CN107029785A - A kind of multiplex catalyst RhB/B12PIL/rGO and its preparation method and application - Google Patents
A kind of multiplex catalyst RhB/B12PIL/rGO and its preparation method and application Download PDFInfo
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- CN107029785A CN107029785A CN201710395347.4A CN201710395347A CN107029785A CN 107029785 A CN107029785 A CN 107029785A CN 201710395347 A CN201710395347 A CN 201710395347A CN 107029785 A CN107029785 A CN 107029785A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 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 claims abstract description 48
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002608 ionic liquid Substances 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 10
- 239000006228 supernatant Substances 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 9
- 229910001868 water Inorganic materials 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 230000003287 optical effect Effects 0.000 claims abstract description 6
- 238000005342 ion exchange Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- 238000006392 deoxygenation reaction Methods 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical class C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 3
- -1 halogen Amine Chemical class 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- UVQPDGXQIPNYNU-UHFFFAOYSA-N 1-ethenyl-3-ethyl-2h-imidazole Chemical class CCN1CN(C=C)C=C1 UVQPDGXQIPNYNU-UHFFFAOYSA-N 0.000 claims 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical class ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 150000001867 cobalamins Chemical class 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000009881 electrostatic interaction Effects 0.000 description 3
- JVRWQHCUISDRGA-UHFFFAOYSA-N 1-ethenyl-3-ethyl-1,2-dihydroimidazol-1-ium;bromide Chemical class [Br-].CCN1C[NH+](C=C)C=C1 JVRWQHCUISDRGA-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002896 organic halogen compounds Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000011715 vitamin B12 Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012360 testing method Methods 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
- 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
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
- B01J31/0294—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by polar or ionic interaction with the substrate, e.g. glass
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- 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
- B01J35/39—Photocatalytic properties
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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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
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Abstract
The present invention relates to a kind of multiplex catalyst RhB/B12PIL/rGO and its preparation method and application.The technical scheme of use is：Graphene oxide (GO) reduction is obtained into compound PIL/rGO first in the presence of polymeric ionic liquid (PIL), then using ion-exchange reactions by carboxyl B12It is immobilized to arrive PIL/rGO sheet surfaces, prepare compound B12‑PIL/rGO.Compound obtained above and rhodamine B (RhB) are dispersed in water stirring at normal temperature 1h again, centrifuged, solid is colourless to supernatant with deionized water cyclic washing, is dried in vacuo to obtain target product.Multiplex catalyst RhB/B prepared by the present invention12PIL/rGO can under visible optical drive efficient degradation organic halogen.
Description
Technical field
The invention belongs to catalyst material field, more particularly to it is a kind of graphene-based compound with visible light catalysis activity
Catalyst and its preparation method and application.
Background technology
In recent years, vitamin B12Derivative is due to abundant redox property and Coordination Properties, in catalysis
Field is used as a kind of efficient photochemical catalyst, and the research for the immobilized and catalytic performance of such compound has obtained chemistry
The extensive concern of researcher.Graphene has good electric conductivity and big specific surface area, can both make in photocatalytic system
For catalyst carrier, again can as electronics transmission body.Therefore, with vitamin B12Based on derivative, construct efficient, green
Color, cheap visible light catalytic dehalogenation system, use it for processing halogenated organic solvent waste liquid and remain in organic in soil
Halo agricultural chemicals, will be with a wide range of applications in catalytic field.
The content of the invention
In order to solve the above-mentioned technical problem, it is an object of the invention to provide a kind of multiplex catalyst RhB/B12-PIL/
RGO, by catalyst B12Derivative and sensitising agent rhodamine B (RhB) are while be immobilized on redox graphene (rGO) lamella table
Face, prepares multiplex catalyst RhB/B12- PIL/rGO, the composite catalyst can be used for processing halogenated organic solvent waste liquid
And the halogenated organic agricultural chemicals remained in soil, have wide practical use in catalytic field.
To achieve the above object, the technical solution adopted by the present invention is：A kind of multiplex catalyst RhB/B12-PIL/
RGO, preparation method comprises the following steps：In the presence of polymeric ionic liquid PIL, graphene oxide GO is reduced, is combined
Thing PIL/rGO；Then ion-exchange reactions is utilized, by carboxyl B12It is immobilized to arrive PIL/rGO sheet surfaces, prepare compound
B12-PIL/rGO；Again by obtained compound B12- PIL/rGO and rhodamine B are scattered in deionized water, stirring at normal temperature, from
The heart, solid is colourless to supernatant with deionized water cyclic washing, vacuum drying, obtains target product.
A kind of above-mentioned multiplex catalyst RhB/B12- PIL/rGO, takes graphene oxide GO, ultrasonic disperse in go from
In sub- water, polymeric ionic liquid PIL and hydrazine hydrate are added thereto, mixture reacts 12h at 95 DEG C, centrifuge, spend successively
Ionized water and ethanol washing, vacuum drying, obtain compound PIL/rGO.
A kind of upper described multiplex catalyst RhB/B12- PIL/rGO, described polymeric ionic liquid PIL preparation
Method is：Take and bromoethane is added dropwise under 1- vinyl imidazoles, magnetic agitation, reacted at 70 DEG C after 24h, mixture is dissolved in second
Nitrile, is precipitated with ethyl acetate, vacuum drying, obtains product 3- ethyl -1- vinyl imidazole bromides；Then 3- ethyl -1- ethene is taken
Base imidazoles bromide and azodiisobutyronitrile are dissolved in chloroform, are passed through after nitrogen deoxygenation, under nitrogen protection back flow reaction 8h, are used chlorine
Imitative washing, vacuum drying obtains product polymeric ionic liquid PIL.
A kind of above-mentioned multiplex catalyst RhB/B12- PIL/rGO, by compound PIL/rGO ultrasonic disperses in go from
In sub- water, B is added thereto1212h is stirred at room temperature in derivative, mixture, centrifugation, be washed with deionized it is colourless to supernatant,
Vacuum drying, obtains compound B12-PIL/rGO。
A kind of above-mentioned multiplex catalyst RhB/B12- PIL/rGO, described B12Derivative is [(CN) (H2O)Cob
(III)7COOH]Cl。
A kind of upper described multiplex catalyst RhB/B12- PIL/rGO, by rhodamine B and compound B12-PIL/rGO
Ultrasonic disperse is in deionized water, normal-temperature reaction, mixture stirring 1h, centrifugation, be washed with deionized it is colourless to supernatant, very
Sky is dried, and obtains multiplex catalyst RhB/B12-PIL/rGO。
It is a further object of the present invention to provide a kind of multiplex catalyst RhB/B12- PIL/rGO is under visible optical drive
Application in degraded organic halogen.Method is as follows：Under normal temperature, above-mentioned multiplex catalyst RhB/B is weighed12-PIL/
RGO, ultrasonic disperse adds triethanolamine in the methanol solution containing organic halogen, and stirring, reaction solution is passed through nitrogen and removed
Oxygen, the lower radiation of visible light of nitrogen protection.It is preferred that, described organic halogen is double (the 4- chlorphenyls) -1 of 2,2-, 1,1- trichlorine
Ethane (DDT).
The present invention, by vitamin B12Derivative and rhodamine B are successively made by ion exchange, electrostatic interaction and π-π
With immobilized redox graphene (PIL/rGO) material surface modified to polymeric ionic liquid.
The present invention, by GO through hydrazine hydrate reduction be rGO, while polymeric ionic liquid electrostatic interaction and π-π effect under repair
RGO surfaces are adornd, PIL/rGO is obtained, then by ion exchange by vitamin B12Derivative is immobilized to arrive PIL/rGO lamellas
Surface, obtains compound B12- PIL/rGO, finally arrives compound B by electrostatic interaction and π-π effects by RhB modifications again12-
PIL/rGO surface, obtains new multicomponent composite catalyst RhB/B12- PIL/rGO, the composite catalyst can be in visible optical drive
Lower efficient degradation organohalogen compounds.
The beneficial effects of the invention are as follows：
1st, the present invention has obtained a kind of new multicomponent composite catalyst RhB/B12-PIL/rGO。
2nd, the composite catalyst prepared by the present invention has catalysis and good electric transmission function concurrently.
3rd, the composite catalyst prepared by the present invention is catalyzed organohalogen compounds degraded field under visible optical drive and had very well
Application prospect.
Brief description of the drawings
Fig. 1 is RhB/B12- PIL/rGO synthetic route chart.
Fig. 2 is rGO, B12-PIL/rGO、RhB/B12- PIL/rGO, vitamin B12Derivative and RhB ultraviolet-visible are inhaled
Receive spectrogram.
Fig. 3 is rGO and RhB/B12- PIL/rGO X-ray powder diffraction figure.
Fig. 4 is photocatalytic degradation DDT reaction equation.
Embodiment
The multiplex catalyst RhB/B of embodiment 112-PIL/rGO
(1) preparation method is as follows
1st, polymeric ionic liquid PIL (Poly (ViEtIm+Br-)) synthesis
Weigh 1- vinyl imidazoles (1.38g, 13mmol), be slowly added dropwise under magnetic stirring bromoethane (1.4g,
15mmol).24h is reacted at 70 DEG C, gained mixture is dissolved in 10mL acetonitrile, then is sunk with 30mL ethyl acetate
Shallow lake is come out, and gained material is dried in vacuo to obtain into product 3- ethyl -1- vinyl imidazole bromides.By obtained 3- ethyl -1- ethene
Base imidazoles bromide (2.0g, 9.8mmol) and azodiisobutyronitrile (0.02g, 2wt%) mixing are dissolved in 25mL chloroform, and are led to
Enter nitrogen deoxygenation 0.5h, flow back 8h under nitrogen protection, then with chloroform three times, 10mL is used every time.By gained material vacuum
Dry final product polymeric ionic liquid PIL (Poly (ViEtIm+Br-))。
2nd, the synthesis of polymeric ionic liquid modification redox graphene (PIL/rGO)
Graphene oxide (GO) (100mg) is taken, by its ultrasonic disperse in 100mL deionized water, is added thereto poly-
Close ionic liquid PIL (Poly (ViEtIm+Br-)) (1g) and hydrazine hydrate (0.2ml).Mixture reacts 12h at 95 DEG C, then
Gained mixture is centrifuged, is washed with deionized three times, it is therefore an objective to unnecessary Poly (ViEtIm are removed+Br-) and hydrazine hydrate,
Washed again with ethanol after three times, gained solid is dried in vacuo, obtain compound PIL/rGO.
3、B12Modify rGO compounds (B12- PIL/rGO) preparation
PIL/rGO (50mg) is taken, by its ultrasonic disperse in 30mL deionized water, then B is added thereto12Derivative
([(CN)(H2O) Cob (III) 7COOH] Cl) (30mg), 12h is stirred at room temperature in mixture, centrifuges, be washed with deionized to
Supernatant is colourless, removes unnecessary B12Derivative ([(CN) (H2O) Cob (III) 7COOH] Cl), gained solid is dried in vacuo
Obtain compound B12-PIL/rGO。
4th, multiplex catalyst RhB/B12- PIL/rGO preparation
By rhodamine B (RhB) and compound B12- PIL/rGO ultrasonic disperses are in deionized water, stirring at normal temperature 1h, centrifugation,
, removing unnecessary rhodamine B (RhB) colourless to supernatant is washed with deionized, multiple elements design catalysis is obtained after vacuum drying
Agent RhB/B12-PIL/rGO。
(2) testing result
Fig. 2 sets forth rGO, B12-PIL/rGO、RhB/B12- PIL/rGO, vitamin B12The purple of derivative and RhB
Outside-visible absorption spectra figure.By contrast it can be found that multiplex catalyst RhB/B12- PIL/rGO in 263nm, 363nm and
Absworption peak at 611nm corresponds respectively to characteristic absorption peaks of the rGO at 273nm, vitamin B12Derivative at 352nm
Characteristic absorption peak, and characteristic absorption peaks of the RhB at 554nm.Thus illustrate that RhB successes are immobilized and arrive compound B12- PIL/rGO's
Surface.
Fig. 3 is rGO and RhB/B12- PIL/rGO X-ray powder diffraction figure.As seen from the figure rGO 2 θ=
24.5 °, by calculating rGO pieces interlamellar spacing for 0.363nm.Compound RhB/B12- PIL/rGO 2 θ=22.8 °, piece interlayer
Away from corresponding to 0.390nm.Pass through contrast, compared with rGO, multiplex catalyst RhB/B12- PIL/rGO piece interlamellar spacings are bright
Aobvious increase, illustrates that rGO piece interlayers have been successfully introduced into polymeric ionic liquid, vitamin B12Derivative and RhB molecules.
The multiplex catalyst RhB/B of embodiment 212- PIL/rGO application
By RhB/B12-PIL/rGO(3mg)、DDT(2.4×10-3) and triethanolamine (0.2M) is added to 5ml methanol M
In, it is passed through after nitrogen deoxygenation, under nitrogen protection, it is seen that light irradiation 2h.Catalyst is centrifuged off, supernatant decompression backspin is except molten
Agent, residue is dissolved in 10ml dichloromethane, is extracted three times with deionized water (10ml), and last dichloromethane layer decompression backspin is except molten
Agent, is dried, and a certain amount of Isosorbide-5-Nitrae-dioxane is added in residue for internal standard compound, using nucleus magnetic hydrogen spectrum to reaction-ure conversion-age and production
Produce rate is analyzed, and it is 96% to determine DDT conversion ratios, and product is that DDD is 94%.Fig. 4 is catalytic degradation under visible optical drive
DDT reaction equation.
Claims (9)
1. a kind of multiplex catalyst RhB/B12- PIL/rGO, it is characterised in that：Preparation method comprises the following steps：In polymerization
In the presence of ionic liquid PIL, graphene oxide GO is reduced, compound PIL/rGO is obtained；Then ion-exchange reactions is utilized,
By carboxyl B12It is immobilized to arrive PIL/rGO sheet surfaces, prepare compound B12-PIL/rGO；Again by obtained compound B12-
PIL/rGO and rhodamine B are scattered in deionized water, stirring at normal temperature, centrifugation, solid deionized water cyclic washing to supernatant
Colourless, vacuum drying obtains target product.
2. a kind of multiplex catalyst RhB/B according to claim 112- PIL/rGO, it is characterised in that：Take oxidation stone
Black alkene GO, ultrasonic disperse adds polymeric ionic liquid PIL and hydrazine hydrate, mixture is at 95 DEG C thereto in deionized water
12h is reacted, centrifugation is washed with deionized water and ethanol, is dried in vacuo, obtains compound PIL/rGO successively.
3. a kind of multiplex catalyst RhB/B according to claim 1 or 212- PIL/rGO, it is characterised in that：It is described
Polymeric ionic liquid PIL preparation method be：Take and bromoethane is added dropwise under 1- vinyl imidazoles, magnetic agitation, at 70 DEG C
React after 24h, mixture is dissolved in acetonitrile, precipitated with ethyl acetate, be dried in vacuo, obtain product 3- ethyl -1- vinyl imidazoles
Bromide；Then take 3- ethyls -1- vinyl imidazoles bromide and azodiisobutyronitrile to be dissolved in chloroform, be passed through after nitrogen deoxygenation,
The lower back flow reaction 8h of nitrogen protection, with chloroform, vacuum drying obtains product polymeric ionic liquid PIL.
4. a kind of multiplex catalyst RhB/B according to claim 112- PIL/rGO, it is characterised in that：By compound
PIL/rGO ultrasonic disperses add B thereto in deionized water1212h is stirred at room temperature in derivative, mixture, centrifugation, spend from
Sub- water washing is colourless to supernatant, vacuum drying, obtains compound B12-PIL/rGO。
5. a kind of multiplex catalyst RhB/B according to claim 412- PIL/rGO, it is characterised in that：Described B12
Derivative is [(CN) (H2O)Cob(III)7COOH]Cl。
6. a kind of multiplex catalyst RhB/B according to claim 112- PIL/rGO is characterized in that：By rhodamine B
With compound B12- PIL/rGO ultrasonic disperses are in deionized water, normal-temperature reaction, and deionized water is used in mixture stirring 1h, centrifugation
Washing is colourless to supernatant, vacuum drying, obtains multiplex catalyst RhB/B12-PIL/rGO。
7. the multiplex catalyst RhB/B described in claim 112- PIL/rGO declines solution organic halogen in visible optical drive
In application.
8. application according to claim 7, it is characterised in that method is as follows：Under normal temperature, weigh many described in claim 1
First composite catalyst RhB/B12- PIL/rGO, ultrasonic disperse adds three ethanol in the methanol solution containing organic halogen
Amine, stirring, reaction solution is passed through nitrogen deoxygenation, the lower radiation of visible light of nitrogen protection.
9. the application according to claim 7 or 8, it is characterised in that：Described organic halogen is double (the 4- chlorobenzenes of 2,2-
Base) -1,1,1- trichloroethanes.
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