CN103432969B - A kind of α-Fe 2o 3the preparation method of/FeOOH nucleocapsid structure complex microsphere - Google Patents

A kind of α-Fe 2o 3the preparation method of/FeOOH nucleocapsid structure complex microsphere Download PDF

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CN103432969B
CN103432969B CN201310408168.1A CN201310408168A CN103432969B CN 103432969 B CN103432969 B CN 103432969B CN 201310408168 A CN201310408168 A CN 201310408168A CN 103432969 B CN103432969 B CN 103432969B
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feooh
mixed liquor
microballoon
nucleocapsid structure
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CN103432969A (en
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宋彩霞
牟红宇
朱义彪
战义曼
王德宝
曹长青
魏晓星
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Xuzhou better tool manufacturing Co., Ltd.
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Qingdao University of Science and Technology
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Abstract

The invention discloses a kind of α-Fe 2o 3the preparation method of/FeOOH nucleocapsid structure complex microsphere.First be reaction medium with water, FeCl 36H 2o and Fe (NO 3) 39H 2o is mixing source of iron, and polyvinylpyrrolidone is coating material, reacts under hydrothermal conditions, and products therefrom centrifuge washing is also dry, obtains the α-Fe of Monodispersed 2o 3egg type microballoon.Then by a certain amount of NH 4fe (SO 4) 212H 2o, urea and polyvinylpyrrolidone add in deionized water, fully dissolve, then the α-Fe that will obtain 2o 3microballoon is dispersed in wherein, obtains suspension.After being reacted at a certain temperature by this suspension, naturally cool to room temperature, product is also dry through centrifugation, washing, obtains α-Fe 2o 3/ FeOOH nucleocapsid structure complex microsphere, shell is constructed by tiny FeOOH nanometer rods and is formed.Preparation α-Fe of the present invention 2o 3/ FeOOH nucleocapsid structure complex microsphere has novel structure form, and the size of microballoon, pattern, structure and assembling mode are controlled.Important application is had in the catalyst, adsorbent etc. of combined oxidation ferrimagnet, sewage disposal.

Description

A kind of α-Fe 2o 3the preparation method of/FeOOH nucleocapsid structure complex microsphere
Technical field
The invention belongs to inorganic functional material preparing technical field, relate to a kind of preparation method of ferric oxide composite material, specifically, relate to a kind of α-Fe 2o 3the preparation method of/FeOOH nucleocapsid structure complex microsphere.
Background technology
Along with deepening continuously of nano materials research, it is found that and two or more nano particle is combined effectively, much new character can be caused to occur.Nucleocapsid structure inorganic particulate be a kind of by a kind of nano particle by chemical bond or other interact by coated for the another kind of nano particle ordered fabrication structure formed.Composite material of core-shell structure has the process based prediction model of the many novelties being different from core and shell because of the structure of its uniqueness, by adjustment core and the chemical composition of shell, size and pattern, can regulate and control the performance of inorganic particle, the range of application of expansion inorganic particle.Along with the development of science and technology, nucleocapsid structure checks particle as a kind of advanced composite material (ACM), becomes the development trend of a positive important in field of compound material.
Iron oxide is the important transition metal oxide of a class, wherein, and α-Fe 2o 3it is a kind of important conductor oxidate, there is physics and chemistry good stability, environmental friendliness, corrosion-resistant, low cost and other advantages, be with a wide range of applications in inorganic pigment, sensitive material, catalyst, heavy metal ion adsorbing material and soft magnetic ferrite and magnetic pipe recording material etc.Its band gap width is narrower, has very strong light absorpting ability in visible region, has important application prospect in photocatalyst material field.FeOOH (FeOOH) is extensively studied in waste water treatment field as very promising lightwave CATV catalyst and adsorbent for heavy metal.So the synthesis and characteries in recent years about different-shape and structure nano iron oxide studies Showed Very Brisk.
By α-Fe 2o 3check with FeOOH, in conjunction with the advantage of the two, after the two compound, the performance of iron oxide can be improved, thus make the combination property of iron oxide especially its photocatalysis performance will be optimized, there is more novel performance.Gao Zhihua etc. have prepared the ammonia water titration method utilizing homogeneous precipitation method, ammonia water titration method and add surfactant and have prepared FeOOH/ α-Fe 2o 3nano particle (Gao Zhihua, Li Chunhu, chemical industry metallurgical, 2000,21 (4): 341-345), grain diameter is less than 100nm.Song etc. adopt hydro-thermal method to prepare the α-Fe of mixed phase 2o 3/ FeOOH nanostructured (L.M.Song, S.J.Zhang, Colloids Surfaces A.2009,348 (1-3): 217-220).Hu etc. have prepared the γ-Fe of particle diameter 15nm 2o 3/ FeOOH nano particle (J.Hu, I.M.C.Lo, G.H.Chen, Separ.Purif.Techn.2007,58:76 – 82).Ferric oxide nano structure prepared above or be the mixed system that two-phase mixtures coexists, otherwise particle diameter is too little, has any problem in production application.
For these reasons, how to find that a kind of technique is relatively simple, reaction condition is gentleer, and different ferric oxide nano particles can be assembled, prepare that appearance structure is controlled, size at the iron oxide nucleocapsid structure microballoon of micron (sub-micron) level, be then subject matter to be solved by this invention.
Summary of the invention
One is the object of the present invention is to provide to prepare α-Fe 2o 3the method of/FeOOH nucleocapsid structure microballoon, material checked by the method gained iron oxide is at α-Fe 2o 3microsphere surface grows the nucleocapsid structure complex microsphere that one deck FeOOH nanometer rods obtains.For solving the problems of the technologies described above, the present invention is achieved by the following technical solutions:
A kind of α-Fe 2o 3the preparation method of/FeOOH nucleocapsid structure complex microsphere, described method comprises the steps:
1. by a certain amount of FeCl 36H 2o, Fe (NO 3) 39H 2o and polyvinylpyrrolidone add in deionized water, fully dissolve, and obtain homogeneous solution.FeCl 36H 2o, Fe (NO 3) 39H 2the mol ratio of O is 1:10 ~ 10:1, FeCl 36H 2the mass ratio of O and polyvinylpyrrolidone is 1:1-10:1, and polyvinylpyrrolidone can be different polymerization degree, comprises K15, K17, K25, K30, K60 or K90.
2. above-mentioned solution is transferred in reactor, react 6-24h at 120-200 DEG C after, naturally cool to room temperature, obtain containing α-Fe 2o 3the mixed liquor of precipitation;
3. contain α-Fe by above-mentioned 2o 3mixed liquor centrifugation washing under 3000-4000r/min rotating speed, outwell supernatant liquid, and use deionized water repeated washing, obtain the α-Fe of Monodispersed 2o 3egg type microballoon;
4. by a certain amount of NH 4fe (SO 4) 212H 2o, urea and polyvinylpyrrolidone add in deionized water, fully dissolve, then the α-Fe that will obtain 2o 3microballoon is distributed to wherein, obtains suspension.In mixed liquor, NH 4fe (SO 4) 212H 2the mol ratio of O and urea is 1:1 ~ 1:4, NH 4fe (SO 4) 212H 2the mass ratio of O and polyvinylpyrrolidone is 1:2-1:10, and polyvinylpyrrolidone can be different polymerization degree, comprises K15, K17, K25, K30, K60 or K90.
5. after this suspension being reacted 6-24h at 85-95 DEG C, naturally cool to room temperature, obtain containing α-Fe 2o 3the mixed liquor of/FeOOH;
6. will containing α-Fe 2o 3the centrifugation washing under 3000-4000r/min rotating speed of the mixed liquor of/FeOOH, then the drying box putting into 60 ~ 90 DEG C is dry, obtains α-Fe 2o 3/ FeOOH microballoon.
Advantage of the present invention is: the method technique is simple, and raw material is easy to get, and reaction condition is gentleer, prepared α-Fe 2o 3/ FeOOH nucleocapsid structure microballoon has good pattern, dimensional controllability and batch production feasibility.Important application is had in the catalyst, adsorbent etc. of combined oxidation ferrimagnet, sewage disposal.
Accompanying drawing explanation
Fig. 1 is the α-Fe utilizing the method for the invention to prepare 2o 3and α-Fe 2o 3sEM (SEM) photo of/FeOOH nucleocapsid structure microballoon;
Wherein: Fig. 1 a is the α-Fe utilizing the method for the invention to prepare 2o 3the SEM photo of microballoon;
Fig. 1 b is the α-Fe utilizing the method for the invention embodiment one to prepare 2o 3the SEM photo of/FeOOH microballoon;
Fig. 1 c is the photo of the multiplication factor of Fig. 1 b.
Fig. 2 is the α-Fe utilizing the method for the invention to prepare 2o 3x-ray diffraction (XRD) collection of illustrative plates of/FeOOH complex microsphere.
Detailed description of the invention
Below in conjunction with accompanying drawing, the present invention is further detailed explanation.
Embodiment one:
(1) in beaker, add the FeCl of 0.1mol/L 36H 2o, 0.02mol/L Fe (NO 3) 39H 2the polyvinylpyrrolidone (K30) of O and 17g/L, fully dissolves, obtains mixed solution;
(2) mixed solution is transferred in reactor, at 150 DEG C of reaction 16h, obtain containing α-Fe 2o 3mixed liquor;
(3) α-Fe is contained by above-mentioned 2o 3mixed liquor cooling after, centrifugal under 3000r/min rotating speed, outwell supernatant liquid, and use water and ethanol repeated washing three times respectively, obtain Monodispersed α-Fe 2o 3egg type microsphere suspension liquid.
(4) in beaker, add the NH of 4mmol/L 4fe (SO 4) 212H 2o, 8mmol/L urea and 10g/L polyvinylpyrrolidone (K30) add in deionized water, fully dissolve, obtain mixed liquor;
(5) the Monodispersed α-Fe will obtained in step (3) 2o 3egg type microsphere suspension liquid joins in the mixed liquor of step (4), at 90 DEG C, react 12h, obtains containing α-Fe 2o 3the mixed liquor of/FeOOH;
(6) α-Fe is contained by above-mentioned 2o 3after the mixed liquor cooling of/FeOOH, centrifugal under 4000r/min rotating speed, outwell supernatant liquid, and with deionized water ethanol repeated washing, then put into drying box drying at 60 ~ 90 DEG C of temperature, obtain α-Fe 2o 3/ FeOOH microballoon;
Embodiment two:
(1) in beaker, add the FeCl of 0.1mol/L 36H 2o, 0.02mol/L Fe (NO 3) 39H 2the polyvinylpyrrolidone (K30) of O and 10g/L, fully dissolves, obtains mixed solution;
(2) mixed solution is transferred in reactor, at 150 DEG C of reaction 24h, obtain containing α-Fe 2o 3mixed liquor;
(3) α-Fe is contained by above-mentioned 2o 3mixed liquor cooling after, centrifugal under 3000r/min rotating speed, outwell supernatant liquid, and use water and ethanol repeated washing three times respectively, obtain Monodispersed α-Fe 2o 3egg type microsphere suspension liquid.
(4) in beaker, add the NH of 2mmol/L 4fe (SO 4) 212H 2o, 8mmol/L urea and 10g/L polyvinylpyrrolidone (K30) add in deionized water, fully dissolve, obtain mixed liquor;
(5) the Monodispersed α-Fe will obtained in step (3) 2o 3egg type microsphere suspension liquid joins in the mixed liquor of step (4), at 90 DEG C, react 12h, obtains containing α-Fe 2o 3the mixed liquor of/FeOOH;
(6) α-Fe is contained by above-mentioned 2o 3after the mixed liquor cooling of/FeOOH, centrifugal under 4000r/min rotating speed, outwell supernatant liquid, and with deionized water ethanol repeated washing, then put into drying box drying at 80 DEG C of temperature, obtain α-Fe 2o 3/ FeOOH microballoon;
Embodiment three:
(1) in beaker, add the FeCl of 0.15mol/L 36H 2o, 0.03mol/L Fe (NO 3) 39H 2the polyvinylpyrrolidone (K30) of O and 10g/L, fully dissolves, obtains mixed solution;
(2) mixed solution is transferred in reactor, at 150 DEG C of reaction 16h, obtain containing α-Fe 2o 3mixed liquor;
(3) α-Fe is contained by above-mentioned 2o 3mixed liquor cooling after, centrifugal under 3000r/min rotating speed, outwell supernatant liquid, and use water and ethanol repeated washing three times respectively, obtain Monodispersed α-Fe 2o 3egg type microsphere suspension liquid.
(4) in beaker, add the NH of 4mmol/L 4fe (SO 4) 212H 2o, 12mmol/L urea and 10g/L polyvinylpyrrolidone (K30) add in deionized water, fully dissolve, obtain mixed liquor;
(5) the Monodispersed α-Fe will obtained in step (3) 2o 3egg type microsphere suspension liquid joins in the mixed liquor of step (4), at 90 DEG C, react 5h, obtains containing α-Fe 2o 3the mixed liquor of/FeOOH;
(6) α-Fe is contained by above-mentioned 2o 3after the mixed liquor cooling of/FeOOH, centrifugal under 3000r/min rotating speed, outwell supernatant liquid, and with deionized water ethanol repeated washing, then put into drying box drying at 80 DEG C of temperature, obtain α-Fe 2o 3/ FeOOH microballoon.
Fig. 1 a is the α-Fe utilizing the method for the invention to prepare 2o 3the SEM photo of microballoon.As can be seen from Fig., gained egg type microspherulite diameter is evenly distributed, good dispersion.Fig. 1 b-c is the α-Fe utilizing the method for the invention embodiment one to prepare 2o 3the SEM photo of/FeOOH microballoon.As can be seen from Fig. 1 b, initial alpha-Fe 2o 3the FeOOH shell of egg type microsphere surface is coated one deck burr shape, as can be seen from photo Fig. 1 c of multiplication factor, the shell of burr shape is at α-Fe by tiny FeOOH nanometer rods 2o 3microsphere surface vertical growth is constructed.
Fig. 2 is the α-Fe utilizing the method for the invention embodiment one to prepare 2o 3the XRD collection of illustrative plates of/FeOOH microballoon.According to standard card determination thing phase, the diffraction maximum indicating " * " in figure corresponds to α-Fe 2o 3diffraction (JCPDS no.33-664), the diffraction maximum indicating " # " corresponds to the diffraction (JCPDS no.29-713) of orthorhombic system FeOOH, and the diffraction maximum of FeOOH is more weak, illustrates that FeOOH shell is thinner and FeOOH nanometer rods size is tiny.Result shows, α-Fe 2o 3the Surface coating of microballoon one deck FeOOH shell generates α-Fe 2o 3/ FeOOH composite construction.By controlling reaction condition, the regulation and control to FeOOH shell pattern and structure can be realized.
Above-described embodiment is better embodiment of the present invention; but embodiments of the present invention are not by the restriction of above-mentioned three embodiments; do not deviate from do under principle of the present invention and technical process other any change, substitute, simplification etc.; be the displacement of equivalence, all should be included within protection scope of the present invention.

Claims (1)

1. a α-Fe 2o 3the preparation method of/FeOOH nucleocapsid structure complex microsphere, is characterized in that, described method comprises the steps:
(1) in beaker, add the FeCl of 0.1 mol/L 36 H 2o, 0.02 mol/L Fe (NO 3) 39 H 2the polyvinylpyrrolidone of O and 17 g/L, fully dissolves, and obtains mixed solution;
(2) mixed solution is transferred in reactor, at 150 DEG C of reaction 16 h, obtain containing α-Fe 2o 3mixed liquor;
(3) α-Fe is contained by above-mentioned 2o 3mixed liquor cooling after, centrifugal under 3000 r/min rotating speeds, outwell supernatant liquid, and use water and ethanol repeated washing three times respectively, obtain Monodispersed α-Fe 2o 3egg type microsphere suspension liquid;
(4) in beaker by the NH of 4 mmol/L 4fe (SO 4) 212H 2o, 8 mmol/L urea and 10 g/L polyvinylpyrrolidones add in deionized water, fully dissolve, obtain mixed liquor;
(5) the Monodispersed α-Fe will obtained in step (3) 2o 3egg type microsphere suspension liquid joins in the mixed liquor of step (4), reacts 12 h at 90 DEG C, obtains containing α-Fe 2o 3the mixed liquor of/FeOOH;
(6) α-Fe is contained by above-mentioned 2o 3after the mixed liquor cooling of/FeOOH, centrifugal under 4000 r/min rotating speeds, outwell supernatant liquid, and with deionized water ethanol repeated washing, then put into drying box drying at 60 ~ 90 DEG C of temperature, obtain α-Fe 2o 3/ FeOOH microballoon.
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CN104190423B (en) * 2014-09-25 2016-05-11 四川理工学院 A kind of spherical shape α-Fe2O3Preparation method
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06304470A (en) * 1993-04-23 1994-11-01 Japan Synthetic Rubber Co Ltd Preparation of composite particle
CN101767835A (en) * 2010-03-23 2010-07-07 青岛科技大学 Method for preparing alpha-Fe2O3 mesomorphic microballoon with high coercivity
CN103111254A (en) * 2013-03-16 2013-05-22 青岛科技大学 Preparation method of hollow microspheres with hierarchical structure
CN103232049A (en) * 2013-03-17 2013-08-07 青岛科技大学 Preparation method of alpha-Al2O3 cage-structure hollow microspheres

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06304470A (en) * 1993-04-23 1994-11-01 Japan Synthetic Rubber Co Ltd Preparation of composite particle
CN101767835A (en) * 2010-03-23 2010-07-07 青岛科技大学 Method for preparing alpha-Fe2O3 mesomorphic microballoon with high coercivity
CN103111254A (en) * 2013-03-16 2013-05-22 青岛科技大学 Preparation method of hollow microspheres with hierarchical structure
CN103232049A (en) * 2013-03-17 2013-08-07 青岛科技大学 Preparation method of alpha-Al2O3 cage-structure hollow microspheres

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
谢小莉等.α-Fe2O3纳米立方体和纳米棒组装空心微球的可控合成及其磁学性能.《中国科学B辑:化学》.2008,第38卷(第7期),第595-606页. *

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