CN103792227B - Nano composite oxide sensitive material for formaldehyde and benzene - Google Patents
Nano composite oxide sensitive material for formaldehyde and benzene Download PDFInfo
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- CN103792227B CN103792227B CN201410042995.8A CN201410042995A CN103792227B CN 103792227 B CN103792227 B CN 103792227B CN 201410042995 A CN201410042995 A CN 201410042995A CN 103792227 B CN103792227 B CN 103792227B
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- benzene
- formaldehyde
- salt
- sensitive material
- manganese
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Abstract
The invention relates to a nano composite oxide sensitive material for monitoring formaldehyde and benzene. The nano composite oxide sensitive material is a nano powder material consisting of the components in percentage by mass: 50-60 percent of Bi2O3, 20-30 percent of TiO2 and 15-25 percent of MnO2. A preparation method comprises the steps of co-dissolving bismuth salt, titanium salt and manganese salt in a citric acid aqueous solution, performing ultrasonic oscillation until the solution is clarified, adding a proper amount of ethylene diamine tetraacetic acid disodium under high-speed stirring to keep the solution clarified, continuing to stir, dropwise adding ammonia water to adjust the pH value of the solution, stewing, aging, filtering and drying the product, performing full grinding, and roasting in a box type resistance furnace to obtain the powder material consisting of the Bi2O3, TiO2 and MnO2. A formaldehyde and benzene catalysis luminous sensor made of the composite oxide sensitive material provided by the invention is wide in linear range, high in selectivity and high in sensitivity, and can monitor the formaldehyde and the benzene in air on line without influence by coexistence substances.
Description
Technical field
The present invention relates to a kind of catalytic luminescence sensitive material for monitoring formaldehyde and benzene, especially by Bi2O3、TiO2With
MnO2The nano composite oxide sensitive material of composition, belongs to field of sensing technologies.
Background technology
Formaldehyde is a kind of colourless volatile industrial chemicals, as adhesive raw materials, disinfectant, preservative and finishing agent quilt
It is widely used in the products such as compression plate, coating, paint, cosmetics and packaging material.The first to the various concentration of in the air for the people
Aldehyde has different reflections, when concentration of formaldehyde reaches 0.06～0.07mg/m in atmosphere3When, child will occur slightly to pant,
Reach 0.1mg/m3When just have abnormal flavour and sense of discomfort, reach 0.5mg/m3When eyes can be stimulated to cause shed tears, reach 0.6mg/m3Can
Cause throat discomfort or pain, reach 1mg/m3When can cause and shed tears in a large number, reach 10mg/m3When then feel dyspnea, reach
30mg/m3When can make one to suffocate.Long Term Contact low dosage formaldehyde (0.1mg/m3Below) chronic respiratory tract disease, female can be caused
Property pregnancy syndrome, neonate body constitution reduce and the pathological changes such as chromosomal abnormality.
Benzene is a kind of industrial chemicals with aromatic odor, the benzene of in the air be mainly derived from building coating, paint for decoration,
Adhesive solvent and vehicle exhaust etc..Chronic Benzene Poisoning mainly has stimulation to skin, eyes and upper respiratory tract；Often connect
Tactile benzene, skin can because of defat desiccation desquamation, some appearance allergic eczemas；The long-term benzene that sucks can lead to aplastic lean
Blood.
Benzene and formaldehyde are all confirmed as carcinogen by IARC (IARC), and the two is all in room air
Major pollutants.Zoopery shows that formaldehyde and benzene all can increase Micronucleus and rate of teratosperm, lead to
Pregnant Mus abortion ratio rises and litter size declines, damages mouse spleen and lungs, has synergism during the two synergy.Grind
Study carefully the report benzene of low concentration and formaldehyde can induce leukemia, because in the environment of our live and works benzene and formaldehyde is not nowhere
Therefore studying rapid and accurate determination Minim Benzene in Gas Phase and the method for formaldehyde has very strong realistic meaning.
Measure trace formaldehyde and the method for benzene mainly has photometry, electrochemical process, chromatography, chemoluminescence method, makings liquid
Matter is combined method and the chromatography of ions etc..Due to these methods be required for preconcentration and proper treatment could to pass through analytical tool complete
Become to measure, therefore time-consuming is difficult scene realization.Inventor in 2006《Assay office》On deliver entitled " nanometer is multiple
It is combined using nanosized copper ferromanganese (atomic ratio 4: 3: 1) in the paper of the benzene homologues of condensation material catalytic luminescence method mensure in the air "
Oxide, can be with on-line checking 1～80mg/m used as sensitive material3Benzene homologues, detection limit is up to 0.5mg/m3But, formaldehyde,
Methanol, ethanol and acetone have certain interference to the mensure of benzene homologues, show that the selectivity of sensitive material has much room for improvement.2008
《Chemical journal》On use in the paper of entitled formaldehyde of in the air " nano composite oxide catalytic luminescence method measure " delivered
Nanoscale molybdenum vanadium titanium (atomic ratio is 2: 3: 5) composite oxides, can be with on-line checking 0.07～34mg/m used as sensitive material3's
Formaldehyde, detection limit is up to 0.04mg/m3, but benzene, the mensure of ammonia, sulfur dioxide and acetone PARA FORMALDEHYDE PRILLS(91,95) have certain interference, invention
Patent 200910223546.2 discloses a kind of nano sensitive material of monitoring benzene homologues, using the sensor of this material preparation
The micro-benzene of in the air can be monitored, but formaldehyde, methanol, hydrogen sulfide and acetic acid etc. also have response signal.
Content of the invention
The purpose of the present invention is to overcome the shortcomings of conventional art, provides a kind of PARA FORMALDEHYDE PRILLS(91,95) and benzene to have the nanometer of more high selectivity
Catalytic luminescence sensitive material and preparation method thereof.The monitoring formaldehyde making of this sensitive material and the gas sensor of benzene, can
Do not disturbed by other concurrents with the quick, trace formaldehyde of Accurate Determining in the air at the scene and benzene.
Nano sensitive material of the present invention is by Bi2O3、TiO2And MnO2The nano-powder material of composition, its preparation
Method is：Bismuth salt, titanium salt and manganese salt are codissolved in the aqueous citric acid solution that mass fraction is 10%, sonic oscillation is extremely clarified,
Add appropriate disodiumedetate to make solution keep clear state more than 5 hours under high velocity agitation, continue stirring with every
Minute is 6.5-7.3 less than ammonia to the pH value of the speed Deca mass fraction 15% of 1mL, and still aging 2-5 hour will be sunk
Shallow lake filtration is placed in drying baker 5-10 hour is dried at a temperature of 95-110 DEG C, after being fully ground, in chamber type electric resistance furnace with
The speed being less than 5 DEG C per minute is warming up to 290-330 DEG C, keeps this temperature calcination 2-3 hour, obtains by Bi2O3、TiO2With
MnO2The powder body material of composition.
Wherein, bismuth salt is anhydride or the hydration of bismuth acetate, Oxalic acid bismuth salt., bismuth nitrate, bismuth sulfate, Bismugel (Biothrax). and bismuth trichloride
The mixture of one or more of thing, titanium salt be Titanium Nitrate, titanium phosphate, the anhydride of titanium sulfate, acetic acid titanium and titanium tetrachloride or
The mixture of one or more of hydrate, manganese salt is the anhydrous of manganese acetate, manganese sulfate, manganese chloride, manganese nitrate and Manganese perchlorate
The mixture of one or more of thing or hydrate.
When prepared particle diameter of nanometer powder is less than 35nm, and each constituent mass fraction meets Bi2O3(50-60%), TiO2
(20-30%) and MnO2(15-25%), when, for the sensitive material as monitoring formaldehyde and benzene, there is very high susceptiveness and choosing
Selecting property.
Specific embodiment
Embodiment 1
Seven water Oxalic acid bismuth salt .s, Titanium Nitrate and acetate dihydrate manganese are codissolved in the aqueous citric acid solution that mass fraction is 10%,
Sonic oscillation, to clarifying, adds appropriate disodiumedetate to make solution keep clear state 6 hours under high velocity agitation, continues
Continue stirring with the ammonia of the speed Deca mass fraction 15% less than 1mL per minute to pH value for 6.6, still aging 3 hours,
Precipitation filtration is placed in drying baker being dried 6 hours at a temperature of 100 DEG C, after being fully ground, with every in chamber type electric resistance furnace
The speed less than 5 DEG C for the minute is warming up to 300 DEG C, keeps this temperature calcination 2 hours, obtains by Bi2O3、TiO2And MnO2Composition
Powder body material.
Analysis：With this powder body material of transmissioning electric mirror test, its maximum particle diameter is less than 35nm, and mean diameter is about 30nm；
Component analyses are carried out to it, recording mass percent is 52.1%Bi2O3, 28.5%TiO2And 19.4%MnO2.
Application：Measure formaldehyde and the benzene of in the air using this powder body material as sensitive material, the range of linearity is formaldehyde 0.5-
75mg/m3With benzene 0.7-86mg/m3, detect and be limited to formaldehyde 0.1mg/m3With benzene 0.3mg/m3, concurrent do not interfere with.
Embodiment 2
Five water bismuth nitrate, bismuth sulfate, phosphate dihydrate titanium and manganese sulfate are codissolved in the citric acid water that mass fraction is 10%
In solution, sonic oscillation, to clarifying, adds appropriate disodiumedetate to make solution keep clear state 7 under high velocity agitation
Hour, continue stirring with the ammonia of the speed Deca mass fraction 15% less than 1mL per minute to pH value for 7.2, standing is old
Change 2 hours, precipitation filtration is placed in drying baker being dried 7 hours at a temperature of 105 DEG C, after being fully ground, in box resistance
It is warming up to 325 DEG C with the speed being less than 5 DEG C per minute in stove, keeps this temperature calcination 3 hours, obtain by Bi2O3、TiO2With
MnO2The powder body material of composition.
Analysis：With this powder body material of transmissioning electric mirror test, its maximum particle diameter is less than 33nm, and mean diameter is about 27nm；
Component analyses are carried out to it, recording mass percent is 55.7%Bi2O3, 24.1%TiO2And 20.2%MnO2.
Application：Measure formaldehyde and the benzene of in the air using this powder body material as sensitive material, the range of linearity is formaldehyde 0.3-
65mg/m3With benzene 0.5-70mg/m3, detect and be limited to formaldehyde 0.08mg/m3With benzene 0.2mg/m3, concurrent do not interfere with.
Embodiment 3
Bismugel (Biothrax)., acetic acid titanium, manganese nitrate and manganese chloride tetrahydrate are codissolved in the aqueous citric acid solution that mass fraction is 10%
In, sonic oscillation, to clarifying, adds appropriate disodiumedetate to make solution keep clear state 8 little under high velocity agitation
When, continue stirring with the ammonia of the speed Deca mass fraction 15% less than 1mL per minute to pH value for 6.8, still aging 5
Hour, precipitation filtration is placed in drying baker being dried 9 hours at a temperature of 95 DEG C, after being fully ground, in chamber type electric resistance furnace
It is warming up to 310 DEG C with the speed being less than 5 DEG C per minute, keeps this temperature calcination 3 hours, obtain by Bi2O3、TiO2And MnO2
The powder body material of composition.
Analysis：With this powder body material of transmissioning electric mirror test, its maximum particle diameter is less than 35nm, and mean diameter is about 30nm；
Component analyses are carried out to it, recording mass percent is 57.4%Bi2O3, 26.1%TiO2And 16.5%MnO2.
Application：Measure formaldehyde and the benzene of in the air using this powder body material as sensitive material, the range of linearity is formaldehyde 0.8-
105mg/m3With benzene 0.9-96mg/m3, detect and be limited to formaldehyde 0.3mg/m3With benzene 0.3mg/m3, concurrent do not interfere with.
Embodiment 4
Bismuth acetate, nine water titanium sulfates and perchlorate hexahydrate's manganese are codissolved in the aqueous citric acid solution that mass fraction is 10%
In, sonic oscillation, to clarifying, adds appropriate disodiumedetate to make solution keep clear state 6 little under high velocity agitation
When, continue stirring with the ammonia of the speed Deca mass fraction 15% less than 1mL per minute to pH value for 6.9, still aging 4
Hour, precipitation filtration is placed in drying baker being dried 8 hours at a temperature of 98 DEG C, after being fully ground, in chamber type electric resistance furnace
It is warming up to 295 DEG C with the speed being less than 5 DEG C per minute, keeps this temperature calcination 2.5 hours, obtain by Bi2O3、TiO2With
MnO2The powder body material of composition.
Analysis：With this powder body material of transmissioning electric mirror test, its maximum particle diameter is less than 35nm, and mean diameter is about 28nm；
Component analyses are carried out to it, recording mass percent is 59.2%Bi2O3, 22.4%TiO2And 18.4%MnO2.
Application：Measure formaldehyde and the benzene of in the air using this powder body material as sensitive material, the range of linearity is formaldehyde 0.2-
54mg/m3With benzene 0.5-71mg/m3, detect and be limited to formaldehyde 0.06mg/m3With benzene 0.1mg/m3, concurrent do not interfere with.
Embodiment 5
Bismuth trichloride, titanium tetrachloride and six water manganese nitrates are codissolved in the aqueous citric acid solution that mass fraction is 10%,
Sonic oscillation, to clarifying, adds appropriate disodiumedetate to make solution keep clear state 7 hours under high velocity agitation, continues
Continue stirring with the ammonia of the speed Deca mass fraction 15% less than 1mL per minute to pH value for 7.0, still aging 3 hours,
Precipitation filtration is placed in drying baker being dried 5 hours at a temperature of 108 DEG C, after being fully ground, with every in chamber type electric resistance furnace
The speed less than 5 DEG C for the minute is warming up to 320 DEG C, keeps this temperature calcination 2 hours, obtains by Bi2O3、TiO2And MnO2Composition
Powder body material.
Analysis：With this powder body material of transmissioning electric mirror test, its maximum particle diameter is less than 35nm, and mean diameter is about 30nm；
Component analyses are carried out to it, recording mass percent is 51.5%Bi2O3, 23.7%TiO2And 24.8%MnO2.
Application：Measure formaldehyde and the benzene of in the air using this powder body material as sensitive material, the range of linearity is formaldehyde 0.3-
65mg/m3With benzene 0.5-76mg/m3, detect and be limited to formaldehyde 0.1mg/m3With benzene 0.3mg/m3, concurrent do not interfere with.
Claims (3)
1. a kind of nano composite oxide sensitive material for monitoring formaldehyde and benzene, is characterized in that by Bi2O3、TiO2And MnO2Group
The nano-powder material becoming, the mass percent scope of wherein each component is 50-60%Bi2O3, 20-30%TiO2And 15-25%
MnO2, its preparation method is：Bismuth salt, titanium salt and manganese salt are codissolved in the aqueous citric acid solution that mass fraction is 10%, ultrasonic
Vibrate to clarification, be dividedly in some parts the disodiumedetate that gross mass is less than citric acid under high velocity agitation, so that solution is protected
Hold clear state more than 5 hours, continue stirring with the ammonia of the speed Deca mass fraction 15% less than 1mL per minute to pH
It is worth for 6.5-7.3, still aging 2-5 hour, precipitation filtration is placed in drying baker being dried 5-10 at a temperature of 95-110 DEG C
Hour, after being fully ground, in chamber type electric resistance furnace, it is warming up to 290-330 DEG C with the speed being less than 5 DEG C per minute, keep this temperature
Degree roasting 2-3 hour, obtains by Bi2O3、TiO2And MnO2The powder body material of composition.
2. a kind of nano composite oxide sensitive material for monitoring formaldehyde and benzene according to claim 1, its feature
The bismuth salt being described is anhydride or the hydrate of bismuth acetate, Oxalic acid bismuth salt., bismuth nitrate, bismuth sulfate, Bismugel (Biothrax). and bismuth trichloride
The mixture of one or more, titanium salt is Titanium Nitrate, titanium phosphate, the anhydride of titanium sulfate, acetic acid titanium and titanium tetrachloride or hydration
The mixture of one or more of thing, manganese salt be manganese acetate, manganese sulfate, manganese chloride, manganese nitrate and Manganese perchlorate anhydride or
The mixture of one or more of hydrate.
3. a kind of nano composite oxide sensitive material for monitoring formaldehyde and benzene according to claim 1, its feature
It is the particle diameter of described nano-powder less than 35nm.
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| CN201410042995.8A CN103792227B (en) | 2014-01-22 | 2014-01-22 | Nano composite oxide sensitive material for formaldehyde and benzene |
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| CN201410042995.8A CN103792227B (en) | 2014-01-22 | 2014-01-22 | Nano composite oxide sensitive material for formaldehyde and benzene |
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| CN103792227B true CN103792227B (en) | 2017-02-15 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104267022B (en) * | 2014-09-04 | 2016-04-20 | 北京联合大学 | Cross sensitivity material of Ammonia in Air and benzene and preparation method thereof |
| CN104297416B (en) * | 2014-11-03 | 2016-04-20 | 北京联合大学 | The catalytic luminescence sensitive material of formaldehyde in air, benzene and ammonia |
| CN104297436B (en) * | 2014-11-03 | 2016-04-20 | 北京联合大学 | A kind of cross sensitivity material detecting formaldehyde and methyl alcohol |
| CN105527276B (en) * | 2015-12-25 | 2018-09-14 | 北京联合大学 | The catalytic luminescence sensitive material of fast measuring formaldehyde and sulfur dioxide |
| CN105628856B (en) * | 2015-12-25 | 2017-10-20 | 北京联合大学 | A kind of catalytic luminescence sensitive material of benzene and sulfur dioxide |
| CN109490375B (en) * | 2018-11-30 | 2020-12-15 | 北京联合大学 | Low-temperature sensitive material of formaldehyde and benzene |
| CN110095559B (en) * | 2019-04-03 | 2021-09-14 | 北京联合大学 | Catalytic luminous sensitive material of low-temperature formaldehyde, benzene and ammonia |
| CN110376196B (en) * | 2019-07-16 | 2021-12-03 | 北京联合大学 | Sensitive material capable of simultaneously responding to hydrogen sulfide and sulfur dioxide |
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