CN102350307B - Preparation method of hybrid nano film - Google Patents
Preparation method of hybrid nano film Download PDFInfo
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- CN102350307B CN102350307B CN 201110182705 CN201110182705A CN102350307B CN 102350307 B CN102350307 B CN 102350307B CN 201110182705 CN201110182705 CN 201110182705 CN 201110182705 A CN201110182705 A CN 201110182705A CN 102350307 B CN102350307 B CN 102350307B
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- ethylenediamine
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- heavy metal
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Abstract
The invention relates to a preparation method of a hybrid nano film. The method comprises steps of: (1) dissolving germanium dioxide and zinc acetate dihydrate in a mixed solvent of deionized water and anhydrous ethylenediamine, stirring and transferring the solution into a reaction kettle, cooling to a room temperature to obtain a Zn2GeO4-ethene diamine nanoribbon. (2) placing the Zn2GeO4-ethene diamine nanoribbon into a dispersant, dispersing uniformly by ultrasonic, removing the dispersant by a heat evaporation method and carrying out a self assembly of the Zn2GeO4-ethene diamine nanoribbon to form a film with uniform thickness. The preparation method of the invention has characteristics of environment friendliness, cheap and easily available raw material, low toxicity, low price and simple operation process, etc. The prepared film has high adsorption performance on heavy metal ions in sewage, can be reused by washing and is environment-friendly, practical and with promising application prospect.
Description
Technical field
The invention belongs to nanometer band film field, particularly the membrane preparation method of a kind of hybridized nanometer.
Background technology
The heavy metal ion that exists in the water causes very big threat to the mankind's life and health.Along with industrial expansion, metallurgical industry, the leather industry, mining industry and battery industry also increasingly sharpen to the heavy metal pollution that environment brings, and environmental protection and improvement become modern industrialization and produce an indispensable part.Prepare a kind of environmental protection thin-film material that contents of many kinds of heavy metal ion is had high adsorption rate and can reuse, seem very necessary.
At present, the film-type adsorbent is generally made by raw materials such as mesoporous material or organic polymers.And these materials are being used for when heavy metal ion adsorbed, must be by the modification of some organo-functional groups, as-SH ,-OH ,-COOH ,-NH
2Deng, method is loaded down with trivial details, and adsorbent lacks active site so that adsorption efficiency is not high, in use owing to be subjected to can not be high temperature resistant, be difficult to the restriction of reasons such as reusing, can not extensive use make the adsorbent of various uses.The fibrous compound of hybrid inorganic-organic---the thin-film material formed of nanometer band, nano wire especially, can overcome multiple shortcoming, as have advantages such as high temperature resistant, that adsorption efficiency is high, can reuse, will become a kind of very promising new material.
The organic-inorganic hybrid nanomaterials of big L/D ratio is because organic principle, can be dispersed in some organic solvents such as acetone and ethanol, and can form uniform thin-film material, because special organic molecule composition in the hybrid material, can good coordination ability be arranged to contents of many kinds of heavy metal ion, thereby reach absorption property.In addition, the thin-film material after adopting stronger chelating agent to the absorption heavy metal carries out wash-out to be handled, and can reach recycling effect.
Summary of the invention
Technical problem to be solved by this invention provides the membrane preparation method of a kind of hybridized nanometer, this method has that environmental friendliness, required raw material are easy to get, low toxicity, cheap, characteristics such as operating process is easy, the film that is prepared into has high absorption property to the heavy metal ion in the sewage, and can reuse by wash-out, the environmental protection practicality has a good application prospect.
The membrane preparation method of a kind of hybridized nanometer comprises:
(1) with mol ratio is the mixed solvent that 1: 1～2 germanium dioxide and Zinc diacetate dihydrate are dissolved in deionized water and anhydrous ethylenediamine, solution gone in the reactor after stirring 30～60min that 170-200 ℃ of reaction 16-36 hour down is cooled to room temperature and namely gets Zn
2GeO
4-ethylenediamine nanometer band;
(2) with above-mentioned Zn
2GeO
4-ethylenediamine nanometer band is put into dispersant, and thermal evaporation is adopted in ultrasonic even dispersion back, removes dispersant, Zn in 50-80 ℃
2GeO
4-ethylenediamine nanometer band is self-assembled into the uniform film of thickness.
Deionized water in the described step (1) and the volume ratio of anhydrous ethylenediamine are 1: 2～3.
Dispersant in the described step (2) is ethanol or acetone.
Film in the described step (2) is applied to remove the heavy metal ion in the sewage.
Need at vessel bottom pad last layer nonwoven before adopting thermal evaporation, the material that will be dispersed in then in the dispersant covers on it, removes dispersant by thermal evaporation again.
Selecting concentration is that the disodium ethylene diamine tetra-acetic acid solution of 2.5-10mM or rare nitric acid are as eluant, eluent, to adsorbing the Zn of heavy metal
2GeO
4-ethylenediamine hybridized nanometer band film has good desorption performance, but makes film have good reuse.
Beneficial effect
Preparation method of the present invention has that environmental friendliness, required raw material are easy to get, low toxicity, cheap, characteristics such as operating process is easy, the film that is prepared into has high absorption property to the heavy metal ion in the sewage, and can reuse by wash-out, the environmental protection practicality has a good application prospect.
Description of drawings
Fig. 1 is the Zn for preparing among the present invention
2GeO
4The SEM picture of-ethylenediamine hybridized nanometer band;
Fig. 2 is that the hybridized nanometer band film for preparing among the present invention is to the absorption figure of contents of many kinds of heavy metal ion;
Fig. 3 is the heavy metal pb of desorbing agent to adsorbing on the film among the present invention
2+The desorption efficiency chart.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
(1) takes by weighing germanium dioxide and Zinc diacetate dihydrate, be dissolved in deionized water, under the condition of magnetic agitation, add ethylenediamine, the volume ratio of deionized water and anhydrous ethylenediamine is 1: 2, the mol ratio of germanium dioxide and Zinc diacetate dihydrate is 1: 1, stir the white solution that forms after half an hour and go in the autoclave, reaction is 24 hours under 180 ℃ of hydrothermal conditions, and back cooling reactor is to room temperature.
(2) the white product microscopic pattern that obtains is Zn
2GeO
4-ethylenediamine overlength nanometer band (as Fig. 1) is with Zn
2GeO
4-ethylenediamine nanometer band is put into ethanol, after the ultrasonic even dispersion, adopts thermal evaporation, removes ethanol, Zn in 60 ℃
2GeO
4-ethylenediamine nanometer band is self-assembled into the uniform film of thickness in vessel.
(3) with Zn
2GeO
4-ethylenediamine hybridized nanometer band film is put into the contaminant water that contains heavy metal, and film can efficiently adsorb contents of many kinds of heavy metal ion (as Fig. 2).
(4) selecting concentration is that the disodium ethylene diamine tetra-acetic acid solution of 2.5mM is as eluant, eluent, to adsorbing the Zn of heavy metal
2GeO
4-ethylenediamine hybridized nanometer band film has good desorption performance (as Fig. 3), but makes film have good reuse.
(1) takes by weighing germanium dioxide and Zinc diacetate dihydrate, be dissolved in deionized water, under the condition of magnetic agitation, add ethylenediamine, the volume ratio of deionized water and anhydrous ethylenediamine is 1: 3, the mol ratio of germanium dioxide and Zinc diacetate dihydrate is 1: 2, stir the white solution that forms after a hour and go in the autoclave, reaction is 16 hours under 190 ℃ of hydrothermal conditions, and back cooling reactor is to room temperature.
(2) the white product microscopic pattern that obtains is Zn
2GeO
4-ethylenediamine overlength nanometer band is with Zn
2GeO
4-ethylenediamine nanometer band is put into ethanol, after the ultrasonic even dispersion, adopts thermal evaporation, removes ethanol, Zn in 60 ℃
2GeO
4-ethylenediamine nanometer band is self-assembled into the uniform film of thickness in vessel.
(3) with Zn
2GeO
4-ethylenediamine hybridized nanometer band film is put into the contaminant water that contains heavy metal, and film can efficiently adsorb contents of many kinds of heavy metal ion.
(4) selecting concentration is that the disodium ethylene diamine tetra-acetic acid solution of 10mM is as eluant, eluent, to adsorbing the Zn of heavy metal
2GeO
4-ethylenediamine hybridized nanometer band film has good desorption performance, but makes film have good reuse.
Embodiment 3
(1) takes by weighing germanium dioxide and Zinc diacetate dihydrate, be dissolved in deionized water, under the condition of magnetic agitation, add ethylenediamine, the volume ratio of deionized water and anhydrous ethylenediamine is 1: 2.5, the mol ratio of germanium dioxide and Zinc diacetate dihydrate is 1: 1.5, stir the white solution that forms after half an hour and go in the autoclave, reaction is 36 hours under 200 ℃ of hydrothermal conditions, and back cooling reactor is to room temperature.
(2) the white product microscopic pattern that obtains is Zn
2GeO
4-ethylenediamine overlength nanometer band is with Zn
2GeO
4-ethylenediamine nanometer band is put into acetone, after the ultrasonic even dispersion, adopts thermal evaporation, removes acetone, Zn in 60 ℃
2GeO
4-ethylenediamine nanometer band is self-assembled into the uniform film of thickness in vessel.
(3) with Zn
2GeO
4-ethylenediamine hybridized nanometer band film is put into the contaminant water that contains heavy metal, and film can efficiently adsorb contents of many kinds of heavy metal ion.
(4) selecting concentration is that the disodium ethylene diamine tetra-acetic acid solution of 5mM is as eluant, eluent, to adsorbing the Zn of heavy metal
2GeO
4-ethylenediamine hybridized nanometer band film has good desorption performance, but makes film have good reuse.
Embodiment 4
(1) takes by weighing germanium dioxide and Zinc diacetate dihydrate, be dissolved in deionized water, under the condition of magnetic agitation, add ethylenediamine, the volume ratio of deionized water and anhydrous ethylenediamine is 1: 2, the mol ratio of germanium dioxide and Zinc diacetate dihydrate is 1: 1, stir the white solution that forms behind the 40min and go in the autoclave, reaction is 18 hours under 170 ℃ of hydrothermal conditions, and back cooling reactor is to room temperature.
(2) the white product microscopic pattern that obtains is Zn
2GeO
4-ethylenediamine overlength nanometer band is with Zn
2GeO
4-ethylenediamine nanometer band is put into acetone, after the ultrasonic even dispersion, adopts thermal evaporation, removes ethanol, Zn in 80 ℃
2GeO
4-ethylenediamine nanometer band is self-assembled into the uniform film of thickness in vessel.
(3) with Zn
2GeO
4-ethylenediamine hybridized nanometer band film is put into the contaminant water that contains heavy metal, and film can efficiently adsorb contents of many kinds of heavy metal ion.
(4) select rare nitric acid as eluant, eluent, to adsorbing the Zn of heavy metal
2GeO
4-ethylenediamine hybridized nanometer band film has good desorption performance, but makes film have good reuse.
Claims (1)
1. membrane preparation method of hybridized nanometer comprises:
(1) with mol ratio is the germanium dioxide of 1:1～2 and the mixed solvent that Zinc diacetate dihydrate is dissolved in deionized water and anhydrous ethylenediamine, behind stirring 30～60min solution gone in the reactor that reaction is 16-36 hour under the 170-200 ° of C, is cooled to room temperature and namely gets Zn
2GeO
4-ethylenediamine nanometer band; Wherein, the volume ratio of deionized water and anhydrous ethylenediamine is 1:2～3;
(2) with above-mentioned Zn
2GeO
4-ethylenediamine nanometer band is put into dispersant, and thermal evaporation is adopted in ultrasonic even dispersion back, removes dispersant, Zn in 50-80 ° of C
2GeO
4-ethylenediamine nanometer band is self-assembled into the uniform film of thickness; Described film is applied to remove the heavy metal ion in the sewage, and selecting concentration is that the disodium ethylene diamine tetra-acetic acid solution of 2.5-10mM or rare nitric acid are as eluant, eluent, to adsorbing the Zn of heavy metal
2GeO
4-ethylenediamine hybridized nanometer band film carries out desorption; Wherein, dispersant is ethanol or acetone; Fill up layer of non-woven fabric in the vessel bottom before the thermal evaporation.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102962049A (en) * | 2012-11-26 | 2013-03-13 | 南京大学 | Method for preparing nanometer photocatalytic material via hydrothermal reaction |
| CN106186049A (en) * | 2016-07-14 | 2016-12-07 | 南京大学 | A kind of hydrothermal preparing process of the bar-shaped zinc germanate of size adjustable |
| CN106824227A (en) * | 2017-03-08 | 2017-06-13 | 济南大学 | A kind of In2S3/Zn2GeO4The preparation method and application of composite visible light catalyst |
| CN106881114A (en) * | 2017-03-09 | 2017-06-23 | 济南大学 | A kind of visible light-responded CdS/Cd2Ge2O6The preparation method of heterojunction photocatalyst |
| CN107089663B (en) * | 2017-03-22 | 2019-01-25 | 同济大学 | A method of it preparing Si fixed point and replaces amorphous nano linear array |
| CN109092356B (en) * | 2018-09-12 | 2021-02-26 | 安徽大学 | Preparation method of ethylenediamine-induced penta-benzoquinone assembly loaded nano-silver composite catalyst |
| CN114538500B (en) * | 2022-03-09 | 2023-11-03 | 郑州轻工业大学 | Rod-shaped structure Zn 2 GeO 4 Material, preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101961648A (en) * | 2010-11-05 | 2011-02-02 | 天津森诺过滤技术有限公司 | Membrane adsorbent for removing heavy metal ions from drinking water effectively and preparation method thereof |
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| JP3834776B2 (en) * | 2003-10-30 | 2006-10-18 | 独立行政法人科学技術振興機構 | Catalyst for photo-water splitting containing germanium nitride structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101961648A (en) * | 2010-11-05 | 2011-02-02 | 天津森诺过滤技术有限公司 | Membrane adsorbent for removing heavy metal ions from drinking water effectively and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| High-yield synthesis of ultralong and ultrathin Zn2GeO4 nanoribbons toward improved photocatalytic reduction of CO2 into renewable hydrocarbon fuel;Q. Liu et al.;《Journal of the American Chemical Society》;20100924;第132卷;第14385-14387页 * |
| J. Yuan et al..Spontaneous formation of inorganic paper-like materials.《Advanced Materials》.2004,第16卷(第19期),第1729-1732页. |
| JP特开2005-131531A 2005.05.26 |
| Q. Liu et al..High-yield synthesis of ultralong and ultrathin Zn2GeO4 nanoribbons toward improved photocatalytic reduction of CO2 into renewable hydrocarbon fuel.《Journal of the American Chemical Society》.2010,第132卷第14385-14387页. |
| Spontaneous formation of inorganic paper-like materials;J. Yuan et al.;《Advanced Materials》;20041004;第16卷(第19期);第1729-1732页 * |
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