Figure 2 it can be seen that
The pattern of presoma be it is spherical, preferably, size uniformity, diameter is 400~800nm to dispersibility, and microsphere surface is relatively rough.
The high magnification SEM figure of presoma in the step of the present embodiment four is as shown in Figure 3, it is found that presoma microballoon
It is to be constructed by the wide nano-plates for being about 80nm, nano-plates are stacked with, and all directions growth, a part is inside spherical shell.
Multilevel structure α-Fe manufactured in the present embodiment2O3/α-MoO3The high magnification SEM of Hollow Sphere Composites schemes such as Fig. 4 institute
Show, from fig. 4, it can be seen that presoma, in air after 450 DEG C of calcining 2h, the construction unit nanometer board size of microballoon slightly becomes
It greatly, is 90nm or so, surface becomes more coarse.
Multilevel structure α-Fe manufactured in the present embodiment2O3/α-MoO3The transmission electron microscope of the low range of Hollow Sphere Composites
(TEM) figure is as shown in figure 5, powerful transmission electron microscope (TEM) figure is as shown in Figure 6.α-Fe as can be seen from Figure 52O3/α-MoO3
Microballoon has hollow structure, and the thickness of spherical shell is about 100nm, and construction unit is nano-plates；Clearer it can find out from Fig. 6
Construction unit is nano-plates, and width is 30~90nm, and is stacked between nano-plates, causes hollow ball surface very thick
It is rough.
By multilevel structure α-Fe manufactured in the present embodiment2O3/α-MoO3Hollow Sphere Composites and terpinol are according to 19:1's
Mass ratio is sufficiently mixed, and is tuned into sticky paste, is then uniformly coated onto slurry on the ceramic tube for being connected with Pt and (is had on pipe
A pair of of gold electrode), after 80 DEG C of drying, 300 DEG C of heat treatment 1h, after being cooled to room temperature, set in ceramic tube in air atmosphere
Enter a Ni-Cr to be used to heat, the both ends of four Pt of ceramic tube and Ni-Cr are welded on to the pedestal of gas sensor
On, thick-film type heater-type gas sensor is made and aging three days under the conditions of on agingtable at 250~300 DEG C.
Air-sensitive performance test uses static volumetric method, and the under test gas or molten of certain volume is injected in 10L vacuum tank
Agent reaches balance with the external and internal pressure of air conditioning vacuum tank after the solvent is volatilized, when gas sensor resistance reaches in air
When to stable state, be transferred into the container containing a certain concentration Triethylamine gas and measure, when gas sensor resistance again
It is moved out when reaching stable state.Measurement range: 92~252 DEG C.Calculation of Sensitivity formula is S=Ra/Rg.Wherein, Ra indicates gas
Steady resistance value of the quick element in pure air, Rg indicate that gas sensor is tested the resistance value in gas in a certain concentration.It rings
Between seasonable and recovery time corresponds respectively to gas sensor and is placed in tested gas resistance value to change to Ra-90% (Ra- from Ra
Rg time needed for) and time needed for resistance value changes to Rg+90% (Ra-Rg) as Rg after removing in tested gas.
Multilevel structure α-Fe2O3/α-MoO3The air-sensitive performance of Hollow Sphere Composites is by gas-selectively and to low concentration mesh
The response of standard gas body is assessed.Fig. 7 is multilevel structure α-Fe2O3/α-MoO3Hollow Sphere Composites gas detecting element is in work
Make response diagram when temperature is 170 DEG C to gas with various, device is to 100ppm ethyl alcohol, formaldehyde, toluene, dimethylbenzene, dimethylamine, three
The response of seven kinds of gases of methylamine and triethylamine is respectively 6.8,1.5,2.4,4.1,7.9,10.7 and 298, is illustrated at 170 DEG C
When, α-Fe2O3/α-MoO3Device has very high selectivity to Triethylamine gas, can be effectively used for triethylamine gas in complex environment
The detection of body.
When Fig. 8 is 170 DEG C of test temperatures, multilevel structure α-Fe2O3/α-MoO3Hollow Sphere Composites gas detecting element
To the response diagram of 10ppb~100ppm TEA gas.It can be seen that with the increase of TEA concentration, multilevel structure α-Fe2O3/
α-MoO3Hollow Sphere Composites gas detecting element is consequently increased the response of TEA gas, to the sound of 100ppmTEA gas
Up to 298 should be worth, the minimum detectability to TEA gas is 10ppb, response 1.6.Fig. 9 is corresponding multilevel structure
α-Fe2O3/α-MoO3Hollow Sphere Composites gas detecting element is bent to the response-recovery of 10ppb~100ppm Triethylamine gas
Line.As seen from the figure, multilevel structure α-Fe2O3/α-MoO3Hollow Sphere Composites gas detecting element has quick sound to TEA
Characteristic is answered, the response time is in 2.6~32s.Show the multilevel structure α-Fe within the scope of concentration 10ppb~100ppm2O3/α-MoO3
Hollow Sphere Composites gas detecting element can be used for quickly measuring trace of triethylamine (TEA) gas.
Embodiment 2: unlike the first embodiment, the operation in step 2 is the present embodiment: by the acetylacetone,2,4-pentanedione of step 1
Oxygen molybdenum solution magnetic agitation 10min, and the HNO that concentration is 1mol/L is added dropwise dropwise3, the pH value of solution is made to reach 3；It is other with it is real
It is identical to apply example 1.
The scanning electron microscope (SEM) photograph of product manufactured in the present embodiment is as shown in Figure 10, from fig. 10 it can be seen that in pH in step 2
The product that value obtains under conditions of being 3 is only partially microballoon, and most of product is particle, so cannot generate under this condition
The uniform multilevel structure hollow sphere of pattern.
Embodiment 3: unlike the first embodiment, in step 5, temperature is 390 DEG C to the present embodiment in air atmosphere
Under the conditions of calcine 2h；It is other same as Example 1.
Complete oxidation is not α-Fe to the product that the present embodiment obtains2O3/α-MoO3.By testing step in the present embodiment
Thermogravimetric (TG) curve of four obtained presomas is learnt in the thermal histories of presoma as shown in figure 11, is lower than 300 in temperature
DEG C when, have an apparent weightless process (4.1%), to lose remaining organic matter in sample surfaces physical absorption water and product
Process；Secondly, having a weight gain stage in 300-380 DEG C of temperature range, show that the oxygen in presoma and air occurs
Reaction, generates α-Fe2O3/α-MoO3；Then at 380~410 DEG C, there is a faint weightless process (0.3%), this is
Caused by the decomposition rate of organic compound is greater than the oxidation rate of presoma in product, finally, when temperature is higher than 410 DEG C, directly
When to 780 DEG C, curve does not have significant change in figure, illustrates that product is stablized in this temperature range, calcination temperature should be higher than that 410 DEG C.
So, in 300 DEG C of calcinings, remaining organic compound combustion decomposes not exclusively in presoma, and gained produces according to the parameter of embodiment 3
Complete oxidation is not α-Fe to product2O3/α-MoO3。
Embodiment 4: unlike the first embodiment, in step 5, temperature is 500 DEG C to the present embodiment in air atmosphere
Under the conditions of calcine 2h；It is other same as Example 1.
The scanning electron microscope (SEM) photograph for the product that the present embodiment obtains is as shown in figure 12, it can be recognized from fig. 12 that in the present embodiment
Under the conditions of the product prepared be not complete hollow microsphere structure, it is seen that after presoma is calcined in 500 DEG C of air atmospheres, α-
Fe2O3/α-MoO3Hollow sphere multilevel structure has collapsed, and multilevel structure is difficult to keep.
By embodiment 2~4 compared with Example 1 compared with it is found that multilevel structure α-Fe2O3/α-MoO3Hollow Sphere Composites
This α-Fe2O3/α-MoO3The formation of the folded hollow structure of composite Nano sheetpile, strict control preparation condition that can just obtain.
Embodiment 5: the multilevel structure α-Fe of the present embodiment2O3/α-MoO3The preparation method of Hollow Sphere Composites, by with
Lower step carries out:
One, acetylacetone,2,4-pentanedione oxygen molybdenum 3.49 × 10 is added in 50mL weighing bottle-4Mol adds n-butanol 30mL, ultrasound point
20min is dissipated, acetylacetone,2,4-pentanedione oxygen molybdenum solution is obtained；
Two, by the acetylacetone,2,4-pentanedione oxygen molybdenum solution magnetic agitation 10min of step 1, and it is 1mol/L that 5mL concentration is added dropwise dropwise
HNO3, the pH value of solution reaches 1.3；
Three, by 2.79 × 10-5The ferric acetyl acetonade of mol is added in the solution of step 2, is continued to stir 30min, be obtained
Mixed solution；The atomic ratio of Fe/Mo is 8:100 in the mixed solution；
Four, the mixed liquor of step 3 is transferred to volume is 50mL in the reaction kettle of polytetrafluoroethyllining lining, is sealed
Solvent thermal reaction 12h under conditions of 210 DEG C afterwards；It is cooled to room temperature, the black precipitate of generation is first washed with distilled water 3 times,
It uses again ethanol washing 3 times, then dry 8h under the conditions of 80 DEG C, obtains presoma；
Five, presoma is placed in roaster, calcines 1.5h under conditions of temperature is 435 DEG C in air atmosphere, obtains
Multilevel structure α-Fe2O3/α-MoO3Hollow Sphere Composites.
Multilevel structure α-the Fe that the present embodiment obtains2O3/α-MoO3The scanning electron microscope (SEM) photograph of Hollow Sphere Composites such as Figure 13 institute
Show, as can be seen from Figure 13, multilevel structure α-Fe2O3/α-MoO3The diameter of hollow sphere is 400~800nm, and microsphere surface compares
Coarse, construction unit is nano-plates, and width is 30~80nm, and is stacked between nano-plates, causes hollow ball surface ten
Divide coarse.Using transmission electron microscope photo it can be seen that the thickness of hollow ball shell is about 100nm.
Multilevel structure α-the Fe that the present embodiment is obtained using method same as Example 12O3/α-MoO3Hollow sphere is multiple
The gas sensing property of condensation material is tested, and learns multilevel structure α-Fe manufactured in the present embodiment2O3/α-MoO3Hollow Sphere Composites
There is selectivity to Triethylamine gas, the minimum detectability to TEA gas is 10ppb, and response 1.4, the response time exists
3.0~30s.
Claims (7)
1. a kind of multilevel structure α-Fe2O3/α-MoO3Hollow Sphere Composites, it is characterised in that the material is a kind of hollow structure
Microballoon, the shell of microballoon is by α-Fe2O3/α-MoO3Composite Nano sheetpile is folded to be formed.
2. a kind of multilevel structure α-Fe according to claim 12O3/α-MoO3Hollow Sphere Composites, it is characterised in that institute
State microballoon outer diameter be 400~800nm, shell with a thickness of 80~120nm.
3. a kind of multilevel structure α-Fe according to claim 1 or 22O3/α-MoO3Hollow Sphere Composites, feature exist
In the α-Fe2O3/α-MoO3Composite Nano plate, width is 30~90nm, with a thickness of 20~40nm.
4. preparing a kind of multilevel structure α-Fe described in claim 12O3/α-MoO3The method of Hollow Sphere Composites, feature
It is that this method sequentially includes the following steps:
One, it is 0.005~0.018mol/L by the concentration of acetylacetone,2,4-pentanedione oxygen molybdenum, acetylacetone,2,4-pentanedione oxygen molybdenum is added in n-butanol, is surpassed
Sound is uniformly dispersed, and obtains acetylacetone,2,4-pentanedione oxygen molybdenum solution；
Two, HNO under agitation, is added dropwise dropwise into acetylacetone,2,4-pentanedione oxygen molybdenum solution3, make the pH value 1.0~2.0 of solution；
Three, it is Fe/Mo=(4~8) by the atomic ratio of the iron of ferric acetyl acetonade and the molybdenum of acetylacetone,2,4-pentanedione oxygen molybdenum: 100, by levulinic
Ketone iron is added in the solution of step 2, is stirred evenly, and mixed solution is obtained；
Four, the mixed liquor of step 3 is transferred in the reaction kettle with polytetrafluoroethyllining lining, after sealing, at 200~230 DEG C
Under conditions of solvent thermal reaction 6~for 24 hours, be cooled to room temperature, then successively with distilled water and ethyl alcohol that the washing of precipitate of generation is clean,
Then it dries, obtains presoma；
Five, presoma is placed in roaster, calcines 1~2h under conditions of temperature is 410~460 DEG C in air atmosphere, obtains
To multilevel structure α-Fe2O3/α-MoO3Hollow Sphere Composites.
5. a kind of multilevel structure α-Fe according to claim 42O3/α-MoO3The preparation method of Hollow Sphere Composites,
It is characterized in that in step 1 that the ultrasonic disperse time is 10~30min.
6. a kind of multilevel structure α-Fe according to claim 4 or 52O3/α-MoO3The preparation side of Hollow Sphere Composites
Method, it is characterised in that HNO in step 23Concentration be 0.8~2.0mol/L.
7. a kind of multilevel structure α-Fe according to claim 4 or 52O3/α-MoO3The preparation side of Hollow Sphere Composites
Method, it is characterised in that the drying in step 4, drying temperature are 60~80 DEG C, and drying time is 8~10h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111735856A (en) * | 2020-06-29 | 2020-10-02 | 黄冈师范学院 | Doped MoO3Nanobelt, preparation method and application thereof |
| CN113447535A (en) * | 2021-08-02 | 2021-09-28 | 上海海洋大学 | Gas sensitive material, preparation method and application thereof, and gas sensor element |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1772363A (en) * | 2004-11-11 | 2006-05-17 | 中国科学院化学研究所 | Template process of preparing hollow ball and composite hollow ball |
| CN101259402A (en) * | 2004-11-11 | 2008-09-10 | 中国科学院化学研究所 | Method for preparing hollow ball with double-layer structure and hollow ball with multi-layer complex structure by template method |
| CN101259401A (en) * | 2004-11-11 | 2008-09-10 | 中国科学院化学研究所 | Method for preparing hollow ball and hollow ball with complex structure by template method |
| CN107293734A (en) * | 2016-03-30 | 2017-10-24 | 韦升鸿 | A kind of preparation method of molybdenum trioxide/ferric oxide composite material |
-
2018
- 2018-12-26 CN CN201811599812.7A patent/CN109607621B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1772363A (en) * | 2004-11-11 | 2006-05-17 | 中国科学院化学研究所 | Template process of preparing hollow ball and composite hollow ball |
| CN101259402A (en) * | 2004-11-11 | 2008-09-10 | 中国科学院化学研究所 | Method for preparing hollow ball with double-layer structure and hollow ball with multi-layer complex structure by template method |
| CN101259401A (en) * | 2004-11-11 | 2008-09-10 | 中国科学院化学研究所 | Method for preparing hollow ball and hollow ball with complex structure by template method |
| CN107293734A (en) * | 2016-03-30 | 2017-10-24 | 韦升鸿 | A kind of preparation method of molybdenum trioxide/ferric oxide composite material |
Non-Patent Citations (4)
| Title |
|---|
| FENGDONG QU等: "Fe2O3 nanoparticles-decorated MoO3 nanobelts for enhanced chemiresistive gas sensing", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| KUAN TIAN等: "Hierarchical and Hollow Fe2O3 Nanoboxes Derived from Metal−Organic Frameworks with Excellent Sensitivity to H2S", 《ACS APPL. MATER. INTERFACES》 * |
| LILI SUI等: "Au-Loaded Hierarchical MoO3 Hollow Spheres with Enhanced Gas-Sensing Performance for the Detection of BTX (Benzene, Toluene, And Xylene) And the Sensing Mechanism", 《ACS APPL. MATER. INTERFACES》 * |
| QIANG WANG等: "Core–Shell a-Fe2O3@a-MoO3 Nanorods as Lithium-Ion Battery Anodes with Extremely High Capacity and Cyclability", 《CHEM. ASIAN J.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111735856A (en) * | 2020-06-29 | 2020-10-02 | 黄冈师范学院 | Doped MoO3Nanobelt, preparation method and application thereof |
| CN111735856B (en) * | 2020-06-29 | 2024-01-26 | 黄冈师范学院 | Doped MoO 3 Nanobelt, preparation method and application thereof |
| CN113447535A (en) * | 2021-08-02 | 2021-09-28 | 上海海洋大学 | Gas sensitive material, preparation method and application thereof, and gas sensor element |
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