CN102513126B - Multilevel core-shell structure magnetic nano gold catalyst and preparation method thereof - Google Patents
Multilevel core-shell structure magnetic nano gold catalyst and preparation method thereof Download PDFInfo
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- CN102513126B CN102513126B CN 201110344754 CN201110344754A CN102513126B CN 102513126 B CN102513126 B CN 102513126B CN 201110344754 CN201110344754 CN 201110344754 CN 201110344754 A CN201110344754 A CN 201110344754A CN 102513126 B CN102513126 B CN 102513126B
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Abstract
The invention relates to a multilevel core-shell structure magnetic nano gold catalyst and a preparation method thereof, belonging to the field of magnetic nano catalytic material. A core-shell structure composite which is formed by taking a lamellar double-hydroxyl composite metal oxide (M2+)(M3+)-LDHs as a shell and Fe3O4 magnetic nano particles as a core is taken as a carrier to load nano gold particles, the shell (M2+)(M3+)-LDHs nano slice is vertically intersected and epitaxially grow and has a honeycomb appearance, the gold nano particles are carried and loaded on the surface of the (M2+)(M3+)-LDHs nano slice, and H2 is reduced, thus the multilevel core-shell structure magnetic nano gold catalyst Fe3O4@(M2+)(M3+)-LDHs@Au is obtained. The invention has the advantages that the multilevel core-shell structure magnetic nano gold catalyst has stronger superparamagnetism and also has excellent catalytic alcohol oxidation activity and selectivity, 1-phenethyl alcohol oxidation is taken as a probe reaction, the air is taken as an oxidant for reaction at the temperature of 80 DEG C, reaction is carried out for 3 hours, and yield of phenylacetaldehyde is 99%; meanwhile, the preparation method is simple, the catalyst is conveniently enriched and recycled by adding an external magnetic field after reaction is finished, and catalytic activity of the catalyst is not reduced after the catalyst is reused for five times.
Description
Technical field
The invention belongs to magnetic Nano catalysis material technical field, a kind of multistage core-shell structure magnetic nano catalyst and preparation method thereof particularly is provided.
Technical background
In organic synthesis, oxidation reaction is an important process, and the functionalized of reaction intermediate of medicine, fine chemistry industry and chemurgy product played an important role.No matter be prepared in laboratory or industrial production, in various types of oxidation conversion, the oxidizing process that alcohol is oxidized to carbonyls is occupied critical role.From chemical property and on various uses, carbonyls occupies special critical positions, the beginning raw material that they synthesize often.Aldehyde, ketonic compound structure are various, of many uses, and the annual carbonyls of producing surpasses 1,000,000 tons in the world, and wherein major part comes from the oxidation of alcohol.Therefore alcohol being oxidized to corresponding carbonyls is one of most important course of reaction in the organic chemistry.In pure oxidation catalysis system, development green, gentleness, economy and tool optionally effective catalyst system are paid close attention to always widely, particularly can under comparatively gentle reaction condition, use the higher oxidant of atom utilization ratio (as: air and oxygen), and adopt and simply to reclaim the focus that always is research with reusable solid-carrying type catalyst.2009, Takato Mitsudome etc. were at " advanced synthetic and catalysis " (Advanced Synthesis ﹠amp; Catalysis) but the 351st the volume 1890～1896 pages of reports be that carrier loaded golden nanometer particle is efficient catalytic alcohol oxidation reaction under the oxidant condition at air with hydrotalcite material.2010, Wang Liang etc. at " catalysis journal " but the 31st the volume 943～947 pages of reports be that carrier loaded golden nanometer particle is efficient catalytic alcohol oxidation reaction under the oxidant condition at oxygen with hydrotalcite material.
A kind of pure oxidation catalyst of efficient grade is provided in the above document, and its reaction condition gentleness does not need to add other auxiliary agent, but because carrier dimensions less adopts traditional filtration and centrifugal separation method to have difficult and the problem consuming time of reclaiming.So far, relevantly as yet prepare a kind of catalytic activity that both had with simple synthetic method, can realize making things convenient for the report of the pure oxidation catalyst of recycling again.2010, my seminar adopted Fe
3O
4Be magnetic nuclear, coat the organic carbon that one deck is rich in hydroxyl on its surface, method by the co-precipitation self assembly coats one deck inorganic anion intercalated houghite on its surface then, obtains having the magnetic targeted nano medicine-carrying particle (Chinese invention patent: CN101647780) of nucleocapsid structure through the roasting restoring method.But this magnetic Nano compound preparation method is complicated.Thereby this patent is planned magnetic nano-particle, layered di-hydroxyl composite metal oxidate (M
2+) (M
3+)-LDHs and Au nano particle are assembled in order, at Fe
3O
4The surface directly coats (M
2+) (M
3+)-LDHs shell prepares the carrier loaded nano Au particle of multistage core-shell structure magnetic, and wherein nano Au particle is active component, is used for alcohol oxidation reaction, provides a kind of reaction condition gentle and be convenient to the Green Chemistry catalyst of recycling.
Summary of the invention
The object of the present invention is to provide a kind of multistage core-shell structure magnetic nano catalyst and preparation method thereof.This catalyst had both had stronger superparamagnetism energy, have the characteristics of good catalytic activity again, and particle size was less, and this magnetic nano-catalyst production technology is simple, finished the back in reaction and can be enriched and recycled easily by externally-applied magnetic field.
Multistage core-shell structure magnetic nano catalyst provided by the present invention is by layered di-hydroxyl composite metal oxidate (M
2+) (M
3+)-LDHs shell (M wherein
2+Can be Mg
2+, Ni
2+, Cu
2+In the bivalent metal ion any one or two kinds, M
3+Be trivalent metal ion Fe
3+, Al
3+Wherein anyly) and Fe
3O
4The nucleocapsid structure compound that the magnetic nano particle daughter nucleus is formed is a kind of nano composite material that integrates magnetic and catalytic alcohol oxidation susceptibility as carrier loaded nano Au particle; Shell (M
2+) (M
3+)-LDHs nanometer sheet vertical interlaced oriented growth has the honeycomb pattern, and golden nanometer particle is supported on (M
2+) (M
3+)-LDHs nanometer sheet surface, H
2Obtain multistage core-shell structure magnetic nano catalyst Fe after the reduction
3O
4(M
2+) (M
3+)-LDHsAu.Particle size is 600～650nm; Saturation magnetization M
sBe 45～55emu/g, the composition of magnetic carrier is Fe
3O
4(M
2+) (M
3+)-LDHs.It forms mass percent: Fe
3O
4Magnetic nano-particle 30%～40%, (M
2+) (M
3+)-LDHs 60%～70%.Active component is nano Au particle, and its quality percentage composition is: 0.5%～2.0%.This catalyst is applicable to alcohol oxidation reaction, be oxidized to probe reaction with the 1-benzyl carbinol, air oxygen is that 80 ℃ of reactions of oxidant 3h phenylacetaldehyde yield is 99%, and reaction can be enriched and recycled easily by externally-applied magnetic field after finishing, and reuses 5 catalytic activitys and does not reduce.
The present invention adopts solvent-thermal method to prepare the Fe that particle diameter is controlled and be evenly distributed in advance
3O
4Magnetic nano-particle coats assembling (M by coprecipitation on its surface then
2+) (M
3+)-LDHs shell (M wherein
2+Can be bivalent metal ion Mg
2+, Ni
2+, Cu
2+In any one or two kinds, M
3+Be trivalent metal ion Fe
3+, Al
3+Wherein any) obtain a kind of surface (M
2+) (M
3+The honeycomb shell of the staggered vertical orientated growth of)-LDHs; By deposition-precipitation method at core-shell structure magnetic compound shell LDHs sheet surfaces loaded with nano gold grain, H
2Obtain a kind of multistage core-shell structure magnetic nano catalyst after the reduction.Concrete preparation process is:
(1) preparation of magnetisable material
Take by weighing 3.25g (0.012mol) Iron(III) chloride hexahydrate (FeCl
36H
2O) and 8.64g (0.063mol) sodium acetate trihydrate (CH
3COONa3H
2O) be dissolved in the 80ml ethylene glycol, change in the 100ml reactor, in 200 ℃ of crystallization 8 hours, naturally cool to room temperature, adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic, wash respectively 3～5 times with ethanol and deionized water, still adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic in the washing process, in 60～100 ℃ of dryings 12～24 hours, obtain the black powder, be designated as Fe
3O
4
(2) preparation of core-shell structure magnetic carrier
Take by weighing 1.0～3.0g Fe
3O
4Powder is scattered in (methyl alcohol and water volume ratio V in 50～100ml methanol aqueous solution
First Alcohol/ V
Water=0～1), ultrasonic dispersion changed in the round-bottomed flask after 5～15 minutes, stirred under room temperature.
Preparation NaOH (0.10～0.20mol/L)/Na
2CO
3(0.05～0.10mol/L) mixed ammonium/alkali solutions is designated as A liquid.
Press M
2+/ M
3+Mol ratio 2～4 takes by weighing M
2+(NO
3)
2NH
2O (M wherein
2+Can be Mg
2+, Ni
2+, Cu
2+In any one or two kinds) and M
3+(NO
3)
3NH
2O (M
3+Can be Fe
3+, Al
3+Wherein any) be dissolved in 100ml alcohol water mixed solution (methyl alcohol and water volume ratio V
Methyl alcohol: V
Water=0～1) in, is designated as B liquid.
Earlier the A drop is added that regulator solution pH is stable at 9～10 in the above-mentioned round-bottomed flask, then with A liquid with B liquid splashes in the above-mentioned round-bottomed flask simultaneously and keep the pH value constant in 9～10, mechanical agitation in the dropping process.B drop speed is 0.5～1.5ml/min, after the B drop is intact round-bottomed flask is transferred in 60～100 ℃ of water-baths and continues mechanical agitation, crystallization obtained black suspension in 12～24 hours, adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic, spend deionised water 3～5 times, still adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic in the washing process, obtain the black powder, called after Fe
3O
4(M
2+) (M
3+)-LDHs (M wherein
2+Can be Mg
2+, Ni
2+, Cu
2+In any one or two kinds, M
3+Can be Fe
3+, Al
3+Wherein any).
(3) preparation of multistage core-shell structure magnetic nano catalyst
Be that (0.0001～0.01M) to be adjusted to pH with 0.1mol/LNaOH solution be 8～9 for 0.5%～2.0% chlorauric acid solution with Au quality percentage composition.Add 0.5～1.0g core-shell structure magnetic carrier Fe
3O
4(M
2+) (M
3+)-LDHs places solution 70～80 ℃ of water-bath mechanical agitation 1～3h then, is cooled to room temperature.Adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic, spend deionised water, still adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic in the washing process, use 0.1mol/LAgNO
3Solution detects to there not being Cl
-Exist, in 60～100 ℃ of dryings 12～24 hours, obtain the black powder, H in the atmosphere reduction furnace then
2The following 200 ℃ of reduction 1～2h of condition obtain multistage core-shell structure magnetic nano catalyst, called after Fe
3O
4(M
2+) (M
3+)-LDHsAu.
Advantage of the present invention is:
(1) provides a kind of new multistage core-shell structure magnetic nano catalyst and preparation method thereof.This catalyst had both had stronger super superparamagnetism energy, had good catalytic alcohol oxidation activity and selective again, and easy magnetic separating cycle is reused 5 catalytic activitys and do not reduced.
(2) provide a kind of new type structure of hud magnetic carrier and preparation method thereof, shell (M
2+) (M
3+)-LDHs nanometer sheet vertical interlaced oriented growth, the specific surface knot is big.For the assembling of inorganic magnetic nano composite material provides new path.
The specific embodiment
Embodiment 1
(1) preparation of magnetisable material
Take by weighing 3.25g (0.012mol) Iron(III) chloride hexahydrate (FeCl
36H
2O) and 8.64g (0.063mol) sodium acetate trihydrate (CH
3COONa3H
2O) be dissolved in the 80ml ethylene glycol, change in the 100ml reactor, in 200 ℃ of crystallization 8 hours, naturally cool to room temperature, adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic, wash respectively 3 times with ethanol and deionized water, still adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic in the washing process, in 60 ℃ of dryings 24 hours, obtain the black powder, be designated as Fe
3O
4
(2) preparation of core-shell structure magnetic carrier
Take by weighing 1.0g Fe
3O
4Solid dispersed is in 100ml methanol aqueous solution (V
Methyl alcohol: V
Water=1) in, ultrasonic dispersion changed in the round-bottomed flask after 5 minutes, stirred under room temperature.
Preparation NaOH (0.10mol/L)/Na
2CO
3(0.05mol/L) mixed ammonium/alkali solutions is designated as A liquid.
Press Mg
2+/ Al
3+Mol ratio 3 takes by weighing 2.31g (0.009mol) Mg (NO
3)
26H
2O and 1.125g (0.003mol) Al (NO
3)
29H
2O is dissolved in 100ml alcohol water mixed solution (V
Methyl alcohol: V
Water=1) in, is designated as B liquid.
Earlier the A drop is added that regulator solution pH is stable at 10 in the above-mentioned round-bottomed flask, then with A liquid with B liquid splashes in the above-mentioned round-bottomed flask simultaneously and keep the pH value constant in 10, mechanical agitation in the dropping process.B drop speed is 1.5ml/min, after the B drop is intact round-bottomed flask is transferred in 60 ℃ of water-baths and continues mechanical agitation, crystallization obtained black suspension in 24 hours, adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic, spend deionised water 3 times, still adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic in the washing process, obtain the black powder, called after Fe
3O
4(Mg
2+) (Al
3+)-LDH.
(3) preparation of multistage core-shell structure magnetic nano catalyst
Be that to be adjusted to pH with 0.15mol/L NaOH solution be 9 for 0.5% chlorauric acid solution (0.0001M) with Au quality percentage composition.Add 0.5g core-shell structure magnetic carrier Fe
3O
4(Mg
2+) (Al
3+)-LDH places solution 80 ℃ of water-bath mechanical agitation 1h then, is cooled to room temperature.Adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic, spend deionised water, still adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic in the washing process, use 0.1mol/L AgNO
3Solution detects to there not being Cl
-Exist, in 60 ℃ of dryings 24 hours, obtain the black powder, H in the atmosphere reduction furnace then
2The following 200 ℃ of reduction 1h of condition obtain multistage core-shell structure magnetic nano catalyst, called after Fe
3O
4(Mg
2+) (Al
3+)-LDHAu.
Embodiment 2
(1) preparation of magnetisable material
Take by weighing 3.25g (0.012mol) Iron(III) chloride hexahydrate (FeCl
36H
2O) and 8.64g (0.063mol) sodium acetate trihydrate (CH
3COONa3H
2O) be dissolved in the 80ml ethylene glycol, change in the 100ml reactor, in 200 ℃ of crystallization 8 hours, naturally cool to room temperature, adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic, wash respectively 4 times with ethanol and deionized water, still adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic in the washing process, in 80 ℃ of dryings 18 hours, obtain the black powder, be designated as Fe
3O
4
(2) preparation of core-shell structure magnetic carrier
Take by weighing 2.0g Fe
3O
4Solid dispersed is in 80ml methanol aqueous solution (V
Methyl alcohol: V
Water=0) in, ultrasonic dispersion changed in the round-bottomed flask after 10 minutes, stirred under room temperature.
Preparation NaOH (0.20mol/L)/Na
2CO
3(0.10mol/L) mixed ammonium/alkali solutions is designated as A liquid.
By (Cu
2++ Mg
2+/ Al
3+) mol ratio 2, Cu
2+/ Mg
2+Mol ratio is 0.5, takes by weighing 0.73g (0.003mol) Cu (NO
3)
23H
2O, 1.54g (0.006mol) Mg (NO
3)
26H
2O and 1.69g (0.0045mol) Al (NO
3)
29H
2O is dissolved in 100ml alcohol water mixed solution (V
Methyl alcohol: V
Water=0) in, is designated as B liquid.
Earlier the A drop is added that regulator solution pH is stable at 10 in the above-mentioned round-bottomed flask, then with A liquid with B liquid splashes in the above-mentioned round-bottomed flask simultaneously and keep the pH value constant in 10, mechanical agitation in the dropping process.B drop speed is 1.0ml/min, after the B drop is intact round-bottomed flask is transferred in 80 ℃ of water-baths and continues mechanical agitation, crystallization obtained black suspension in 18 hours, adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic, spend deionised water 4 times, still adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic in the washing process, obtain the black powder, called after Fe
3O
4(Cu
2+-Mg
2+) (Al
3+)-LDH.
(3) preparation of multistage core-shell structure magnetic nano catalyst
Be that to be adjusted to pH with 0.2mol/L NaOH solution be 9 for 1.0% chlorauric acid solution (0.001M) with Au quality percentage composition.Add 0.5g core-shell structure magnetic carrier Fe
3O
4(Cu
2+-Mg
2+) (Al
3+)-LDH places solution 70 ℃ of water-bath mechanical agitation 2h then, is cooled to room temperature.Adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic, spend deionised water, still adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic in the washing process, use 0.1mol/L AgNO
3Solution detects to there not being Cl
-Exist, in 80 ℃ of dryings 18 hours, obtain the black powder, H in the atmosphere reduction furnace then
2The following 200 ℃ of reductase 12 h of condition obtain the magnetic Nano Au catalyst, called after Fe
3O
4(Cu
2+-Mg
2+) (Al
3+)-LDHAu.
Embodiment 3
(1) preparation of magnetisable material
Take by weighing 3.25g (0.012mol) Iron(III) chloride hexahydrate (FeCl
36H
2O) and 8.64g (0.063mol) sodium acetate trihydrate (CH
3COONa3H
2O) be dissolved in the 80ml ethylene glycol, change in the 100ml reactor, in 200 ℃ of crystallization 8 hours, naturally cool to room temperature, adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic, wash respectively 5 times with ethanol and deionized water, still adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic in the washing process, in 100 ℃ of dryings 12 hours, obtain the black powder, be designated as Fe
3O
4
(2) preparation of core-shell structure magnetic carrier
Take by weighing 3.0g Fe
3O
4Solid dispersed is in 100ml methanol aqueous solution (V
Methyl alcohol: V
Water=0.5) in, ultrasonic dispersion changed in the round-bottomed flask after 15 minutes, stirred under room temperature.
Preparation NaOH (0.15mol/L)/Na
2CO
3(0.10mol/L) mixed ammonium/alkali solutions is designated as A liquid.
By (Ni
2+/ Al
3+) mol ratio 3, Ni
2+/ Mg
2+Mol ratio is 0.5, takes by weighing 2.62g (0.009mol) Ni (NO
3)
26H
2O and 1.13g (0.003mol) Al (NO
3)
29H
2O is dissolved in 100ml alcohol water mixed solution (V
First Alcohol: V
Water=0.5) in, is designated as B liquid.
Earlier the A drop is added that regulator solution pH is stable at 9 in the above-mentioned round-bottomed flask, then with A liquid with B liquid splashes in the above-mentioned round-bottomed flask simultaneously and keep the pH value constant in 9, mechanical agitation in the dropping process.B drop speed is 0.5ml/min, after the B drop is intact round-bottomed flask is transferred in 100 ℃ of water-baths and continues mechanical agitation, crystallization obtained black suspension in 12 hours, adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic, spend deionised water 5 times, still adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic in the washing process, obtain the black powder, called after Fe
3O
4(Ni
2+) (Al
3+)-LDH.
(3) preparation of multistage core-shell structure magnetic nano catalyst
Be that to be adjusted to pH with 0.1mol/L NaOH solution be 8 for 1.5% chlorauric acid solution (0.01M) with Au quality percentage composition.Add 1.0g core-shell structure magnetic carrier Fe
3O
4(Ni
2+) (Al
3+)-LDH places solution 70 ℃ of water-bath mechanical agitation 3h then, is cooled to room temperature.Adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic, spend deionised water, still adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic in the washing process, use 0.1mol/L AgNO
3Solution detects to there not being Cl
-Exist, in 100 ℃ of dryings 12 hours, obtain the black powder, H in the atmosphere reduction furnace then
2The following 200 ℃ of reduction 1.5h of condition obtain the magnetic Nano Au catalyst, called after Fe
3O
4(Ni
2+) (Al
3+)-LDHAu.
Embodiment 4
(1) preparation of magnetisable material
Take by weighing 3.25g (0.012mol) Iron(III) chloride hexahydrate (FeCl
36H
2O) and 8.64g (0.063mol) sodium acetate trihydrate (CH
3COONa3H
2O) be dissolved in the 80ml ethylene glycol, change in the 100ml reactor, in 200 ℃ of crystallization 8 hours, naturally cool to room temperature, adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic, wash respectively 5 times with ethanol and deionized water, still adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic in the washing process, in 60 ℃ of dryings 24 hours, obtain the black powder, be designated as Fe
3O
4
(2) preparation of core-shell structure magnetic carrier
Take by weighing 1.0g Fe
3O
4Solid dispersed is in 100ml methanol aqueous solution (V
Methyl alcohol: V
Water=1: 1), ultrasonic dispersion changed in the round-bottomed flask after 15 minutes, stirred under room temperature.
Preparation NaOH (0.10mol/L)/Na
2CO
3(0.10mol/L) mixed ammonium/alkali solutions is designated as A liquid.
By (Cu
2++ Ni
2+/ Al
3+) mol ratio 3, Cu
2+/ Ni
2+Mol ratio is 0.5, takes by weighing 0.73g (0.003mol) Cu (NO
3)
23H
2O, 1.75g (0.006mol) Ni (NO
3)
26H
2O and 1.13g (0.003mol) Al (NO
3)
29H
2O is dissolved in 100ml alcohol water mixed solution (V
Methyl alcohol: V
Water=1) in, is designated as B liquid.
Earlier the A drop is added that regulator solution pH is stable at 9 in the above-mentioned round-bottomed flask, then with A liquid with B liquid splashes in the above-mentioned round-bottomed flask simultaneously and keep the pH value constant in 9, mechanical agitation in the dropping process.B drop speed is 0.5ml/min, after the B drop is intact round-bottomed flask is transferred in 60 ℃ of water-baths and continues mechanical agitation, crystallization obtained black suspension in 24 hours, adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic, spend deionised water 5 times, still adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic in the washing process, obtain the black powder, called after Fe
3O
4(Cu
2+-Ni
2+) (Al
3+)-LDH.
(3) preparation of multistage core-shell structure magnetic nano catalyst
Be that to be adjusted to pH with 0.1mol/L NaOH solution be 8 for 2.0% chlorauric acid solution (0.1M) with Au quality percentage composition.Add 1.0g core-shell structure magnetic carrier Fe
3O
4(Cu
2+-Ni
2+) (Al
3+)-LDH places solution 80 ℃ of water-bath mechanical agitation 1h then, is cooled to room temperature.Adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic, spend deionised water, still adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic in the washing process, use 0.1mol/L AgNO
3Solution detects to there not being Cl
-Exist, in 60 ℃ of dryings 24 hours, obtain the black powder, H in the atmosphere reduction furnace then
2The following 200 ℃ of reductase 12 h of condition obtain the magnetic Nano Au catalyst, called after Fe
3O
4(Cu
2+-Ni
2+) (Al
3+)-LDHAu.
Embodiment 5
(1) preparation of magnetisable material
Take by weighing 3.25g (0.012mol) Iron(III) chloride hexahydrate (FeCl
36H
2O) and 8.64g (0.063mol) sodium acetate trihydrate (CH
3COONa3H
2O) be dissolved in the 80ml ethylene glycol, change in the 100ml reactor, in 200 ℃ of crystallization 8 hours, naturally cool to room temperature, adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic, wash respectively 5 times with ethanol and deionized water, still adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic in the washing process, in 60 ℃ of dryings 24 hours, obtain the black powder, be designated as Fe
3O
4
(2) preparation of core-shell structure magnetic carrier
Take by weighing 1.0g Fe
3O
4Solid dispersed is in 100ml methanol aqueous solution (V
Methyl alcohol: V
Water=1) in, ultrasonic dispersion changed in the round-bottomed flask after 15 minutes, stirred under room temperature.
Preparation NaOH (0.1mol/L)/Na
2CO
3(0.10mol/L) mixed ammonium/alkali solutions is designated as A liquid.
Press Mg
2+/ Al
3+Mol ratio 4 takes by weighing 2.31g (0.009mol) Mg (NO
3)
26H
2O and 0.91g (0.0023mol) Fe (NO
3)
29H
2O is dissolved in 100ml alcohol water mixed solution (V
Methyl alcohol: V
Water=1) in, is designated as B liquid.
Earlier the A drop is added that regulator solution pH is stable at 10 in the above-mentioned round-bottomed flask, then with A liquid with B liquid splashes in the above-mentioned round-bottomed flask simultaneously and keep the pH value constant in 10, mechanical agitation in the dropping process.B drop speed is 01.5ml/min, after the B drop is intact round-bottomed flask is transferred in 60 ℃ of water-baths and continues mechanical agitation, crystallization obtained black suspension in 24 hours, adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic, spend deionised water 5 times, still adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic in the washing process, obtain the black powder, called after Fe
3O
4(Mg
2+) (Fe
3+)-LDH.
(3) preparation of multistage core-shell structure magnetic nano catalyst
Be that to be adjusted to pH with 0.1mol/L NaOH solution be 9 for 1.0% chlorauric acid solution (0.001M) with Au quality percentage composition.Add 1.0g core-shell structure magnetic carrier Fe
3O
4(Mg
2+) (Fe
3+)-LDH places solution 80 ℃ of water-bath mechanical agitation 1h then, is cooled to room temperature.Adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic, spend deionised water, still adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic in the washing process, use 0.1mol/L AgNO
3Solution detects to there not being Cl
-Exist, in 60 ℃ of dryings 24 hours, obtain the black powder, H in the atmosphere reduction furnace then
2The following 200 ℃ of reductase 12 h of condition obtain multistage core-shell structure magnetic nano catalyst, called after Fe
3O
4(Mg
2+) (Fe
3+)-LDHAu.
Claims (3)
1. a multistage core-shell structure magnetic nano catalyst is characterized in that: by layered di-hydroxyl composite metal oxidate (M
2+) (M
3+)-LDHs shell and Fe
3O
4The nucleocapsid structure compound that the magnetic nano particle daughter nucleus is formed is as carrier loaded nano Au particle, shell (M
2+) (M
3+)-LDHs nanometer sheet vertical interlaced oriented growth has the honeycomb pattern, and golden nanometer particle is supported on (M
2+) (M
3+)-LDHs nanometer sheet surface, H
2Obtain multistage core-shell structure magnetic nano catalyst Fe after the reduction
3O
4(M
2+) (M
3+)-LDHsAu;
The particle size of catalyst is 600～650 nm; Saturation magnetization M
sBe 45～55 emu/g, the composition of magnetic carrier is Fe
3O
4(M
2+) (M
3+)-LDHs, its composition mass percent is: Fe
3O
4Magnetic nano-particle 30%～40%, (M
2+) (M
3+)-LDHs 60%～70%;
M wherein
2+Be Mg
2+, Ni
2+, Cu
2+In the bivalent metal ion any one or two kinds, M
3+Be trivalent metal ion Fe
3+, Al
3+Wherein any.
2. multistage hud typed structure magnetic nano catalyst according to claim 1 is characterized in that: Fe
3O
4Magnetic nano-particle is of a size of 450～500 nm, shell (M
2+) (M
3+)-LDHs thickness is 80～100 nm, and the gold nano particle size is 5～10 nm.
3. the preparation method of the described multistage core-shell structure magnetic nano catalyst of claim 1 is characterized in that, may further comprise the steps:
(1) preparation of magnetisable material
Taking by weighing 3.25 g Iron(III) chloride hexahydrates and 8.64 g sodium acetate trihydrates is dissolved in the 80 ml ethylene glycol, change in the 100 ml reactors, in 200 ℃ of crystallization 8 hours, naturally cool to room temperature, adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic, wash respectively 3～5 times with ethanol and deionized water, still adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic in the washing process, in 60～100 ℃ of dryings 12～24 hours, obtain the black powder, be designated as Fe
3O
4
(2) preparation of core-shell structure magnetic carrier
Take by weighing 1.0～3.0 g Fe
3O
4Powder is scattered in 50～100 ml methanol aqueous solutions, and ultrasonic dispersion changed in the round-bottomed flask after 5～15 minutes, stirred under room temperature; Methyl alcohol and water volume ratio V
Methyl alcohol/ V
Water=0～1;
Preparation NaOH/ Na
2CO
3Mixed ammonium/alkali solutions, wherein, NaOH is 0.1～0.2 mol/L, Na
2CO
3Be 0.05～0.10 mol/L, be designated as A liquid;
Press M
2+/ M
3+Mol ratio 2～4 takes by weighing M
2+(NO
3)
2NH
2O and M
3+(NO
3)
3NH
2O is dissolved in the 100 ml alcohol water mixed solution, is designated as B liquid; Wherein, M
2+Be Mg
2+, Ni
2+, Cu
2+In any one or two kinds, M
3+Be Fe
3+, Al
3+Wherein any; Methyl alcohol and water volume ratio V
Methyl alcohol: V
Water=0～1
Earlier the A drop is added that regulator solution pH is stable at 9～10 in the above-mentioned round-bottomed flask, then with A liquid with B liquid splashes in the above-mentioned round-bottomed flask simultaneously and keep the pH value constant in 9～10, mechanical agitation in the dropping process, B drop speed is 0.5～1.5 ml/min, after the B drop is intact round-bottomed flask is transferred in 60～100 ℃ of water-baths and continues mechanical agitation, crystallization obtained black suspension in 12～24 hours, adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic, spend deionised water 3～5 times, still adopt the ferromagnetic separation of Nd-Fe-B permanent magnetic in the washing process, obtain the black powder, called after Fe
3O
4(M
2+) (M
3+)-LDHs;
(3) preparation of multistage core-shell structure magnetic nano catalyst
With Au quality percentage composition be 0.5%～2.0% chlorauric acid solution 0.0001～0.1 M to be adjusted to pH with 0.1～0.2 mol/L NaOH solution be 8～9, add 0.5～1.0 g core-shell structure magnetic carrier Fe
3O
4(M
2+) (M
3+)-LDHs places solution 70～80 ℃ of water-bath mechanical agitation 1～3 h then, is cooled to room temperature, adopts the ferromagnetic separation of Nd-Fe-B permanent magnetic, spends deionised water, still adopts the ferromagnetic separation of Nd-Fe-B permanent magnetic in the washing process, with 0.1 mol/L AgNO
3Solution detects to there not being Cl
-Exist, in 60～100 ℃ of dryings 12～24 hours, obtain the black powder, H in the atmosphere reduction furnace then
2Following 200 ℃ of reduction 1～2 h of condition obtain the magnetic Nano Au catalyst, called after Fe
3O
4(M
2+) (M
3+)-LDHsAu.
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