CN115155663A - Preparation method of magnetic Wells-Dawson heteropoly acid composite material - Google Patents
Preparation method of magnetic Wells-Dawson heteropoly acid composite material Download PDFInfo
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- CN115155663A CN115155663A CN202210860331.7A CN202210860331A CN115155663A CN 115155663 A CN115155663 A CN 115155663A CN 202210860331 A CN202210860331 A CN 202210860331A CN 115155663 A CN115155663 A CN 115155663A
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- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 82
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 3
- 229960002089 ferrous chloride Drugs 0.000 claims abstract description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000005185 salting out Methods 0.000 claims description 2
- 238000004873 anchoring Methods 0.000 claims 1
- 239000013460 polyoxometalate Substances 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 abstract description 7
- 229940043267 rhodamine b Drugs 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- -1 ammonium ions Chemical class 0.000 abstract description 3
- 238000000975 co-precipitation Methods 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- VFQXVTODMYMSMJ-UHFFFAOYSA-N isonicotinamide Chemical compound NC(=O)C1=CC=NC=C1 VFQXVTODMYMSMJ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012876 carrier material Substances 0.000 abstract description 2
- 229920000447 polyanionic polymer Polymers 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 12
- 238000004064 recycling Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 239000002122 magnetic nanoparticle Substances 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000001907 polarising light microscopy Methods 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- BQFYGYJPBUKISI-UHFFFAOYSA-N potassium;oxido(dioxo)vanadium Chemical compound [K+].[O-][V](=O)=O BQFYGYJPBUKISI-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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- B01J35/33—
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- B01J35/39—
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- B01J35/61—
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a preparation method of a magnetic Wells-Dawson heteropoly acid composite material, belonging to the field of photocatalytic organic wastewater; the method mixes Polyoxometallate (POMs) and concentrated phosphoric acid according to a certain proportion in a high-temperature environment to prepare a Well-Dawson type heteropoly acid; by coprecipitation, ferric chloride, ferrous chloride hydrate crystal and ammonia water are reactedTo produce magnetic Fe 3 O 4 Material using TPI (N- [3- (triethoxysilyl) -propyl)]Isonicotinamide) pair of generated magnetic Fe 3 O 4 Modifying the material to obtain pyridine function modified magnetic Fe 3 O 4 Carrier (TPI-Fe) 3 O 4 ) (ii) a And fully mixing the pyridine functionalized magnetic carrier with Wells-Dawson type heteropoly acid, and attaching the pyridine functionalized magnetic carrier to the carrier through the reaction of the pyridine functionalized magnetic carrier material and the Well-Dawson type heteropoly acid and the interaction of ammonium ions and heteropoly acid polyanions to obtain the magnetic Well-Dawson heteropoly acid composite material. The degradation rate of the composite material to rhodamine B can reach 85% when the composite material is placed in a natural light irradiation environment, and the composite material is easy to recycle.
Description
Technical Field
The heteropoly acid is formed by heteroatoms (such as P, si, fe, co and the like) and polyatomic atoms (Mo, W, V, nb, ta and the like) through a certain structure according to a peroxy atom coordination bridging effect, is essentially protonic acid with uniform strength, has the characteristics of high acid strength, excellent catalytic activity, good oxidation-reduction property and the like, and can be used as a novel multifunctional catalyst in practical application. However, since the surface area of heteropoly-acid is relatively small, the access of active sites is hindered, and high solubility in aqueous solution is inconvenient for recycling and reuse, resulting in limited applications thereof.
Background
The magnetic nano-particle material has the main characteristics of large specific surface area, good dispersibility, easy surface modification and the like, is widely applied to the medical field, and is researched by the catalysis field in recent times due to the special advantage of easy recovery of magnetism. CN101733148B proposes a magnetic heteropoly acid catalyst, which not only maintains the specific catalytic ability of heteropoly acid, but also introduces the characteristics of small particle size, good dispersibility and the like of magnetic nanoparticles, but the catalyst is used for catalyzing Friedel-crafts reaction and limits the application thereof. CN109225288A describes a preparation method of a magnetic nano phosphotungstic heteropoly acid ionic liquid loaded silica composite material, and the synthesis of the magnetic nano silica composite material is carried out by a solid phase ball milling method. The addition of phosphotungstic acid effectively improves the desulfurization rate of oil products, but the technical reaction system is complex, the intermediate product is difficult to control, and the stability of the catalyst is influenced.
The heteropoly acid can be divided into six classical structure types such as Keggin, dawson, silverton, anderson, waugh, lindqvist and the like according to ions contained in the heteropoly acid. Among them, keggin type heteropoly acid is the most fully studied and is the only commercial heteropoly acid. Among them, the research on the Keggin-type heteropoly acid is the most systematic and intensive, and the Keggin-type heteropoly acid is the only relevant substance for realizing commercialization. Research on the Dawson type heteropoly acid shows that the Dawson type heteropoly acid has a more stable structure, higher catalytic activity, more excellent oxidation property and regenerationThe speed is faster. The method develops related research on the application of Dawson type heteropoly acid in the directions of industrial production, environmental energy conservation and the like, and has very important significance for the current industrial development and research application. The invention provides magnetic Fe coated on the basis of amino-propyl modified silicon dioxide 3 O 4 The preparation method of the catalytic material generated by the interaction of the nano particles and the Wells-Dawson heteropoly acid is used as a photocatalyst for treating organic pollutants, and the application field of the magnetic heteropoly acid material is expanded.
Disclosure of Invention
The invention aims to solve the current situations that the Dawson type heteropoly acid is difficult to synthesize and difficult to recover, and the primary purpose is to provide a magnetic Wells-Dawson heteropoly acid composite catalyst which is green and environment-friendly, low in cost, simple in preparation method, easy in magnetic recovery and recyclable.
In order to achieve the purpose, the invention is realized by the following technical scheme, which comprises the following steps:
(1) Polyoxometallate (POMs) and concentrated phosphoric acid solution are fully mixed to react by self to generate the Well-Dawson type heteropoly acid.
(2) Magnetic ferroferric oxide nano material is obtained by coprecipitation method, and TPI (N- [3- (triethoxysilyl) -propyl) is used]Isonicotinamide) is used for modifying the obtained magnetic ferroferric oxide nano material to obtain a pyridine functionalized magnetic carrier material (TPI-Fe) 3 O 4 ）。
(3) Self-made TPI-Fe 3 O 4 The magnetic carrier is dispersed in Wells-Dawson type heteropoly acid, and the heteropoly acid is successfully coated on the magnetic carrier by utilizing the mutual reaction between the magnetic ferroferric oxide carrier and the heteropoly acid and the mutual action between ammonium ions and polyanions in the heteropoly acid to obtain the magnetic Wells-Dawson heteropoly acid composite material.
(4) The prepared magnetic Well-Daswon heteropoly acid composite material can be used as an efficient catalyst to realize photocatalytic degradation of rhodamine B solution.
The purpose of the invention is realized by the following technical scheme: the method mainly comprises the following steps:
1) Weighing FeCl according to the mass ratio of 3 3 ·6H 2 O and FeCl 2 ·4H 2 O in 150mL deionized water, and in N 2 Strongly stirring for 15-30 min under the condition, and then selecting NH with the mass fraction of 32% 3 ·H 2 Dripping 10-30 mL of O solution into a mixed solution of ferric chloride and ferrous chloride drop by drop, and stirring for 60 min to obtain a black product;
2) Separating the black product obtained in the step 1) by using a magnet, washing the black product by using 0.1mol/L NaCl solution, absolute ethyl alcohol and deionized water respectively until the pH value is =7, and drying the black product in vacuum to obtain the magnetic Fe 3 O 4 Particles;
3) Taking the magnetic Fe prepared in the step 2) 3 O 4 Adding 1.0 g-3.5 g of particles into 70 mL of toluene, uniformly stirring for 70min, dropwise adding 3-10mL of TPI, refluxing for 24 h, filtering to remove black solids, washing with toluene, ethanol and deionized water for 3 times, drying at normal temperature to constant weight to obtain the pyridine functionalized TPI-Fe 3 O 4 The magnetic composite material is stored for later use;
4) Fully mixing 12 g-20 g POMS and 15 mL-30 mL deionized water until the mixture is dissolved to prepare solution
5) Heating the polyoxometallate solution prepared in the step 4), adding 10-15 mL of 85% concentrated phosphoric acid solution into the mixed solution after the polyoxometallate solution is boiled, fully stirring the mixture to uniformly mix the polyoxometallate solution and the mixed solution, continuously keeping boiling in a reflux device for 6-10 hours, and naturally cooling to room temperature;
6) Adding KCl particles into the solution in the step 5) to ensure that the solution is subjected to salting-out reaction crystallization to generate a precipitate;
7) Recrystallizing and purifying the precipitate obtained in the step 6), cooling for 24 hours at the temperature of 5 ℃, filtering and washing, and then drying for 8-10 hours in vacuum to obtain alpha/beta-isomer polymetallic salt;
8) Dissolving the alpha/beta-isomer polymetallic salt in the step 7) in 37% concentrated hydrochloric acid, extracting the mixed solution by using diethyl ether, and recrystallizing in water to obtain yellow crystals, namely Well-Dawson heteropoly acid;
9) Weighing the TPI-Fe self-made in the step 3) 3 O 4 0.5-3.0 g of magnetic composite material, 0.3-1.2 g of Wells-Dawson heteropoly acid in the step 8), and fully mixing with 50mL of methanol solution, and refluxing for 3 h;
10 Taking methanol as a solvent, filtering and extracting the refluxed mixed solution in the step 9) in a Soxhlet extractor for 12 hours, and drying in a vacuum oven at 105 ℃ to obtain the magnetic Wells-Dawson heteropoly acid composite material with good catalytic performance.
Wherein, the polyoxometallate in the step 1) is preferably sodium tungstate (Na) 2 WO 4 ) Potassium tungstate (K) 2 WO 4 ) Calcium tungstate (CaWO) 4 ) Sodium molybdate (Na) 2 MoO 4 ) Potassium molybdate (K) 2 MoO 4 ) Calcium molybdate (CaMoO) 4 ) Sodium vanadate (Na) 3 VO 4 ) Potassium vanadate (K) 3 VO 4 ) One or more of (a); in the step 5), adding deionized water at any time during the reflux reaction period, so that the total volume of the solution is kept at 30mL; said TPI (N- [3- (triethoxysilyl) -propyl) in said step 3)]Isonicotinamide) functions as a linking agent, and can anchor the Wells-Dawson type heteropoly acid in the step 8) to the functionalized TPI-Fe in a covalent bond mode 3 O 4 On the magnetic composite material.
The invention has the beneficial effects that:
1. the invention relates to functional TPI-Fe prepared by a coprecipitation method 3 O 4 The magnetic material is a carrier, has large specific surface area, TPI plays the role of a connecting agent, and the heteropoly acid is anchored on the carrier in a covalent bond form, so that the catalytic activity of the Wells-Dawson type heteropoly acid is retained, the supermagnetism is convenient to recycle, and the reaction cost is reduced.
2. The invention provides a preparation method of a magnetic Wells-Dawson heteropoly acid composite material, which has the advantages of simple synthesis process, simple equipment requirement, easily obtained raw materials, low cost, better photocatalysis effect under the same conditions, simple and convenient recovery method and high recycling rate, and overcomes the problems of difficult synthesis, difficult recovery and the like of the Dawson heteropoly acid.
Drawings
FIG. 1 is a diagram of the preparation steps of a magnetic Wells-Dawson heteropoly acid composite material;
FIG. 2 is a reaction equation diagram of a magnetic Wells-Dawson heteropoly acid composite material;
FIG. 3 shows TPI-Fe 3 O 4 Scanning electron microscope images of the materials;
FIG. 4 shows TPI-Fe 3 O 4 A material magnetic test pattern;
FIG. 5 is an X-ray diffraction pattern of a magnetic Wells-Dawson heteropolyacid composite;
FIG. 6 is an infrared spectrum of a magnetic Wells-Dawson heteropoly acid composite;
FIG. 7 is a schematic view of a photocatalytic reaction apparatus;
FIG. 8 is a data diagram of photocatalytic rhodamine B of the magnetic Wells-Dawson heteropoly acid composite material.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, which obviously are some, but not all, of the embodiments of the present invention; all other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to the attached figures 1-8, the preparation process of the magnetic Wells-Dawson heteropoly acid composite material is as follows:
example 1:
1) Preparation of Wells-Dawson heteropoly acid material:
mixing 12.5 g sodium tungstate (Na) 2 WO 4 ) Fully mixing the mixture with 15mL of deionized water to prepare a solution, heating the solution to boiling, adding 10mL of concentrated phosphoric acid (85 mass percent), mixing, continuously keeping boiling in a reflux device for 7 hours, and naturally cooling to room temperature; then adding KCl particles to generate yellow precipitate; precipitating, recrystallizing, purifying the obtained yellow precipitate, cooling at 5 deg.C for 24 hr, filtering, washing, and vacuum dryingDrying for 8 hours until the solid matter has constant weight to obtain alpha/beta-isomer polymetallic salt; dissolving alpha/beta-isomer polymetallic salt in 37% concentrated hydrochloric acid, extracting with diethyl ether, and recrystallizing in water to obtain yellow crystal, namely Wells-Dawson heteropoly acid.
2) Preparation of magnetic Fe 3 O 4 Particles
6.6g of FeCl were weighed out separately 3 ·6H 2 O and 4.4g FeCl 2 ·4H 2 O in a beaker, add 150mL of deionized water after 2 Stirring vigorously for 15 min, taking NH with the content of 32% 3 ·H 2 Adding 18 mL of O solution dropwise into the mixed black solution, stirring strongly for 60 min, separating the components of the solution by using a magnet, washing the solution by using 0.1mol/L NaCl solution, absolute ethyl alcohol and deionized water until the pH value is =7, and drying in vacuum to obtain magnetic Fe 3 O 4 Particles.
3) Preparation of pyridine functionalized TPI-Fe 3 O 4 Magnetic composite material
Placing 1.2 g of magnetic ferroferric oxide particles in 70 mL of toluene, stirring for 70min, dropwise adding 7 mL of TPI into the mixed solution, refluxing for 24 h, filtering to remove black solids, washing with toluene, ethanol and deionized water for 3 times, drying at room temperature to obtain pyridine functionalized TPI-Fe 3 O 4 A magnetic composite material.
4) And preparing the magnetic Wells-Dawson heteropoly acid composite material.
Weighing self-made TPI-Fe 3 O 4 1.2 g of magnetic composite material, 0.5 g of Wells-Dawson heteropoly acid, and 50mL of methanol solution are fully mixed, refluxed for 3 hours, filtered and extracted for 12 hours in a Soxhlet extractor by taking methanol as a solvent, and dried in a vacuum oven at 105 ℃ to obtain the magnetic Wells-Dawson heteropoly acid composite material with good catalytic performance.
Example 2:
1) Preparation of Wells-Dawson heteropoly acid material:
18 g of sodium tungstate (Na) 2 WO 4 ) Stirring thoroughly in 25 mL deionized water until completely dissolved, heating to boil, and adding 15mL concentrated phosphoric acid(s) ((R))85 mass percent), continuously keeping boiling in a reflux device for 10 hours, and naturally cooling to room temperature; subsequently, KCl particles are added to generate yellow precipitates; recrystallizing and purifying the precipitate, cooling for 24 h at 5 ℃, filtering and washing, and drying the filtered substance for 8 h in a vacuum environment to obtain alpha/beta-isomer polymetallic salt for later use; dissolving alpha/beta-isomer polymetallic salt in 37% concentrated hydrochloric acid, extracting with diethyl ether, and recrystallizing in water to obtain yellow crystal, namely Wells-Dawson heteropoly acid.
2) Preparation of magnetic Fe 3 O 4 Particles
Separately weighing 4g of FeCl 3 ·6H 2 O and 4.7g FeCl 2 ·4H 2 O in a beaker, then 150mL of deionized water was added in N 2 Stirring vigorously for 15 min, taking NH with the content of 32% 3 ·H 2 Adding 18 mL of O solution dropwise into the mixed black solution, strongly stirring for 60 min, separating the components of the solution by using a magnet, washing the solution by using 0.1mol/L NaCl solution, absolute ethyl alcohol and deionized water until the pH value is =7, and drying the solution in vacuum to obtain magnetic Fe 3 O 4 Particles.
3) Preparation of pyridine functionalized TPI-Fe 3 O 4 Magnetic composite material
Placing 3.3 g of magnetic ferroferric oxide particles in 70 mL of toluene, stirring for 70min, dropwise adding 10mL of TPI into the mixed solution, refluxing for 24 h, filtering to remove black solids, washing for 3 times by using toluene, ethanol and deionized water respectively, and drying at room temperature to obtain the pyridine functionalized TPI-Fe 3 O 4 A magnetic composite material;
4) And preparing the magnetic Wells-Dawson heteropoly acid composite material.
Weighing self-made TPI-Fe 3 O 4 2.8 g of magnetic composite material, 1.2 g of Wells-Dawson heteropoly acid and 50mL of methanol solution are fully mixed, and after refluxing for 3 h, methanol is used as a solvent, and after filtration and extraction are carried out for 12 h in a Soxhlet extractor, the mixture is dried in a vacuum oven at 105 ℃ to obtain the magnetic Wells-Dawson heteropoly acid composite material with good catalytic performance.
2. Catalytic performance test and characterization of magnetic Wells-Dawson heteropolyacid catalyst
FIG. 2 is a reaction equation diagram of the magnetic Wells-Dawson heteropoly acid composite material, and it can be known from FIG. 2 that the proposed preparation method is feasible from the analysis of chemical reaction mechanism. FIG. 3 shows TPI-Fe 3 O 4 Transmission electron micrograph of the material, TPI-Fe from FIG. 3 3 O 4 The particles exhibited a morphology having a hemispherical shape with an average diameter of about 10 nm. FIG. 4 is a view of self-made TPI-Fe 3 O 4 As can be seen from the graph, when an external magnetic field is added, the magnetic composite material can be quickly separated from the solution under the environment of the external magnetic field, and after standing for 3 min, the powder can be attached to the wall of the test tube to clarify the aqueous solution, which indicates that the TPI-Fe prepared by the method 3 O 4 The dispersibility and the magnetic response performance of the particles in water are very good, and the magnetic composite material can be fully separated and recycled by an external magnetic field for recycling. FIG. 5 is an X-ray diffraction diagram of magnetic Wells-Dawson heteropoly acid composite material, wherein a is magnetic Wells-Dawson heteropoly acid composite material, and b is TPI-Fe 3 O 4 The material c is synthesized Wells-Dawson heteropoly acid; as can be seen in FIG. 5, the magnetic TPI-Fe 3 O 4 The peak shape of the composite material is sharp, which indicates that Fe 3 O 4 The core particles can be well reserved under the action of TPI, and TPI-Fe is reserved in the curve of the magnetic Wells-Dawson heteropoly acid composite material 3 O 4 Diffraction peaks but no obvious diffraction peak of Wells-Dawson heteropoly acid, which indicates that Wells-Dawson heteropoly acid is uniformly loaded on TPI-Fe 3 O 4 On the magnetic material. FIG. 6 is an infrared spectrum of a magnetic Wells-Dawson heteropoly acid composite material, wherein a is a synthesized Wells-Dawson heteropoly acid and b is TPI-Fe 3 O 4 The material c is a magnetic Wells-Dawson heteropoly acid composite material; as can be seen from FIG. 6, at 1030 cm -1 The appearance of a weak shoulder, which confirms TPI-modified Fe 3 O 4 Strong interaction with heteropoly acids; at 800-1000 cm -1 The characteristic absorption peak band of the Wells-Dawson structure is observed regionally, and the Wells-Dawson heteropoly acid is proved to be loaded on TPI-Fe 3 O 4 On the surface.
FIG. 7 is a diagram of photocatalytic degradation of magnetic Wells-Dawson heteropoly acid composite material to rhodamine B, wherein a-d are respectively catalyst-free and TPI-Fe 3 O 4 The material, the Wells-Dawson heteropoly acid and the magnetic Wells-Dawson heteropoly acid composite material; as can be seen from the graph 7, under the same conditions, the magnetic Well-Dawson heteropoly acid composite material has an obvious degradation effect on rhodamine B due to excellent photocatalysis, when the reaction time is 100 min, the magnetic Well-Dawson heteropoly acid composite material can degrade the rhodamine B solution by 85%, the degradation effect is obviously higher than that of a corresponding single hybrid polyacid catalyst, and the magnetism of the magnetic Well-Dawson heteropoly acid composite material can be utilized for recycling. FIG. 8 is a graph showing the recycling of a magnetic Wells-Dawson heteropoly acid composite material, and it can be seen from the graph that the degradation rate of the catalyst in the recycling of rhodamine B is studied, and after the catalyst is recycled for three times, although the degradation capability of the catalyst is reduced along with the increase of the recycling times, the degradation rate can still reach more than 60% when the catalyst is irradiated for 120 min, which shows that the magnetic Well-Dawson heteropoly acid composite material still has good photocatalytic activity after being recycled for many times, and proves that the material of the invention is easy to recycle magnetically.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (4)
1. A preparation method of a magnetic Wells-Dawson heteropoly acid composite material is characterized by comprising the following steps:
1) Weighing FeCl according to the mass ratio of 3 3 ·6H 2 O and FeCl 2 ·4H 2 O in 150mL deionized water and N 2 Selecting 32% by weight after strong stirring for 15-30 minNH 3 ·H 2 10-30 mL of O solution, dropwise adding the O solution into the mixed solution of ferric chloride and ferrous chloride, and stirring for 60 min to obtain a black product;
2) Separating the black product obtained in the step 1) by using a magnet, respectively washing the black product with 0.1mol/L NaCl solution, absolute ethyl alcohol and deionized water until the pH value is =7, and drying the black product in vacuum to obtain the magnetic Fe 3 O 4 Particles;
3) Taking the magnetic Fe prepared in the step 2) 3 O 4 Adding 1.0 g-3.5 g of particles into 70 mL of toluene, uniformly stirring for 70min, dropwise adding 3-10mL of TPI, refluxing for 24 h, filtering to remove black solids, washing with toluene, ethanol and deionized water for 3 times, and drying at normal temperature to constant weight to obtain the pyridine functionalized TPI-Fe 3 O 4 The magnetic composite material is stored for later use;
4) Fully mixing 12 g-20 g of POMS and 15 mL-30 mL of deionized water until the POMS and the deionized water are dissolved to prepare a solution;
5) Heating the solution prepared in the step 4), adding 10-15 mL of concentrated phosphoric acid solution with the concentration of 85% into the mixed solution after the solution is boiled, fully stirring the solution and the mixed solution to uniformly mix the solution and the mixed solution, continuously keeping boiling in a reflux device for 6-10 h, and naturally cooling to room temperature;
6) Adding KCl particles into the solution in the step 5) so as to enable the solution to be subjected to salting-out reaction crystallization to generate precipitates;
7) Recrystallizing and purifying the precipitate obtained in the step 6), cooling at 5 ℃ for 24 h, filtering and washing, and then vacuum drying for 8-10 h to obtain alpha/beta-isomer polymetallic salt;
8) Dissolving the alpha/beta-isomer polymetallic salt obtained in the step 7) in 37% concentrated hydrochloric acid, extracting the mixed solution by using diethyl ether, and recrystallizing in water to obtain a yellow crystal, namely the Well-Dawson heteropoly acid;
9) Weighing the TPI-Fe self-made in the step 3) 3 O 4 0.5-3.0 g of magnetic composite material, 0.3-1.2 g of Wells-Dawson heteropoly acid in the step 8), and fully mixing with 50mL of methanol solution, and refluxing for 3 h;
10 Using methanol as a solvent, filtering and extracting the refluxed mixed solution in the step 9) in a Soxhlet extractor for 12 hours, and drying in a vacuum oven at 105 ℃ to obtain the magnetic Wells-Dawson heteropoly acid composite material with good catalytic performance.
2. The method according to claim 1, wherein the polyoxometalate in the step 4) is Na 2 WO 4 、K 2 WO 4 、CaWO 4 、Na 2 MoO 4 、K 2 MoO 4 、CaMoO 4 、Na 3 VO 4 、K 3 VO 4 One or more of (a).
3. The method according to claim 1, wherein deionized water is added at any time during the reflux reaction in the step 5) so that the total volume of the solution is maintained at 30mL.
4. The method of claim 1, wherein the TPI of step 3) functions as a linking agent for covalently anchoring the Wells-Dawson type heteropoly acid of step 8) to the functionalized TPI-Fe 3 O 4 On a magnetic composite material.
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