CN109775739B - Anti-poison graded porous nano aluminum oxide material and preparation method thereof - Google Patents
Anti-poison graded porous nano aluminum oxide material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of an anti-poison graded porous nano aluminum oxide material, which comprises the following steps of forming an aluminum oxide precursor by using an amphiphilic block polymer/inorganic hybrid aluminum isopropoxide; preparing the hierarchical porous nano-alumina by a sol-gel method. The invention utilizes the self-assembly capability of the amphiphilic block polymer in the process of forming the nano-alumina by the sol-gel method, and the prepared hierarchical porous nano-alumina has the advantages of large specific surface area, controllable particle size, stable structure, uniform dispersion in fiber spinning solution, good anti-toxic effect, high-efficiency adsorption of chemical toxicants and wide prospect in the field of anti-toxic clothing.
Description
Technical Field
The invention relates to the technical field of nano metal oxide materials, in particular to an anti-poison graded porous nano aluminum oxide material and a preparation method thereof.
Background
In recent years, terrorist attacks and dangerous chemical leakage and other emergencies occur, and the use of chemical warfare agents brings great threat to the life safety of people. The breathable gas protection suit widely used at present is skin protection equipment which can permeate air and moisture and prevent external toxic gas, droplet-shaped toxicant, bacteria and radioactive dust from causing harm to human bodies. Through the development of a century, relatively mature breathable gas-proof clothes are published in various countries, and most of the breathable gas-proof clothes are made of activated carbon adsorption materials. Although the protective performance of the activated carbon adsorption type material is good, the problems of no selective adsorption, poor protective performance to large toxic agent drops, easy generation of secondary pollution and the like exist. With the continuous development and improvement of new materials and new technologies, the breathable gas protective clothing material is not limited to the existing activated carbon adsorption technology, but is made of the new materials, and develops towards high performance, multiple functions, light weight and comfort.
The nano metal oxide has the characteristics of large specific surface area, more surface defects, small crystal grains and the like, has super-strong adsorption capacity on chemical warfare agents, viruses and bacteria, and has high-efficiency catalytic degradation performance on chemical toxicants so as to degrade the chemical toxicants. In recent years, researchers have made many relevant researches on the detoxification capability of each nano metal, the structure of the nano metal, the application of the nano metal in the fabric and the like, so as to provide help for the research work in the aspect of chemical warfare agent protection in the future.
The amphiphilic block copolymer can self-assemble into microphase separation micelles with a plurality of different structures in a selective solvent on the scale of tens of nanometers or even microns. The ability to self-assemble can greatly facilitate integration of nanotechnology with other technologies, particularly micro-scale fabrication. The sol-gel reaction in the preparation of nano alumina particles can be easily used to synthesize hierarchical porous nano alumina with tunable morphology, which is difficult to obtain by current strategies.
In summary, the traditional anti-virus clothes and the preparation method of nano-alumina have the problems of long synthesis route, high preparation cost and the like, so that the large-scale production is difficult to realize. The method for preparing the anti-poison grading porous alumina is simple, is easy and convenient to operate, is beneficial to improving the stability and the particle size controllability of the grading porous nano alumina, only uses the amphiphilic block polymer in the process, reduces the preparation cost, simplifies the preparation process, improves the preparation efficiency, and is more beneficial to industrial production.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an anti-poison graded porous nano aluminum oxide material and a preparation method thereof. The preparation method has the advantages of simple preparation process, stable structure of the obtained material, controllable particle size and large specific surface area.
The technical scheme of the invention is as follows:
the preparation method of the anti-poison graded porous nano aluminum oxide material comprises the following steps:
(1) preparing an amphiphilic block polymer/inorganic hybrid alumina precursor;
① adding amphiphilic block polymer polyethylene glycol hexadecyl ether into a flask, and heating to 40 ℃ for melting;
②, rapidly adding aluminum isopropoxide into the flask under high-speed stirring, and continuously reacting the mixture for 5-6 hours under the conditions of medium-speed stirring and 40 ℃;
③ continuously fractionating the isopropanol in vacuum, supplying heat until the distillation of isopropanol is stopped, and cooling the product;
(2) preparing graded porous nano alumina;
①, adding the amphiphilic block polymer/inorganic hybrid alumina precursor prepared in the step (1) into a mixed solvent of ethanol and water under high-speed stirring at room temperature, stirring for 30-90 min, and adding the obtained Al2O3The colloidal suspension was centrifuged and washed with the same type of solvent for 3 cycles;
② mixing Al2O3Dispersing the colloid into a mixed solvent of ethanol and water, further aging for 10-20 h at 100-160 ℃, cooling the mixture, collecting the precipitate, washing for 3 times by using the same type of solvent, and drying in vacuum at 30 ℃;
③ calcining in air at 300-450 ℃ for 1.5-3 h to obtain the hierarchical porous Al2O3A ball.
The molar ratio of the polyethylene glycol cetyl ether to the aluminum isopropoxide is 1: 1.
The volume ratio of ethanol to water in the mixed solvent of ethanol and water is 5: 1-3: 1.
The high-speed stirring speed is 6000 r/min; the rotating speed of the medium-speed stirring is 3000 r/min.
The mass ratio of the amphiphilic polymer/inorganic hybrid alumina precursor to the mixed solvent in the step (2) ① is 1: 30-1: 70.
Al in step (2) ②2O3Colloid and BThe mass ratio of the alcohol to the water mixed solvent is 1:4000 to 1: 6000.
The beneficial technical effects of the invention are as follows:
(1) the hydrolysis and condensation reactions of this novel hybrid precursor are controlled and mild to monomeric Al2O3Precursors are impossible to achieve;
(2) the mixed precursor and the sol-gel reaction thereof can be easily used for synthesizing the hierarchical porous nanostructure Al with larger specific surface area2O3Balls, which are difficult to obtain with current strategies;
(3) due to the high specific surface area, narrow pore diameter distribution and specific surface property, the prepared layered nano-structure Al2O3The spheres have a very high adsorption capacity for chemical poisons.
Drawings
FIG. 1 is a schematic view of the present invention.
Detailed Description
The present invention will be further specifically described with reference to the drawings and examples.
Example 1
The preparation method of the anti-poison graded porous nano aluminum oxide material specifically comprises the following steps:
(1) preparing an amphiphilic block polymer/inorganic hybrid alumina precursor;
① amphiphilic block polymer polyethylene glycol cetyl ether (13.66g, 20mmol) was added to the flask and heated to 40 ℃ for melting;
② aluminium isopropoxide (4.08g, 20mmol) was added rapidly to the flask at a stirring speed of 6000r/min, and the mixture was stirred continuously for 5 hours at a stirring speed of 3000r/min, maintaining the temperature at 40 ℃;
③ continuously fractionating the isopropanol in vacuum, continuing to supply heat until the distillation of isopropanol stops, and cooling the product for use;
(2) preparing graded porous nano alumina;
① stirring the mixture obtained in step (1) at room temperature at 6000r/minAdding an amphiphilic block polymer/inorganic hybrid alumina precursor (3g) into 150mL of mixed solvent of ethanol and water (the volume ratio of the ethanol to the water is 4:1), stirring for 60 minutes, and then adding the obtained Al2O3The colloidal suspension was centrifuged and washed with the same type of solvent for 3 cycles;
② mixing Al2O3The colloid (0.1g) was redispersed in 500ml of a mixed solvent of ethanol and water and, after further aging at 100 ℃ for 20 hours, the mixture was cooled, and the precipitate was collected and washed 3 times with the same type of solvent and vacuum-dried at 30 ℃;
③ calcining in air at 300 deg.C for 3h to obtain hierarchical porous Al2O3A ball.
Example 2
The preparation method of the anti-poison graded porous nano aluminum oxide material specifically comprises the following steps:
(1) preparing an amphiphilic block polymer/inorganic hybrid alumina precursor;
① amphiphilic block polymer polyethylene glycol cetyl ether (13.66g, 20mmol) was added to the flask and heated to 40 ℃ for melting;
② aluminium isopropoxide (4.08g, 20mmol) was added rapidly to the flask at a stirring speed of 6000r/min, and the mixture was stirred continuously for 6 hours at a stirring speed of 3000r/min, maintaining the temperature at 40 ℃;
③ continuously fractionating the isopropanol in vacuum, continuing to supply heat until the distillation of isopropanol stops, and cooling the product for use;
(2) preparing graded porous nano alumina;
① at room temperature, adding the amphiphilic block polymer/inorganic hybrid alumina precursor (3g) prepared in the step (1) into 90mL of mixed solvent of ethanol and water (the volume ratio of ethanol to water is 3:1) at the stirring speed of 6000r/min, stirring for 90 minutes, and then adding the obtained Al2O3The colloidal suspension was centrifuged and washed with the same type of solvent for 3 cycles;
② mixing Al2O3The colloid (0.1g) is redispersed in 600ml ethanol and waterIn a mixed solvent and after further aging at 130 ℃ for 15h, the mixture was cooled, the precipitate was collected and washed 3 times with the same type of solvent and dried under vacuum at 30 ℃;
③ calcining in air at 400 deg.C for 2h to obtain hierarchical porous Al2O3A ball.
Example 3
The preparation method of the anti-poison graded porous nano aluminum oxide material specifically comprises the following steps:
(1) preparing an amphiphilic block polymer/inorganic hybrid alumina precursor;
① amphiphilic block polymer polyethylene glycol cetyl ether (13.66g, 20mmol) was added to the flask and heated to 40 ℃ for melting;
② aluminum isopropoxide (4.08g, 20mmol) is rapidly added into the flask at a stirring speed of 6000r/min, and the mixture is continuously stirred for 5-6 hours under the conditions of a stirring speed of 3000r/min and a temperature of 40 ℃;
③ continuously fractionating the isopropanol in vacuum, continuing to supply heat until the distillation of isopropanol stops, and cooling the product for use;
(2) preparing graded porous nano alumina;
① at room temperature, adding the amphiphilic block polymer/inorganic hybrid alumina precursor (3g) prepared in the step (1) into 210mL of mixed solvent of ethanol and water (the volume ratio of ethanol to water is 5:1) at the stirring speed of 6000r/min, stirring for 30 minutes, and then adding the obtained Al2O3The colloidal suspension was centrifuged and washed with the same type of solvent for 3 cycles;
② mixing Al2O3The colloid (0.1g) was redispersed in 400ml of a mixed solvent of ethanol and water and, after further aging at 160 ℃ for 10 hours, the mixture was cooled, and the precipitate was collected and washed 3 times with the same type of solvent and vacuum-dried at 30 ℃;
③ calcining in air at 450 deg.C for 1.5h to obtain hierarchical porous Al2O3A ball.
Test example:
1. the anti-poison graded porous nano aluminum oxide material prepared by the method is detected with a standard commercially available nano aluminum oxide material. The particle size of the material was observed by a bench scanning electron microscope manufactured by Hitachi corporation of japan; testing the surface area and the porosity of the material by using a full-automatic specific surface area and porosity analyzer produced by Micromeritics company in America; the pore volume of the material was measured using a pore size analyzer for porous materials manufactured by PMI, USA. 10ml of methyl nonafluorobutyl ether solvent, 15. mu.l of decane as internal standard, 15. mu.l of 2-CEES (mustard gas simulant) and the material to be tested were placed together in the flask. Vials were stored at room temperature for detoxification reactions. Samples were periodically withdrawn (0.1, 5, 10, 20, 30, 60, 120, 240, 1440min), solutions were extracted and tested by gas chromatography-mass spectrometry (GC-MS) to determine the residual concentration of 2-CEES. Using methyl nonafluorobutyl ether solvent and decane as internal standards, a certain amount of the material to be measured was placed in a flask, and 2-CEES (mustard gas simulant) was passed through at a rate of 5. mu.l/min, and samples (1, 5, 10, 20, 30, 60, 120, 240, 480, 960, 1920min) were periodically withdrawn from the solution and tested by gas chromatography-mass spectrometry (GC-MS) to determine the adsorption amount of 2-CEES. The test results are shown in table 1 below.
TABLE 1
As can be seen from the table, the nano-alumina of the embodiments 1 to 3 has larger specific surface area and more pores, has better adsorption capacity to the substitute of the chemical poison, and has wide application prospect in the field of poison prevention.
Claims (4)
1. The preparation method of the anti-poison graded porous nano aluminum oxide material is characterized by comprising the following steps of:
(1) preparing an amphiphilic block polymer/inorganic hybrid alumina precursor;
① adding amphiphilic block polymer polyethylene glycol hexadecyl ether into a flask, and heating to 40 ℃ for melting;
②, rapidly adding aluminum isopropoxide into the flask under high-speed stirring, and continuously reacting the mixture for 5-6 hours under the conditions of medium-speed stirring and 40 ℃;
③ continuously fractionating the isopropanol in vacuum, supplying heat until the distillation of isopropanol is stopped, and cooling the product;
(2) preparing graded porous nano alumina;
①, adding the amphiphilic block polymer/inorganic hybrid alumina precursor prepared in the step (1) into a mixed solvent of ethanol and water under high-speed stirring at room temperature, stirring for 30-90 min, and adding the obtained Al2O3The colloidal suspension was centrifuged and washed with the same type of solvent for 3 cycles;
② mixing Al2O3Dispersing the colloid into a mixed solvent of ethanol and water, further aging for 10-20 h at 100-160 ℃, cooling the mixture, collecting the precipitate, washing for 3 times by using the same type of solvent, and drying in vacuum at 30 ℃;
③ calcining in air at 300-450 ℃ for 1.5-3 h to obtain the hierarchical porous Al2O3A ball;
the molar ratio of the polyethylene glycol cetyl ether to the aluminum isopropoxide is 1: 1;
the high-speed stirring speed is 6000 r/min; the rotating speed of the medium-speed stirring is 3000 r/min.
2. The preparation method of the anti-poison graded porous nano aluminum oxide material according to claim 1, wherein the volume ratio of ethanol to water in the mixed solvent of ethanol and water is 5: 1-3: 1.
3. The preparation method of the anti-poison graded porous nano aluminum oxide material according to claim 1, wherein the mass ratio of the amphiphilic polymer/inorganic hybrid alumina precursor to the mixed solvent in the step (2) ① is 1: 30-1: 70.
4. The method for preparing the poison-proof graded porous nano alumina material according to claim 1, wherein the Al in the step (2) ②2O3The mass ratio of the colloid to the mixed solvent of ethanol and water is 1:4000 to 1: 6000.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101671052A (en) * | 2009-09-08 | 2010-03-17 | 西安瑞联近代电子材料有限责任公司 | Method for preparing anatase-shaped nano TiO2 |
| CN103274435A (en) * | 2013-05-22 | 2013-09-04 | 复旦大学 | Titanium aluminum oxide thin film and preparation method and application thereof |
| CN104923215A (en) * | 2015-05-07 | 2015-09-23 | 中国石油大学(北京) | Precious-metal-supported ordered mesoporous alumina material, and synthetic method and application thereof |
| CN108585798A (en) * | 2018-05-09 | 2018-09-28 | 安徽中航名坤新材料科技有限公司 | A kind of nano-porous alumina aeroge ceramic bead and preparation method thereof |
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| JP2010150090A (en) * | 2008-12-25 | 2010-07-08 | Sumitomo Chemical Co Ltd | alpha-ALUMINA POWDER |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101671052A (en) * | 2009-09-08 | 2010-03-17 | 西安瑞联近代电子材料有限责任公司 | Method for preparing anatase-shaped nano TiO2 |
| CN103274435A (en) * | 2013-05-22 | 2013-09-04 | 复旦大学 | Titanium aluminum oxide thin film and preparation method and application thereof |
| CN104923215A (en) * | 2015-05-07 | 2015-09-23 | 中国石油大学(北京) | Precious-metal-supported ordered mesoporous alumina material, and synthetic method and application thereof |
| CN108585798A (en) * | 2018-05-09 | 2018-09-28 | 安徽中航名坤新材料科技有限公司 | A kind of nano-porous alumina aeroge ceramic bead and preparation method thereof |
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