CN106268950A - Has the preparation method of magnetic heteropoly acid Graphene composite catalyzing material - Google Patents
Has the preparation method of magnetic heteropoly acid Graphene composite catalyzing material Download PDFInfo
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- CN106268950A CN106268950A CN201610590391.6A CN201610590391A CN106268950A CN 106268950 A CN106268950 A CN 106268950A CN 201610590391 A CN201610590391 A CN 201610590391A CN 106268950 A CN106268950 A CN 106268950A
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- 239000000463 material Substances 0.000 title claims abstract description 55
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 38
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000012876 carrier material Substances 0.000 claims abstract description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012153 distilled water Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 7
- 238000002955 isolation Methods 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000002604 ultrasonography Methods 0.000 claims abstract description 5
- 235000013877 carbamide Nutrition 0.000 claims abstract description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 3
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims 1
- 239000001117 sulphuric acid Substances 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 3
- 230000005389 magnetism Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000696 magnetic material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000002122 magnetic nanoparticle Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- -1 polyethylene pyrrole Polymers 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
Have the preparation method of magnetic heteropoly acid Graphene composite catalyzing material, belong to chemical catalysis Material Field, carry out hydro-thermal reaction after ferrous sulfate, sodium hydroxide, polyvinylpyrrolidone and urea element being mixed with graphene solution, obtain magnetic carrier material；Under ultrasound condition, magnetic carrier material is dissolved in distilled water, is subsequently adding cetyl trimethylammonium bromide and heteropolyacid material, Magnetic Isolation after stirring, obtain solids, scrubbed, dry, obtain magnetic heteropolyacid composite catalyzing material.The inventive method is simple, and raw material is easy to get, and the magnetism of material particle morphology prepared is homogeneous, is evenly distributed, and magnetic carrier has bigger specific surface area.
Description
Technical field
The invention belongs to chemical catalysis Material Field, be specifically related to the magnetic novel heteropoly acid-Graphene of a kind of tool multiple
Close the preparation method of catalysis material.
Background technology
Along with the fast development of nanotechnology, magnetic nano-particle studied widely and physics, medical science, biology,
The aspects such as material science are widely used.Magnetic composite nanoparticles has more preferable biocompatibility relative to magnetic nano-particle
With the feature of easy functionalization and physically better and chemical property, it is more conducive to it and is widely applied.
Heteropoly acid is the one of solid acid, has the oxidation-reduction quality of uniqueness, and acid and bi-functional, in many
Learn and reaction can show the strongest catalysis activity.This green of heteropoly acid, environment-friendly type catalyst nontoxic, non-corrosive are
Through achieving successful Application in various organic reactions, such as: esterification and etherification, condensation reaction, alkylation, hydration dehydration and polymerization are anti-
Should wait, reaction presents the plurality of advantages such as reactivity is high, corrosivity is little, pollution rate is low, but due to heteropoly acid specific surface area
The problems such as little, recovery difficulty make heteropoly acid receive certain restriction in the application of catalytic field.
Graphene as a kind of new carbon, due to its high-specific surface area, easily disperses, is prone to functionalization and chemical environment
Stability high, has obtained paying close attention to widely in catalyst system and catalyzing.Catalytic applications is graphene-based composite application neck
Important research direction in territory, current graphene-based catalysis material in addition to being commonly applied to photocatalysis, electro-catalysis, its hydrogenation with
And the aspect such as oxidation there has also been large development.
Therefore, in the field of current catalysis material, it is intended to loaded by heteropoly acid is improved on suitable carrier it and compares table
Area, it is thus achieved that the efficient and catalysis material of easily separated recovery, it is achieved catalytic reaction is efficiently, recyclingization, reduction cost, carry
High usage, the always important content of research.
Summary of the invention
Preparation cost is cheap, preparation method is simple, magnetic is preferable and is prone to magnetic to it is an object of the invention to propose one
Property separate composite catalyzing material tool magnetic novel heteropoly acid-Graphene composite catalyzing material preparation method.
The present invention comprises the following steps:
1) under ultrasound condition, graphene oxide is dissolved in distilled water solution, obtains graphene solution；Then by ferrous sulfate,
Sodium hydroxide, polyvinylpyrrolidone and urea element carry out hydro-thermal reaction after mixing with graphene solution, react after terminating product
Filter, take solid phase washing, be dried, obtain magnetic carrier material；
2) sodium tungstate and zinc nitrate are mixed in distilled water carry out condensing reflux reacting by heating, after reaction terminates, filter and receive
Collection filtrate, crystallized, obtain heteropolyacid material (heteropoly acid-Na12[WZn3(ZnW9O34)2])；
3) magnetic heteropolyacid-Graphene composite catalyzing material is prepared: under ultrasound condition, magnetic carrier material is dissolved in distilled water
In, it is subsequently adding cetyl trimethylammonium bromide and heteropolyacid material, Magnetic Isolation after stirring, acquirement solids, scrubbed,
It is dried, obtains magnetic heteropolyacid composite catalyzing material.
The advantage of present invention process is: preparation method simple possible, and equipment requirements is simple, and needed raw material is easy to get, and is prepared as
This is relatively low, particularly adds cetyl trimethylammonium bromide, heteropoly acid can be made to be relatively easy to be attached on magnetic carrier.
The magnetism of material particle morphology using the inventive method to prepare is homogeneous, is evenly distributed, and magnetic carrier has bigger specific surface
Long-pending, the avtive spot that can be used to combine heteropolyacid material is more, can effectively be combined with heteropolyacid material, the most miscellaneous
Compound through with magnetic carrier of polyacid material, has good magnetic, the beneficially separation of composite catalyzing material, recovery and
Recycling.
Further, in step 1) of the present invention, described graphene oxide, ferrous sulfate, sodium hydroxide, polyethylene pyrrole
The mixing quality ratio of pyrrolidone and urea element is 1: 17: 5: 37.5: 45.Advantage is: suitably material proportion so as to get magnetic grain
Sub-size uniformity, is evenly distributed.
In described step 1), graphene oxide and distilled water mixing quality ratio are 8: 5.Under this ratio, oxidation can be made
Graphene dispersion is uniform, it is provided that the carrier of material.
Hydrothermal temperature in described step 1) is condition 180 DEG C, and the response time is 6h.This reaction temperature and time chien shih
Reaction is fully carried out, and magnetic carrier material morphology is the most uniform.
The temperature environment being dried described in described step 1) is 60 DEG C.The water in product can be preferably removed at a temperature of this
Point, the driest.
In order to obtain ideal crystal, described step 2) in, described sodium tungstate and zinc nitrate mixing quality ratio are 12.7: 3.
Described step 2) in, the temperature conditions of described reacting by heating is 85 DEG C.At this temperature, single pure crystalline substance is obtained
Body.
Described step 3) is, described magnetic carrier material, cetyl trimethylammonium bromide and the mixing of heteropolyacid material
Mass ratio is 10: 1: 30.Suitably material proportion, obtains size uniformity, the composite being evenly distributed.
In described step 3), described dry temperature environment is 60 DEG C.Moisture removal can well be removed, simultaneously at a temperature of this
Structure and the crystal formation of material can also be protected, in order to avoid damaging.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the magnetic carrier material using the present invention to prepare.
Fig. 2 is the transmission electron microscope picture of the magnetic carrier material using the present invention to prepare.
Fig. 3 is the magnetic schematic diagram of the magnetic carrier material using the present invention to prepare.
Fig. 4 is the magnetic carrier material X-ray diffractogram using the present invention to prepare.
Fig. 5 is the magnetic carrier material and magnetic heteropolyacid-Graphene composite catalyzing material using the present invention to prepare
Infrared spectrogram.
Detailed description of the invention
One, preparation technology
Embodiment 1:
1) prepare magnetic carrier material: by 40mg graphene oxide ultrasonic dissolution in 25ml distilled water solution, stir 30min,
Then the ferrous sulfate of 0.68g is joined in graphene solution, be subsequently added into sodium hydroxide 0.20g, polyvinylpyrrolidone
1.50g and urea element 1.80g.Above-mentioned solution is transferred in reactor, at 180 DEG C, carries out hydro-thermal reaction 6h, after reaction terminates
Filtering product, washing, 60 DEG C are dried and collect solid, prepare magnetic carrier material.
2) heteropoly acid-Na is prepared12[WZn3(ZnW9O34)2] material: 6.35g sodium tungstate is dissolved in 50ml distilled water,
85 DEG C of heated and stirred to being completely dissolved；1.50g zinc nitrate is dissolved in 5ml distilled water, joins in above-mentioned solution, at 85 DEG C
Lower condensing reflux reacting by heating 2h, after reaction terminates, filters and collects filtrate, waiting to be crystallized, obtain heteropolyacid material.
3) magnetic heteropolyacid-Graphene composite catalyzing material is prepared: by 20mg magnetic carrier material ultrasonic dissolution in 20ml
In distilled water, add the cetyl trimethylammonium bromide of 2mg, be subsequently added into the heteropolyacid material obtained by 60mg, stir 1h,
Then Magnetic Isolation, washing, product is dried at 60 DEG C, obtains magnetic heteropolyacid composite catalyzing material.
Embodiment 2
1) prepare magnetic carrier material: by 80mg graphene oxide ultrasonic dissolution in 50ml distilled water solution, stir 30min；
Then the ferrous sulfate of 1.36g is joined in graphene solution, be subsequently added into sodium hydroxide 0.40g, polyvinylpyrrolidone
3.00g and urea element 3.60g.Above-mentioned solution is transferred in reactor, at 180 DEG C, carries out hydro-thermal reaction 6h, after reaction terminates
Filtering product, washing, 60 DEG C are dried and collect solid, prepare magnetic carrier material.
2) heteropoly acid-Na is prepared12[WZn3(ZnW9O34)2] material: 12.70g sodium tungstate is dissolved in 100ml distilled water
In, 85 DEG C of heated and stirred to being completely dissolved；3.00g zinc nitrate is dissolved in 10ml distilled water, joins in above-mentioned solution,
Condensing reflux reacting by heating 2h at 85 DEG C, after reaction terminates, filters and collects filtrate, waiting to be crystallized, obtain heteropolyacid material.
3) magnetic heteropolyacid-Graphene composite catalyzing material is prepared: by 40mg magnetic carrier material ultrasonic dissolution in 40ml
In distilled water, add the cetyl trimethylammonium bromide of 4mg, be subsequently added into the heteropolyacid material obtained by 120mg, stirring
1h, then Magnetic Isolation, washing, product is dried at 60 DEG C, obtains magnetic heteropolyacid composite catalyzing material.
Embodiment 3
1) magnetic carrier material is prepared: by 160mg graphene oxide ultrasonic dissolution in 100ml distilled water solution, stirring
30min, then joins in graphene solution by the ferrous sulfate of 2.72g, is subsequently added into sodium hydroxide 0.80g, polyethylene pyrrole
Pyrrolidone 6.00g and urea element 7.20g.Above-mentioned solution is transferred in reactor, at 180 DEG C, carries out hydro-thermal reaction 6h, reaction
After end filtering product, washing, 60 DEG C are dried and collect solid, prepare magnetic carrier material.
2) heteropoly acid-Na is prepared12[WZn3(ZnW9O34)2] material: 25.40g sodium tungstate is dissolved in 200ml distilled water
In, 85 DEG C of heated and stirred to being completely dissolved；6.00g zinc nitrate is dissolved in 20ml distilled water, joins in above-mentioned solution,
Condensing reflux reacting by heating 2h at 85 DEG C, after reaction terminates, filters and collects filtrate, waiting to be crystallized, obtain heteropolyacid material.
3) magnetic heteropolyacid-Graphene composite catalyzing material is prepared: by 80mg magnetic carrier material ultrasonic dissolution in 80ml
In distilled water, add the cetyl trimethylammonium bromide of 8mg, be subsequently added into the heteropolyacid material obtained by 240mg, stirring
1h, then Magnetic Isolation, washing, product is dried at 60 DEG C, obtains magnetic heteropolyacid composite catalyzing material.
Two, product checking
Fig. 1 is the scanning electron microscope (SEM) photograph of the magnetic carrier material using the present invention to prepare.As seen from Figure 1: be loaded with relatively on Graphene
Many bar-shaped magnetic materials.
Fig. 2 is the transmission electron microscope picture of the magnetic carrier material using the present invention to prepare.As seen from Figure 2: load on Graphene
Magnetic material size uniformity, be evenly distributed.
Fig. 3 is the magnetic schematic diagram of the magnetic carrier material using the present invention to prepare.Fig. 3 places one piece in beaker bottom
Magnetic material, can quickly isolate magnetic carrier material from the mixture dissolved with magnetic carrier material of the present invention, it is seen that: institute
Magnetic heteropolyacid-Graphene composite catalyzing the material prepared has good Magnetic Isolation effect.
Fig. 4 is the magnetic carrier material X-ray diffractogram using the present invention to prepare.As seen from Figure 4: magnetic carrier material peak
Shape is sharp-pointed, accurately, illustrates that its crystal formation is good.
Fig. 5 is the magnetic carrier material and magnetic heteropolyacid-Graphene composite catalyzing material using the present invention to prepare
Infrared spectrogram.In Fig. 5, solid line represents the infrared spectrum spectral line of magnetic carrier material, and dotted line represents magnetic heteropolyacid-graphite
The infrared spectrum spectral line of alkene composite catalyzing material.
As seen from Figure 5: magnetic carrier material is corresponding good with magnetic heteropolyacid-Graphene composite catalyzing material goes out peak position
Good.
Claims (9)
1. have the preparation method of magnetic heteropoly acid-Graphene composite catalyzing material, it is characterised in that comprise the following steps:
1) under ultrasound condition, graphene oxide is dissolved in distilled water solution, obtains graphene solution；Then by ferrous sulfate,
Sodium hydroxide, polyvinylpyrrolidone and urea element carry out hydro-thermal reaction after mixing with graphene solution, react after terminating product
Filter, take solid phase washing, be dried, obtain magnetic carrier material；
2) sodium tungstate and zinc nitrate are mixed in distilled water carry out condensing reflux reacting by heating, after reaction terminates, filter and receive
Collection filtrate, crystallized, obtain heteropolyacid material；
3) under ultrasound condition, magnetic carrier material is dissolved in distilled water, is subsequently adding cetyl trimethylammonium bromide and miscellaneous
Polyacid material, Magnetic Isolation after stirring, obtain solids, scrubbed, dry, obtain magnetic heteropolyacid composite catalyzing material.
Preparation method the most according to claim 1, it is characterised in that in described step 1), described graphene oxide, sulphuric acid
The mixing quality ratio of ferrous iron, sodium hydroxide, polyvinylpyrrolidone and urea element is 1: 17: 5: 37.5: 45.
Preparation method the most according to claim 2, it is characterised in that in described step 1), graphene oxide and distilled water are mixed
Closing mass ratio is 8: 5.Under this ratio, graphene oxide can be made to be uniformly dispersed, it is provided that the carrier of material.
Preparation method the most according to claim 1, it is characterised in that the hydrothermal temperature in described step 1) is condition
180 DEG C, the response time is 6h.
5. according to the preparation method described in claim 1 or 2 or 3 or 4, it is characterised in that the temperature being dried described in described step 1)
Degree environment is 60 DEG C.
Preparation method the most according to claim 1, it is characterised in that described step 2) in, described sodium tungstate and zinc nitrate mix
Closing mass ratio is 12.7: 3.
7. according to the preparation method described in claim 1 or 6, it is characterised in that described step 2) in, the temperature of described reacting by heating
Degree condition is 85 DEG C.
Preparation method the most according to claim 1, it is characterised in that described step 3) is, described magnetic carrier material, ten
The mixing quality ratio of six alkyl trimethyl ammonium bromides and heteropolyacid material is 10: 1: 30.
9. according to the preparation method described in claim 1 or 8, it is characterised in that in described step 3), described dry temperature ring
Border is 60 DEG C.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106984325A (en) * | 2017-06-02 | 2017-07-28 | 扬州大学 | Two step hydrothermal preparing process of magnetic heteropolyacid graphene composite catalyst |
| CN107029723A (en) * | 2017-06-02 | 2017-08-11 | 扬州大学 | A kind of preparation method of magnetic heteropolyacid salt catalyst |
| CN107029735A (en) * | 2017-06-02 | 2017-08-11 | 扬州大学 | Has the preparation method of magnetic heteropoly acid graphene composite catalyst |
| CN107175131A (en) * | 2017-06-02 | 2017-09-19 | 扬州大学 | The method that cation modified method prepares magnetic heteropolyacid salt catalyst |
| CN110993963A (en) * | 2019-11-25 | 2020-04-10 | 河北科技大学 | Phosphomolybdic acid/reduced graphene oxide/polyaniline composite material and preparation method and application thereof |
| CN112436114A (en) * | 2020-11-16 | 2021-03-02 | 扬州大学 | Three-dimensional graphene/carbon nanotube/phosphotungstic acid/sulfur composite material, preparation method and application thereof |
| CN114813885A (en) * | 2022-04-01 | 2022-07-29 | 上海大学 | Preparation method and application of multi-channel micro-fluidic electrochemical sensing chip |
| CN115430701A (en) * | 2022-08-23 | 2022-12-06 | 西安建筑科技大学 | Magnetic oleophylic iron catalyst and method for catalytic oxidation of petroleum hydrocarbon in soil |
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