CN101106002A - Superparamagnetism material carrying CuO and preparation method thereof - Google Patents
Superparamagnetism material carrying CuO and preparation method thereof Download PDFInfo
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- CN101106002A CN101106002A CNA2007100286047A CN200710028604A CN101106002A CN 101106002 A CN101106002 A CN 101106002A CN A2007100286047 A CNA2007100286047 A CN A2007100286047A CN 200710028604 A CN200710028604 A CN 200710028604A CN 101106002 A CN101106002 A CN 101106002A
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Abstract
The invention relates to an ultra-paramagnetic material of load CuO, which is composed of ultra-paramagnetic particles, a mesoporous material layer, and CuO loaded on the internal and the external surfaces of mesoporous material layer; the preparation method includes: produce ultra-paramagnetic particle or its infusible precursor with the common sedimentation method; cover a layer of compact SiO2 or molecular sieve on the surface of the ultra-paramagnetic particle or the infusible precursor chemically with the sol-gel method; increase the temperature and maintain the temperature in gas atmosphere; samples obtained are placed into infusible cupric salt solution for separation, washing, filtering, and drying; burn in gas atmosphere; obtain the material with performances such as ultra-paramagnetism, catalyzing, and decoking. On one hand, the invention solves the problem of stability and conglobation of ultra-paramagnetic particle in the using process, and on the other hand, the invention makes it easier to separate catalyzer and desulfurizer in the using process. Meanwhile, the ultra-paramagnetic material of load CuO is also an infrared radiation material or microwave absorption material with high performance.
Description
Technical field
The present invention relates to new material and synthetic technology thereof, specifically comprise superparamagnetic material of Supported CuO and preparation method thereof
Background technology
Superparamagnetic material is meant that the magnetic particle size reaches or during less than certain critical dimension, demonstrates magnetic but its magnetic disappears after removing magnetic field a class nano material in externally-applied magnetic field.At present, superparamagnetic nanomaterial is applied in industries such as chemical industry, machinery, electronics, printing, medical science, as fields such as high density magnetic recording material, gas-sensitive sensor device, magnetic immuno cell separation, Magnetic resonance imaging and medicine control releases.Because nanoparticle is reunited easily, thereby has lost some special nature of having only nanostructure just to have.Adopt to add surfactant such as oleic acid and can prevent to reunite, but its application that the surfactant that exists in system has limited.In addition, directly be exposed to very easy oxidized or degraded in the environment.
The cupric oxide (CuO) that loads on carrier surface is the catalyst of the multiple redox reaction of excellence, still well behaved desulfurizing agent.Carry CuO as cordierite honeycomb ceramic and can select Reduction of NO, CuO/ nano-carrier catalysis of phenol hydroxylating, flake nano CuO are used for cumene oxidation reaction or the like; Honeycomb-like cordierite base CuO/Al and for example
2O
3Catalyst is used for flue gas and desulfurizing and denitrifying etc.Yet these catalyst or desulfurizing agent in use all face in the use and separate a difficult problem with newly-generated species.
Summary of the invention
The objective of the invention is at deficiency of the prior art, the superparamagnetic material and preparation method thereof of the Supported CuO of a class favorable dispersibility is provided, this material has possessed performances such as superparamagnetism, catalysis, desulfurization simultaneously.On the one hand, particles with superparamagnetism in use stability and agglomeration traits have been solved, on the other hand, well solved a separation difficult problem (only needing to use externally-applied magnetic field just to be easy to this functional material is separated) that faces in catalyst/desulfurizing agent use from reactor.Simultaneously, the superparamagnetic material of this Supported CuO still is well behaved infrared radiant material and microwave absorbing material.
The superparamagnetic material of Supported CuO of the present invention is made of particles with superparamagnetism, mesoporous material layer and the CuO that loads on mesoporous material layer surfaces externally and internally, and particles with superparamagnetism is coated by mesoporous layer, and CuO is positioned at mesoporous material layer duct surfaces externally and internally; Described particles with superparamagnetism is made up of in metal oxide with superparamagnetism and the magnetic metal one or more; Metal oxide is ferrite or class ferrite, and the ferrite chemical composition is RFe2O4, and the class ferrite consists of R
IIM
III 2O
4, R is one or more among Fe, Zn, Co, Ni, Ba, Cu, the Mn, M is one or more among Co, Ni, Cr, Sm, Dy, Nd, Pr, the Gd;
Described magnetic metal comprises the alloy of Fe, Co or Ni or itself and Cr, Sm, Dy, Nd, Pr, Gd;
Described mesoporous material layer is a molecular sieve, or by the unformed SiO of internal layer
2Constitute with outer molecular sieve; When described mesoporous material layer was molecular sieve, molecular sieve directly coated particles with superparamagnetism; Described mesoporous material layer is by the unformed SiO of internal layer
2When constituting with outer molecular sieve, particles with superparamagnetism is earlier by unformed SiO
2Coat, then SiO
2The superparamagnetic material that coats is coated by molecular sieve again, forms the complex nucleus shell structure.
Described molecular sieve is silica-based molecular sieve.Silica-based molecular sieve comprises MCM series molecular sieve, SBA-n series molecular sieve or MSU-X series molecular sieve.
Wherein MCM series molecular sieve can be MCM-41, MCM-49, MCM-22, MCM-50, MCM-56 or MCM-48; SBA-n series molecular sieve can be SBA-1, SBA-2, SBA-3, SBA-6, SBA-11, SBA-12, SBA-15 or SBA-16.
Described CuO be particle diameter less than 15nm, the particles with superparamagnetism particle diameter is 5-25nm;
The preparation method of the superparamagnetic material of Supported CuO of the present invention may further comprise the steps:
(1) coprecipitation makes particles with superparamagnetism or its insoluble predecessor, washing;
(2) sol-gel process on particles with superparamagnetism surface or its insoluble predecessor surface chemical reaction cover the SiO of one deck densification
2Or/and molecular sieve separates, drying is filtered in washing;
(3) program is warming up to 823K in the atmosphere, and 823K-1123K insulation 1-8 hour, promptly obtains powder sample;
(4) step (3) gained sample is immersed in the soluble copper salting liquid, separate, drying is filtered in washing; 573K-873K calcination 1-5 hour, cool off in the atmosphere, promptly get the superparamagnetic material of Supported CuO.
Perhaps comprise following two steps:
(1) coprecipitation makes particles with superparamagnetism or its insoluble predecessor, washing;
(2) containing Cu by sol-gel process
2+Solution in, realize that particles with superparamagnetism surface or its insoluble predecessor surface chemical reaction cover one deck molecular sieve, simultaneously toward molecular sieve surfaces externally and internally loaded copper oxide predecessor, separate, drying is filtered in washing; Program is warming up to 823K in the atmosphere, and 823K-1123K insulation 1-8 hour
Its insoluble predecessor in the step (1) is meant the precipitation or the colloidal sol that can generate particles with superparamagnetism under the heating and decomposition condition, comprises and contains Fe
III, R
IIOxide, oxalates, carbonate, hydroxide, R is one or more among Fe, Zn, Co, Ni, Ba, the Cu; Or contain M
III, R
IIOxide, oxalates, carbonate, hydroxide, M is one or more among Cr, Sm, Dy, Nd, Pr, the Gd, R is one or more among Fe, Zn, Co, Ni, Ba, Cu, the Mn.
In the step (2), described sol-gel process is meant the synthetic method of utilizing esters of silicon acis hydrolysis in aqueous solution to generate Si oxide, the esters of silicon acis hydrolysis does not generate SiO2 layer and molecular sieve layer respectively when not adding with the interpolation template in the solution that contains particles with superparamagnetism or its predecessor precipitation, in the 273K-363K scope, under temperature 373K-473K, carry out under the hydrothermal condition during the non-hydro-thermal of reaction temperature; Described template is cation or non-ionic surface active agent.
In step (3) and (4), described atmosphere is inert atmosphere or the reducing atmosphere of using always, and inert atmosphere comprises N
2, He, Ar, CO
2Deng, reducing atmosphere comprises active carbon, CO, N
2+ H
2Deng.
In the step (3), described temperature programming is that the speed with 0.5-5K/min rises to 823K by room temperature;
The present invention compared with prior art has following advantage:
(1) provides a kind of superparamagnetic material of novel hud typed monodispersed Supported CuO;
(2) the superparamagnetic material chemical stability of this novel hud typed monodispersed Supported CuO is good, owing to be molecular sieve area load nanometer CuO at high-specific surface area, therefore be excellent catalyst, still good desulfurizing agent, infrared radiant material and microwave absorbing material;
(3) the selected raw material of the present invention extensively is easy to get, and is simple to operate.
Concrete execution mode
Embodiment 1 Fe
3O
4/ MCM-41/CuO's is synthetic
(1) has super-paramagnetism nano Fe
3O
4Synthetic
Under the nitrogen protection with 1.1263g (NH
4)
2C
2O
4, 9.0016gFeSO
47H
2O and 12.9054gFe
2(SO
4)
3Be dissolved in the 150mL80 ℃ of water, add concentrated ammonia liquor to pH=9, reaction 1.5h, washing, Magnetic Isolation promptly gets Fe
3O
4Precipitation.
(2) Fe
3O
4/ MCM-41's is synthetic
Under the room temperature, with above-mentioned Fe
3O
4Be deposited in N
2Protection dispersed with stirring down adds 3.6mL NH in the 23mL deionized water
3H
2O (25%, mass percent).With 0.2220g TBAB (tetrabutyl ammonium bromide, TBAB) is dissolved in the 10mL deionized water, 1.0026g CTAB (cetyl trimethyl ammonium bromide, softex kw) is dissolved in the 10mL deionized water.TBAB, CTAB solution joined successively contain above-mentioned Fe
3O
4In the dispersion of precipitation, stir and drip 4.05mLTEOS (tetraethoxysilane) down.Continue reaction 3h after dripping off.Reactant molar ratio is CTAB: TEOS: NH
3: H
2O: TBAB=0.152: 1: 2.8: 141.2: 0.038.Magnetic Isolation, with behind the deionized water wash at the dry 12h of 363K, obtain the powder sample of brown.Powder sample is placed the tube furnace that is connected with nitrogen, and (0.5K/min) in constant temperature 823K calcining 8h, obtains MCM-41 and coats Fe then from the room temperature temperature programming to 823K
3O
4Superparamagnetism Fe
3O
4/ MCM-41 nano composite material.
(3) Fe of Supported CuO
3O
4/ MCM-41.
With gained Fe
3O
4/ MCM-41 sample immerses in the 0.2 mol Schweinfurt green solution, separates, and the 363K drying is filtered in washing.N
2In 673K calcination 5 hours, cooling, promptly get the superparamagnetic material Fe of Supported CuO in the atmosphere
3O
4/ MCM-41.This composite nano materials specific saturation magnetization is 45emu/g, and 80 ℃ are used for the hydrogen peroxide catalytic oxidation methyl orange solution and have effect preferably, and the methyl orange clearance reaches more than 90%.The effect (about 60%) that is better than the catalyst of the simple Supported CuO of MCM-41, and this product is easy to separate from Treatment Solution by magnetic field.
Embodiment 2 Fe/MCM-48/CuO's is synthetic
(1) super-paramagnetism nano Fe
3O
4Synthetic
Under the nitrogen protection with 1.1260g (NH
4)
2C
2O
4, 9.0057gFeSO
47H
2O and 12.9042gFe
2(SO
4)
3Be dissolved in the 150mL80 ℃ of water, ammoniacal liquor is adjusted pH=8.6 and is continued reaction 1.5h, washing, and Magnetic Isolation promptly gets Fe
3O
4Precipitation.
(2) Fe/MCM-48/CuO's is synthetic
Temperature 273K is to Fe under the nitrogen atmosphere
3O
4The middle 50mL ionized water that adds stirs, and adds 14mL NH
3H
2O (32%, mass fraction) adds 5mg copper nitrate solid, adds 2.4g CTAB and 50mL absolute ethyl alcohol (EtOH).Drip 3.66mL TEOS (tetraethoxysilane) down in quick stirring after stirring 0.5h.Under room temperature, react 3h after dripping off.Reactant molar ratio is CTAB: TEOS: NH
3: H
2O: EtOH=0.4: 1: 12.5: 174: 54.Put into hydrothermal reaction kettle, 480K constant temperature 68 hours, filter, precipitate with deionized water washing back is at the dry 12h of 363K, the powder sample that obtains places the tube furnace that is connected with hydrogen, (1K/min) calcining at constant temperature 6h then from the room temperature temperature programming to 823K, cooling promptly obtains the single Fe/MCM-48/CuO of dispersion composite Nano magnetic material.This composite nano materials specific saturation magnetization is 48emu/g, is used for the hydrogen peroxide catalytic oxidation methyl orange solution under the room temperature and has effect preferably, and the methyl orange clearance reaches more than 95%.The effect (about 60%) that is better than the catalyst of the simple Supported CuO of MCM-41, and this product is easy to separate from Treatment Solution by magnetic field.
Embodiment 3 Fe
3O
4/ SBA-15/CuO's is synthetic
(1) super-paramagnetism nano Fe
3O
4Synthetic
Under the nitrogen protection with 1.5050g (NH
4)
2C
2O
4, 12.0085gFeSO
47H
2O and 17.1995gFe
2(SO
4)
3Be dissolved in the 200g70-80 ℃ of water, add ammoniacal liquor, stirring reaction 1.5h, washing promptly gets Fe
3O
4Precipitation, magnetic field condition are separated down, after the washing, be distributed to it in 10mL deionized water and the 60mL isopropyl alcohol mixed liquor and regulate pH=9.8 with ammoniacal liquor, after dropwise drip TEOS (tetraethoxysilane) to pH=9.1, react 3h.Take out, magnet separates, and washing obtains SiO
2The Fe that coats
3O
4
(2) Fe
3O
4/ SBA-15's is synthetic
6.0g (poly-oxireme ether-propylene oxide ether-oxireme ether triblock polymer surfactant, mean molecule quantity is 5800 to P123, molecular formula EO
20PEO
70EO
20) be dissolved among 135mL distilled water and 616mL (4mol/L) HCl solution P; P is transferred to SiO
2The Fe that coats
3O
4In, after the logical nitrogen of 313K stirs 5min, add 45gDMF (DMF is N, dinethylformamide), add 14.35mLTEOS (tetraethoxysilane) after stirring 1h, after 1 day, put into the polytetrafluoroethyllining lining hydrothermal reaction kettle in stirring reaction under the 313K, 468K constant temperature 78 hours, filter, after (room temperature) drying the bronzing solid placed the tube furnace under the nitrogen atmosphere in air, (2K/min) constant temperature 9h then obtains Fe from the room temperature temperature programming to 823K
3O
4/ SBA-15 nucleocapsid list disperses the composite Nano magnetic material.
(3) Fe of Supported CuO
3O
4/ SBA-15.
With gained Fe
3O
4/ SBA-15 sample immerses in the 0.1 mol copper nitrate solution, separates, and the 363K drying is filtered in washing.N
2573K calcination 5 hours, cool off in the atmosphere, promptly get the superparamagnetic material Fe of Supported CuO
3O
4/ SBA-15.This composite nano materials specific saturation magnetization is 35emu/g, and 50 ℃ are used for the hydrogen peroxide catalytic oxidation phenol solution and have effect preferably, and the phenol clearance reaches more than 95%.The effect (about 50%) that is better than the catalyst of the simple Supported CuO of common molecular sieve, and this product is easy to separate from Treatment Solution by magnetic field.
Embodiment 4 ZnFe
2O
4/ MSU-1/CuO's is synthetic
(1) has super-paramagnetism nano ZnFe
2O
4Synthetic
With 1.1260g (NH
4)
2C
2O
4, 5.2161gZnSO
4And 12.9054gFe
2(SO
4)
3Be dissolved in the 150g water, keep 70-80 ℃ of water-bath; Regulate pH=9 with ammoniacal liquor, continue reaction 1.5h, washing promptly gets ZnFe
2O
4Precipitation.In precipitation, add deionized water, drip 10% Na
2SiO
3Solution 15ml, control pH=9.5 also reacts 1h.Take out, Magnetic Isolation, washing obtains amorphous Si O
2The ZnFe that coats
2O
4
(2) ZnFe
2O
4/ MSU-1's is synthetic
Be coated with SiO
2ZnFe
2O
4Precipitation is distributed to (A) in the 40mL deionized water.2.3801g AEO-9 (AEO non-ionic surface active agent) is mixed with 30mL deionized water, 26gHCl (1mol/l), after the 333K dissolving, be cooled to 271K and get solution (B), B is added among the A, stir 1h; With 9.4008g waterglass (10% Na
2SiO
3Solution) mix with the 90mL deionized water, also be cooled to 271K.Under brute force stirs, the water glass solution after the dilution is slowly joined in the aqueous surfactant solution of acidifying, obtain translucent mixed liquor (～200ml), this moment, the pH value was 2～3, each material mol ratio is SiO in the mixed liquor
2: AEO-9: H
2O=1: 0.1: 280, be rapidly heated to 295K.Stir 20h, precipitate after filtration, wash, after the 333K oven dry, place Muffle furnace temperature programming (3K/min) to 823K, to continue roasting 8h, obtain hud typed ZnFe
2O
4The monodispersed super-paramagnetism nano composite material of/MSU-1.
(3) ZnFe of Supported CuO
2O
4/ MSU-1.
With gained ZnFe
2O
4/ MSU1 sample immerses in the 0.2 mol copper chloride solution, separates, and the 363K drying is filtered in washing.773K calcination 5 hours, cool off in the Ar atmosphere, promptly get the superparamagnetic material ZnFe of Supported CuO
2O
4/ MSU-1.This composite nano materials specific saturation magnetization is 18emu/g, and the PMMA (polymethyl methacrylate) that adds this powder 0.05% has higher microwave absorbing effect at 2～18GHz, and the Insertion Loss peak value reaches 15dB.
Embodiment 5 CoFe
2O
4/ SBA-3/CuO's is synthetic
(1) has super-paramagnetism nano CoFe
2O
4Synthetic
With 1.1289g (NH
4)
2C
2O
4, 9.2163gCoSO
47H
2O and 12.9157gFe
2(SO
4)
3Be dissolved under the nitrogen atmosphere in the 150mL75 ℃ of water, add NaOH solution and regulate pH=9.6, continue reaction 1.5h, washing, Magnetic Isolation promptly gets CoFeO
4Precipitation.
(2) CoFe
2O
4/ SBA-3's is synthetic
In nitrogen atmosphere to the CoFe that obtains
2O
4The middle 60mL water that adds 298K stirs, and adds the dense NH of 10.23mL
3H
2O is dissolved in 0.6125g TBAB (tetrabutyl ammonium bromide) in the 10mL deionized water, and 2.7698g CTAB (cetyltrimethyl ammonium bromide) is dissolved in the 50mL deionized water, and adds the 10mL heptane.Under quick stirring, dropwise drip 11.27mL TEOS (tetraethoxysilane) after mixing stirring 0.5h, drip off afterwards in reaction 3h.Reactant molar ratio is CTAB: TEOS: NH
3: H
2O: TBAB=0.152: 1: 2.8: 141.2: 0.038.Put into the polytetrafluoroethyllining lining hydrothermal reaction kettle,, filter 480K constant temperature 88 hours, with behind the deionized water wash at the dry 12h of 363K, place tube furnace then, under He atmosphere from the room temperature temperature programming to 823K (5K/min) calcining at constant temperature 9h then, obtain CoFe
2O
4The nano composite material of the monodispersed superparamagnetism of/SBA-3.
(3) CoFe of Supported CuO
2O
4/ SBA-3.
With gained CoFe
2O
4/ SBA-3 sample immerses in the 0.5 mol glycerine copper solution, separates, and the 363K drying is filtered in washing.773K calcination 5 hours, cool off in the Ar atmosphere, promptly get the superparamagnetic material CoFe of Supported CuO
2O
4/ SBA-3.This material saturation magnetization is 20emu/g.Be used for fixing an adsorption desulfurize, every gram CuO-CoFe
2O
4After/SBA-3 normal temperature was handled the high sulfur oil 0.5h of 100mL400ppm, the gasoline gas chromatography after the processing detected not have and detects sulphur, is better than existing C uO-MCM41 product, and separates from liquid phase easily.
Embodiment 6 NiFe
2O
4/ MSU-1/CuO's is synthetic
(1) has super-paramagnetism nano NiFe
2O
4Synthetic
In nitrogen atmosphere with 1.1259g (NH
4)
2C
2O
4, 9.0714gNiSO
47H
2O and 12.9058gFe
2(SO
4)
3Be dissolved in the 150mL80 ℃ of water, regulate pH=9.2 with NaOH, continue reaction 1.5h, washing promptly gets NiFe
2O
4Precipitation.In precipitation, add deionized water, drip 10% Na
2SiO
3Solution 15mL, control pH=9 also reacts 1h.Take out, magnet separates, and washing obtains amorphous Si O
2The NiFe that coats
2O
4
(2) NiFe
2O
4/ MSU-1's is synthetic
In the atmosphere of nitrogen, will be coated with SiO
2NiFe
2O
4Precipitation is distributed to (A) in the 40mL deionized water.2.3807g AEO-9 (AEO non-ionic surface active agent) is mixed with 30mL deionized water, 26mLHCl (1mol/L), after the 333K dissolving, be cooled to 271K and get solution (B), B is added among the A, stir 1h; Na with 9.4002g10%
2SiO
3Solution mixes with the 90mL deionized water, also is cooled to 271K.Under brute force stirs, the water glass solution after the dilution is slowly joined in the aqueous surfactant solution of above-mentioned acidifying, this moment pH=3, each material mol ratio is SiO in the mixed liquor
2: AEO-9: H
2O=1: 0.1: 280, be rapidly heated to 295K.Stir 20h, put into the polytetrafluoroethyllining lining hydrothermal reaction kettle, 473K constant temperature 50 hours, product filtered, and in the 333K oven dry, the tube furnace temperature programming (3K/min) that places nitrogen atmosphere continuation roasting 8h to the 823K obtains hud typed NiFe through washing after
2O
4The monodispersed super-paramagnetism nano composite material of/MSU-1.
(3) NiFe of Supported CuO
2O
4/ MSU-1.
With gained NiFe
2O
4/ MSU-1 sample immerses in the 0.5 mol glycerine copper solution, separates, and the 363K drying is filtered in washing.823K calcination 5 hours, cool off in the Ar atmosphere, promptly get the superparamagnetic material NiFe of Supported CuO
2O
4/ MSU-1.This material saturation magnetization is 21emu/g, is the infrared enamel that active ingredient is made with it, has stable high IR absorptivity in 2.5～25 μ m infrared bands, and the normal direction total emissivity is that 0.88. is used for fixing an adsorption desulfurize, every gram CuO-NiFe
2O
4After/MSU-1 handled the high sulfur oil of 100mL400ppm, the gasoline gas chromatography after the processing detected not have and detects sulphur.
Embodiment 7 Fe-Fe
3O
4/ SBA-15/CuO's is synthetic
(1) has super-paramagnetism nano CuFe
2O
4Synthetic
With 1.1268g (NH
4)
2C
2O
4, 12.0085gFeSO
47H
2O and 12.9100gFe
2(SO
4)
3Be dissolved in the 150g water, keep 80 ℃ of water-baths; Add NH
3H
2O (25%, mass percent) regulates pH=10, continues reaction 1.5h, and washing promptly gets Fe
3O
4Precipitation.In gained precipitation, add appropriate amount of deionized water and 60mL isopropyl alcohol and add ammoniacal liquor and regulate pH=10, after dropwise drip positive tetraethyl orthosilicate (TEOS) to pH=9.1, reaction 3h.Take out, magnet separates, and washing obtains amorphous Si O
2The Fe that coats
3O
4
(2) Fe-Fe
3O
4/ SBA-15's is synthetic
With 0.5001g amorphous Si O
2The Fe that coats
3O
4, (poly-oxireme ether-propylene oxide ether-oxireme ether triblock polymer surfactant, mean molecule quantity is 5800 to 2.0120g P123, molecular formula EO
20PEO
70EO
20) be dissolved among 45mL distilled water and 30mL (4mol/L) HCl, under 313K, add 15gDMF (DMF is N, dinethylformamide), add 4.48mLTEOS (positive tetraethyl orthosilicate behind the stirring 1h, 0.929-0.936g/mL), after 1 day, put into the polytetrafluoroethyllining lining hydrothermal reaction kettle in stirring reaction under the 313K, 380K constant temperature 68 hours, filter, (room temperature) drying is placed in the tube furnace in air, in the blanket of nitrogen from the room temperature temperature programming to 823K (2K/min) constant temperature 1h then, obtain Fe-Fe
3O
4The hud typed single composite Nano magnetic material that disperses of/SBA-15.
(3) Fe-Fe of Supported CuO
3O
4/ SBA-15.
With gained Fe-Fe
3O
4/ SBA-15 sample immerses 0.2 mol ethylenediamine tetra-acetic acid and closes in the copper solution, separates, and the 363K drying is filtered in washing.CO
2873K calcination 5 hours, cool off in the atmosphere, promptly get the superparamagnetic material Fe-Fe of Supported CuO
3O
4/ SBA-15.This material saturation magnetization is 46emu/g.Be used for fixing an adsorption desulfurize, every gram CuO-Fe-Fe
3O
4After/SBA-15 handled the high sulfur diesel of 100mL400ppm, gas chromatograph did not have and detects, and is better than existing C uO-MCM-41 product, and very easily separates from liquid phase.
Embodiment 8 CoFe
2O
4/ MCM-41/CuO's is synthetic
(1) has super-paramagnetism nano CuFe
2O
4Synthetic
With 1.1267g (NH
4)
2C
2O
4, 9.2163gCoSO
47H
2O and 12.9008gFe
2(SO
4)
3Be dissolved in the 150mL water, keep 80 ℃ of water-baths; Add NH
3H
2O (25%, mass percent) regulates pH=9, continues reaction 1.5h, washing, and Magnetic Isolation promptly gets CoFe
2O
4Precipitation.
(2) CoFe
2O
4/ MCM-41/CuO's is synthetic
To the CuFe that obtains
2O
4Add 60mL deionized water and 10.23mL NH in the precipitation
3H
2O (25%), 0.05gCuCl
2Solid stirs; 0.6125g TBAB (tetrabutyl ammonium bromide) is dissolved in the 10mL deionized water, and 2.7698gCTAB (cetyl trimethyl ammonium bromide) is dissolved in the 50mL deionized water.All liq is mixed, dropwise drip 11.27mL TEOS (positive silicic acid four esters) behind the stirring 0.5h under quick stirring, 1.5h drips off.React 3h down in 363K after dripping off.Reactant molar ratio is CTAB: TEOS: NH
3: H
2O: TBAB=0.152: 1: 2.8: 141.2: 0.038.Filter, with behind the deionized water wash at the dry 12h of 363K, (1K/min) 823K calcining at constant temperature 1h respectively then obtains CoFe from the room temperature temperature programming to 823K
2O
4/ MCM-41/CuO composite magnetic nano material.This material saturation magnetization is 15emu/g.Generate dipropyl disulphide as catalyst oxidation propanethiol, catalyst activity is higher.With this catalyst 1g that contains 8%CuO catalytic oxidation 10.0mmol propanethiol when normal pressure, the 293K, reaction 0.5h, propanethiol conversion ratio and disulphide selectivity are 100%, use 10 times after its activity constant substantially.
Embodiment 9 (BaMn)
0.5Fe
2O
4/ MCM-22/CuO's is synthetic
(1) superparamagnetism (BaMn)
0.5Fe
2O
4Synthesizing of nano particle
Ratio by amount of substance takes by weighing BaCl at 1: 2
2, MnCl
2(BaCl
2, MnCl
2The ratio of amount of substance 1: 1) and FeCl
36H
2O is dissolved in the 150g deionized water, drips NH under 80 ℃ of water bath condition
3H
2O regulates pH=9, continues reaction 1.5h, washing, and Magnetic Isolation promptly gets (BaMn)
0.5Fe
2O
4
(2) (BaMn)
0.5Fe
2O
4Synthesizing of/MCM-22 composite nano materials
To gained (BaMn)
0.5Fe
2O
4Middle 135mL deionized water, 0.8g NaOH, 1.7 gram sodium aluminates, the cyclohexylamine 10.3g of adding stirred 10 minutes, dripped TEOS (tetraethoxysilane) 12.90mL.Continue reaction 3h.Then reactant mixture is changed in the polytetrafluoroethyllining lining autoclave over to 423K hydro-thermal reaction 96h.Filter, wash the back in the 363K drying.Place Muffle furnace temperature programming (2K/min) roasting 8h to the 823K, obtain (BaMn)
0.5Fe
2O
4/ MCM-22 core-shell nano magnetic material.
(3) (BaMn) of Supported CuO
0.5Fe
2O
4/ MCM-22.
With gained (BaMn)
0.5Fe
2O
4/ MCM-22 sample immerses and contains in the solution of 0.3 mol, four ammino copper.Magnetic Isolation, the 363K drying is filtered in washing.853K calcination 5 hours, cool off in the He atmosphere, promptly get the superparamagnetic material (BaMn) of Supported CuO
0.5Fe
2O
4/ MCM-22.This material saturation magnetization is 12emu/g.Microwave absorption as X-band (8.2-12.4GHz) reaches 30-40dB.
Embodiment 10 Fe-Fe
2O
4/ MCM-41/CuO's is synthetic
(1) has super-paramagnetism nano Fe
3O
4Synthetic
Under the nitrogen protection with 1.1263g (NH
4)
2C
2O
4, 9.0016gFeSO
47H
2O and 12.9054gFe
2(SO
4)
3Be dissolved in the 150mL deionized water, keep 70-80 ℃ of water-bath; Adjust PH to 8.6 and continue reaction 1.5h, washing promptly gets Fe
3O
4Precipitation.
(2) Fe-Fe
3O
4/ MCM-41's is synthetic
With Fe
3O
4Be deposited in N
2Protection dispersed with stirring down adds 3.6mL NH in the 23mL deionized water
3H
2O (25%, mass percent).With 0.2220g TBAB (tetrabutyl ammonium bromide, TBAB) is dissolved in the 10mL deionized water, 1.0026g CTAB (cetyl trimethyl ammonium bromide, softex kw) is dissolved in the 10mL deionized water.Above-mentioned several solns is mixed, stir and dropwise drip 4.05mLTEOS (tetraethoxysilane) down, reaction 3h.Reactant molar ratio is CTAB: TEOS: NH
3: H
2O: TBAB=0.152: 1: 2.8: 141.2: 0.038.Magnet separates, with behind the deionized water wash at the dry 12h of 363K, obtain powder sample.Powder is placed the tube furnace of CO gas atmosphere, and (0.5K/min) in constant temperature 823K calcining 1h, obtains MCM-41 and coats Fe-Fe then from the room temperature temperature programming to 823K
3O
4Fe
3O
4/ MCM-41 magnetic nanometer composite material Al, this composite material show extremely strong superparamagnetism adding under the action of a magnetic field.
(3) Fe-Fe of Supported CuO
3O
4/ MCM-41.
With gained Fe-Fe
3O
4/ MCM-41 sample immerses and contains in the solution of 0.5 mol copper nitrate.Magnetic Isolation, the 363K drying is filtered in washing.873K calcination 5 hours, cool off in the Ar atmosphere, promptly get the superparamagnetic material Fe-Fe of Supported CuO
3O
4/ MCM-41.This material saturation magnetization is 42emu/g.Be used for fixing an adsorption desulfurize, every gram CuO-Fe-Fe
3O
4After/MCM-41 handled the high sulfur diesel of 100mL400ppm, gas chromatograph did not have and detects, and is better than existing C uO-MCM41 product, and very easily separates from liquid phase.This material is applicable to one step of ethanol synthesizing ethyl acetate as catalyst.Experimental result shows on the miniature fixed-bed reactor of 10mL, normal pressure, and reaction temperature is 250 ℃, the charging air speed is 1.5L.h
-1Condition under ethanol conversion reach 68%, the selectivity of ethyl acetate reaches 70%.
Embodiment 11 CoNdFe/MCM-41/CuO's is synthetic
(1) has super-paramagnetism nano Co (Nd, Fe) O
4Synthetic
Ratio CoCl with amount of substance
2: Nd (NO
3)
3: Fe
2(SO
4)
3=1: 1: 1 CoCl
2, Nd (NO
3)
3And Fe
2(SO
4)
3Be dissolved in 80 ℃ of water, NaOH solution is adjusted pH to 8.6 reaction 1.5h, and washing promptly gets Co (Nd, Fe) O
4Precipitation.
(2) CoNdFe/MCM-41's is synthetic
With Co (Nd, Fe) O
4The precipitation dispersed with stirring adds 3.6mL NH in the 23mL deionized water
3H
2O (25%, mass percent).With 0.2221g TBAB (tetrabutyl ammonium bromide, TBAB) is dissolved in the 10mL deionized water, 1.0028g CTAB (cetyl trimethyl ammonium bromide, softex kw) is dissolved in the 10mL deionized water.Above-mentioned several solns is mixed, stir and dropwise drip 4.05mLTEOS (tetraethoxysilane) down.Continue reaction 3h after dripping off.Reactant molar ratio is CTAB: TEOS: NH
3: H
2O: TBAB=0.152: 1: 2.8: 141.2: 0.038.Magnet separates, with behind the deionized water wash at the dry 12h of 363K, obtain powder sample, be numbered A1.A1 is placed the tube furnace that is connected with hydrogen, and (0.5K/min) in constant temperature 823K calcining 8h, obtains the magnetic nanometer composite material CoNdFe/MCM-41 that MCM-41 coats CoNdFe then from the room temperature temperature programming to 823K.
(3) CoNdFe/MCM-41/CuO's is synthetic
CoNdFe/MCM-41 is immersed in the 0.2 mol copper nitrate solution, stir, washing, the gained solid is put in the 363K baking oven to moisture all till the evaporation, the solid transfer that obtains is to the tube furnace of nitrogen atmosphere, be warming up to 573K and constant temperature 2h, be cooled to room temperature, promptly get the powder of hud typed monodisperse superparamagnetic nanometer CoNdFe/MCM-41/CuO.This material saturation magnetization is 58emu/g.0.05% is added among the PMMA, and as the microwave absorption of broadband (750MHz-20GHz), peak value reaches 40dB.
Embodiment 12 CoSmFe/SBA-3/CuO's is synthetic
(1) has super-paramagnetism nano Co (Sm, Fe) O
4Synthetic
Ratio CoCl with amount of substance
2: Sm (NO
3)
3: Fe
2(SO
4)
3=1: 1: 1 CoCl
2, Sm (NO
3)
3And Fe
2(SO
4)
3Be dissolved in 80 ℃ of water, NaOH solution is adjusted pH to 8.6 reaction 1.5h, washing, and Magnetic Isolation promptly gets Co (Sm, Fe) O
4Precipitation.
(2) CoSmFe/SBA-3's is synthetic
In nitrogen atmosphere to the CoFe that obtains
2O
4The middle 60mL water that adds stirs, and adds the dense NH of 10.23mL
3H
2O is dissolved in 0.6125gTBAB (tetrabutyl ammonium bromide) in the 10mL deionized water, and 2.7698g CTAB (cetyl trimethylammonium bromide) is dissolved in the 50mL deionized water, and adds the 10mL heptane.Under quick stirring, dropwise drip 11.27mL TEOS (tetraethoxysilane) after mixing stirring 0.5h, under room temperature, react 3h after dripping off.Reactant molar ratio is CTAB: TEOS: NH
3: H
2O: TBAB=0.152: 1: 2.8: 141.2: 0.038.Filter, with behind the deionized water wash at the dry 12h of 363K, place tube furnace then, at N
2With H
2Under the gaseous mixture atmosphere from the room temperature temperature programming to 823K (3K/min) calcining at constant temperature 8h then, obtain the nano composite material of the monodispersed superparamagnetism of CoSmFe/SBA-3.
(3) CoSmFe/SBA-3 of Supported CuO.
Gained CoSmFe/SBA-3 sample is immersed in the 0.1 mol copper formate solution, separate, the 363K drying is filtered in washing.773K calcination 5 hours, cool off in the Ar atmosphere, promptly get the superparamagnetic material CoSmFe/SBA-3 of Supported CuO.This material saturation magnetization is 56emu/g.0.05% is added among the PMMA, and as the microwave absorption of broadband (750MHz-20GHz), peak value reaches 35dB.
Embodiment 13 FeGd
0.05Cr
0.05Fe
1.9O
4/ SBA-11/CuO's is synthetic
(1) has super-paramagnetism nano FeGd
0.05Cr
0.05Fe
1.9O
4Synthetic
Under the blanket of nitrogen with the ratio FeCl of amount of substance
2: Gd (NO
3)
3: Cr (NO
3)
3: Fe
2(SO
4)
3=1: 0.05: 0.05: 1.9 FeCl
2, Gd (NO
3)
3, Cr (NO
3)
3With Fe
2(SO
4)
3Be dissolved in 80 ℃ of water, ammoniacal liquor is adjusted pH to 8.6 reaction 1.5h, washing, and Magnetic Isolation promptly gets FeGd
0.05Cr
0.05Fe
1.9O
4Precipitation.In gained precipitation, add appropriate amount of deionized water and 60mL isopropyl alcohol and add ammoniacal liquor and regulate pH=10, after dropwise drip positive tetraethyl orthosilicate (TEOS) to pH=9.1, reaction 3h.Take out, magnet separates, and washing obtains amorphous Si O
2The FeGd that coats
0.05Cr
0.05Fe
1.9O
4
(2) FeGd
0.05Cr
0.05Fe
1.9O
4/ SBA-11's is synthetic
With 0.5001g amorphous Si O
2The FeGd that coats
0.05Cr
0.05Fe
1.9O
4, (poly-oxireme ether-propylene oxide ether-oxireme ether triblock polymer surfactant, mean molecule quantity is 5800 to 2.0120g P123, molecular formula EO
20PEO
70EO
20) be dissolved among 45mL distilled water and 30mL (2mol/L) HCl, under 313K, add 15gDMF (DMF is N, dinethylformamide), add 4.48mL TEOS (positive tetraethyl orthosilicate) behind the stirring 1h, in stirring reaction under the 313K after 1 day, put into the polytetrafluoroethyllining lining hydrothermal reaction kettle,, filter 450K constant temperature 60 hours, washing back is in air after (room temperature) drying, place muffle furnace, in blanket of nitrogen from the room temperature temperature programming to 823K (2K/min) constant temperature 6h then, obtain FeGd
0.05Cr
0.05Fe
1.9O
4The hud typed single composite Nano magnetic material that disperses of/SBA-11.
(3) FeGd of Supported CuO
0.05Cr
0.05Fe
1.9O
4/ SBA-11.
With gained FeGd
0.05Cr
0.05Fe
1.9O
4/ SBA-11 sample immerses 0.3 mol ethylenediamine tetra-acetic acid and closes in the copper solution, separates, and the 363K drying is filtered in washing.813K calcination 5 hours, cool off in the active carbon protective atmosphere, promptly get the superparamagnetic material FeGd of Supported CuO
0.05Cr
0.05Fe
1.9O
4/ SBA-11.This material saturation magnetization is 28emu/g.Be used for catalytic oxidation 1-methoxyl group 2-propyl alcohol synthesizing methoxy acetone as catalyst at 363K, the conversion ratio of 1-methoxyl group-2-propyl alcohol can reach 70%, and the yield of methoxy acetone can reach 65%, and catalyst is easy to Magnetic Isolation from solution.
Embodiment 14 Pr
0.3Dy
0.2Fe
0.5/ MCM-41/CuO's is synthetic
(1) predecessor Pr
0.3Dy
0.2Fe
0.5(OH)
3Synthetic
Ratio Pr (NO with amount of substance
3)
3: Dy (NO
3)
3: Fe
2(SO
4)
3=0.3: 0.2: 0.5 Pr (NO
3)
3, Dy (NO
3)
3And Fe
2(SO
4)
3Be dissolved in 80 ℃ of water, add ammoniacal liquor and adjust pH to 8.6 reaction 1.5h, washing promptly gets Pr
0.3Dy
0.2Fe
0.5(OH)
3Precipitation.
(2) Pr
0.3Dy
0.2Fe
0.5/ MCM-41's is synthetic
With 0.5g Pr
0.3Dy
0.2Fe
0.5(OH)
3The precipitation dispersed with stirring adds 3.6mL NH in the 23mL deionized water
3H
2O (25%, mass percent).With 0.2221g TBAB (tetrabutyl ammonium bromide, TBAB) is dissolved in the 10mL deionized water, 1.0028g CTAB (cetyl trimethyl ammonium bromide, softex kw) is dissolved in the 10mL deionized water.Above-mentioned several solns is mixed, stir and dropwise drip 4.05mLTEOS (tetraethoxysilane) down.Continue reaction 3h after dripping off.Reactant molar ratio is CTAB: TEOS: NH
3: H
2O: TBAB=0.152: 1: 2.8: 141.2: 0.038.Put into the polytetrafluoroethyllining lining hydrothermal reaction kettle, in 390K constant temperature 68 hours, isolated by filtration, with behind the deionized water wash at the dry 12h of 363K, obtain powder sample, be numbered A1.A1 is placed the tube furnace that is connected with hydrogen, and (0.5K/min) in constant temperature 883K calcining 8h, obtains MCM-41 and coats Pr then from the room temperature temperature programming to 823K
0.3Dy
0.2Fe
0.5The super-paramagnetism nano composite material.
(3) Pr
0.3Dy
0.2Fe
0.5/ MCM-41/CuO's is synthetic
With Pr
0.3Dy
0.2Fe
0.5/ MCM-41 immerses in the 0.2 mol glycerine copper solution, stir, washing, the gained solid is put in the 363K baking oven to moisture all till the evaporation, the solid transfer that obtains is to the tube furnace of nitrogen atmosphere, temperature programming is cooled to room temperature to 823K and at 873K constant temperature 8h, promptly gets hud typed monodisperse superparamagnetic nanometer Pr
0.3Dy
0.2Fe
0.5The powder of/MCM-41/CuO.This material saturation magnetization is 50emu/g.0.04% is added among the PMMA, and as the microwave absorption of broadband (750MHz-20GHz), peak value reaches 38dB.
Embodiment 15 Gd
0.2Fe
0.8/ MCM-41/CuO's is synthetic
(1) predecessor compound carbonate precipitation is synthetic
Ratio Gd (NO with amount of substance
3)
3: Fe
2(SO
4)
3=0.2: 0.8 Gd (NO
3)
3And Fe
2(SO
4)
3Be dissolved in 80 ℃ of water, add ammonium carbonate and adjust pH to 7.5 reaction 1.5h, washing promptly gets the compound carbonate precipitation.
(2) Gd
0.2Fe
0.8/ MCM-41's is synthetic
0.5g compound carbonate precipitation dispersed with stirring in the 23mL deionized water, is added 3.6mL NH
3H
2O (25%, mass percent).With 0.2221g TBAB (tetrabutyl ammonium bromide, TBAB) is dissolved in the 10mL deionized water, 1.0028g CTAB (cetyl trimethyl ammonium bromide, softex kw) is dissolved in the 10mL deionized water.Above-mentioned several solns is mixed, stir and dropwise drip 4.05mLTEOS (tetraethoxysilane) down.Continue reaction 3h after dripping off.Reactant molar ratio is CTAB: TEOS: NH
3: H
2O: TBAB=0.152: 1: 2.8: 141.2: 0.038.Isolated by filtration, with behind the deionized water wash at the dry 12h of 363K, obtain powder sample, be numbered A1.A1 is placed the tube furnace that is connected with hydrogen, and (0.5K/min) in constant temperature 883K calcining 8h, obtains MCM-41 and coats Gd then from the room temperature temperature programming to 823K
0.2Fe
0.8The super-paramagnetism nano composite material.
(3) Gd
0.2Fe
0.8/ MCM-41/CuO's is synthetic
With Gd
0.2Fe
0.8/ MCM-41 immerses in the 0.2 mol copper nitrate solution, stir, washing, the gained solid is put in the 363K baking oven to moisture all till the evaporation, the solid transfer that obtains is to the tube furnace of nitrogen atmosphere, temperature programming is cooled to room temperature to 823K and at 1123K constant temperature 2h, promptly gets hud typed monodisperse superparamagnetic nanometer Gd
0.2Fe
0.8The powder of/MCM-41/CuO.This material saturation magnetization is 40emu/g.0.02% is added among the PMMA, and as the microwave absorption of broadband (750MHz-20GHz), peak value reaches 30dB.
Embodiment 16 Ni
0.2Nd
0.8/ MCM-49/CuO's is synthetic
(1) predecessor compound carbonate precipitation is synthetic
Ratio Ni (NO with amount of substance
3)
2: Nd (NO
3)
3=0.2: 0.8 Ni (NO
3)
2, Nd (NO
3)
3Be dissolved in 80 ℃ of water, add ammonium oxalate reaction 1.5h, washing promptly gets compound oxalate precipitation.
(2) Ni
0.2Nd
0.8/ MCM-49's is synthetic
The 0.5g compound carbonate is precipitated dispersed with stirring in the 160ml distilled water solution that is dissolved with 2.02g NaOH and 1.8g (or 1.2g) sodium metaaluminate, under the room temperature intense stirring condition, add 12.5ml hexamethylene imine (HMI), drip 16gTEOS then, behind the 1h, 423K crystallization 72h in the stainless steel autoclave of the inner liner polytetrafluoroethylene of packing into (400ml).Synthetic product after suction filtration, washing, oven dry, put in people's tube furnace under nitrogen current speed with 5K/min from the room temperature temperature programming to 823K, then in hydrogen stream in 823K again roasting 3h promptly obtain MCM one 49 molecular sieves and coat Ni
0.2Nd
0.8Nano composite material Ni
0.2Nd
0.8/ MCM-49
(3) Ni
0.2Nd
0.8/ MCM-49/CuO's is synthetic
With Ni
0.2Nd
0.8/ MCM-49 immerses in the 0.3 mol copper nitrate solution, stir, washing, the gained solid is put in the 363K baking oven to moisture all till the evaporation, the solid transfer that obtains is to the tube furnace of nitrogen atmosphere, temperature programming to 823K and and constant temperature 2h, be cooled to room temperature, promptly get the super-paramagnetism nano Ni of hud typed single spread loads CuO
0.2Nd
0.8The powder of/MCM-49.This material saturation magnetization is 25emu/g.0.03% is added among the PMMA, and as the microwave absorption of broadband (750MHz-20GHz), peak value reaches 35dB.
Embodiment 17 (ZnMn)
0.5Fe
2O
4/ MCM-22/CuO's is synthetic
(1) superparamagnetism (ZnMn)
0.5Fe
2O
4Synthesizing of nano particle
Press the ratio ZnCl of amount of substance under the blanket of nitrogen
2: MnCl
2: FeCl
36H
2O=0.5: take by weighing ZnCl at 0.5: 2
2, MnCl
2And FeCl
36H
2O is dissolved in the 150g80 ℃ of deionized water, drips NH
3H
2O regulates pH=8.5, continues reaction 1.5h, washing, and Magnetic Isolation promptly gets (ZnMn)
0.5Fe
2O
4
(2) (ZnMn)
0.5Fe
2O
4Synthesizing of/MCM-22 composite nano materials
To gained (ZnMn)
0.5Fe
2O
4Middle 135mL deionized water, 0.8g NaOH, 1.7 gram sodium aluminates, the cyclohexylamine 10.3g of adding stirred 10 minutes, dripped TEOS (tetraethoxysilane) 12.90mL.Continue reaction 3h.Then reactant mixture is changed in the polytetrafluoroethyllining lining autoclave over to 473K hydro-thermal reaction 76h.Filter, wash the back in the 363K drying.Place Muffle furnace temperature programming (2K/min) roasting 8h to the 823K, obtain (ZnMn)
0.5Fe
2O
4/ MCM-22 core-shell nano magnetic material.
(3) (ZnMn) of Supported CuO
0.5Fe
2O
4/ MCM-22.
With gained (ZnMn)
0.5Fe
2O
4/ MCM-22 sample immerses and contains in the solution of 0.3 mol, four ammino copper.Magnetic Isolation, the 363K drying is filtered in washing.N
2Program is warming up to 823K and 853K calcination 5 hours in the atmosphere, and cooling promptly gets the superparamagnetic material (ZnMn) of Supported CuO
0.5Fe
2O
4/ MCM-22.This material saturation magnetization is 14emu/g.0.05% is added among the PMMA, and as the microwave absorption of broadband (750MHz-20GHz), peak value reaches 39dB.
Claims (9)
1. the superparamagnetic material of a Supported CuO is characterized in that being made of particles with superparamagnetism, mesoporous material layer and the CuO that loads on mesoporous material layer surfaces externally and internally, and particles with superparamagnetism is coated by mesoporous layer, and CuO is positioned at mesoporous material layer duct surfaces externally and internally; Described particles with superparamagnetism is made up of in metal oxide with superparamagnetism and the magnetic metal one or more; Metal oxide is ferrite or class ferrite, and the ferrite chemical composition is RFe
2O
4, the class ferrite consists of R
IIM
III 2O
4, R is one or more among Fe, Zn, Co, Ni, Ba, Cu, the Mn, M is one or more among Co, Ni, Cr, Sm, Dy, Nd, Pr, the Gd; Described magnetic metal comprises the alloy of Fe, Co or Ni or itself and Cr, Sm, Dy, Nd, Pr, Gd; Described mesoporous material layer is a molecular sieve, or by the unformed SiO of internal layer
2Constitute with outer molecular sieve; When described mesoporous material layer was molecular sieve, molecular sieve directly coated particles with superparamagnetism; Described mesoporous material layer is by the unformed SiO of internal layer
2When constituting with outer molecular sieve, particles with superparamagnetism is earlier by unformed SiO
2Coat, then SiO
2The superparamagnetic material that coats is coated by molecular sieve again, forms the complex nucleus shell structure.
2. the superparamagnetic material of Supported CuO according to claim 1 is characterized in that described molecular sieve is silica-based molecular sieve, and silica-based molecular sieve comprises MCM series molecular sieve, SBA-n series molecular sieve or MSU-X series molecular sieve.
3. the superparamagnetic material of Supported CuO according to claim 2 is characterized in that described MCM series molecular sieve is MCM-41, MCM-49, MCM-22, MCM-50, MCM-56 or MCM-48; SBA-n series molecular sieve is SBA-1, SBA-2, SBA-3, SBA-6, SBA-11, SBA-12, SBA-15 or SBA-16.
4. the superparamagnetic material of Supported CuO according to claim 3 is characterized in that described CuO particle diameter less than 15nm, and the particles with superparamagnetism particle diameter is 5-25nm.
5. the preparation method of the superparamagnetic material of a Supported CuO is characterized in that may further comprise the steps:
(1) coprecipitation makes particles with superparamagnetism or its insoluble predecessor, washing; Described insoluble predecessor is meant the precipitation or the colloidal sol that can generate particles with superparamagnetism under the heating and decomposition condition, comprises and contains Fe
III, R
IIOxide, oxalates, carbonate, hydroxide, R is one or more among Fe, Zn, Co, Ni, Ba, the Cu; Or contain M
III, R
IIOxide, oxalates, carbonate, hydroxide, M is one or more among Cr, Sm, Dy, Nd, Pr, the Gd, R is one or more among Fe, Zn, Co, Ni, Ba, Cu, the Mn.
(2) sol-gel process on particles with superparamagnetism surface or its insoluble predecessor surface chemical reaction cover the SiO of one deck densification
2Or/and molecular sieve separates, drying is filtered in washing;
(3) program is warming up to 823K in the atmosphere, and 823K-1123K insulation 1-8 hour, promptly obtains powder sample;
(4) step (3) gained sample is immersed in the soluble copper salting liquid, separate, drying is filtered in washing; 573K-873K calcination 1-5 hour, cool off in the atmosphere, promptly get the superparamagnetic material of Supported CuO.
6. method according to claim 5, it is characterized in that in the step (2), described sol-gel process is meant the synthetic method of utilizing esters of silicon acis hydrolysis in aqueous solution to generate Si oxide, and the esters of silicon acis hydrolysis does not generate SiO respectively when not adding with the interpolation template in the solution that contains particles with superparamagnetism or its predecessor precipitation
2Layer and molecular sieve layer in the 273K-363K scope, carry out under temperature 373K-473K under the hydrothermal condition during the non-hydro-thermal of reaction temperature; Described template is cation or non-ionic surface active agent; In step (3) and (4), described atmosphere is inert atmosphere or the reducing atmosphere of using always, and inert atmosphere comprises N
2, He, Ar or CO
2, reducing atmosphere comprises active carbon, CO, N
2Or H
2
7. according to claim 5 or 6 described methods, it is characterized in that in the step (3) that described temperature programming is that the speed with 0.5-5K/min rises to 823K by room temperature.
8. the preparation method of the superparamagnetic material of a Supported CuO is characterized in that comprising the steps:
(1) coprecipitation makes particles with superparamagnetism or its insoluble predecessor, washing; Described insoluble predecessor is meant the precipitation or the colloidal sol that can generate particles with superparamagnetism under the heating and decomposition condition, comprises and contains Fe
III, R
IIOxide, oxalates, carbonate, hydroxide, R is one or more among Fe, Zn, Co, Ni, Ba, the Cu; Or contain M
III, R
IIOxide, oxalates, carbonate, hydroxide, M is one or more among Cr, Sm, Dy, Nd, Pr, the Gd, R is one or more among Fe, Zn, Co, Ni, Ba, Cu, the Mn.
(2) containing Cu by sol-gel process
2+Solution in, realize that particles with superparamagnetism surface or its insoluble predecessor surface chemical reaction cover one deck molecular sieve, simultaneously toward molecular sieve surfaces externally and internally loaded copper oxide predecessor, separate, drying is filtered in washing; Program is warming up to 823K in the atmosphere, and 823K-1123K insulation 1-8 hour.
9. the preparation method of the superparamagnetic material of Supported CuO according to claim 8, it is characterized in that in the step (2), described sol-gel process is meant the synthetic method of utilizing esters of silicon acis hydrolysis in aqueous solution to generate Si oxide, and the esters of silicon acis hydrolysis does not generate SiO respectively when not adding with the interpolation template in the solution that contains particles with superparamagnetism or its predecessor precipitation
2Layer and molecular sieve layer in the 273K-363K scope, carry out under temperature 373K-473K under the hydrothermal condition during the non-hydro-thermal of reaction temperature; Described template is cation or non-ionic surface active agent.
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