CN108285175A - The preparation method and applications of pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy - Google Patents
The preparation method and applications of pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy Download PDFInfo
- Publication number
- CN108285175A CN108285175A CN201810150415.5A CN201810150415A CN108285175A CN 108285175 A CN108285175 A CN 108285175A CN 201810150415 A CN201810150415 A CN 201810150415A CN 108285175 A CN108285175 A CN 108285175A
- Authority
- CN
- China
- Prior art keywords
- nanocages
- cubic
- pseudo
- iron trioxide
- multilevel hierarchy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000002091 nanocage Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001514 detection method Methods 0.000 claims abstract description 10
- 230000035945 sensitivity Effects 0.000 claims abstract description 10
- 239000012901 Milli-Q water Substances 0.000 claims abstract description 5
- 235000019441 ethanol Nutrition 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 22
- 238000012360 testing method Methods 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 12
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 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 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 230000006641 stabilisation Effects 0.000 claims description 4
- 238000011105 stabilization Methods 0.000 claims description 4
- 238000004364 calculation method Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002513 implantation Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000010276 construction Methods 0.000 abstract description 5
- 239000011540 sensing material Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000010189 synthetic method Methods 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910002588 FeOOH Inorganic materials 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 206010019345 Heat stroke Diseases 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000012795 verification Methods 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]
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/121—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid for determining moisture content, e.g. humidity, of the fluid
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
-
- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The preparation method and applications of pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy, it is related to a kind of preparation method of di-iron trioxide nanocages and its application as humidity sensing materials.The present invention is that the step of existing method synthesizes di-iron trioxide hollow-core construction is complicated, of high cost in order to solve, and when as humidity-sensitive material response time length technical problem.This method is as follows：Prepare predecessor；Predecessor is used respectively ethyl alcohol and milli-Q water, drying, heat treatment to get.The pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy are used for Humidity Detection as the material for preparing dew cell；Material of the present invention not only stable structure, and there is excellent Unordered system, wet journey ranging from 11%RH to 95%RH, sensitivity 996, response time 2s, maximum humidity hysteresis value is 0.5%.The invention belongs to the preparation fields of humidity sensing materials.
Description
Technical field
The present invention relates to a kind of preparation method of di-iron trioxide nanocages and its as the application of humidity sensing materials.
Background technology
Air humidity refers to moisture content and moistening degree in air.In daily life, if summer humidity is excessive,
People can be allowed to feel very irritated, or even cause heatstroke.Winter humidity crosses conference and increases the probability that people obtain rheumatism.It is raw in industry
In production, the control of humidity is directly related to the quality of product；In bioengineering field, the breeding of bacterium and the culture of cell with
Humidity is closely related.In national defence, firearms and ammunition, military equipment, to equip with arms requirement of the preservation of equipment to humidity also high.Cause
This, the detection of humidity is all extremely important in every field.Currently, semiconductor humidity sensor is especially sense with di-iron trioxide
The humidity sensor of wet stock has become because environmental-friendly, cost of manufacture are cheap applies wider one kind in humidity sensor.It presses
The synthetic method of document report, the humidity-sensitive material based on di-iron trioxide can substantially be divided into following a few classes：One, with
FeOOH is that presoma obtains di-iron trioxide by pyrolysis；Two, enhanced by adulterating the electrolyte such as LiCl in di-iron trioxide
Response of the electric conductivity and then increase humidity-sensitive material of di-iron trioxide in different humidity；Three, synthesis di-iron trioxide/Si etc. is multiple
Close the wet sensitive performance that object increases di-iron trioxide.In existing several synthetic methods pure phase is obtained by being pyrolyzed FeOOH presomas
Di-iron trioxide method simple economy the most, but when di-iron trioxide synthesized is as humidity-sensitive material usually will appear sound
The problems such as answering overlong time, to seriously limit its application.Although and the wet of material can be made with synthetic composite material by adulterating
Quick performance makes moderate progress but building-up process is complicated, and intermediate uncontrollable factor is excessive, to considerably increase synthesis difficulty and cost.
Therefore, the synthetic method for developing new di-iron trioxide humidity-sensitive material will have prodigious Practical significance and value.
In the method for existing two kinds typical synthesis di-iron trioxide hollow-core constructions, although the method for chemical etching can have
The formation hollow-core construction of effect, but synthesis needs several steps such as the synthesis by presoma, the etching of presoma, pyrolysis, step
Very complicated considerably increases synthesis difficulty and cost；And it is existing pyrolysis MOF presomas method because synthesis temperature it is relatively low, when
Between it is longer so that obtained precursor construction is fine and close, lead to that multilevel hierarchy can not be formed in pyrolysis.It thus greatly reduces
The specific surface area of product.For sensitive material, larger specific surface area mean can to provide more active sites and
Superior sensitive property.Therefore, existing synthetic method in terms of the excellent di-iron trioxide humidity-sensitive material of synthesis performance all
It is short of.
Invention content
The complicated, cost of the step of synthesizing di-iron trioxide hollow-core construction the purpose of the present invention is to solve existing method
Height, and when as humidity-sensitive material response time length technical problem, provide a kind of three oxygen of pseudo-cubic with multilevel hierarchy
Change the preparation method and applications of two iron nanocages.
The preparation method of pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy follows the steps below：
One, 2.5~5.5g polyvinylpyrrolidones are dissolved in 25~40mL water, magnetic agitation is to being completely dissolved, then
0.15~0.24g K are added3[Fe(CN)]6, pH value is adjusted to≤3.0 with HCl solution, the acidic mixed solution of acquisition is shifted
Into hydrothermal reaction kettle, 1h is reacted at 170~200 DEG C, is centrifuged after cooled to room temperature, obtain predecessor；
Two, after predecessor being used ethyl alcohol and milli-Q water respectively, 6~8h is dried in vacuo at 60~80 DEG C, then in sky
Predecessor is heat-treated to 1h in gas atmosphere at 350~450 DEG C, obtains the pseudo-cubic di-iron trioxide nanometer with multilevel hierarchy
Cage.
The pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy are used for as the material for preparing dew cell
Humidity Detection；
The preparation method of the dew cell is as follows：
Pseudo-cubic di-iron trioxide nanocages powder with multilevel hierarchy is mixed into uniform slurry with terpinol,
The mass content of terpinol is 5%~10% in slurry, then coats slurry to the alumina ceramic tube table for being coated with gold electrode
Face is dried at 70~90 DEG C, is then heat-treated at 250~300 DEG C in 1~2h, then ceramic tube after baking and is implanted into one
Heater strip is welded on gas sensor pedestal by root heater strip, and the di-iron trioxide with multilevel hierarchy pseudo-cubic is made and receives
Rice cage thick-film type dew cell；
The method of the Humidity Detection is as follows：
It can be tested moisture sensitivity is carried out after dew cell age stability, at ambient temperature, by the full of solution to be measured
Be put into 2.5L narrow-mouthed bottles and sealed at least for 24 hours with salting liquid, first by dew cell be put into equipped with relative humidity be 11% it is to be measured
In the saturated salt solution narrow-mouthed bottle of solution, after resistance stabilization, dew cell is placed into and is waited for higher than 11% equipped with relative humidity
It surveys in the saturated salt solution narrow-mouthed bottle of solution and is recorded by test system after resistance value is stablized again, dew cell needs after test
It places back in the saturated salt solution narrow-mouthed bottle for the solution to be measured for being 11% equipped with relative humidity,
Calculation of Sensitivity formula is S=R11%/Rx, x ＞ 11%, wherein R11%Indicate relative humidity of the dew cell 11%
In steady resistance value, RxIndicate steady resistance value of the dew cell in the relative humidity of x%, the response time is dew cell
Resistance value is placed in tested relative humidity from R11%Change to R11%- 90% (R11%-Rx) needed for time, recovery time be wet sensitive member
Part is from resistance value after removal in tested gas by RxChange to Rx+ 90% (R11%-Rx) needed for time.
The present invention has the advantages that：
(1) size (150nm) of di-iron trioxide nanocages is burnt much smaller than most of reported by MOF in the present invention
Tie the metal oxide (1 μm) obtained.Meanwhile the metal oxide usually obtained by the sintering of MOF presomas is difficult to keep former
Have and contains multilevel hierarchy on the basis of pattern.Di-iron trioxide multilevel hierarchy in the present invention is apparent.Small grain size and more
Level structure is effectively increased the specific surface area of di-iron trioxide.In addition, the metal oxide obtained by the calcining of MOF presomas exists
The application of every field has more report, but there is not been reported for the application in terms of wet sensitive.
(2) synthetic method of material of the present invention is simple, of low cost, and solvent for use is environmentally friendly for water, and product
It is easily isolated and purifies, be suitble to large-scale production.
(3) material of the present invention not only stable structure, and there is excellent Unordered system, wet journey ranging from 11%RH to arrive
95%RH, sensitivity 996, response time 2s, maximum humidity hysteresis value be 0.5%, these wet sensitive performances be much better than it has been reported that
Many humidity sensors.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph for testing the pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy that one prepares；
Fig. 2 is the transmission electron microscope picture for testing the pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy that one prepares；
Fig. 3 be test one prepare the pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy responded at 25 DEG C-
Recovery curve；
Fig. 4 is to test the pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy of a preparation to different relative humidity
The linear relationship curve of Sensitirity va1ue；
Fig. 5 is the humidity hysteresis relationship song for testing the pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy that one prepares
Line.
Specific implementation mode
Technical solution of the present invention is not limited to act specific implementation mode set forth below, further includes between each specific implementation mode
Arbitrary combination.
Specific implementation mode one：The system of pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy in present embodiment
Preparation Method follows the steps below：
One, 2.5~5.5g polyvinylpyrrolidones are dissolved in 25~40mL water, magnetic agitation is to being completely dissolved, then
0.15~0.24g K are added3[Fe(CN)]6, pH value is adjusted to≤3.0 with HCl solution, the acidic mixed solution of acquisition is shifted
Into hydrothermal reaction kettle, 1h is reacted at 170~200 DEG C, is centrifuged after cooled to room temperature, obtain predecessor；
Two, after predecessor being used ethyl alcohol and milli-Q water respectively, 6~8h is dried in vacuo at 60~80 DEG C, then in sky
Predecessor is heat-treated to 1h in gas atmosphere at 350~450 DEG C, obtains the pseudo-cubic di-iron trioxide nanometer with multilevel hierarchy
Cage.
Specific implementation mode two：The present embodiment is different from the first embodiment in that by the poly- second of 3~5g in step 1
Alkene pyrrolidone is dissolved in 28~38mL water.It is other same as the specific embodiment one.
Specific implementation mode three：By 4g in step 1 unlike one of present embodiment and specific implementation mode one or two
Polyvinylpyrrolidone is dissolved in 30mL water.It is other identical as one of specific implementation mode one or two.
Specific implementation mode four：In step 1 unlike one of present embodiment and specific implementation mode one to three
1h is reacted at 175~195 DEG C.It is other identical as one of specific implementation mode one to three.
Specific implementation mode five：In step 1 unlike one of present embodiment and specific implementation mode one to four
1h is reacted at 180 DEG C.It is other identical as one of specific implementation mode one to four.
Specific implementation mode six：70 in step 2 unlike one of present embodiment and specific implementation mode one to five
DEG C vacuum drying 7h.It is other identical as one of specific implementation mode one to five.
Specific implementation mode seven：In sky in step 2 unlike one of present embodiment and specific implementation mode one to six
Predecessor is heat-treated to 1h in gas atmosphere at 360~440 DEG C.It is other identical as one of specific implementation mode one to six.
Specific implementation mode eight：In sky in step 2 unlike one of present embodiment and specific implementation mode one to seven
Predecessor is heat-treated to 1h in gas atmosphere at 370~430 DEG C.It is other identical as one of specific implementation mode one to seven.
Specific implementation mode nine：In sky in step 2 unlike one of present embodiment and specific implementation mode one to eight
Predecessor is heat-treated to 1h in gas atmosphere at 400 DEG C.It is other identical as one of specific implementation mode one to eight.
Specific implementation mode ten：Pseudo-cubic di-iron trioxide nanometer with multilevel hierarchy described in specific implementation mode one
Cage is used for Humidity Detection as the material for preparing dew cell；
The preparation method of the dew cell is as follows：
Pseudo-cubic di-iron trioxide nanocages powder with multilevel hierarchy is mixed into uniform slurry with terpinol,
The mass content of terpinol is 5%~10% in slurry, then coats slurry to the alumina ceramic tube table for being coated with gold electrode
Face is dried at 70~90 DEG C, is then heat-treated at 250~300 DEG C in 1~2h, then ceramic tube after baking and is implanted into one
Heater strip is welded on gas sensor pedestal by root heater strip, and the di-iron trioxide with multilevel hierarchy pseudo-cubic is made and receives
Rice cage thick-film type dew cell；
The method of the Humidity Detection is as follows：
It can be tested moisture sensitivity is carried out after dew cell age stability, at ambient temperature, by the full of solution to be measured
Be put into 2.5L narrow-mouthed bottles and sealed at least for 24 hours with salting liquid, first by dew cell be put into equipped with relative humidity be 11% it is to be measured
In the saturated salt solution narrow-mouthed bottle of solution, after resistance stabilization, dew cell is placed into and is waited for higher than 11% equipped with relative humidity
It surveys in the saturated salt solution narrow-mouthed bottle of solution and is recorded by test system after resistance value is stablized again, dew cell needs after test
It places back in the saturated salt solution narrow-mouthed bottle for the solution to be measured for being 11% equipped with relative humidity,
Calculation of Sensitivity formula is S=R11%/Rx, x ＞ 11%, wherein R11%Indicate relative humidity of the dew cell 11%
In steady resistance value, RxIndicate steady resistance value of the dew cell in the relative humidity of x%, the response time is dew cell
Resistance value is placed in tested relative humidity from R11%Change to R11%- 90% (R11%-Rx) needed for time, recovery time be wet sensitive member
Part is from resistance value after removal in tested gas by RxChange to Rx+ 90% (R11%-Rx) needed for time.
Using following experimental verifications effect of the present invention：
Experiment one：
The preparation method of pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy follows the steps below：
One, 2.5g polyvinylpyrrolidones (PVP) are dissolved in 30mL water, then magnetic agitation is added to being completely dissolved
0.18g K3[Fe(CN)]6, magnetic agitation 10 minutes obtains faint yellow mixed solution, with the HCl solution general of a concentration of 6mol/L
PH value is adjusted to 3.0, and the acidic mixed solution of acquisition is transferred in hydrothermal reaction kettle, 1h is reacted at 170 DEG C, naturally cools to
It is centrifuged after room temperature, obtains the predecessor of Prussia's blue；
Two, after predecessor being used ethyl alcohol and milli-Q water respectively, 8h is dried in vacuo at 80 DEG C, then in air atmosphere
Predecessor is heat-treated 1h at 350 DEG C, obtains the pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy.
The nanocages are the pseudo-cubic with multilevel hierarchy, and pseudo-cubic is constructed by nano-particle, and standard is vertical
The length of side of cube nanocages is about 150nm.
The preparation method of dew cell is as follows：
Pseudo-cubic di-iron trioxide nanocages powder with multilevel hierarchy is mixed into uniform slurry with terpinol,
The mass content of terpinol is 6% in slurry, then coats slurry to the aluminium oxide ceramics pipe surface for being coated with gold electrode, 80
It is dried at DEG C, is then heat-treated 2h at 280 DEG C, then a heater strip is implanted into ceramic tube after baking, wire bond will be heated
It is connected on gas sensor pedestal, the di-iron trioxide nanocages thick-film type dew cell with multilevel hierarchy pseudo-cubic is made；
The method of the Humidity Detection is as follows：
It can be tested moisture sensitivity is carried out after dew cell age stability, at ambient temperature, by solution to be measured
LiCl solution, which is put into 2.5L narrow-mouthed bottles, to be sealed at least for 24 hours, and dew cell is first put into the LiCl for being 11% equipped with relative humidity
In solution narrow-mouthed bottle, after resistance stabilization, dew cell is placed into the LiCl solution narrow-mouthed bottles equipped with relative humidity 95% and is waited for
Resistance value is recorded after stablizing again by test system, and it is 11% that dew cell, which need to be placed back in equipped with relative humidity, after test
In LiCl solution narrow-mouthed bottles,
Di-iron trioxide nanocages powder with multilevel hierarchy pseudo-cubic is assembled into thick-film type dew cell, to it
Wet sensitive performance test is carried out, which shows excellent wet sensitive performance at room temperature (25 DEG C).11%RH's and 95%RH
In transfer process, response time 2s, sensitivity 996, and the dew cell has preferably within the scope of the wet journey of detection
Linear relationship (fitting coefficient R2=0.9989).The material can carry out humidity within the scope of 11% to 95% wet journey quick
It is effective to measure.
Claims (10)
1. the preparation method of the pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy, it is characterised in that have multilevel hierarchy
The preparation methods of pseudo-cubic di-iron trioxide nanocages follow the steps below：
One, 2.5~5.5g polyvinylpyrrolidones are dissolved in 25~40mL water, then magnetic agitation is added to being completely dissolved
0.15~0.24g K3[Fe(CN)]6, pH value is adjusted to≤3.0 with HCl solution, the acidic mixed solution of acquisition is transferred to water
In thermal response kettle, 1h is reacted at 170~200 DEG C, is centrifuged after cooled to room temperature, obtain predecessor；
Two, after predecessor being used ethyl alcohol and milli-Q water respectively, 6~8h is dried in vacuo at 60~80 DEG C, then in air gas
Predecessor is heat-treated to 1h in atmosphere at 350~450 DEG C, obtains the pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy.
2. the preparation method of the pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy according to claim 1, special
Sign is in step 1 3~5g polyvinylpyrrolidones being dissolved in 28~38mL water.
3. the preparation method of the pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy according to claim 1, special
Sign is in step 1 4g polyvinylpyrrolidones being dissolved in 30mL water.
4. the preparation method of the pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy according to claim 1, special
Sign is in step 1 to react 1h at 175~195 DEG C.
5. the preparation method of the pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy according to claim 1, special
Sign is in step 1 to react 1h at 180 DEG C.
6. the preparation method of the pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy according to claim 1, special
Sign is in step 2 to be dried in vacuo 7h at 70 DEG C.
7. the preparation method of the pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy according to claim 1, special
Sign is in step 2 in air atmosphere for predecessor to be heat-treated 1h at 360~440 DEG C.
8. the preparation method of the pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy according to claim 1, special
Sign is in step 2 in air atmosphere for predecessor to be heat-treated 1h at 370~430 DEG C.
9. the preparation method of the pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy according to claim 1, special
Sign is in step 2 in air atmosphere for predecessor to be heat-treated 1h at 400 DEG C.
10. the application of the pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy described in claim 1, it is characterised in that institute
It states the pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy and is used for Humidity Detection as the material for preparing dew cell；
The preparation method of the dew cell is as follows：
Pseudo-cubic di-iron trioxide nanocages powder with multilevel hierarchy is mixed into uniform slurry, slurry with terpinol
The mass content of middle terpinol is 5%~10%, then coats slurry to the aluminium oxide ceramics pipe surface for being coated with gold electrode,
It is dried at 70~90 DEG C, piece heating of implantation in 1~2h, then ceramic tube after baking is then heat-treated at 250~300 DEG C
Silk, heater strip is welded on gas sensor pedestal, and it is thick that the di-iron trioxide nanocages with multilevel hierarchy pseudo-cubic are made
Membranous type dew cell；
The method of the Humidity Detection is as follows：
It can be tested moisture sensitivity is carried out after dew cell age stability, at ambient temperature, by the saturated salt of solution to be measured
Solution, which is put into 2.5L narrow-mouthed bottles, to be sealed at least for 24 hours, and dew cell is first put into the solution to be measured for being 11% equipped with relative humidity
Saturated salt solution narrow-mouthed bottle in, after resistance stabilization, by dew cell place into equipped with relative humidity higher than 11% it is to be measured molten
It is recorded by test system after resistance value is stablized again in the saturated salt solution narrow-mouthed bottle of liquid, dew cell needs again after test
It puts back in the saturated salt solution narrow-mouthed bottle for the solution to be measured for being 11% equipped with relative humidity,
Calculation of Sensitivity formula is S=R11%/Rx, x ＞ 11%, wherein R11%Indicate dew cell in 11% relative humidity
Steady resistance value, RxIndicate that steady resistance value of the dew cell in the relative humidity of x%, response time are placed in for dew cell
Resistance value is from R in tested relative humidity11%Change to R11%- 90% (R11%-Rx) needed for time, recovery time be dew cell from
Resistance value is by R after being removed in tested gasxChange to Rx+ 90% (R11%-Rx) needed for time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810150415.5A CN108285175B (en) | 2018-02-13 | 2018-02-13 | Application of quasi-cubic iron sesquioxide nano cage with multi-stage structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810150415.5A CN108285175B (en) | 2018-02-13 | 2018-02-13 | Application of quasi-cubic iron sesquioxide nano cage with multi-stage structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108285175A true CN108285175A (en) | 2018-07-17 |
| CN108285175B CN108285175B (en) | 2020-06-23 |
Family
ID=62832984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810150415.5A Active CN108285175B (en) | 2018-02-13 | 2018-02-13 | Application of quasi-cubic iron sesquioxide nano cage with multi-stage structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108285175B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113295739A (en) * | 2021-04-19 | 2021-08-24 | 济南大学 | Based on hollow Fe2O3The dual-mode electrochemical aptamer sensor and the method for determining acetamiprid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103730664A (en) * | 2014-01-06 | 2014-04-16 | 中国科学院宁波材料技术与工程研究所 | Positive electrode material of lithium sulfur battery and preparation method and application of material |
| CN104556245A (en) * | 2014-12-31 | 2015-04-29 | 中国地质大学（武汉） | Hamburger-shaped nanometer ferric oxide material, and preparation method and usage thereof |
| CN107091860A (en) * | 2017-05-22 | 2017-08-25 | 苏州大学 | Moisture sensor based on the sour cyanines polymer in golden doping side and its production and use |
| CN107381653A (en) * | 2017-07-25 | 2017-11-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Micro- cube di-iron trioxide lithium ion battery electrode material of hollow structure |
| CN107572595A (en) * | 2017-08-17 | 2018-01-12 | 合肥国轩高科动力能源有限公司 | Preparation method of iron oxide negative electrode material with hollow porous structure |
-
2018
- 2018-02-13 CN CN201810150415.5A patent/CN108285175B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103730664A (en) * | 2014-01-06 | 2014-04-16 | 中国科学院宁波材料技术与工程研究所 | Positive electrode material of lithium sulfur battery and preparation method and application of material |
| CN104556245A (en) * | 2014-12-31 | 2015-04-29 | 中国地质大学（武汉） | Hamburger-shaped nanometer ferric oxide material, and preparation method and usage thereof |
| CN107091860A (en) * | 2017-05-22 | 2017-08-25 | 苏州大学 | Moisture sensor based on the sour cyanines polymer in golden doping side and its production and use |
| CN107381653A (en) * | 2017-07-25 | 2017-11-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Micro- cube di-iron trioxide lithium ion battery electrode material of hollow structure |
| CN107572595A (en) * | 2017-08-17 | 2018-01-12 | 合肥国轩高科动力能源有限公司 | Preparation method of iron oxide negative electrode material with hollow porous structure |
Non-Patent Citations (3)
| Title |
|---|
| P. V. ADHYAPAK ET AL.: "a-Fe2O3 nanorods: Low temperature synthesis,characterization and humidity response properties", 《PHYSICS AND TECHNOLOGY OF SENSORS (ISPTS), 2012 1ST INTERNATIONAL SYMPOSIUM ON》 * |
| QIANQIAN TENG ET AL.: "Formation of Fe2O3 microboxes/ macroporous carbon hybrids from Prussian blue template for electrochemical applications", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| XIAOPING SHEN ET AL.: "Morphology syntheses and properties of well-defined Prussian Blue nanocrystals by a facile solution approach", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113295739A (en) * | 2021-04-19 | 2021-08-24 | 济南大学 | Based on hollow Fe2O3The dual-mode electrochemical aptamer sensor and the method for determining acetamiprid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108285175B (en) | 2020-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109046429B (en) | Spongy gold nanoparticle/graphite phase carbon nitride composite material electrochemical sensor for chloramphenicol detection | |
| Okubo et al. | Low-temperature preparation of nanostructured zirconia and YSZ by sol-gel processing | |
| CN108706637B (en) | A kind of preparation method of adjustable magnetic iron oxide mesomorphic material of uniform size | |
| CN101811888A (en) | Method for preparing composite air-sensitive membrane of carbon nano tube embedded with oxide quantum dots | |
| CN108996557B (en) | Hollow sphere structured nickel oxide/copper oxide composite nano material and preparation method thereof | |
| CN111848161A (en) | Preparation method of nano zirconia powder | |
| WO2015158272A1 (en) | Method for manufacturing hydrogen gas sensor by using noble metal doped titanium dioxide nano-powder | |
| CN108285175A (en) | The preparation method and applications of pseudo-cubic di-iron trioxide nanocages with multilevel hierarchy | |
| CN114956828A (en) | Silicon carbide ceramic and preparation method and application thereof | |
| JPS61101462A (en) | Zirconia ceramic | |
| CN114563449A (en) | Method for visually detecting ochratoxin A based on self-powered photoelectric analysis | |
| CN107298583A (en) | A kind of tin ash composite coating and preparation method thereof | |
| JPH05170532A (en) | Production of zirconia sintered product | |
| CN109020542A (en) | The preparation method of medium dielectric constant microwave medium ultra high quality factor microwave-medium ceramics | |
| CN113680311B (en) | Preparation method of zinc-based composite metal oxide | |
| CN115096974B (en) | Mixed-potential acetone sensor and preparation method thereof | |
| CN108217749B (en) | Hollow spherical zinc ferrite gas sensor and preparation method thereof | |
| CN116297710A (en) | Multifunctional pressure-gas sensor and preparation method and application thereof | |
| CN109856203A (en) | Mosaic alloy/titanium dioxide cerium tablet/carbon fiber composite nano materials preparation method and applications research | |
| CN109626441B (en) | Multilevel structure α -Fe2O3Preparation method of hollow sphere nano material | |
| CN113433174A (en) | Ethanol sensor based on ZnO porous structure microsphere sensitive material, preparation method and application thereof | |
| CN112255277A (en) | Acetone gas sensor based on branched heterojunction array, preparation method and application | |
| CN104391025A (en) | Preparation method of electrochemical carbon oxide gas sensor electrode | |
| CN112255279A (en) | Flower-shaped V2O5Preparation of microsphere and application of microsphere in acetone gas sensor | |
| CN117949500B (en) | Preparation and application of high-response zinc cobaltate/indium trioxide composite gas-sensitive material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |