CN108620134A - A kind of preparation method of composite magnetic photochemical catalyst - Google Patents
A kind of preparation method of composite magnetic photochemical catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 48
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001338 self-assembly Methods 0.000 claims abstract description 8
- 239000000084 colloidal system Substances 0.000 claims abstract description 6
- 239000011258 core-shell material Substances 0.000 claims abstract description 6
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 6
- 238000010298 pulverizing process Methods 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 27
- 239000013207 UiO-66 Substances 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 24
- 239000002105 nanoparticle Substances 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000005642 Oleic acid Substances 0.000 claims description 7
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- -1 enuatrol Chemical compound 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 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 10
- 229940043267 rhodamine b Drugs 0.000 abstract description 10
- 238000001035 drying Methods 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 4
- 230000005389 magnetism Effects 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002122 magnetic nanoparticle Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 5
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 5
- 241000276457 Gadidae Species 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000003628 tricarboxylic acids Chemical class 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000013177 MIL-101 Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
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- 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
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Abstract
The present invention provides a kind of preparation methods of composite magnetic photochemical catalyst, first prepare Fe3O4Magnetic nanoparticle, then by Fe3O4UiO 66 is grown on particle surface, is obtained with UiO 66 as shell, Fe3O4For the Fe of core3O4@UiO 66 are core-shell structure material；Then graphene colloid is crushed in cell Ultrasonic Pulverization instrument, freeze-drying obtains carbon quantum dot colloidal sol, by carbon quantum dot colloidal sol and Fe3O4@UiO 66 are mixed, and carbon quantum dot is riveted to the 66 shell surfaces UiO by way of self assembly, and filtering, drying finally obtain CQDs@UiO 66/Fe3O4Composite magnetic photochemical catalyst.Stability is good in water for composite magnetic photochemical catalyst prepared by the present invention, and high catalytic efficiency has good degradation effect to rhodamine B under simulated solar irradiation, and do not generate secondary pollution, can be recycled using magnetism, reuses.
Description
Technical field
The invention belongs to inorganic functional material fields, are related to a kind of catalyst, and specifically a kind of composite magnetic light is urged
Agent CDs@UiO-66/Fe3O4Preparation method.
Background technology
Energy and environmental problem is two severe problems that today's society faces, and seriously constrains the development of society.
In numerous technological means, low energy consumption because of it for photocatalysis, environmental-friendly, efficient feature due to be considered as solving the energy and environment
One of most promising method of problem.Metal-organic framework material（metal-organic frameworks, MOFs）It is a kind of
The three-dimensional netted porous material formed by self assembly by metal center ion and organic ligand.Because it is with specific surface area
Greatly, the advantages that porosity is high, and stability is good, and topological structure is adjustable, thus it is widely studied separation and storage applied to gas,
Drug delivery, catalysis, the fields such as luminescent material.Currently, many MOFs, which are studied, is applied to photocatalysis field, such as MIL-101,
ZIF-8, UiO-66 etc., wherein UiO-66 because of its huge specific surface area, good stability in water and under acid or alkali environment and
It receives significant attention, still, as most of MOFs materials, the band gap of UiO-66 is wider, causes it that can only absorb and accounts for
The ultraviolet light of sunlight total amount about 5%, this makes it be limited by very large in practical applications.In fact, in solar radiation
In, infrared and near infrared radiation has accounted for 53%.Therefore, in photocatalysis, how spectral response range is widened, fully profit
There is prodigious researching value with the infrared and near infrared light in sunlight.
Recently, carbon quantum dot（CQDs）It is had received widespread attention because of its unique Upconversion luminescence, studies table
It is bright, by longer wavelengths of visible and near infrared light（500~1000nm）When excitation, CQDs can absorb and be converted into wavelength
Shorter ultraviolet light and some visible light（325~425nm）It sends out, this is enabled it to well using infrared and close in sunlight
Infrared light, moreover, it also has preferable photostability.In addition, CQDs also has some excellent physics, chemical properties, example
Such as, there are preferable dispersibility and stability in water and itself be a kind of excellent electron acceptor.These features make CQDs at
For a kind of ideal catalysis material.But the quantum efficiency of CQDs is relatively low, specific surface area is small, it is difficult to the shortcomings that recycling, limitation
Its practical application.
The problem for recycling and reusing problem and being most important in practical application of photochemical catalyst.Magnetic recovery is a kind of behaviour
It is convenient to make, simple effective method.In various magnetic nanoparticles, Fe3O4Magnetic Nano material since it has superparamagnetism,
The advantages that performance is stablized and toxic side effect is small is especially concerned.Therefore, by Fe3O4With CQDs and UiO-66 threes are compound is expected to
There is the photocatalysis that magnetic, table specific area is big, stablizes and can be responded to ultraviolet light, infrared light and near infrared light to a kind of
Agent.
A kind of MODIFIED Fe is disclosed in 10702967 A of patent CN3O4The preparation method of@MOF composite materials, but the patent
The Fe3O4@MOF composite materials are the metal mercury ions being applied in absorption industrial wastewater, are not had to its photo-catalysis capability
It makes further research.A kind of carbon quantum dot/Bi of near-infrared response is disclosed in 105771962 A of patent CN2MoO6Light
Catalyst and preparation method, the photochemical catalyst described in the patent can carry out catalysis drop under near infrared light to rhodamine B
Solution, still, catalytic efficiency is relatively low, to 10 in 10h-5The degradation rate of the rhodamine B of mol/L is 93.6%, and catalyst recycling is asked
Topic does not solve.It discloses and a kind of is synthesized with copper nano-wire assemble in situ based on UiO-66 in 107159126 A of patent CN
Composite photo-catalyst, but the catalyst can only respond ultraviolet light and less a part of visible light, and cannot fill
Divide and utilizes the major part in sunlight infrared and near infrared light.
Invention content
For the above-mentioned technical problem in prior art problem, the present invention provides a kind of systems of composite magnetic photochemical catalyst
The preparation method of Preparation Method, this composite magnetic photochemical catalyst will solve the photochemical catalyst prepared in the prior art catalysis
Technical problem ineffective, recycling is difficult and sun light utilization efficiency is not high.The it is proposed of patent innovation of the present invention is with magnetism
Ferriferrous oxide nano-particle is core, while using thioacetic acid as dressing agent, is modified in thioacetic acid by solvent-thermal method
Ferriferrous oxide nano-particle surface grows UiO-66, obtains the magnetic material of UiO-66 coated ferriferrous oxides.Then pass through
Carbon quantum dot is riveted to UiO-66 shells surface by the mode of self assembly, finally obtains CQDs@UiO-66/Fe3O4Composite magnetic light is urged
Change material.
The present invention provides a kind of preparation methods of composite magnetic photochemical catalyst, include the following steps：
1) Iron(III) chloride hexahydrate, enuatrol, oleic acid, the Iron(III) chloride hexahydrate, enuatrol, oleic acid are weighed by material ratio
Material ratio be 1mmol:6~8mmol:4 ~ 6ml, then ultrasonic mixing, cooling in 180 ~ 220 DEG C after 10 ~ 12h of back flow reaction
To room temperature, then magnetic collection, is washed with deionized, and Fe is obtained after dry3O4Nano particle；
2) Fe is weighed3O4Nano particle, trimesic acid, ZrCl4, N,N-dimethylformamide and ethyl alcohol mixture, sulfydryl second
Acid, the Fe3O4Nano particle, trimesic acid, ZrCl4, N,N-dimethylformamide and ethyl alcohol mixture, sulfydryl second
The material ratio of acid is 1g:6~10mmol：6~10mmol：60~80ml：0.1 ~ 0.2mmol, the n,N-Dimethylformamide and
Ethyl alcohol volume ratio is 1：1,20 ~ 40min of ultrasound, is then transferred to autoclave at room temperature, and 6 ~ 8h is reacted at 120 ~ 160 DEG C,
Wherein, the carboxyl and Fe in trimesic acid3O4Nano-particle coupling modification, two carboxyls form UiO- with Zr
66, it is shell, Fe to finally obtain UiO-663O4For the Fe of core3O4@UiO-66 core-shell structure copolymer composite catalysts；
3) graphene colloid is added in cell Ultrasonic Pulverization instrument, under 20 ~ 25KHz frequencies, crushes 10 ~ 20min, and carry out 10
The freeze-drying of ~ 15h obtains carbon quantum dot colloidal sol；
4) according to step 2）Gained catalyst with core-casing structure and step 3）Gained carbon quantum dot is according to mass ratio 1g:0.1 ~ 0.5g is mixed
It closes, stirs 10 ~ 14h, carbon quantum dot colloidal sol is riveted to UiO-66 shells surface by way of self assembly, filter, is dry, finally
Obtain CQDs@UiO-66/Fe3O4。
The magnetic composite photocatalyst of the present invention, which not only has sunlight, preferably to be absorbed, but also has higher carrier
Separative efficiency and photocatalysis performance.Under the irradiation of simulated solar irradiation, CQDs@UiO-66/Fe3O4Composite material is right in 2h
The degradation rate of the rhodamine B of 10mg/L reaches 95%, and can be recycled using magnetism after having reacted, and reuses, tool
There are higher actual application value and wide application prospect.The present invention is compound using CQDs and UiO-66 progress, can not only
The spectral response range of compound is widened using the Upconversion luminescence of CQDs, additionally it is possible to utilize the electronics transfer and electricity of CQDs
Sub- storage capacity improves the separative efficiency of photo-generated carrier, to bring effective promotion of photocatalysis performance.In addition, and Fe3O4It is multiple
Conjunction makes photochemical catalyst have magnetism, can carry out magnetic force recycling.
The content that detection carbon quantum dot is tested using elemental analysis is detected the content of Zr, Fe using ICP, determines Fe3O4：
UiO-66：The mass ratio of CODs is 1：1.5~2.5：0.25~1.7.
The present invention is compared with prior art, and technological progress is significant.CQDs@UiO-66/Fe of the present invention3O4Complex light
Catalyst has wider spectral response range, higher carrier separation efficiency and photocatalytic activity, and can utilize magnetic point
It from recycling, recycles, and preparation method is simple, controllability is strong, large-scale production easy to implement, is not necessarily to special installation and harshness
Condition.
Description of the drawings：
Fig. 1 is composite magnetic photochemical catalyst CQDs@UiO-66/Fe prepared by embodiment 23O4XRD diagram.
Specific implementation mode
With reference to embodiment and related chart, the present invention will be described in detail, but real the present invention is not limited to give
Example：
Embodiment 1
1) material ratio Iron(III) chloride hexahydrate is pressed：Enuatrol：Oleic acid=1mmol:6mmol:The ratio of 4ml weighs raw material and ultrasound
Mixing, in 180 DEG C after back flow reaction 10h, is cooled to room temperature, then magnetic collection, is washed with deionized, and is obtained after dry
Fe3O4Nano particle；
2) (1) obtained Fe is pressed3O4：Trimesic acid：ZrCl4：N,N-dimethylformamide/ethyl alcohol（v/v=1:1）：Sulfydryl second
Acid=1g:6mmol：6mmol：60ml：The ratio of 0.1mmol weighs Fe3O4, trimesic acid, ZrCl4, N, N- dimethyl formyls
Amine, ethyl alcohol and thioacetic acid, ultrasound 20min, is then transferred to autoclave at room temperature, reacts 6h at 120 DEG C, wherein equal benzene
A carboxyl in tricarboxylic acid and Fe3O4Nano-particle coupling modification, two carboxyls form UiO-66 with Zr, finally obtain UiO-
66 be shell, Fe3O4For the Fe of core3O4@UiO-66 are core-shell structure copolymer composite catalyst.
3) in order to further increase its visible light-responded property,（2）Gained catalyst with core-casing structure area load carbon quantum
Point.It is specific as follows：By from company's graphene colloid of the limited purchase of Ningbo Mo Xi science and technology, in Shanghai Yu Ming Instrument Ltd
In cell Ultrasonic Pulverization instrument, under 20KHz frequencies, 10min is crushed, and the freeze-drying for carrying out 10h obtains carbon quantum dot colloidal sol.
4) according to（2）Gained catalyst with core-casing structure with（3）Gained carbon quantum dot ratio 1g:0.1g is mixed, and stirs 12h,
Carbon quantum dot is riveted to UiO-66 shells surface by way of self assembly, filtering, drying finally obtain CQDs@UiO-66/
Fe3O4。
The content that detection carbon quantum dot is tested using elemental analysis is detected the content of Zr, Fe using ICP, determines Fe3O4：
UiO-66：The mass ratio of CODs is 1：1.5：0.25.
By the composite magnetic photochemical catalyst CQDs@UiO-66/Fe prepared by the present embodiment3O4, with the ratio of 0.05g/100mL
Example is added in the rhodamine B of 10mg/L, and under simulated solar irradiation irradiation, rhodamine B solution is degradable 94% in 2h.
Embodiment 2
1) material ratio Iron(III) chloride hexahydrate is pressed：Enuatrol：Oleic acid=1mmol:7mmol:The ratio of 5ml weighs raw material and ultrasound
Mixing, in 200 DEG C after back flow reaction 11h, is cooled to room temperature, then magnetic collection, is washed with deionized, and is obtained after dry
Fe3O4Nano particle；
2) (1) obtained Fe is pressed3O4：Trimesic acid：ZrCl4：N,N-dimethylformamide/ethyl alcohol（v/v=1:1）：Sulfydryl second
Acid=1g：8mmol：8mmol：70ml：The ratio of 0.15mmol weighs Fe3O4, trimesic acid, ZrCl4, N, N- dimethyl formyls
Amine, ethyl alcohol and thioacetic acid, ultrasound 30min, is then transferred to autoclave at room temperature, reacts 7h at 140 DEG C, wherein equal benzene
A carboxyl in tricarboxylic acid and Fe3O4Nano-particle coupling modification, two carboxyls form UiO-66 with Zr, finally obtain UiO-
66 be shell, Fe3O4For the Fe of core3O4@UiO-66 are core-shell structure copolymer composite catalyst.
3) in order to further increase its visible light-responded property,（2）Gained catalyst with core-casing structure area load carbon quantum
Point.It is specific as follows：By from company's graphene colloid of the limited purchase of Ningbo Mo Xi science and technology, in Shanghai Yu Ming Instrument Ltd
In cell Ultrasonic Pulverization instrument, under 23KHz frequencies, 15min is crushed, and the freeze-drying for carrying out 13h obtains carbon quantum dot colloidal sol.
4) according to（2）Gained catalyst with core-casing structure with（3）Gained carbon quantum dot ratio 1g:0.3g is mixed, and stirs 14h,
Carbon quantum dot is riveted to UiO-66 shells surface by way of self assembly, filtering, drying finally obtain CQDs@UiO-66/
Fe3O4。
The content that detection carbon quantum dot is tested using elemental analysis is detected the content of Zr, Fe using ICP, determines Fe3O4：
UiO-66：The mass ratio of CODs is 1：2：0.8
By the composite magnetic photochemical catalyst CQDs@UiO-66/Fe prepared by the present embodiment3O4, added with the ratio of 0.05g/100mL
Enter into the rhodamine B of 10mg/L, under simulated solar irradiation irradiation, rhodamine B solution is degradable 95% in 2h.
Embodiment 3
1) material ratio Iron(III) chloride hexahydrate is pressed：Enuatrol：Oleic acid=1mmol：8mmol：The ratio of 6ml weighs raw material and ultrasound
Mixing, in 220 DEG C after back flow reaction 12h, is cooled to room temperature, then magnetic collection, is washed with deionized, and is obtained after dry
Fe3O4Nano particle；
2) (1) obtained Fe is pressed3O4：Trimesic acid：ZrCl4：N,N-dimethylformamide/ethyl alcohol（v/v=1:1）：Sulfydryl second
Acid=1g：10mmol：10mmol：80ml：The ratio of 0.2mmol weighs Fe3O4, trimesic acid, ZrCl4, N, N- dimethyl methyls
Amide, ethyl alcohol and thioacetic acid, 20 ~ 40min of ultrasound, is then transferred to autoclave at room temperature, reacts 8h at 160 DEG C,
A carboxyl in middle trimesic acid and Fe3O4Nano-particle coupling modification, two carboxyls form UiO-66 with Zr, final to obtain
It is shell, Fe to UiO-663O4For the Fe of core3O4@UiO-66 are core-shell structure copolymer composite catalyst.
3) in order to further increase its visible light-responded property,（2）Gained catalyst with core-casing structure area load carbon quantum
Point.It is specific as follows：By from company's graphene colloid of the limited purchase of Ningbo Mo Xi science and technology, in Shanghai Yu Ming Instrument Ltd
In cell Ultrasonic Pulverization instrument, under 25KHz frequencies, 20min is crushed, and the freeze-drying for carrying out 15h obtains carbon quantum dot colloidal sol.
4) according to（2）Gained catalyst with core-casing structure with（3）Gained carbon quantum dot ratio 1g:0.5g is mixed, and stirs 16h,
Carbon quantum dot is riveted to UiO-66 shells surface by way of self assembly, filtering, drying finally obtain CQDs@UiO-66/
Fe3O4。
The content that detection carbon quantum dot is tested using elemental analysis is detected the content of Zr, Fe using ICP, determines Fe3O4：
UiO-66：The mass ratio of CODs is 1：2.5：1.7.
By the composite magnetic photochemical catalyst CQDs@UiO-66/Fe prepared by the present embodiment3O4, with the ratio of 0.05g/100mL
Example is added in the rhodamine B of 10mg/L, and under simulated solar irradiation irradiation, rhodamine B solution is degradable 93% in 2h.
Claims (1)
1. a kind of preparation method of composite magnetic photochemical catalyst, it is characterised in that include the following steps：
1) Iron(III) chloride hexahydrate, enuatrol, oleic acid, the Iron(III) chloride hexahydrate, enuatrol, oleic acid are weighed by material ratio
Material ratio be 1mmol:6~8mmol:4 ~ 6ml, then ultrasonic mixing, cooling in 180 ~ 220 DEG C after 10 ~ 12h of back flow reaction
To room temperature, then magnetic collection, is washed with deionized, and Fe is obtained after dry3O4Nano particle；
2) Fe is weighed3O4Nano particle, trimesic acid, ZrCl4, N,N-dimethylformamide and ethyl alcohol mixture, sulfydryl second
Acid, the Fe3O4Nano particle, trimesic acid, ZrCl4, N,N-dimethylformamide and ethyl alcohol mixture, sulfydryl second
The material ratio of acid is 1g:6~10mmol：6~10mmol：60~80ml：0.1 ~ 0.2mmol, the n,N-Dimethylformamide and
Ethyl alcohol volume ratio is 1：1,20 ~ 40min of ultrasound, is then transferred to autoclave at room temperature, and 6 ~ 8h is reacted at 120 ~ 160 DEG C,
Wherein, the carboxyl and Fe in trimesic acid3O4Nano-particle coupling modification, two carboxyls form UiO-66 with Zr,
It is shell, Fe to finally obtain UiO-663O4For the Fe of core3O4@UiO-66 core-shell structure copolymer composite catalysts；
3) graphene colloid is added in cell Ultrasonic Pulverization instrument, under 20 ~ 25KHz frequencies, crushes 10 ~ 20min, and carry out 10
The freeze-drying of ~ 15h obtains carbon quantum dot colloidal sol；
4) according to step 2）Gained catalyst with core-casing structure and step 3）Gained carbon quantum dot is according to mass ratio 1g:0.1 ~ 0.5g is mixed
It closes, stirs 10 ~ 14h, carbon quantum dot colloidal sol is riveted to UiO-66 shells surface by way of self assembly, filter, is dry, finally
Obtain CQDs@UiO-66/Fe3O4。
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