CN101249430A - Method of magnetic nano photochemical catalyst material preparation - Google Patents
Method of magnetic nano photochemical catalyst material preparation Download PDFInfo
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- CN101249430A CN101249430A CNA200810102502XA CN200810102502A CN101249430A CN 101249430 A CN101249430 A CN 101249430A CN A200810102502X A CNA200810102502X A CN A200810102502XA CN 200810102502 A CN200810102502 A CN 200810102502A CN 101249430 A CN101249430 A CN 101249430A
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- water
- photochemical catalyst
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Abstract
The invention relates to a method for preparing magnetic nano-scale photocatalytic material and belongs to technical fields of nanomaterial, magnetic material, environmental catalysis, etc. The nano-scale photocatalytic material is prepared in the micro-emulsion method by the nano-scale magnetic nuclei precursor; carrying out in-situ coating of the surface photocatalytic layer of the magnetic nuclei precursor by a micro emulsion interface sol-gel coupling method; and washing, drying and sintering the generated precursor to obtain superparamagnetic magnetic nano-scale photocatalytic material with a magnetic nuclei-catalytic shell structure. The material has an average particle diameter of 8-14nm and good photocatalytic effect, and can be recovered and reutilized with a recovery of 90% or higher. The method has the advantages of controllable particle morphology and size, simple device, easy operation, high catalytic efficiency, high catalyst recovery rate and easy achievement of large-scale industrial production.
Description
Technical field
The present invention relates to a kind of magnetic nano photochemical catalyst preparation methods, belong to the nano magnetic material technical field.
Background technology
Along with environmental pollution and resource scarcity are on the rise, environmental protection and resource circulation utilization occupy an important position in national economy and social sustainable development strategy.Advantages such as that solid catalyst has is easily separated, reusable edible have remarkable advantages in fields such as chemistry, chemical industry, pharmacy, environment, develop the attention that eco-friendly solid catalyst more and more is subjected to researcher.Yet, its development of restriction such as conventional solid catalyst reaction interface is little, resistance to mass tranfer is big.The nano-solid catalyst is little because of its primary partical size, specific area is big, the surface atom number is many, surface energy and surface tension are big, and have quantum size effect, bulk effect, skin effect and macro quanta tunnel effect, bring characteristics such as excellent light, electricity, catalysis to catalyst.Such as: nano-TiO
2, the ZnO semi-conducting material shows very strong catalytic oxidation ability under the irradiation of light, can with in the water or airborne organic molecule structure thoroughly destroy even mineralising.Nanometer WO
3Electromagnetic wave there is very strong absorbability, can be used as absorbing material and military stealth material that solar energy utilizes; Because of it has characteristic of semiconductor, can be used as in addition NO
x, H
2S, NH
3Etc. sensitive material of multiple gases or the like., the problem that is difficult to separate that tiny nano-solid catalyst brings limits its application in liquid-phase system.The magnetic particle that will have excellent magnetic performance combines with catalytic performance and prepares the nano-magnetic catalyst, the characteristics that not only have magnetic material and catalysis material, and specific performance with nano material, given catalyst some excellent specific functions, for the separation of nano-solid catalyst provides new thinking.
The preparation of conductor photocatalysis material is one of hot issue of current research, and TiO
2For the photocatalytic environmental-protection material of representing obtains extensive studies, wherein, most active research direction is eliminated and is degraded in photocatalysis.Certain TiO
2Self have the very easily compound problem in electronics and hole, people pass through TiO in preparation process
2Modification improve its photocatalytic activity.As: patent CN1554479 (Pan Haibo, gold mound, Chen Naisheng etc. a kind of sol-gel original position of composite photocatalyst material and self assembling process of synthesizing .CN1554479 2004.12.15) disclose a kind of inorganic TiO
2Base Metal phthalocyanine complex composite photo-catalyst can be widened the visible absorption frequency spectrum, significantly improves photocatalytic degradation efficient; Patent CN1799688 (Yang Huaming, Hu Yuehua, Zhang Ke etc. a kind of method .CN1799688 for preparing composite photocatalysis material of titanium dioxide 2006.07.12) discloses a kind of employing sol-gel process and has prepared TiO
2Add tungsten salt and vanadic salts behind the presoma, obtain WO behind the roast
3-V
2O
5/ TiO
2Composite photocatalyst material; Patent CN101015793 (in great waves, Tan Xin, Li Enbang etc. a kind of novel nano TiO
2The preparation method .CN101015793 of catalysis material 2007.08.15) discloses a kind of employing sol-gel process at silica fibre surface preparation modification TiO
2Light is urged CN101015793,2007.08.15) discloses a kind of employing sol-gel process at silica fibre surface preparation modification TiO
2Catalysis material; Patent CN01118119.2 (Zhang Lingjuan, Hu Xiaoming, river thunder. the preparation method .CN01118119.2 of the titanium dioxide nano photocatalysis material of modification 2002.12.18) discloses the additive agent modified photocatalysis material of titanium dioxide of a kind of adding JL-1.These different method of modifying have all increased TiO
2Photocatalysis performance, but all do not consider nano level TiO
2The separation problem of catalysis material after processing.Chen Jinyuan etc. (Chen Jinyuan, Peng Tuzhi. chemical journal, 2004,62:2093-2097) adopt sol-gel process, in magnetic Fe
3O
4Off normal and coat TiO in the surface
2Having prepared a kind of novel average-size is the TiO of 35～50nm
2/ Fe
3O
4The nano-photo catalytic composite.This composite red shift occurs to the absorption of light, and absorption intensity increases; Percent of decolourization to the reactive brilliant red dyestuff reaches 100%, is a kind of recovery, reusable high efficiency photocatalyst be convenient to.(Shchukin DG, Kulak AI.Photochemical ﹠amp such as Shchukin DG; Photobiological Sciences, 2002,1 (10): 742-744) adopt prepared by co-precipitation to mix zinc-nickel ferrite Zn
0.35Ni
0.65Fe
2O
4, be that magnetic is examined the deposition SiO that offs normal on its surface successively with it again
2Layer and TiO
2Layer, thus prepared the Zn that is used for the oxidation operation degraded
0.35Ni
0.65Fe
2O
4/ SiO
2/ TiO
2, reaction presents significant photocatalytic activity to the oxalic acid photocatalytic degradation for it.Present most of document and patent all adopt the method for the load of offing normal to prepare composite catalyst, and it exists the magnetic karyosome to reunite and distribute widely through size, and magnetic nuclear clad ratio is low, and defective such as preparation technology's long flow path.
Characteristics in view of above nano-photocatalyst, the present invention is a media with the microemulsion that contains nanometer magnetic nuclear presoma, utilize microemulsion interface sol-gel process to carry out magnetic nuclear surface in situ and coat photocatalysis layer, preparation " magnetic nuclear-catalysis shell " nano-photocatalyst material that the structural type magnetic responsiveness is strong.This method can be controlled pattern, particle diameter and the distribution thereof of nano-photocatalyst material effectively, and magnetic nuclear clad ratio.
Summary of the invention
The present invention at first adopts two micro-emulsion method for preparing nano magnetic nuclear presomas, and the original position that adopts microemulsion interface sol-gel process to carry out magnetic nuclear surface light Catalytic Layer then coats, thereby prepares " magnetic nuclear-catalysis shell " structural type magnetic nano photochemical catalyst material.Purpose is to provide the nano-photocatalyst material of the magnetic that a kind of granule-morphology is controlled, catalytic efficiency is high, production method is simple, be easy to separate.
Concrete operation method is as follows: 1) preparation contains the w/o type microemulsion and the w/o type microemulsion that contains alkaline precipitating agent of metal ion, these two parts of abundant stirring reactions of microemulsion is obtained containing the w/o type microemulsion of nanometer magnetic nuclear presoma; 2) will contain butyl titanate, chelating agent and diluent solution joins in the above-mentioned microemulsion that obtains, under 20～80 ℃ of counterflow conditions, abundant stirring reaction, the complex of being made up of butyl titanate and chelating agent in this course of reaction slowly to the water diffusion, obtains containing the microemulsion that the surperficial nanometer magnetic that is coated by titanium hydroxide is examined by oil phase; 3) will obtain precursor after this microemulsion breakdown of emulsion, separation, washing, the drying.This presoma is obtained " magnetic nuclear-catalysis shell " structural type magnetic nano photochemical catalyst material after the calcining down at 300～800 ℃.
The W/O microemulsion that contains metal ion is made up of surfactant, cosurfactant, oil phase and water (metal ion) four parts.The surfactant that is adopted is anion surfactant or cationic surfactant or nonionic surface active agent; The cosurfactant that is adopted is C
4～C
10Medium carbon chain lengths straight chain alcohol; Oil phase is C
5～C
16Alkane; Metal ion comprises Fe
3+And bivalent metal ion, as: Fe
2+, Co
2+, Zn
2+, Ni
2+, Mg
2+, Cu
2+, Mn
2+Deng.
The W/O microemulsion that contains alkaline precipitating agent is made up of surfactant, cosurfactant, oil phase and water (containing alkaline precipitating agent) four parts.The surfactant that is adopted, cosurfactant and oil phase are identical with the W/O microemulsion that contains metal ion; The contained alkaline precipitating agent of aqueous phase can be NaOH or Na
2C
2O
4Or ammoniacal liquor or organic amine or urea etc., the pH value of this water is regulated by the alkaline precipitating agent consumption, is controlled at 7-14.
The W/O microemulsion that contains nanometer magnetic nuclear presoma: water is examined size with the amount of substance of surfactant than water in (ω) decision system, in 3～20 scopes; Pure and surface-active amount of substance affects the stability at water/oily interface than (m), in 3～12 scopes; Oil (has reflected that v) unit volume contains water check figure order in the system, in 0.25～4 scope with the volume ratio of surfactant.
The solution that contains butyl titanate, chelating agent and diluent: chelating agent is ethyl acetoacetate or carbonyls such as acetylacetone,2,4-pentanedione or acetate.The amount of substance of chelating agent and butyl titanate than (p) in 0.1～0.6 scope; In the microemulsion amount of substance of water and butyl titanate than (n) in 1～6 scope.
The breakdown of emulsion mode of microemulsion adopts demulsifiers such as adding acetone, alcohols or improves temperature or solvent evaporation or solvent heat.
The present invention has following advantage and high-lighting effect:
The present invention proposes a kind of preparation method of simple original position synthesizing magnetic nano-photocatalyst material.Conventional " magnetic nuclear-catalysis shell " structural type magnetic Nano composite photocatalyst material generally adopts the ex situ methods preparation, and the inventive method is a medium with the microemulsion of the synthetic nanometer magnet precursor of original position, utilize the microemulsion interface that reactant in the oil phase is controlled the aqueous phase collosol and gel to the water diffusion effect and form speed, thereby pattern, particle diameter and the layer thickness of realizing " magnetic nuclear-catalysis shell " structural type magnetic Nano composite photocatalyst material are controlled, the reduction operating procedure reduces production costs.The present invention utilizes microemulsion and sol-gel process coupling, and sol-gel process is carried out in " nano-reactor " water nuclear in the microemulsion medium, can control the primary particle size of product effectively; And the oxide precursor surface that obtains is wrapped in surfactant, avoided easily taking place in the conventional sol-gal process calcination process problem of reuniting, thereby it is little to reach the preparation diameter of particle, requirements such as pattern is regular, narrowly distributing.Another outstanding feature of the present invention is to adopt original position to coat, and not only magnetic is examined surperficial coating degree and efficient apparently higher than coatings of offing normal, and to examine size little for magnetic in the prepared magnetic photocatalytic material, not only simplifies preparation flow greatly.
Description of drawings
Fig. 1 is a magnetic nano photochemical catalyst material preparation process schematic diagram.
Wherein: the 1-surfactant; The 2-cosurfactant; The 3-oil phase; The water of 4-metal ion; 5-contains the water of alkaline precipitating agent; 6-magnetic nuclear presoma; 7-colloidal sol zone; The 8-gel; 9-TiO
2Layer; 10-magnetic nuclear.
Specific implementation method
Embodiment one TiO
2/ CoFe
2O
4Preparation
50.83gTX-100,32.12g n-hexyl alcohol, 58.60g n-hexane are divided into two parts after mixing, and portion dissolves in 2.24ml0.5346mol/L CoCl
2With 1.069mol/L Fe (NO
3)
3Mixed aqueous solution, another part dissolves in the methylamine water solution of 2ml 7.7mol/L, ultrasonic respectively dispersion obtains the microemulsion system A and the B of transparent homogeneous, then two parts of microemulsions abundant stirring reaction 0.5h under 35 ℃ of conditions is obtained containing the microemulsion system C of nanometer magnetic nuclear presoma.20.06g butyl titanate, 2.065g acetylacetone,2,4-pentanedione and 31.56g n-hexane are mixed, and ultrasonic dispersion obtains homogeneous organic solution D, and it is joined among the microemulsion system C that contains nanometer magnetic nuclear presoma, fully stirs and reacts 2h.After appearring in system, takes out gel, gel and centrifugation, and repeatedly wash with acetone, remove foreign ion, obtaining TiO after the calcining down at 500 ℃ after drying
2/ CoFe
2O
4Powder diameter is at 8～12nm.Catalyst is applied to carry out magnetic behind the organic pollution in the photocatalysis examination degradation water separates, not only catalytic effect does not descend, and the rate of recovery can reach more than 95%.
Embodiment two TiO
2/ ZnFe
2O
4Preparation
38.13gTX-100,24.09g n-hexyl alcohol, 43.95g n-hexane are divided into two parts after mixing, and portion dissolves in 2.24ml0.3393mol/L ZnSO
4With 0.6786mol/L Fe (NO
3)
3Mixed aqueous solution, the oxalic acid that another part dissolves in 2ml 1.520mol/L is received, ultrasonic respectively dispersion obtains the microemulsion system A and the B of transparent homogeneous, then two parts of microemulsions abundant stirring reaction 0.5h under 35 ℃ of conditions is obtained containing the microemulsion system C of nanometer magnetic nuclear.20.06g butyl titanate, 2.12g acetylacetone,2,4-pentanedione and 28.77g n-hexane are mixed, and ultrasonic dispersion obtains homogeneous organic solution D, and it is joined contains among the nanometer magnetic nuclear microemulsion system C, fully stirs and reacts 2h.With gelatin phenomenon occurring in its immigration water heating kettle, take out gel and centrifugation then, and repeatedly wash with ethanol, remove foreign ion, obtaining TiO after the calcining down at 450 ℃ after drying
2/ ZnFe
2O
4Powder diameter is at 10～14nm.Catalyst is applied to carry out magnetic behind the organic pollution in the photocatalysis examination degradation water separates, not only catalytic effect does not descend, and the rate of recovery can reach more than 90%.
Embodiment three TiO
2/ MnFe
2O
4Preparation and photocatalysis characterize
30.50gTX-100,19.27g n-hexyl alcohol, 35.16g n-hexane are divided into two parts after mixing, and portion dissolves in 2.24ml0.4971mol/L MnSO
4With 0.9942mol/L Fe (NO
3)
3Mixed aqueous solution, another part dissolves in the NaOH of 2ml 3mol/L, obtain the microemulsion system A and the B of transparent homogeneous through ultrasonic dispersion, then two parts of microemulsions abundant stirring reaction 0.5h under 35 ℃ of conditions is obtained containing the microemulsion system of nanometer magnetic nuclear, it is 10 that the additional a small amount of methylamine in reaction back makes the pH value of microemulsion system.23.42g butyl titanate, 2.12g acetylacetone,2,4-pentanedione and 18.93g n-hexane are mixed, and ultrasonic dispersion obtains homogeneous organic solution and it is joined containing in the nanometer magnetic nuclear microemulsion system, fully stirs and reacts 2h.Improve reaction temperature subsequently and make and gel occurs, take out gel and centrifugation then, and repeatedly wash, remove foreign ion, obtaining TiO after the calcining down at 450 ℃ after drying with acetone and ethanol
2/ MnFe
2O
4Powder diameter is at 9～14nm.Catalyst is applied to carry out magnetic behind the organic pollution in the photocatalysis examination degradation water separates, not only catalytic effect does not descend, and the rate of recovery can reach more than 90%.
Claims (8)
1. magnetic nano photochemical catalyst preparation methods, it is characterized in that: concrete operation method is as follows: 1) preparation contains the w/o type microemulsion and the w/o type microemulsion that contains alkaline precipitating agent of metal ion, these two parts of abundant stirring reactions of microemulsion is obtained containing the w/o type microemulsion of nanometer magnetic nuclear presoma; 2) will contain butyl titanate, chelating agent and diluent solution joins in the above-mentioned w/o type microemulsion that obtains, under 20～80 ℃ of counterflow conditions, abundant stirring reaction, the complex of being made up of butyl titanate and chelating agent in this course of reaction slowly to the water diffusion, obtains containing the microemulsion that the surperficial nanometer magnetic that is coated by titanium hydroxide is examined by oil phase; 3) obtain precursor after the microemulsion breakdown of emulsion that nanometer magnetic is examined, separation, washing, the drying, this presoma is being obtained " magnetic nuclear-catalysis shell " structural type magnetic nano photochemical catalyst material after the calcining down at 300～800 ℃.
2. a kind of magnetic nano photochemical catalyst preparation methods according to claim 1 is characterized in that: the described W/O microemulsion that contains metal ion is made up of surfactant, cosurfactant, oil phase and water (metal ion) four parts.
3. a kind of magnetic nano photochemical catalyst preparation methods according to claim 2 is characterized in that: the surfactant of employing is anion surfactant or cationic surfactant or nonionic surface active agent; The cosurfactant that is adopted is C
4～C
10Medium carbon chain lengths straight chain alcohol; Oil phase is C
5～C
16Alkane; Metal ion comprises Fe
3+And bivalent metal ion.
4. a kind of magnetic nano photochemical catalyst preparation methods according to claim 1 is characterized in that: the described W/O microemulsion that contains alkaline precipitating agent is made up of surfactant, cosurfactant, oil phase and water (containing alkaline precipitating agent) four parts.
5. a kind of magnetic nano photochemical catalyst preparation methods according to claim 4 is characterized in that: the surfactant that is adopted, cosurfactant and oil phase are identical with the W/O microemulsion that contains metal ion; The contained alkaline precipitating agent of aqueous phase is NaOH or Na
2C
2O
4Or ammoniacal liquor or organic amine or urea; The pH value of this water is regulated by the alkaline precipitating agent consumption, is controlled at 7-14.
6. a kind of magnetic nano photochemical catalyst preparation methods according to claim 1 is characterized in that: the W/O microemulsion water in the described method is examined size with the amount of substance of surfactant than water in (ω) decision system, in 4～12 scopes; Pure and surface-active amount of substance affects the stability at water/oily interface than (m), in 5～12 scopes; Oil (has v) reflected the water check figure order that unit volume contains in the system, in 0.4～1.6 scope with the volume ratio of surfactant.
7. a kind of magnetic nano photochemical catalyst preparation methods according to claim 1 is characterized in that: describedly contain that chelating agent is ethyl acetoacetate or carbonyls such as acetylacetone,2,4-pentanedione or acetate in butyl titanate, chelating agent and the diluent solution; In 0～0.5 scope, in 2～5 scopes, n and p are the characteristic parameters of control sol-gel process to the amount of substance of water and butyl titanate to the amount of substance of chelating agent and butyl titanate than (n) in the microemulsion than (p).
8. a kind of magnetic nano photochemical catalyst preparation methods according to claim 1 is characterized in that: the breakdown of emulsion mode of described microemulsion adopts demulsifiers such as adding acetone or alcohols or improves temperature or solvent evaporation or solvent heat.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101662041A (en) * | 2008-08-29 | 2010-03-03 | 深圳市比克电池有限公司 | Method for preparing gel polymer lithium ion battery |
| CN101662042A (en) * | 2008-08-29 | 2010-03-03 | 深圳市比克电池有限公司 | Polymer lithium ion battery and preparation method of diaphragm thereof |
| CN103464213A (en) * | 2013-06-30 | 2013-12-25 | 中北大学 | Polypyrrole-TiO2 magnetically supported photocatalytic composite material and preparation method thereof |
| CN105833882A (en) * | 2016-04-05 | 2016-08-10 | 山东大学 | Performance enhanced Fenton catalyst and application thereof |
| CN106582592A (en) * | 2016-12-13 | 2017-04-26 | 湖北工业大学 | Spherical core-shell type TiO2/TiO2 material and preparation method thereof |
| CN108855034A (en) * | 2018-06-15 | 2018-11-23 | 中国科学院宁波材料技术与工程研究所 | A kind of photo-catalysis function microballoon of size adjustable and its preparation method and application |
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2008
- 2008-03-21 CN CNA200810102502XA patent/CN101249430A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101662041A (en) * | 2008-08-29 | 2010-03-03 | 深圳市比克电池有限公司 | Method for preparing gel polymer lithium ion battery |
| CN101662042A (en) * | 2008-08-29 | 2010-03-03 | 深圳市比克电池有限公司 | Polymer lithium ion battery and preparation method of diaphragm thereof |
| CN101662042B (en) * | 2008-08-29 | 2014-04-30 | 深圳市比克电池有限公司 | Polymer lithium ion battery and preparation method of diaphragm thereof |
| CN101662041B (en) * | 2008-08-29 | 2014-08-27 | 深圳市比克电池有限公司 | Method for preparing gel polymer lithium ion battery |
| CN103464213A (en) * | 2013-06-30 | 2013-12-25 | 中北大学 | Polypyrrole-TiO2 magnetically supported photocatalytic composite material and preparation method thereof |
| CN103464213B (en) * | 2013-06-30 | 2015-06-17 | 中北大学 | Polypyrrole-TiO2 magnetically supported photocatalytic composite material and preparation method thereof |
| CN105833882A (en) * | 2016-04-05 | 2016-08-10 | 山东大学 | Performance enhanced Fenton catalyst and application thereof |
| CN105833882B (en) * | 2016-04-05 | 2018-08-24 | 山东大学 | A kind of fenton catalyst of performance enhancement and its application |
| CN106582592A (en) * | 2016-12-13 | 2017-04-26 | 湖北工业大学 | Spherical core-shell type TiO2/TiO2 material and preparation method thereof |
| CN106582592B (en) * | 2016-12-13 | 2019-07-09 | 湖北工业大学 | A kind of spherical nuclei shell mould TiO2/TiO2Material and preparation method thereof |
| CN108855034A (en) * | 2018-06-15 | 2018-11-23 | 中国科学院宁波材料技术与工程研究所 | A kind of photo-catalysis function microballoon of size adjustable and its preparation method and application |
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Open date: 20080827 |