CN107138130A - A kind of preparation method of functionalization graphene and its application in formaldehyde absorbing - Google Patents
A kind of preparation method of functionalization graphene and its application in formaldehyde absorbing Download PDFInfo
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- CN107138130A CN107138130A CN201710341874.7A CN201710341874A CN107138130A CN 107138130 A CN107138130 A CN 107138130A CN 201710341874 A CN201710341874 A CN 201710341874A CN 107138130 A CN107138130 A CN 107138130A
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Abstract
The invention belongs to adsorption technology field, functional modification is carried out to graphene by using ammoniacal liquor and hydrazine hydrate, meanwhile, titanium dioxide is uniformly adhered to the surface of graphene during ultrasonic disperse is carried out to graphene.The amino groups on one side functionalization graphene surface are reacted with formaldehyde during formaldehyde adsorption, and another aspect titanium dioxide can promote the decomposition of formaldehyde, under the synergy of the two, significantly reduce the appearance of formaldehyde dissociation after absorption.
Description
Technical field
Inhaled the invention belongs to adsorption technology field, the preparation method of more particularly to a kind of functionalization graphene and its in formaldehyde
The application of attached middle school.
Background technology
China is using one of formaldehyde and the most country of production formaldehyde.Formaldehyde is mainly used in Chemical Manufacture, real estate
Building trade, interior decoration industry, medical industry and Wood Products Industry.Being used as a kind of weight in Chemical Manufacture, formaldehyde more
The Organic Chemicals and solvent wanted, are not only the important industrial chemicals of synthetic resin, rubber, plastics, are also many chemical industry productions
The intermediate material of product, is filled with formaldehyde Just because of this, around us, seriously threatens daily life and health.
Formaldehyde can cause various influences to health, and such as poisoning, allergy, asthma, impairment of pulmonary function, the case of cancer even death are shown in not repeatly
It is fresh.Formaldehyde causes stimulation, sensitization and acute poisoning to skin, eyes and upper respiratory tract mucous membrane etc., slow poisoning,
The problems such as formaldehyde exposure then can produce neurotoxicity, genotoxicity, genetoxic, carcinogenesis and respiratory system damage.
At present, indoor formaldehyde preventing and treating mainly has with the technical method controlled:Ventilation purification techniques, ozone oxidation skill
Art, adsorption technology, photocatalysis oxidation technique, MOS Technology, negative aeroion technology, plant purification technology and biological drop
Solution technology etc..Adsorption technology is to utilize porous type adsorbent layer, by the pollutant absorption in air, enrichment so as to reach that purification is empty
The purpose of gas, conventional adsorbent have porous carbon materials, bamboo charcoal, NACF, novel absorbent charcoal, macroporous absorbent resin, zeolite,
Silica gel, activated silica, activated alumina etc..Air cleaning adsorbent typically has, high adsorption capacity very bigger than surface, had to gas
Higher adsorption capacity, can adsorb rapidly, the low feature of environmentally friendly, pollution-free, manufacturing cost.Adsorption technology purification air-operated letter
It is single, it is easy to promote, but absorption has invertibity, when temperature, humidity, wind speed are raised to a certain extent, the pollutant of absorption is again
Possible separate out.
The content of the invention
The purpose of the present invention:Not thorough to solve the purification of formaldehyde absorbing present in prior art, the pollutant of absorption exists
Under certain condition again may separate out the problem of, the present invention provides a kind of preparation method of functionalization graphene and its in formaldehyde
Application in absorption.
The preparation method of functionalization graphene of the present invention, step is as follows:
(1) graphene oxide and titanium dioxide are added in deionized water, stirs and carry out ultrasonic disperse processing, obtain oxygen
Graphite alkene, titanium oxide dispersion, are placed in round-bottomed flask;
(2) ammoniacal liquor and hydrazine hydrate are added into the flask of step (1), is sufficiently mixed uniformly, obtains mixed liquor;
(3) mixed liquor for obtaining step (2) is placed in oil bath pan and reacted, and obtains reaction solution;
(4) centrifuged after the reaction solution cooling obtained step (3), wash to weakly acidic pH, obtained through vacuum freeze drying
To functionalization graphene powder.
Wherein, the mass ratio of titanium dioxide and graphene oxide is in step (1):20:1~30:1, preferably 20:1;Oxygen
The mass concentration of graphite alkene is 0.03~0.06%, preferably 0.05%;Mixing speed is 200~300 revs/min, ultrasound
Jitter time is:20~30 minutes, it is preferably:Mixing speed is 250 revs/min, and the ultrasonic disperse time is:25 minutes.
The volume ratio of ammoniacal liquor and hydrazine hydrate is 10 in step (2):1~20:1, be preferably:15:1.
Reaction temperature in step (3) is 80~100 DEG C, and the reaction time is:0.5~2 hour, it is preferably:Reaction temperature
For 95 DEG C, reaction time 1h.
Functionalization graphene prepared by this method is used for formaldehyde absorbing, using fixed methylene oxide detecting instrument to through function fossil
Formaldehyde gas concentration after black alkene absorbs is detected that initial concentration of formaldehyde is 0.5ppm, sample temperature after the baseline of instrument is steady
Degree is constant at 20 DEG C, and the concentration of formaldehyde after being adsorbed through functionalization graphene changes with time as shown in Figure 4.
Beneficial effect:Graphene is as a kind of new carbon, with very high specific surface area, easily by function dough,
The present invention carries out functional modification by using ammoniacal liquor and hydrazine hydrate to graphene, and amino groups are formed on the surface of graphene,
And titanium dioxide, the surface for making it be dispersed in graphene are added during ultrasonic disperse.Due to the Gao Bibiao of graphene
Area PARA FORMALDEHYDE PRILLS(91,95) has good adsorption effect, during formaldehyde adsorption, the amino on one side functionalization graphene surface
Group is reacted with formaldehyde, and another aspect titanium dioxide can promote the decomposition of formaldehyde, is existed so as to significantly reduce formaldehyde
The appearance of dissociation after absorption, therefore, prepared by the inventive method is modified obtained function graphite through ammoniacal liquor and hydrazine hydrate
Alkene, under the synergy of titanium dioxide, while having extraordinary adsorption effect to the formaldehyde in air, effectively suppresses
Formaldehyde is free after absorption.
Brief description of the drawings
Fig. 1:The XRD test charts of functionalization graphene;
Fig. 2:The SEM figures of functionalization graphene;
Fig. 3:The FT-IR figures of functionalization graphene;
Fig. 4:Embodiment 1 adsorbed through functionalization graphene after concentration of formaldehyde versus time curve.
Embodiment
Embodiment 1
(1) by titanium dioxide:Graphene oxide is according to 20:1 mass ratio is added in deionized water, makes graphene oxide
Mass concentration is 0.03%, and low whipping speed is 200 revs/min of lower ultrasonic disperses 25 minutes, obtains graphene oxide, titanium dioxide
Titanium dispersion liquid, is placed in round-bottomed flask;
(2) according to 10:1 mass ratio adds ammoniacal liquor and hydrazine hydrate into the flask of step (1), is sufficiently mixed uniformly, obtains
To mixed liquor;
(3) mixed liquor for obtaining step (2) is placed in 85 DEG C of oil bath pans and reacted 2 hours, obtains reaction solution;
(4) centrifuged after the reaction solution cooling obtained step (3), wash to weakly acidic pH, obtained through vacuum freeze drying
To functionalization graphene powder.
Formaldehyde gas concentration after being absorbed using fixed methylene oxide detecting instrument to the functionalization graphene prepared through this method
Detected, initial concentration of formaldehyde is 0.5ppm after the baseline of instrument is steady, and sample temperature is constant at 20 DEG C.As can be seen from Figure 4:Through
Concentration of formaldehyde after functionalization graphene absorption prepared by this method reached that steadily formaldehyde clearance reaches by absorption in 6 hours
97%.
Embodiment 2
(1) by titanium dioxide:Graphene oxide is according to 20:1 mass ratio is added in deionized water, makes graphene oxide
Mass concentration is 0.05%, and low whipping speed is 250 revs/min of lower ultrasonic disperses 25 minutes, obtains graphene oxide, titanium dioxide
Titanium dispersion liquid, is placed in round-bottomed flask;
(2) according to 15:1 mass ratio adds ammoniacal liquor and hydrazine hydrate into the flask of step (1), is sufficiently mixed uniformly, obtains
To mixed liquor;
(3) mixed liquor for obtaining step (2) is placed in 95 DEG C of oil bath pans and reacted 1 hour, obtains reaction solution;
(4) centrifuged after the reaction solution cooling obtained step (3), wash to weakly acidic pH, obtained through vacuum freeze drying
To functionalization graphene powder.
Method of testing be the same as Example 1, the functionalization graphene formaldehyde adsorption prepared through this method was adsorbed, first by 6 hours
Aldehyde clearance reaches 98.2%.
Embodiment 3
(1) by titanium dioxide:Graphene oxide is according to 30:1 mass ratio is added in deionized water, makes graphene oxide
Mass concentration is 0.05%, and low whipping speed is 250 revs/min of lower ultrasonic disperses 25 minutes, obtains graphene oxide, titanium dioxide
Titanium dispersion liquid, is placed in round-bottomed flask;
(2) according to 15:1 mass ratio adds ammoniacal liquor and hydrazine hydrate into the flask of step (1), is sufficiently mixed uniformly, obtains
To mixed liquor;
(3) mixed liquor for obtaining step (2) is placed in 100 DEG C of oil bath pans and reacted 0.5 hour, obtains reaction solution;
(4) centrifuged after the reaction solution cooling obtained step (3), wash to weakly acidic pH, obtained through vacuum freeze drying
To functionalization graphene powder.
Method of testing be the same as Example 1, the functionalization graphene prepared through this method is used for formaldehyde adsorption, is inhaled by 6 hours
Attached, formaldehyde clearance reaches 97.6%.
Embodiment 4
(1) by titanium dioxide:Graphene oxide is according to 20:1 mass ratio is added in deionized water, makes graphene oxide
Mass concentration is 0.06%, and low whipping speed is 300 revs/min of lower ultrasonic disperses 25 minutes, obtains graphene oxide, titanium dioxide
Titanium dispersion liquid, is placed in round-bottomed flask;
(2) according to 20:1 mass ratio adds ammoniacal liquor and hydrazine hydrate into the flask of step (1), is sufficiently mixed uniformly, obtains
To mixed liquor;
(3) mixed liquor for obtaining step (2) is placed in 100 DEG C of oil bath pans and reacted 0.5 hour, obtains reaction solution;
(4) centrifuged after the reaction solution cooling obtained step (3), wash to weakly acidic pH, obtained through vacuum freeze drying
To functionalization graphene powder.
Method of testing be the same as Example 1, the functionalization graphene formaldehyde adsorption prepared through this method was adsorbed, first by 6 hours
Aldehyde clearance reaches 97.9%.
Comparative example 1
(1) add graphene oxide into deionized water, the mass concentration for making graphene oxide is 0.05%, in stirring speed
Spend for 250 revs/min of lower ultrasonic disperses 25 minutes, obtain graphene oxide dispersion, be placed in round-bottomed flask;
(2) according to 15:1 mass ratio adds ammoniacal liquor and hydrazine hydrate into the flask of step (1), is sufficiently mixed uniformly, obtains
To mixed liquor;
(3) mixed liquor for obtaining step (2) is placed in 95 DEG C of oil bath pans and reacted 1 hour, obtains reaction solution;
(4) centrifuged after the reaction solution cooling obtained step (3), wash to weakly acidic pH, obtained through vacuum freeze drying
To functionalization graphene powder.
Method of testing be the same as Example 1, the functionalization graphene formaldehyde adsorption prepared through this method, after 6 hours adsorb,
Formaldehyde clearance is 87.9%.
Comparative example 2
Method of testing be the same as Example 1, is used for formaldehyde adsorption by commercially available graphene, is adsorbed by 6 hours, formaldehyde clearance is only
For 65.9%.
Claims (8)
1. a kind of preparation method of functionalization graphene, it is characterised in that:The preparation method step is as follows:
(1) graphene oxide and titanium dioxide are added in deionized water, stirs and carry out ultrasonic disperse processing, obtain aoxidizing stone
Black alkene, titanium oxide dispersion, are placed in round-bottomed flask;
(2) ammoniacal liquor and hydrazine hydrate are added into the flask of step (1), is sufficiently mixed uniformly, obtains mixed liquor;
(3) mixed liquor for obtaining step (2) is placed in oil bath pan and reacted, and obtains reaction solution;
(4) centrifuged after the reaction solution cooling obtained step (3), wash to weakly acidic pH, work(is obtained through vacuum freeze drying
Can graphite alkene powder.
2. the preparation method of functionalization graphene as claimed in claim 1, it is characterised in that:In step (1) titanium dioxide and
The mass ratio of graphene oxide is:20:1~30:1;The mass concentration of graphene oxide is 0.03~0.06%;Mixing speed is
200~300 revs/min, the ultrasonic disperse time is:20~30 minutes.
3. the preparation method of functionalization graphene as claimed in claim 1, it is characterised in that:Ammoniacal liquor and hydration in step (2)
The volume ratio of hydrazine is 10:1~20:1.
4. the preparation method of functionalization graphene as claimed in claim 1, it is characterised in that:Reaction temperature in step (3)
For 80~100 DEG C, the reaction time is:0.5~2 hour.
5. the preparation method of functionalization graphene as claimed in claim 2, it is characterised in that:In step (1) titanium dioxide and
The mass ratio of graphene oxide is:20:1;The mass concentration of graphene oxide is 0.05%;Mixing speed is 250 revs/min,
The ultrasonic disperse time is:25 minutes.
6. the preparation method of functionalization graphene as claimed in claim 3, it is characterised in that:Ammoniacal liquor and hydration in step (2)
The volume ratio of hydrazine is 15:1.
7. the preparation method of functionalization graphene as claimed in claim 4, it is characterised in that:Reaction temperature in step (3)
For 95 DEG C, the reaction time is:1 hour.
8. the application of functionalization graphene prepared by method as claimed in claim 1 in formaldehyde absorbing.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107998813A (en) * | 2017-09-25 | 2018-05-08 | 浙江海洋大学 | Remove the inorganic agent of indoor formaldehyde and indoor organic volatile matter |
CN108187633A (en) * | 2018-01-23 | 2018-06-22 | 天津科创复兴科技咨询有限公司 | A kind of formaldehyde adsorbent and its preparation method and application |
CN109569519A (en) * | 2018-10-22 | 2019-04-05 | 江汉大学 | The method for preparing active sludge carbon base formaldehyde adsorbent using municipal sludge |
CN110736722A (en) * | 2019-10-29 | 2020-01-31 | 广州特种承压设备检测研究院 | Manufacturing method of graphene quantum dot composite material optical fiber gas sensor |
CN111111431A (en) * | 2019-12-25 | 2020-05-08 | 山东吉鑫节能科技有限公司 | Formula for removing formaldehyde by graphene and preparation method thereof |
CN113952933A (en) * | 2021-01-15 | 2022-01-21 | 冯天生 | Amino modified nitrogen-doped porous carbon and application thereof in formaldehyde adsorption |
-
2017
- 2017-05-16 CN CN201710341874.7A patent/CN107138130A/en active Pending
Non-Patent Citations (2)
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FANGJUN WU ET AL.: "The properties and enhanced photocatalytic behaviour of TiO2-RGO nanocomposites", 《APPLIED MECHANICS AND MATERIALS》 * |
黄青武: "氧化物/石墨烯纳米复合材料可控合成及其气敏与光催化性能研究", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107998813A (en) * | 2017-09-25 | 2018-05-08 | 浙江海洋大学 | Remove the inorganic agent of indoor formaldehyde and indoor organic volatile matter |
CN107998813B (en) * | 2017-09-25 | 2021-03-16 | 浙江海洋大学 | Treating agent for removing indoor formaldehyde and indoor organic volatile matter |
CN108187633A (en) * | 2018-01-23 | 2018-06-22 | 天津科创复兴科技咨询有限公司 | A kind of formaldehyde adsorbent and its preparation method and application |
CN109569519A (en) * | 2018-10-22 | 2019-04-05 | 江汉大学 | The method for preparing active sludge carbon base formaldehyde adsorbent using municipal sludge |
CN110736722A (en) * | 2019-10-29 | 2020-01-31 | 广州特种承压设备检测研究院 | Manufacturing method of graphene quantum dot composite material optical fiber gas sensor |
CN111111431A (en) * | 2019-12-25 | 2020-05-08 | 山东吉鑫节能科技有限公司 | Formula for removing formaldehyde by graphene and preparation method thereof |
CN113952933A (en) * | 2021-01-15 | 2022-01-21 | 冯天生 | Amino modified nitrogen-doped porous carbon and application thereof in formaldehyde adsorption |
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Effective date of registration: 20180313 Address after: No. 303, Wuyi Road, Jiangsu, Changzhou, Jiangsu Applicant after: Changzhou city industry new Mstar Technology Ltd Address before: No. 303, Wuyi Road, Qishuyan, Changzhou, Jiangsu Applicant before: City, Jiangsu work builds Science and Technology Ltd. |
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