CN103111254A - Preparation method of hollow microspheres with hierarchical structure - Google Patents
Preparation method of hollow microspheres with hierarchical structure Download PDFInfo
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- CN103111254A CN103111254A CN2013100847827A CN201310084782A CN103111254A CN 103111254 A CN103111254 A CN 103111254A CN 2013100847827 A CN2013100847827 A CN 2013100847827A CN 201310084782 A CN201310084782 A CN 201310084782A CN 103111254 A CN103111254 A CN 103111254A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000004005 microsphere Substances 0.000 title abstract description 8
- 229910006636 γ-AlOOH Inorganic materials 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 229910002706 AlOOH Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229940037003 alum Drugs 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 229920005604 random copolymer Polymers 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims 1
- 238000009413 insulation Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 abstract description 2
- 239000012429 reaction media Substances 0.000 abstract description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 230000009466 transformation Effects 0.000 abstract description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 abstract 4
- 239000003607 modifier Substances 0.000 abstract 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 abstract 1
- 239000012716 precipitator Substances 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 229940043267 rhodamine b Drugs 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 239000003463 adsorbent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910001593 boehmite Inorganic materials 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 241000257465 Echinoidea Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 244000241257 Cucumis melo Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention provides a preparation method of gamma-AlOOH and gamma-Al2O3 hollow microspheres with hierarchical structure. The preparation method comprises the following steps of: based on water as a reaction medium, aluminium potassium sulfate (KAl(SO4)2.12H2O) as an aluminum source, urea as a precipitator, and polyvinyl pyrrolidone and C9-AA as surface modifiers, reacting under a hydrothermal condition, centrifugally washing and drying obtained products to obtain the gamma-AlOOH hollow microspheres with hierarchical structure and regular and controlled morphology; and placing the dried gamma-AlOOH hollow microspheres with hierarchical structure in a muffle furnace, raising temperature to 500-800 DEG C at a certain temperature raise speed, carrying out heat preservation for 1-4 hours, and decomposing gamma-AlOOH to obtain the gamma-Al2O3 hollow microspheres with hierarchical structure, wherein the structure and the morphology are kept in good condition in a transformation process from gamma-AlOOH to gamma-Al2O3. The preparation method of the gamma-AlOOH and gamma-Al2O3 hollow microspheres with hierarchical structure is simple; the size, structure and morphology of the products are easy to control; the product yield is high; and the products have very good adsorption property on organic dyestuffs such as congo red and Rhodamine B.
Description
Technical field
The invention belongs to the inorganic functional material field, relate to a kind of γ-AlOOH and γ-Al
2O
3The preparation method of hierarchy tiny balloon specifically, relates to a kind of γ-AlOOH and γ-Al
2O
3The preparation method of hierarchy tiny balloon adsorbent.
Background technology
Nanometer γ-AlOOH(boehmite) and γ-Al
2O
3(activated alumina) has strong absorption property, surface-active and catalytic activity and good heat endurance, is used as adsorbent and catalyst carrier in a lot of chemical reactions.The performance of nano material not only depends on the size of its particulate, the shape that also depends on its particle with and assembling morphology and micro-structural.Thereby, γ-AlOOH that microscopic appearance is controlled and γ-Al
2O
3The preparation of nano structural material has been subject to widely paying close attention in recent years, and the nano particle of various sizes and one dimension (band shape, wire, tubulose, bar-shaped etc.), two-dimentional (sheet, plate-like etc.) nano material are successfully prepared.For the new capability of nano-scale material, have γ-AlOOH and the γ-Al of various diverse microcosmic appearances
2O
3Labyrinth nanometer assembly is also successfully prepared, such as flower-shaped, "Hami" melon shape structure aluminium oxide etc.These have γ-AlOOH and the γ-Al of diverse microcosmic appearance
2O
3Labyrinth plays huge impetus for expanding and improving the alumina base applications of functional material.
In addition, γ-Al
2O
3Can obtain by calcining γ-AlOOH presoma, the morphosis of γ-AlOOH presoma is to forming the γ-Al of labyrinth
2O
3The nanometer assembly has conclusive impact.Therefore, research is controlled the morphosis of presoma nanometer γ-AlOOH to labyrinth γ-Al
2O
3Preparation seem particularly important.Cao Kui is take neopelex as template, flower-shaped γ-AlOOH(Cao Kui take aluminum nitrate as the raw water thermal synthesis. Xi'an Technological University's journal, 2009,29 (2): 156-158).Xu Bing etc. utilize aluminum trichloride (anhydrous) to be raw material in methanol-water solution, have prepared sea urchin shape γ-AlOOH(Xu Bing, Wang Jing, and Teng Yingli, in big waves, high grand. Liaoning Normal University's journal natural science edition, 2008,31 (4): 482-484).The hot methods of employing using microwave assisted aqueous extraction such as Liu Hui have been synthesized AlOOH and γ-Al
2O
3The sheet self-assembly microspheres (Liu Hui, He Xuanmeng, Li Guangjun, Cai Zijuan, Zhu Zhenfeng. functional material, 2011,42 (5): 854-857).Zhang etc. adopt the hot legal system of microwave-assistant sol agent for AlOOH and the γ-Al of hierarchy
2O
3Microballoon (L. Zhang, Y.J. Zhu, J. Phys. Chem. C, 2008,112 (43): 16764 – 16768).Kim etc. have synthesized AlOOH and the γ-Al of different-shape take ionic liquid [bdmim] [Cl] as template
2O
3Nanostructured (T. Kim, J. Lian, J. Ma, X.n Duan, W. Zheng, Cryst. Growth Des., 2010,10 (7): 2928 – 2933).Patent of invention CN200810037731.8 and CN200710047476.0 disclose respectively the preparation method of one kind of multiple pattern nm boehmite AlOOH, relate to nano rod bundle, spherical, sea urchin shape structure etc.Patent of invention CN201210227502.9 provides a kind of method and device that regulates and controls the boehmite pattern, regulates the pattern of AlOOH by the relative amount of regulating aluminum mixture salt.But further do not prepare aluminium oxide.
The report that some preparation hollow aluminum oxide microspheres are also arranged in document, but spherical shell constructed by the aluminium oxide nano particle and forms, and do not have the labyrinth of classification.Although in document, the preparation research of related complicated structure γ-AlOOH is paid close attention to more and more, for γ-AlOOH to complex topography γ-Al
2O
3Study on Transformation less.The invention provides a kind of hierarchy γ-AlOOH and γ-Al
2O
3The preparation method, at γ-AlOOH to γ-Al
2O
3In the process that changes mutually, the structure and morphology of microballoon remains intact.
Summary of the invention
The purpose of this invention is to provide a kind of γ-AlOOH and γ-Al
2O
3The preparation method of tiny balloon.Further purpose of the present invention is to provide a kind of γ-AlOOH and γ-Al as organic dye adsorbent namely
2O
3The preparation method of tiny balloon.Above-mentioned purpose of the present invention is to realize by following technology path and measure, at first prepares γ-AlOOH hierarchy microballoon, then obtains γ-Al by thermal decomposition with changing mutually
2O
3Hierarchy is hollow.
The preparation method of a kind of γ-AlOOH tiny balloon comprises the steps:
1. the alum crystal is dissolved in the solution that obtains 0.01～0.2 mol/L in deionized water; Then add successively urea, polyvinylpyrrolidone (PVP), C under the state of stirring at room
9-AA amphiphilic random copolymer makes its dissolving, stirs 10 min it is dissolved fully, mixes to guarantee reactant;
2. above-mentioned mixed liquor is transferred to and had in the teflon-lined stainless steel cauldron, 3～48 h are reacted in sealing under 120-200 ℃, obtain containing the mixed liquor of γ-AlOOH;
3. after the above-mentioned mixed liquor that contains γ-AlOOH is cooling, centrifugal 5-10 min, outwell supernatant liquid under 2000-4000 r/min rotating speed, with sediment water and the ethanol repeated washing that obtains, put into again 60-80 ℃ of drying box dry, obtain γ-AlOOH hierarchy tiny balloon.
A kind of γ-Al
2O
3The preparation method of tiny balloon except above-mentioned steps 1-3, also comprises:
4. the γ of drying-AlOOH hierarchy microballoon is put into Muffle furnace, be warming up to 600-800 ℃, then be incubated 1-4 h, obtain γ-Al
2O
3The hierarchy tiny balloon.
In above-mentioned steps 1, the concentration of urea is that the concentration of 0.1～2.0 mol/L, PVP is 1.0～4.0 g/L, C
9The concentration of-AA is 0.1～1.0 g/L.
The programming rate of above-mentioned steps 4 is that 1～5 ℃/min is warming up to 600-800 ℃.
C9-AA amphiphilic random copolymer is to be obtained with acrylic acid random copolymerization by C9 oil (a kind of accessory substance of cracking legal system ethene), C9 oil is that the C9 cut is to tell (C8～C11), the C9 cut auto polymerization and obtain the C9 Petropols under existing at acidic catalyst of residue cut after benzene,toluene,xylene from heavy by-product cracked oil; Carry out copolymerization with C9 cut and acrylic acid and obtain water-soluble C9-AA amphiphilic random copolymer, for having surface-active water soluble polymer.
The method technique is simple, and reaction condition is gentleer, and prepared hierarchy microballoon size, pattern, structure and assembling mode are controlled; At hierarchy γ-AlOOH to γ-Al
2O
3In the process that changes, structure and morphology remains intact.In the present invention, this reaction system has been avoided the use of organic solvent take water as reaction medium, take alum and urea as raw material, saves cost in actual production; γ-AlOOH or γ-Al
2O
3The hierarchy tiny balloon can be used as the high-efficiency adsorbent of organic dyestuff in the aqueous solution.γ-AlOOH and the γ-Al of the present invention's preparation
2O
3The hierarchy microballoon not only helps its novel absorption property of developmental research, catalytic performance, and is also significant to exploitation alumina base new function material.
Description of drawings
Fig. 1 utilizes the method for the invention to prepare the X ray diffracting spectrum of sample.
Fig. 2 is SEM (SEM) photo of the γ that utilizes the method for the invention preparation-AlOOH sample.
Fig. 3 is the γ-Al that utilizes the method for the invention preparation
2O
3The SEM of sample (SEM) photo.
The specific embodiment
Below by specific embodiment, the present invention is described in further detail, but content of the present invention has more than and is limited to described embodiment.
Embodiment one:
1. the alum crystal is dissolved in the solution that obtains 0.02 mol/L in deionized water, then adds successively urea, PVP, C under the state of stirring at room
9-AA makes its dissolving, and the concentration of urea is that the concentration of 0.2 mol/L, PVP is 2.0 g/L, C
9The concentration of-AA is 0.5 g/L, stirs 10 min it is dissolved fully, mixes to guarantee reactant;
2. above-mentioned mixed liquor is transferred to and had in the teflon-lined stainless steel cauldron, sealing, reaction 5 h under 150 ℃ obtain containing the mixed liquor of γ-AlOOH;
3. after the above-mentioned mixed liquor that contains γ-AlOOH is cooling, centrifugal 5 min, outwell supernatant liquid under 3000 r/min rotating speeds, with sediment water and the ethanol repeated washing that obtains, put into again 80 ℃ of drying boxes dry, obtain γ-AlOOH hierarchy tiny balloon;
4. the γ of drying-AlOOH hierarchy microballoon is put into Muffle furnace, rise to 800 ℃ with the programming rate of 1 ℃/min, then be incubated 1 h, obtain γ-Al
2O
3The hierarchy tiny balloon.
Embodiment two:
1. the alum crystal is dissolved in the solution that obtains 0.05 mol/L in deionized water, then adds successively urea, PVP, C under the state of stirring at room
9-AA makes its dissolving, and the concentration of urea is that the concentration of 0.4 mol/L, PVP is 2.0 g/L, C
9The concentration of-AA is 0.1 g/L, stirs 10 min it is dissolved fully, mixes to guarantee reactant;
2. above-mentioned mixed liquor is transferred to and had in the teflon-lined stainless steel cauldron, sealing, reaction 5 h under 180 ℃ obtain containing the mixed liquor of γ-AlOOH;
3. after the above-mentioned mixed liquor that contains γ-AlOOH is cooling, centrifugal 5 min, outwell supernatant liquid under 2000 r/min rotating speeds, with sediment water and the ethanol repeated washing that obtains, put into again 80 ℃ of drying boxes dry, obtain γ-AlOOH hierarchy tiny balloon;
4. the γ of drying-AlOOH hierarchy microballoon is put into Muffle furnace, rise to 600 ℃ with the programming rate of 2 ℃/min, then be incubated 2 h, obtain γ-Al
2O
3The hierarchy tiny balloon.
Embodiment three:
1. the alum crystal is dissolved in the solution that obtains 0.02 mol/L in deionized water, then adds successively urea, PVP, C under the state of stirring at room
9-AA makes its dissolving, and the concentration of urea is that the concentration of 0.1 mol/L, PVP is 1.0 g/L, C
9The concentration of-AA is 0.5 g/L, stirs 10 min it is dissolved fully, mixes to guarantee reactant;
2. above-mentioned mixed liquor is transferred to and had in the teflon-lined stainless steel cauldron, sealing is reacted 8h under 180 ℃, obtain containing the mixed liquor of γ-AlOOH;
3. after the above-mentioned mixed liquor that contains γ-AlOOH is cooling, centrifugal 5 min, outwell supernatant liquid under 3000 r/min rotating speeds, with sediment water and the ethanol repeated washing that obtains, put into again 80 ℃ of drying boxes dry, obtain γ-AlOOH hierarchy tiny balloon;
4. the γ of drying-AlOOH hierarchy microballoon is put into Muffle furnace, rise to 600 ℃ with the programming rate of 2 ℃/min, then be incubated 1 h, obtain γ-Al
2O
3The hierarchy tiny balloon.
Fig. 1 is γ-AlOOH and the γ-Al that utilizes the described method preparation of the embodiment of the present invention one
2O
3The X-ray diffraction of hierarchy tiny balloon (XRD) collection of illustrative plates.All diffraction maximums in Fig. 1 a are all through contrasting (JCPDS card No. 21-1307) with the standard spectrogram, in figure the position of diffraction maximum all with γ-AlOOH(boehmite) the position consistency of standard diffraction maximum, therefore can judge that the gained sample is pure boehmite-type γ-AlOOH.Fig. 1 b is the XRD collection of illustrative plates of the sample that obtains after heat treatment, and collection of illustrative plates shows that γ-AlOOH has been converted into γ-Al fully
2O
3
Fig. 2 is SEM (SEM) photo under the γ that utilizes the preparation of the described method of the embodiment of the present invention one-AlOOH sample different multiples.Can find out that from photo γ-AlOOH sample is that particle diameter is evenly distributed by the tiny balloon of the hierarchy of the nano crystal constructed one-tenth of γ-AlOOH of sheet, and by controlling reaction condition, can realize the regulation and control to γ-AlOOH product pattern and structure.
Fig. 3 is the γ-Al that utilizes the described method preparation of the embodiment of the present invention one
2O
3SEM under the sample different multiples (SEM) photo.As seen from the figure, the prepared γ-Al of embodiment one
2O
3The hierarchy tiny balloon is also constructed by nano flake and is formed, and at γ-AlOOH to γ-Al
2O
3In the process that changes, the structure and morphology of microballoon remains intact.But loose spherical shell becomes finer and close, and γ-AlOOH nanometer sheet also becomes more tiny γ-Al
2O
3Nanometer sheet.
γ-AlOOH and γ-Al
2O
3The hierarchy tiny balloon has good adsorption effect to organic dyestuff such as Congo red, rhodamine Bs, can be used for the adsorbent of organic dyestuff in the aqueous solution.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; do not deviate from other any change of doing under principle of the present invention and technical process, substitute, simplification etc.; be the displacement of equivalence, within all protection scope of the present invention should being included in.
Claims (5)
1. a γ-AlOOH and γ-Al
2O
3The preparation method of hierarchy tiny balloon is characterized in that, described method comprises the steps:
(1) the alum crystal is dissolved in obtains its solution in deionized water; Then add successively urea, polyvinylpyrrolidone (PVP), C under the state of stirring at room
9-AA amphiphilic random copolymer stirs 10 min it is dissolved fully, mixes to guarantee reactant;
(2) above-mentioned mixed liquor is transferred to had in the teflon-lined stainless steel cauldron, hydro-thermal reaction is carried out in sealing, obtains containing the mixed liquor of γ-AlOOH;
(3) after the above-mentioned mixed liquor that contains γ-AlOOH is cooling, supernatant liquid is outwelled in centrifugation, and with sediment water and the ethanol repeated washing that obtains, then it is dry to put into 60-80 ℃ of drying box, obtains γ-AlOOH hierarchy tiny balloon;
(4) γ of drying-AlOOH sample is put into Muffle furnace, roasting under certain condition obtains γ-Al
2O
3The hierarchy tiny balloon.
2. preparation method according to claim 1, is characterized in that, in the mixed liquor of step (1), the concentration of alum is 0.01～0.2 mol/L, and the concentration of urea is that the concentration of 0.1～2.0 mol/L, PVP is 1.0～4.0 g/L, C
9The concentration of-AA is 0.1～1.0 g/L.
3. preparation method according to claim 1, is characterized in that, in step (2), reaction temperature is 120-200 ℃, and the reaction time is 3～48 h.
4. preparation method according to claim 1, is characterized in that, in step (3), centrifugation is centrifugal 5-10 min under 2000-4000 r/min rotating speed.
5. preparation method according to claim 1, is characterized in that, in step (4), Muffle furnace rises to 600-800 ℃ with the programming rate of 1～5 ℃/min, insulation 1-4 h.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103432969A (en) * | 2013-09-09 | 2013-12-11 | 青岛科技大学 | Preparation method of alpha-Fe2O3/FeOOH core-shell structure composite microspheres |
| CN103433018A (en) * | 2013-09-09 | 2013-12-11 | 青岛科技大学 | Preparation method of CeO2/gamma-Al2O3 multi-level structure composite microspheres |
| CN103613109A (en) * | 2013-12-06 | 2014-03-05 | 重庆理工大学 | Boehmite adsorbing material in 3D structure, preparation method and use thereof |
| CN104709932A (en) * | 2015-02-13 | 2015-06-17 | 上海交通大学 | Gamma-aluminium oxide nanometer material and preparation method of nickel/gamma-aluminium oxide catalyst |
| CN104907036A (en) * | 2015-05-15 | 2015-09-16 | 燕山大学 | Graded dandelion-flower-shaped ZnO-Al2O3 compound and preparation method therefor |
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| CN103433018A (en) * | 2013-09-09 | 2013-12-11 | 青岛科技大学 | Preparation method of CeO2/gamma-Al2O3 multi-level structure composite microspheres |
| CN103432969A (en) * | 2013-09-09 | 2013-12-11 | 青岛科技大学 | Preparation method of alpha-Fe2O3/FeOOH core-shell structure composite microspheres |
| CN103613109A (en) * | 2013-12-06 | 2014-03-05 | 重庆理工大学 | Boehmite adsorbing material in 3D structure, preparation method and use thereof |
| CN104709932B (en) * | 2015-02-13 | 2016-08-17 | 上海交通大学 | Gama-alumina nano material and the preparation method of nickel/gamma-alumina catalyst |
| CN104709932A (en) * | 2015-02-13 | 2015-06-17 | 上海交通大学 | Gamma-aluminium oxide nanometer material and preparation method of nickel/gamma-aluminium oxide catalyst |
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| CN106865587A (en) * | 2015-12-13 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of preparation method of the aluminum oxide micro-sphere of micron-scale |
| CN106865587B (en) * | 2015-12-13 | 2018-10-09 | 中国科学院大连化学物理研究所 | A kind of preparation method of the aluminum oxide micro-sphere of micron-scale |
| CN106830024A (en) * | 2017-02-16 | 2017-06-13 | 曲阜师范大学 | A kind of red mud is the hydro-thermal thermal conversion process that raw material prepares active boehmite and aluminum oxide porous microballoon |
| CN107876002A (en) * | 2017-11-09 | 2018-04-06 | 济南大学 | A kind of preparation method of landscape water sorbing material and products obtained therefrom and application |
| CN107876002B (en) * | 2017-11-09 | 2020-07-07 | 济南大学 | Preparation method of adsorption material for landscape water, obtained product and application |
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