CN105289510A - Preparation method of core-shell structured composite material with breathable effect - Google Patents
Preparation method of core-shell structured composite material with breathable effect Download PDFInfo
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- CN105289510A CN105289510A CN201510834820.5A CN201510834820A CN105289510A CN 105289510 A CN105289510 A CN 105289510A CN 201510834820 A CN201510834820 A CN 201510834820A CN 105289510 A CN105289510 A CN 105289510A
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Abstract
The invention relates to preparation of a core-shell structured composite material with a breathable effect. A preparation method comprises: preparing an MIL-47 flexible porous adsorption material through a hydrothermal method; adding the MIL-47 flexible porous adsorption material after complete washing, purifying, and activating into an ethanol solution of butyl titanate; and performing high-temperature hydrolysis reaction to finally prepare a TiO2-MIL-47 composite material used for enrichment and catalytic degradation of an organic matter. The method is simple in process and easy to operate. It is shown through an adsorption and degradation experiment that the prepared composite material is regular in structure and large in hole capacity, and has an excellent degradation effect on an organic matter. According to the method, an addition ratio of TiO2 to MIL-47 is not limited, that is, any ratio can be adopted for loading according to research or practical application requirements.
Description
Technical field
The present invention relates to a kind of composite material of core-shell structure with cell breath, this composite is cladding titanium dioxide (TiO
2) nanocrystalline porous MIL-47 particle, after water heat transfer MIL-47 particle, at employing solvent-thermal method, nanometer titanium dioxide-coated is surperficial in it, finally obtain advanced composite material (ACM), and develop a kind of fast simple Adsorption of Organic and degraded new method with this.
Background technology
MIL-47 is the flexible back bone porous adsorbing material with cell breath that a class is formed by self assembly effect by metal ion and organic ligand.The well-regulated pore passage structure of MIL-47 tool, (BET specific surface area is up to 1000m for the specific area of super large
2/ g), the remarkable advantages such as good heat endurance and solvent stability, therefore, have been widely used in sample adsorption field.The present invention adopts this novel flexible, porous sorbing material of MIL-47 as adsorbent, comes for the preparation of enrichment and the organic advanced composite material (ACM) of catalytic degradation.
Be used for since catalytic degradation organic matter makes a breakthrough from semi-conducting material, titanium dioxide because its catalytic activity is high, chemistry and biologically inert is good, to human non-toxic, the particular advantages such as inexpensive, become the most active catalysis material of Recent study.Compared with the titanium dioxide of stock size, nano titanium oxide has higher catalytic activity and selective, can form Strong oxdiative-reduction system, decomposed by substance oxidation that is not oxidizable or that be difficult to degrade, this technology has been widely used in the organic wastewater processing the generation of the industry such as dyestuff, papermaking.But because particle diameter is minimum, nano titanium oxide very easily runs off in oxidizing process, therefore, find the carrier can fixing nano titanium oxide, absorption, oxidation Decomposition are combined, is just more conducive to the extensive use in actual production.
Advanced composite material (ACM) designed by the present invention adopts the flexible cellular material MIL-47 with cell breath as binding matrix, after porous MIL-47 materials synthesis, adopt solvent-thermal method to have the nano titanium oxide of catalytic degradation activity in its particle surface load, finally make the composite material of core-shell structure with cell breath.The object of the invention is in conjunction with above-mentioned bi-material characteristics and advantages separately, prepare a kind of novel Mobyneb composite, and to be applied in sewage or waste water in organic absorption and degradation process.
Summary of the invention
For realizing technical scheme provided by the present invention be:
Prepare MIL-47 porous adsorbing material with hydro-thermal method, through washing fully, purification, after activation, adopts mortar to be ground into the comparatively homogeneous MIL-47 powder of granularity.MIL-47 powder after overactivation is joined in the ethanolic solution of butyl titanate, after stirring, is placed in reactor and carries out high-temperature hydrolysis, and product is carried out high-temperature activation, namely obtain the composite material of core-shell structure with cell breath.
Show through adsorption experiment, TiO prepared by this method
2-MIL-47 composite structure rule, pore capacities is large, to organic absorption and catalytic degradation functional.
Wherein, the hydrothermal synthesis method of porous adsorbing material MIL-47 is: by vanadium trichloride, and terephthalic acid (TPA) is dissolved in ultra-pure water, ultrasonic make it dissolve after, mixed solution is placed in polytetrafluoroethylene (PTFE) reactor, carries out pyroreaction in an oven.After reaction terminates, reactor is cooled, the solid matter in reactor is carried out repeatedly, repeatedly washs, with being placed on dry for standby in baking oven.
TiO
2the synthetic method of-MIL-47 composite: take a certain amount of MIL-47 powder, join butyl titanate, in the mixed liquor of ethanol, and stir.Reactant liquor is placed in reactor and carries out high-temperature hydrolysis.After reaction terminates, centrifugally white solid can be obtained.
TiO
2the activation method of-MIL-47 composite: by the washing of above-mentioned white solid ethanol for several times, and solid is placed in baking oven dries, subsequently high-temperature activation a few hours in an oven.
TiO
2the using method of-MIL-47 composite: will through washing, dry, composite after activation joins in the waste water containing organic matter or organic dyestuff, mechanical agitation is carried out to sample solution simultaneously, composite is contacted fully with sample solution, with high-pressure sodium lamp, sample solution is irradiated simultaneously.Meanwhile, can gas chromatography be adopted, liquid chromatography, spectra methods etc., the content of organic matter in sample solution or organic dyestuff is measured.
The present invention adopts the flexible cellular material MIL-47 with cell breath as binding matrix, has the TiO of catalytic organism degrading activity at its duct internal burden
2nanocrystalline, make the novel composite for enrichment and catalyze and degrade organic pollutants with cell breath.Advanced composite material (ACM) involved in the present invention has good absorption and degradation effect to the organic matter in sewage or waste water, can be with a wide range of applications in actual production or life.
Detailed description of the invention
For better understanding the present invention, below in conjunction with embodiment the present invention done and describe in detail further, but the scope of protection of present invention being not limited to the scope that embodiment represents.
Embodiment:
Prepare MIL-47 porous adsorbing material with hydro-thermal method, adopt pyrohydrolytic method that nanometer titanium dioxide-coated is surperficial in MIL-47 sorbing material, composite is purified, after activation, is prepared into the hud typed composite with cell breath:
The hydrothermal synthesis method of porous adsorbing material MIL-47 is: by 1.5729 grams of vanadium trichlorides, 0.4153 gram of terephthalic acid (TPA) is dissolved in 18 milliliters of ultra-pure waters, after within ultrasonic 10 minutes, making it dissolve, mixed solution is placed in 30 milliliters of polytetrafluoroethylene (PTFE) reactors, 200 DEG C are reacted 96 hours.Question response still cools, and ultra-pure water, ethanolic solution washs obtained metallic organic framework sorbing material, 200 DEG C of dry for standby.
TiO
2the synthetic method of-MIL-47 composite: adopt mortar MIL-47 to be ground into the comparatively homogeneous powder of granularity.Take 50mgMIL-47 powder, join 25ml butyl titanate, in the mixed liquor of 10ml ethanol, and carry out magnetic agitation.Reactant liquor is placed in reactor and carries out high-temperature hydrolysis.After reaction terminates, centrifugally white solid can be obtained.
TiO
2the activation method of-MIL-47 composite: by above-mentioned white solid ethanol washing for several times, and solid is placed in the oven dry of 60 DEG C, baking oven, activates 3 hours subsequently in 200 DEG C of baking ovens.
TiO
2the using method of-MIL-47 composite: will through washing, dry, composite after activation joins in the waste water containing organic matter or organic dyestuff, mechanical agitation is carried out to sample solution simultaneously, composite is contacted fully with sample solution, with high-pressure sodium lamp, sample solution is irradiated simultaneously.Meanwhile, can gas chromatography be adopted, liquid chromatography, spectra methods etc., the content of organic matter in sample solution or organic dyestuff is measured.
Claims (5)
1. a MIL-47 porous adsorbent, it is characterized in that: it is the white solid particle adopting hydro-thermal method to prepare, this solid particle needs first repeatedly to clean with ultra-pure water, to remove unreacted slaine, repeatedly clean with ethanol again, remove unreacted terephthalic acid (TPA).
2. a MIL-47 adsorbent for high-specific surface area, good adsorption characteristic, is characterized in that: MIL-47 adsorbent according to claim 1 is needed 200 DEG C of high-temperature roasting a few hours.
3.TiO
2the synthetic method of-MIL-47 composite, is characterized in that: joined by the MIL-47 be ground into powder in ethanol (or other solvents) solution of butyl titanate, after fully stirring and evenly mixing, then carry out high-temperature hydrolysis.
4.TiO
2the activation method of-MIL-47 composite, is characterized in that: gained composite need wash for several times with ethanol, and to remove unreacted butyl titanate, the composite after purification needs 200 DEG C of high-temperature roasting a few hours with activated nano TiO
2catalytic activity.
5. TiO according to claim 3
2the synthetic method of-MIL-47 composite, is characterized in that: TiO
2without any restrictions with the adding proportion of MIL-47, can need to adopt any ratio to carry out load according to research needs or practical application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510834820.5A CN105289510A (en) | 2015-11-24 | 2015-11-24 | Preparation method of core-shell structured composite material with breathable effect |
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| CN201510834820.5A CN105289510A (en) | 2015-11-24 | 2015-11-24 | Preparation method of core-shell structured composite material with breathable effect |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107519942A (en) * | 2016-11-17 | 2017-12-29 | 天津工业大学 | Advanced composite material (ACM) with cell breath is prepared using " one kettle way " |
| CN110152741A (en) * | 2019-05-28 | 2019-08-23 | 浙江天蓝环保技术股份有限公司 | A kind of high efficiency composition visible light catalyst of core-shell structure and its preparation method and application |
Citations (3)
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| WO2009130251A2 (en) * | 2008-04-22 | 2009-10-29 | Faculte Polytechnique De Mons | Gas adsorbent |
| CN104307484A (en) * | 2014-11-12 | 2015-01-28 | 天津工业大学 | Novel breathing-effect composite material for enriching and carrying out catalytic degradation on organic matter |
| CN104353423A (en) * | 2014-11-11 | 2015-02-18 | 天津工业大学 | Novel preparation and application method of water treatment film doped with composite material with breath effect |
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2015
- 2015-11-24 CN CN201510834820.5A patent/CN105289510A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009130251A2 (en) * | 2008-04-22 | 2009-10-29 | Faculte Polytechnique De Mons | Gas adsorbent |
| CN104353423A (en) * | 2014-11-11 | 2015-02-18 | 天津工业大学 | Novel preparation and application method of water treatment film doped with composite material with breath effect |
| CN104307484A (en) * | 2014-11-12 | 2015-01-28 | 天津工业大学 | Novel breathing-effect composite material for enriching and carrying out catalytic degradation on organic matter |
Non-Patent Citations (2)
| Title |
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| LIANG RW 等: ""MIL-53(Fe) as a highly efficient bifunctional photocatalyst for the simultaneous reduction of Cr(VI) and oxidation of dyes"", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
| 唐培松 等: ""高温水解溶剂热法合成纳米TiO2及其光催化性能研究"", 《材料导报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107519942A (en) * | 2016-11-17 | 2017-12-29 | 天津工业大学 | Advanced composite material (ACM) with cell breath is prepared using " one kettle way " |
| CN110152741A (en) * | 2019-05-28 | 2019-08-23 | 浙江天蓝环保技术股份有限公司 | A kind of high efficiency composition visible light catalyst of core-shell structure and its preparation method and application |
| CN110152741B (en) * | 2019-05-28 | 2020-11-10 | 浙江天蓝环保技术股份有限公司 | Efficient composite visible-light-driven photocatalyst with core-shell structure and preparation method and application thereof |
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Application publication date: 20160203 |