CN105347403A - High-selectivity formaldehyde gas-sensitive material and preparation method and application thereof - Google Patents
High-selectivity formaldehyde gas-sensitive material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a high-selectivity formaldehyde gas-sensitive material and a preparation method and application thereof. The material is prepared from lanthanum nitrate, ferric nitrate, citric acid, dispersing agent, doping metal ions, template molecules, functional monomer and initiator according to the molar ratio of 1 to 1 to 0.05-1.5 to 0.001-0.1 to 0.001-0.05 to 0.1-0.4 to 0.05-0.8 to 0.1-0.5. The preparation method includes the steps of solution mixing, microwave reacting, ultrasonic vibrating, molecule printing, drying, grinding, sintering and the like. The application is application of the high-selectivity formaldehyde gas-sensitive material in preparation of a formaldehyde gas sensor. The raw materials and ratio for preparing lanthanum ferrite base molecularly imprinted polymers are provided first, the method for preparing the lanthanum ferrite base molecularly imprinted polymer formaldehyde gas-sensitive material is provided on the basis of the provided raw materials and the provided ratio, and the lanthanum ferrite base formaldehyde gas-sensitive material high in sensitivity and selectivity and low in working temperature is obtained.
Description
Technical field
The invention belongs to field of material technology, be specifically related to a kind of highly selective formaldehyde gas sensitive material and preparation method thereof and application.
Background technology
In recent years, along with the fast development of China's economy, particularly growth in the living standard, and the high speed development of the indoor decorating industry brought thus, the pollution caused by building materials, decorations has become the main source of indoor environmental pollution.In addition in order to energy-conservation, building structure has good sealing function usually, more exacerbates the deterioration of IAQ (indoor air quality).During current indoor formaldehyde, benzene and benzene homologues, ammonia and radioactivity four are polluted greatly, what endanger maximum, the most difficult radical cure is formaldehyde pollution.Formaldehyde pollution is mainly derived from the smog etc. that the various finishing material such as various artificial board, WALL CLOTH, coating and smoking etc. produce, and wherein in artificial board, the release period of formaldehyde reaches 3 ~ 15 years.Very harmful to HUMAN HEALTH of formaldehyde, indoor air formaldehyde content is greater than 0.1mg/m
3will produce harm to respiratory system, high-concentration formaldehyde is larger to harm such as neural system, immunity system, livers, is thus classified as first kind carcinogenic substance by international cancer research institution (IARC).In " in indoor air formaldehyde hygienic standard " (GB/T16127-1995) regulation Indoor Air, formaldehyde content is less than 0.08mg/m
3, but concentration of formaldehyde average out to 0.2mg/m after general house decoration
3, what have even reaches 3mg/m
3, seriously exceed safety standards.Current employing multiple technologies method reduces the free formaldehyde in building materials, though achieve certain effect, due to the restriction of technology and economy, Formaldehyde Pollution of Indoor Air is still very serious.For the ease of taking measures in time in the formaldehyde environment of high density if window ventilation, charcoal absorption etc. are to reduce indoor formaldehyde concentration, reduce it to the healthy harm brought, the accurate Real-Time Monitoring of PARA FORMALDEHYDE PRILLS(91,95) is very important.
The detection method of formaldehyde mainly contains: spectrophotometry, chromatography, electrochemical process, catalytic luminescence method, gas sensor method etc., wherein spectrophotometry has detection speed advantage very fast, with low cost, but need the spectrophotometer of specialty, be difficult to large-area penetration and promotion application, simultaneously also there is accuracy of detection and accuracy is not high, preparation and use reagent requirement strictly and to be easily affected by other factors (as: temperature, detection time etc.); Chromatography accuracy in detection is high, quick, but also existence needs compared with expensive specific equipment, volume is large, testing cost is high and derivative reagent isomers is difficult to the problems such as separation; Electrochemical process working stability, susceptibility are better, but electrochemical sensor price is higher, the military service phase is short, testing process is easily disturbed; Catalytic luminescence method is emerging a kind of formaldehyde gas detection method in recent years, although detect highly sensitive, selectivity good, because the problems such as test set is complicated, testing cost is high limit the widespread use of the method; Gas sensor method be utilize gas sensor measure formaldehyde content, have highly sensitive, easy and simple to handle, cost is low and device is small and exquisite, be applicable to the Real-Time Monitoring of formaldehyde content in indoor air and apply.Gas sensor kind is many, and wherein oxide semiconductor gas sensor is main product, and its principle is the conductivity variations after utilizing the adsorbed gas of semi-conductor sensitive material, measures the change in concentration of gas to be measured in its surrounding atmosphere.Semiconductor gas sensor because having highly sensitive, stable performance, price is low, volume is little, the feature such as easy to use and generally being favored, recent two decades obtains and develops fast.
At present, for the research of formaldehyde gas sensor, (N.G.Pramod, S.N.Pandey, EffectofLidopingonthestructural, the opticalandformaldehydesensingpropertiesofIn such as foreign study personnel N.G.Pramo
2o
3thinfilms,
ceramInt, 41 (2015) 527-532.) and adopt chemical spray pyrolysis technology to prepare Li-In
2o
3film, result shows 2at.%Li:In
2o
3the formaldehyde air-sensitive performance of film is better, can detect, but do not study the selectivity of film in article at 300 DEG C to the formaldehyde of 60ppm.(X.W.Li, J.Y.Liu, H.Guo, X.Zhou, C.Wang, P.Sun, X.L.Hu, G.Y.Lu, the AuIn such as domestic Lu Geyu
2o
3core-shellcomposites:ametal-semiconductorheterostructure forgassensingapplications,
rscAdv, 5 (2015) 545-551.) and adopt Aucarbon to be that AuIn prepared by model
2o
3nucleocapsid structure, this sensor can detect the formaldehyde of 100ppm at 200 DEG C, improves the sensitivity of PARA FORMALDEHYDE PRILLS(91,95) to a certain extent, but the selectivity of element PARA FORMALDEHYDE PRILLS(91,95) does not improve.(J.R.Huang, L.Y.Wang, C.P.Gu, Z.J.Wang, Y.F.Sun, J.J.Shim, the PreparationofporousSnO such as Huang Jiarui
2microcubesandtheirenhancedgas-sensingproperty,
sensActuators, B207 (2015) 782-790.) prepare porous SnO
2micro-cube, units test formaldehyde optimal working temp made by this material is 280 DEG C, is 58 at such a temperature to the sensitivity of 100ppm formaldehyde, and also very high to the sensitivity of 100ppm ethanol, is about 49, or is short of to some extent in selectivity.
Generally, still there is the problems such as the poor or sensitivity of working temperature high (being generally 190-350 DEG C), selectivity is not high in current formaldehyde gas sensor, is difficult to practical.Therefore studying also preparation work temperature and at room temperature, have highly selective, highly sensitive formaldehyde gas sensor, will be the Research Emphasis of such sensor and inevitable development trend.Therefore, develop a kind of gas sensitive to be very important to solve gas sensor technical problem.
Summary of the invention
The first object of the present invention is to provide a kind of highly selective formaldehyde gas sensitive material; Second object is to provide the preparation method of described highly selective formaldehyde gas sensitive material; 3rd object is to provide the application of described highly selective formaldehyde gas sensitive material.
The first object of the present invention realizes like this, described highly selective formaldehyde gas sensitive material comprises raw material lanthanum nitrate, iron nitrate, citric acid, dispersion agent, doped metal ion, template molecule, function monomer and initiator, through preparing, its material molar ratio is 1 ﹕ 1 ﹕ (0.05 ~ 1.5) ﹕ (0.001 ~ 0.1) ﹕ (0.001 ~ 0.05) ﹕ (0.1 ~ 0.4) ﹕ (0.05 ~ 0.8) ﹕ (0.1 ~ 0.5).
The second object of the present invention is achieved in that and comprises the following steps:
A, weigh lanthanum nitrate and iron nitrate by formulation ratio, be dissolved in distilled water, the citric acid and the dispersion agent mixing that add formulation ratio obtain solution a;
B, solution a is heated to 40 ~ 100 DEG C, adds the doped metal ion of formulation ratio, mix rear ageing 0 ~ 72h and obtain solution b;
C, solution b is placed in microwave reaction device and at normal pressure, temperature 40 ~ 90 DEG C, reacts 0.5 ~ 10h be placed on 50 ~ 100 DEG C of stirred in water bath 1 ~ 3h and obtain gel c;
D, by the template molecule of formulation ratio and function monomer mixing after with frequency 10 ~ 40KHz sonic oscillation 30 ~ 60min, leave standstill 5 ~ 20h obtain solution d;
E, gel c and solution d to be mixed, add the initiator of formulation ratio, at 40 ~ 100 DEG C, polyreaction 12 ~ 48h obtains reaction solution e, is 2 ~ 7% by reaction solution e dry 1 ~ 2d at 50 ~ 250 DEG C to water ratio, grinding, then sintering 2 ~ 4h obtains target compound at 600 ~ 800 DEG C.
The third object of the present invention is achieved in that described highly selective formaldehyde gas sensitive material is preparing the application in formaldehyde gas sensor.
Because sensor sensing material shows instability under extraneous factor is as the impact of temperature, chemical reagent, and lack suitable target induction substance in some conditions.Utilize molecular imprinting, can synthesize stable, certain material is had to the material of special role, by these materials application in sensing technology, these deficiencies can be made up.The work of this respect has made some progress.
From 1987, Tabushi(WLian, JHuang, JYu, etal., Amolecularlyimprintedsensorbasedon β-cyclodextrinincorporatedmultiwalledcarbonnanotubeandgold nanoparticles-polyamideaminedendrimernanocompositescombi ningwithwater-solublechitosanderivativeforthedetectionof chlortetracycline, FoodControl26 (2012) 620-627.) use molecularly imprinted polymer as sensitive material first, since VITAMIN is detected, molecularly imprinted polymer sensor causes people's interest widely.(the Xu Jie such as Xu Jie, Ye Zhixiang, Zhang Li, Deng, based on the development of the Trichlorphon agricultural chemicals sensor of molecular imprinting, chemical research and application 19 (2007) 1021-1024.) utilize molecular imprinting, take Trichlorphon as template molecule, cyclic voltammetry prepares molecular engram film, be deposited on piezoelectric quartz crystal platinum electrode surface as recognition component and make Trichlorphon piezoelectric transducer, the shortcoming of traditional detection method can be overcome, have simple to operate, respond fast, simple to operate, highly sensitive feature.(the MLehmann such as Lehmann, HBrunner, GTovar, Molekulargepr gteNanopartikelalsselektivePhaseinKompositmembranen:Hydr odynamikundStofftrennunginnanoskaligenSch ü ttungen, ChemieIngenieurTechnik75 (2003) 149-153.) develop a kind of novel composite membrane, surface-area high for trace nanoparticle and selectivity are combined with the supporting role of film, it is high that such separatory membrane not only has treatment capacity, the features such as easy amplification, and to target molecule, there is very high adsorption selectivity and capacity.(the circuit such as circuit, leaf is glorious, Yuan Ruo, Deng, T-3762 molecular imprinting chirality capacitance type transducers, Chinese science: B collects 37 (2007) 48-53.) adopt molecular imprinting, prepare T-3762 molecularly imprinted polymer, it can be used as selective good, highly sensitive, the regenerability of the honoured sensor of point prepared by recognition material and the feature such as stability is excellent, for actual sample analysis.
Because molecular imprinting has feature such as structure effect precordainment, specific recognition etc., paid close attention in fields such as catalysis, separation and analyses, but at present its application mainly organic macromolecule identification be separated, the molecular imprinting method recognition detection of organic molecule gas as formaldehyde be there is no to product and the report of this aspect.
First the present invention is to provide the raw material and proportioning of preparing cadmium ferrite base molecularly imprinted polymer, and provide a kind of method preparing cadmium ferrite base molecularly imprinted polymer formaldehyde gas sensitive material based on provided raw material and proportioning, thus obtain highly sensitive, that selectivity good, working temperature is low cadmium ferrite base formaldehyde gas sensitive material and preparation method thereof.
The positively effect that cadmium ferrite base molecularly imprinted polymer formaldehyde gas sensitive material provided by the invention has is as follows:
(1) PARA FORMALDEHYDE PRILLS(91,95) gas is highly sensitive: by carrying out molecular imprinting modification to Ag doping cadmium ferrite, can detect the low concentration formaldehyde gas of 0.001ppm.
(2) selectivity is good: by carrying out molecular imprinting modification to Ag doping cadmium ferrite, to the sensitivity of formaldehyde gas under same concentrations far above the sensitivity to methyl alcohol or acetone or toluene or gasoline or water.
(3) working temperature is low: by carrying out molecular imprinting modification to Ag doping cadmium ferrite, and made sensing member minimum operating temperature is 40 DEG C, and comparatively reported in literature has and significantly reduces.
(4) the response-recovery time is fast: by carrying out molecular imprinting modification to Ag doping cadmium ferrite, and the response-recovery time of PARA FORMALDEHYDE PRILLS(91,95) gas, all lower than 1 minute, is applicable to quick test formaldehyde gas.
To sum up, the susceptibility of the cadmium ferrite material PARA FORMALDEHYDE PRILLS(91,95) gas that the present invention's molecular imprinting is modified, especially sensitivity and selectivity are higher than current known technology level, and have raising by a relatively large margin, directly can make formaldehyde gas sensor with it.
Accompanying drawing explanation
Fig. 1 is that the sensing member made of the material prepared by the present invention is to the sensitivity of different concns formaldehyde gas;
In figure, X-coordinate is concentration of formaldehyde, and unit is ppm, and ordinate zou is sensitivity;
As figure shows, the present invention can detect formaldehyde 0.001ppm concentration;
Fig. 2 be the sensing member made of prepared material under different working temperatures to the sensitivity of gas with various;
Visible at working temperature 40 DEG C, the sensitivity of element PARA FORMALDEHYDE PRILLS(91,95), far above the sensitivity to methyl alcohol, acetone, toluene, gasoline, water, shows that gas sensor PARA FORMALDEHYDE PRILLS(91,95) has good selectivity;
In figure, X-coordinate is working temperature, and unit is DEG C, and ordinate zou is sensitivity;
Fig. 3 is the response-recovery time curve of the sensing member PARA FORMALDEHYDE PRILLS(91,95) gas that prepared material is made;
Its time of response 40s, time of recovery 50s, be applicable to quick test formaldehyde gas;
From figure, also can find out that sensitivity substantially linearly changes with the increase of concentration of formaldehyde, can realize the real-time monitoring of PARA FORMALDEHYDE PRILLS(91,95).In figure, X-coordinate is the time, and unit is second, and ordinate zou is sensitivity.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is further illustrated, but limited the present invention never in any form, and any conversion done based on training centre of the present invention or replacement, all belong to protection scope of the present invention.
Highly selective formaldehyde gas sensitive material of the present invention, comprise raw material lanthanum nitrate, iron nitrate, citric acid, dispersion agent, doped metal ion, template molecule, function monomer and initiator, through preparing, its material molar ratio is 1 ﹕ 1 ﹕ (0.05 ~ 1.5) ﹕ (0.001 ~ 0.1) ﹕ (0.001 ~ 0.05) ﹕ (0.1 ~ 0.4) ﹕ (0.05 ~ 0.8) ﹕ (0.1 ~ 0.5).
Described highly selective formaldehyde gas sensitive material comprises raw material lanthanum nitrate, iron nitrate, citric acid, dispersion agent, doped metal ion, template molecule, function monomer and initiator, through preparing, its material molar ratio is 1 ﹕ 1 ﹕ (0.05 ~ 1.5) ﹕ (0.001 ~ 0.1) ﹕ (0.001 ~ 0.05) ﹕ (0.1 ~ 0.4) ﹕ (0.05 ~ 0.8) ﹕ (0.1 ~ 0.5).
Described dispersion agent is triethyl hexyl phosphoric acid, methyl amyl alcohol, polyacrylamide, guar gum or polyoxyethylene glycol.
Described dispersion agent is polyacrylamide or polyoxyethylene glycol.
Described doped metal ion is silver ions, zine ion or zirconium ion.
Described doped metal ion is for being selected from nitrate, vitriol, muriatic silver ions, zine ion or zirconium ion.
Described doped metal ion is be selected from the silver ions of nitrate, zine ion or zirconium ion.
Described template molecule is formaldehyde, acetaldehyde or methyl alcohol.
Described function monomer is vinylformic acid and derivative, methylene-succinic acid, N-acryl L-Ala, acrylamide, methacrylic acid or vinyl pyridine.
Described initiator is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
The preparation method of highly selective formaldehyde gas sensitive material of the present invention, comprises the following steps:
A, weigh lanthanum nitrate and iron nitrate by formulation ratio, be dissolved in distilled water, the citric acid and the dispersion agent mixing that add formulation ratio obtain solution a;
B, solution a is heated to 40 ~ 100 DEG C, adds the doped metal ion of formulation ratio, mix rear ageing 0 ~ 72h and obtain solution b;
C, solution b is placed in microwave reaction device and at normal pressure, temperature 40 ~ 90 DEG C, reacts 0.5 ~ 10h be placed on 50 ~ 100 DEG C of stirred in water bath 1 ~ 3h and obtain gel c;
D, by the template molecule of formulation ratio and function monomer mixing after with frequency 10 ~ 40KHz sonic oscillation 30 ~ 60min, leave standstill 5 ~ 20h obtain solution d;
E, gel c and solution d to be mixed, add the initiator of formulation ratio, at 40 ~ 100 DEG C, polyreaction 12 ~ 48h obtains reaction solution e, is 2 ~ 7% by reaction solution e dry 1 ~ 2d at 50 ~ 250 DEG C to water ratio, grinding, then sintering 2 ~ 4h obtains target compound at 600 ~ 800 DEG C.
The time of the ageing described in step B is 12 ~ 36h.
The preparation method of described highly selective formaldehyde gas sensitive material, comprises the following steps:
A, weigh lanthanum nitrate and iron nitrate by formulation ratio, be dissolved in distilled water, the citric acid and the dispersion agent mixing that add formulation ratio obtain solution a;
B, solution a is heated to 60 ~ 80 DEG C, adds the doped metal ion of formulation ratio, mix rear ageing 12 ~ 36h and obtain solution b;
C, solution b is placed in microwave reaction device and at normal pressure, temperature 60 ~ 75 DEG C, reacts 1.5 ~ 3h be placed on 60 ~ 90 DEG C of stirred in water bath 80 ~ 120min and obtain gel c;
D, by the template molecule of formulation ratio and function monomer mixing after with frequency 25 ~ 40KHz sonic oscillation 30 ~ 60min, leave standstill 8 ~ 10h obtain solution d;
E, gel c and solution d to be mixed, add the initiator of formulation ratio, at 40 ~ 70 DEG C, polyreaction 12 ~ 15h obtains reaction solution e, is 4 ~ 5% by reaction solution e dry 24 ~ 36h at 100 ~ 200 DEG C to water ratio, grinding, then sintering 2 ~ 4h obtains target compound at 600 ~ 800 DEG C.
Of the present inventionly be applied as described highly selective formaldehyde gas sensitive material and preparing the application in formaldehyde gas sensor.
With specific embodiment, the present invention will be further described below:
Embodiment 1
The mol ratio that material composition is lanthanum nitrate, iron nitrate, citric acid, polyoxyethylene glycol, silver ions, formaldehyde, acrylamide, Diisopropyl azodicarboxylate are corresponding to this material composition is 1 ﹕ 1 ﹕ 0.05 ﹕ 0.005 ﹕ 0.01 ﹕ 0.1 ﹕ 0.3 ﹕ 0.1, silver ions raw material is Silver Nitrate, and raw material is analytical pure.
Weigh lanthanum nitrate, iron nitrate, be dissolved in distilled water, add citric acid and polyoxyethylene glycol, be made into mixing solutions.By this solution heated and stirred at 60 DEG C, add silver ions, react in microwave reaction device after mixing and stirring and take out for 1 hour, solution is placed in 80 DEG C of stirred in water bath and makes it to become colloidal sol, continue to be stirred to colloidal sol and change gel state into, stand-by; Formaldehyde is mixed with acrylamide and ultrasonic vibration 60 minutes, itself and Diisopropyl azodicarboxylate are added in aforesaid gel, polyreaction 24 hours at 50 DEG C, be placed in baking oven 80 DEG C of dryings, gained xerogel grinds, be placed in stove and sinter 2 hours at 750 DEG C, obtain formaldehyde-acrylamide series Ag doping cadmium ferrite base molecularly imprinted polymer.
Embodiment 2
The mol ratio that material composition is lanthanum nitrate, iron nitrate, citric acid, polyoxyethylene glycol, silver ions, formaldehyde, methacrylic acid, Diisopropyl azodicarboxylate are corresponding to this material composition is 1 ﹕ 1 ﹕ 0.05 ﹕ 0.005 ﹕ 0.01 ﹕ 0.1 ﹕ 0.3 ﹕ 0.1, silver ions raw material is Silver Nitrate, and raw material is analytical pure.
Weigh lanthanum nitrate, iron nitrate, be dissolved in distilled water, add citric acid and polyoxyethylene glycol, be made into mixing solutions.By this solution heated and stirred at 60 DEG C, add silver ions, react in microwave reaction device after mixing and stirring and take out for 1 hour, solution is placed in 80 DEG C of stirred in water bath and makes it to become colloidal sol, continue to be stirred to colloidal sol and change gel state into, stand-by; Formaldehyde is mixed with methacrylic acid and ultrasonic vibration 60 minutes, itself and Diisopropyl azodicarboxylate are added in aforesaid gel, polyreaction 24 hours at 50 DEG C, be placed in baking oven 80 DEG C of dryings, gained xerogel grinds, be placed in stove and sinter 2 hours at 750 DEG C, obtain formaldehyde-methacrylic acid series Ag doping cadmium ferrite base molecularly imprinted polymer.
Embodiment 3
The mol ratio that material composition is lanthanum nitrate, iron nitrate, citric acid, polyoxyethylene glycol, silver ions, acetaldehyde, acrylamide, Diisopropyl azodicarboxylate are corresponding to this material composition is 1 ﹕ 1 ﹕ 0.05 ﹕ 0.005 ﹕ 0.01 ﹕ 0.1 ﹕ 0.2 ﹕ 0.1, silver ions raw material is Silver Nitrate, and raw material is analytical pure.
Weigh lanthanum nitrate, iron nitrate, be dissolved in distilled water, add citric acid and polyoxyethylene glycol, be made into mixing solutions.By this solution heated and stirred at 60 DEG C, add silver ions, react in microwave reaction device after mixing and stirring and take out for 1 hour, solution is placed in 80 DEG C of stirred in water bath and makes it to become colloidal sol, continue to be stirred to colloidal sol and change gel state into, stand-by; Acetaldehyde is mixed with acrylamide and ultrasonic vibration 60 minutes, itself and Diisopropyl azodicarboxylate are added in aforesaid gel, polyreaction 24 hours at 50 DEG C, be placed in baking oven 80 DEG C of dryings, gained xerogel grinds, be placed in stove and sinter 2 hours at 750 DEG C, obtain acetaldehyde-acrylamide series Ag doping cadmium ferrite base molecularly imprinted polymer.
Embodiment 4
The mol ratio that material composition is lanthanum nitrate, iron nitrate, citric acid, polyoxyethylene glycol, silver ions, acetaldehyde, methacrylic acid, Diisopropyl azodicarboxylate are corresponding to this material composition is 1 ﹕ 1 ﹕ 0.05 ﹕ 0.005 ﹕ 0.01 ﹕ 0.1 ﹕ 0.4 ﹕ 0.1, silver ions raw material is Silver Nitrate, and raw material is analytical pure.
Weigh lanthanum nitrate, iron nitrate, be dissolved in distilled water, add citric acid and polyoxyethylene glycol, be made into mixing solutions.By this solution heated and stirred at 60 DEG C, add silver ions, react in microwave reaction device after mixing and stirring and take out for 1 hour, solution is placed in 80 DEG C of stirred in water bath and makes it to become colloidal sol, continue to be stirred to colloidal sol and change gel state into, stand-by; By acetaldehyde and methacrylic acid mixing and ultrasonic vibration 60 minutes, itself and Diisopropyl azodicarboxylate are added in aforesaid gel, polyreaction 24 hours at 50 DEG C, be placed in baking oven 80 DEG C of dryings, gained xerogel grinds, be placed in stove and sinter 2 hours at 750 DEG C, obtain acetaldehyde-methacrylic acid series Ag doping cadmium ferrite base molecularly imprinted polymer.
Claims (10)
1. a highly selective formaldehyde gas sensitive material, it is characterized in that described highly selective formaldehyde gas sensitive material comprises raw material lanthanum nitrate, iron nitrate, citric acid, dispersion agent, doped metal ion, template molecule, function monomer and initiator, through preparing, its material molar ratio is 1 ﹕ 1 ﹕ (0.05 ~ 1.5) ﹕ (0.001 ~ 0.1) ﹕ (0.001 ~ 0.05) ﹕ (0.1 ~ 0.4) ﹕ (0.05 ~ 0.8) ﹕ (0.1 ~ 0.5).
2. highly selective formaldehyde gas sensitive material according to claim 1, it is characterized in that described highly selective formaldehyde gas sensitive material comprises raw material lanthanum nitrate, iron nitrate, citric acid, dispersion agent, doped metal ion, template molecule, function monomer and initiator, its mol ratio is 1 ﹕ 1 ﹕ (0.05 ~ 1.5) ﹕ (0.001 ~ 0.1) ﹕ (0.001 ~ 0.05) ﹕ (0.1 ~ 0.4) ﹕ (0.05 ~ 0.8) ﹕ (0.1 ~ 0.5).
3. highly selective formaldehyde gas sensitive material according to claim 1 and 2, is characterized in that described dispersion agent is triethyl hexyl phosphoric acid, methyl amyl alcohol, polyacrylamide, guar gum or polyoxyethylene glycol.
4. highly selective formaldehyde gas sensitive material according to claim 1 and 2, is characterized in that described doped metal ion is silver ions, zine ion or zirconium ion.
5. highly selective formaldehyde gas sensitive material according to claim 1 and 2, is characterized in that described template molecule is formaldehyde, acetaldehyde or methyl alcohol.
6. highly selective formaldehyde gas sensitive material according to claim 1 and 2, is characterized in that described function monomer is vinylformic acid and derivative, methylene-succinic acid, N-acryl L-Ala, acrylamide, methacrylic acid or vinyl pyridine.
7. highly selective formaldehyde gas sensitive material according to claim 1 and 2, is characterized in that described initiator is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
8. a preparation method for the arbitrary described highly selective formaldehyde gas sensitive material of claim 1 ~ 7, is characterized in that comprising the following steps:
A, weigh lanthanum nitrate and iron nitrate by formulation ratio, be dissolved in distilled water, the citric acid and the dispersion agent mixing that add formulation ratio obtain solution a;
B, solution a is heated to 40 ~ 100 DEG C, adds the doped metal ion of formulation ratio, mix rear ageing 0 ~ 72h and obtain solution b;
C, solution b is placed in microwave reaction device and at normal pressure, temperature 40 ~ 90 DEG C, reacts 0.5 ~ 10h be placed on 50 ~ 100 DEG C of stirred in water bath 1 ~ 3h and obtain gel c;
D, by the template molecule of formulation ratio and function monomer mixing after with frequency 10 ~ 40KHz sonic oscillation 30 ~ 60min, leave standstill 5 ~ 20h obtain solution d;
E, gel c and solution d to be mixed, add the initiator of formulation ratio, at 40 ~ 100 DEG C, polyreaction 12 ~ 48h obtains reaction solution e, is 2 ~ 7% by reaction solution e dry 1 ~ 2d at 50 ~ 250 DEG C to water ratio, grinding, then sintering 2 ~ 4h obtains target compound at 600 ~ 800 DEG C.
9. the preparation method of highly selective formaldehyde gas sensitive material according to claim 8, is characterized in that the time of the ageing described in step B is 12 ~ 36h.
10. an application for the arbitrary described highly selective formaldehyde gas sensitive material of claim 1 ~ 7, is characterized in that described highly selective formaldehyde gas sensitive material is preparing the application in formaldehyde gas sensor.
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| CN106198856A (en) * | 2016-06-25 | 2016-12-07 | 云南大学 | A kind of high sensitivity, the formaldehyde gas sensitive material and preparation method and application of low operating temperature |
| CN106749809A (en) * | 2016-12-26 | 2017-05-31 | 云南大学 | A kind of high selectivity acetone air-sensitive material and preparation method and application |
| CN107121454A (en) * | 2017-04-17 | 2017-09-01 | 云南大学 | A kind of different element doping graphene quantum dots are respectively with molecular engram compound gas sensitive and preparation method and application |
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| CN107121454B (en) * | 2017-04-17 | 2019-08-30 | 云南大学 | A kind of difference element doping graphene quantum dot is respectively with molecular engram compound gas sensitive and the preparation method and application thereof |
| CN112624202A (en) * | 2021-01-13 | 2021-04-09 | 中国计量大学 | Preparation method of lanthanum ferrite gas-sensitive material with high specific surface area |
| CN113198309A (en) * | 2021-04-30 | 2021-08-03 | 广东新利斯环保科技有限公司 | Peculiar smell scavenger and preparation method and application thereof |
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