CN108855221A - A kind of [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite composite photo-catalyst preparation method - Google Patents
A kind of [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite composite photo-catalyst preparation method Download PDFInfo
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- CN108855221A CN108855221A CN201810425770.9A CN201810425770A CN108855221A CN 108855221 A CN108855221 A CN 108855221A CN 201810425770 A CN201810425770 A CN 201810425770A CN 108855221 A CN108855221 A CN 108855221A
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- znpc
- ethyoxyl
- ethyl
- attapulgite
- phenylamino
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- -1 N- ethyl phenylamino Chemical group 0.000 title claims abstract description 57
- 229960000892 attapulgite Drugs 0.000 title claims abstract description 50
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 10
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 claims description 8
- 150000002825 nitriles Chemical class 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- XMVJITFPVVRMHC-UHFFFAOYSA-N roxarsone Chemical group OC1=CC=C([As](O)(O)=O)C=C1[N+]([O-])=O XMVJITFPVVRMHC-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 3
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- WEUCTTBUEWINIJ-UHFFFAOYSA-N acetic acid;zinc;dihydrate Chemical compound O.O.[Zn].CC(O)=O WEUCTTBUEWINIJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims 1
- 239000003208 petroleum Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 abstract description 9
- 229940107698 malachite green Drugs 0.000 abstract description 9
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 6
- 239000004575 stone Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite composite photo-catalyst preparation methods, including step：The pretreatment of attapulgite, the preparation and [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite composite photo-catalyst preparation of [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc.The beneficial effects of the invention are as follows：Composite photo-catalyst preparation cost is low, purity is high, and preparation process is simple；Effective degradation to pollutant malachite green is realized, photocatalytic activity will be significantly better than pure [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc particle, can be applied to the processing of pollutant in environment.
Description
Technical field
Present invention relates particularly to [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite composite photo-catalysts
Preparation method
Background technique
In recent years, metal phthalocyanine has attracted more and more due to its novel material property in terms of photocatalysis research
Concern.Phthalocyanine is due to good catalytic activity, stable chemical property and good light heat stability.The center of phthalocyanine
Can be by the hydrogen atom replaced other elements containing 2 in inner cavity, substitutive element is about by more than 70 kinds.Phthalocyanine compound
Electron conjugated structure with 18 π, and the electron density of phthalocyanine is highly uniform.Axial direction in plane can occur for catalysis reaction
Position, aromatic ring can be used as electron acceptor and electron donor.Since special structure phthalocyanine can be by generating singlet oxygen
Big logarithm organic pollutant in Xie Shui.The super-hydrophobicity of phthalocyanine is advantageous in photocatalytic degradation machine pollutant in water simultaneously,
Avoid result in the secondary pollution of water environment.Therefore, part metals phthalocyanine or phthalocyanine derivates will show excellent catalytic performance.
In addition, zinc (Zn (II)) phthalocyanine has been widely studied, is conducive to phthalocyanine and preferably combines and live to improve photocatalysis with oxygen molecule
Property.Meanwhile the main problem of metal phthalocyanine is that agglomeration occurs easily in the solution to will affect photocatalysis performance in it.It is recessed
Convex stick stone (ATP) is a kind of argillaceous object of the chain layer structure of aqueous rich magnesium silicate, has unique 2:1 phyllosilicate
Structure is used widely on the catalytic fields such as catalysis oxidation, organic synthesis and photocatalysis.With ultrasonic immersing method by phthalein
Cyanines are fixed on the surface ATP and effectively prevent the aggregation of phthalocyanine, to enhance the photocatalytic activity of phthalocyanine.It is design and opens
Sending out, there is the composite material of unique catalytic performance to open new opportunity.
Summary of the invention
The technical problem to be solved by the present invention is to：Based on the above issues, the present invention provides a kind of [3-2- (N- ethyl phenylamino
Base) ethyoxyl] ZnPc/attapulgite composite photo-catalyst and preparation method thereof.
The present invention solves a technical solution used by its technical problem：A kind of [3-2- (N- ethyl phenylamino) second
Oxygroup] ZnPc/attapulgite composite photo-catalyst, by [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc and attapulgite
It is combined, [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc structural formula is as follows：
One kind [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite composite photo-catalyst of the present invention
Preparation method, include the following steps：
(1) pretreatment of attapulgite
Concave-convex clay rod is weighed, is put into three-necked flask, the concentrated nitric acid of 50~70wt%, 120~150 DEG C of heating are added
8~10h is stirred, cools down, is washed with water to neutrality after reaction；
(2) preparation of phthalocyanine presoma
3- nitro phthalic nitrile and 2- (N-ethylaniline base) ethyl alcohol are poured into flask, stirred at room temperature for 24 hours, reaction terminates
After cool down, pour into ice water, filter, be washed to neutrality with distillation, crude product recrystallized, obtain phthalocyanine presoma；
(3) preparation of [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc
By phthalocyanine presoma, acetic acid dihydrate zinc, the 11 carbon -7- alkene of catalyst 1,8- diazabicylo [5,4,0] and molten
Reaction vessel is added in agent n-amyl alcohol, under nitrogen protection heating stirring, reflux condensation mode, 140 DEG C of reaction 6h, cooling and standings to room
Temperature filters, and washs, and drying obtains crude product, is purified by column chromatography；
(4) [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite composite photo-catalyst preparation
[3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc and attapulgite are added in ethanol solution, ultrasound load 2
~4h obtains [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite composite photo-catalyst.
Further, it is purified in step (2) by re-crystallizing in ethyl acetate, the step (3) eluant pet
The volume ratio of ether and ethyl acetate is 5:1.
Further, in step (4) [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc and attapulgite mass ratio
It is 4:1.
The beneficial effects of the invention are as follows：Composite photo-catalyst preparation cost is low, purity is high, and preparation process is simple；It realizes
Effective degradation to pollutant malachite green, photocatalytic activity will be significantly better than pure [3-2 (N- ethyl phenylamino) ethyoxyl]
ZnPc particle can be applied to the processing of pollutant in environment.
Detailed description of the invention
The present invention will be further described with reference to the accompanying drawings and examples：
Fig. 1 is [3-2- (the N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite UV absorption prepared in embodiment 1
Spectrogram；
Fig. 2 is [3-2- (the N- ethyl phenylamino) ethyoxyl] ZnPc/concave convex rod prepared in attapulgite and embodiment 1
The SEM of stone composite catalyzing material schemes, wherein a is attapulgite, and b is [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/recessed
Convex stick stone composite catalyzing material；
Fig. 3 is [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite composite photocatalyst prepared by embodiment 1
The UV absorption luminosity figure of material degradation malachite green.
Specific embodiment
For a better understanding of the present invention, below with reference to embodiment and the application examples content that the present invention is furture elucidated, but
The contents of the present invention are not limited solely to embodiment and application examples below.
Embodiment 1
(1) pretreatment of attapulgite
Attapulgite 2g and concentrated nitric acid 200ml are put into 250ml three-necked flask, temperature is 120 DEG C, reflux condensation mode reaction
HNO is removed after 10h cooled to room temperature3The stillness of night, then HNO is removed again after being diluted with deionized water3Clear liquid repeats to dilute, then
It is filtered with Buchner funnel, can finally be obtained with baking oven drying.
(2) preparation of [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc
2.60g (15mmol) 3- nitro phthalic nitrile and 4.96g (30mmol) 2- (N-ethylaniline base) ethyl alcohol are poured into
In reaction vessel, it is added 20mL DMF (n,N-Dimethylformamide), is stirred at room temperature, 5g potassium carbonate is added portionwise
(36mmol) reacts 12h afterwards, pours into reaction solution faint yellow solid is precipitated in ice water after reaction, filters and uses deionized water
It rinses, filter cake is finally put into baking oven and dries to obtain 3-2- (N- ethylo benzene amino ethoxy) phthalic nitrile crude product.Then pass through
Re-crystallizing in ethyl acetate purify and obtains white solid 3-2- (N- ethyl phenylamino) ethyoxyl phthalic nitrile by filtering
Sterling.
(3) [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite composite photo-catalyst preparation
0.01g attapulgite is dissolved in 10ml ethyl alcohol, 0.04g [3-2- (N- ethylo benzene is added dropwise under ultrasound-enhanced
Amino) ethyoxyl] ZnPc 20ml ethanol solution in, then at room temperature after ultrasound 3h, drying collect obtain [3-2- (N-
Ethyl phenylamino) ethyoxyl] ZnPc/attapulgite composite photo-catalyst.
Embodiment 2
(1) pretreatment of attapulgite
Attapulgite 5g and concentrated nitric acid 200ml are put into 250ml three-necked flask, temperature is 150 DEG C, reflux condensation mode reaction
HNO is removed after 8h cooled to room temperature3The stillness of night, then HNO is removed again after being diluted with deionized water3Clear liquid repeats to dilute, then
It is filtered with Buchner funnel, can finally be obtained with baking oven drying.
(2) preparation of [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc
2.60g (15mmol) 3- nitro phthalic nitrile and 4.96g (30mmol) 2- (N-ethylaniline base) ethyl alcohol are poured into
In reaction vessel, it is added 20mL DMF (n,N-Dimethylformamide), is stirred at room temperature, 5g potassium carbonate is added portionwise
(36mmol) reacts for 24 hours afterwards, pours into reaction solution faint yellow solid is precipitated in ice water after reaction, filters and uses deionized water
It rinses, filter cake is finally put into baking oven and dries to obtain 3-2- (N- ethyl phenylamino) ethyoxyl phthalic nitrile crude product.Then pass through
Re-crystallizing in ethyl acetate purify and obtains white solid 3-2- (N- ethyl phenylamino) ethyoxyl phthalic nitrile by filtering
Sterling.
(3) [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite composite photo-catalyst preparation
0.02g attapulgite is dissolved in 10ml ethyl alcohol, 0.08g [3-2- (N- ethylo benzene is added dropwise under ultrasound-enhanced
Amino) ethyoxyl] ZnPc 20ml ethanol solution in, then at room temperature after ultrasound 6h, drying collect obtain [3-2- (N-
Ethyl phenylamino) ethyoxyl] ZnPc/attapulgite composite photo-catalyst.
[3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite complex light obtained in embodiment 1 is urged
Change material and carries out phenetic analysis.It should [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite XRD diagram such as Fig. 1 institute
Show, [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc characteristic peak is obvious, after with attapulgite load, in contrast to [3-2-
(N- ethyl phenylamino) ethyoxyl] ZnPc characteristic diffraction peak [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/bumps
The specific diffraction maximum of stick stone obviously dies down, this illustrates that the load of attapulgite has made [3-2- (N- ethyl phenylamino) ethyoxyl]
The dispersibility of ZnPc becomes good, effectively prevents the clustering phenomena of nitro ZnPc.[3-2- (N- ethyl phenylamino) second
Oxygroup] ZnPc/attapulgite scanning electron microscope is as shown in Fig. 2, [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/bumps
The volume of stick stone is obviously bigger than attapulgite, and it is recessed to illustrate that [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc is successfully supported on
On convex stick stone, metal phthalocyanine can be overcome to be easy to happen clustering phenomena in this way thus the shortcomings that reducing catalytic efficiency.
Application examples
Light-catalyzed reaction carries out in photo catalysis reactor, and reactor is three layers of concentric circles tubular glass container, and centre is outstanding
There is a 1000w xenon lamp, lead to recirculated cooling water in inner sleeve, by reactor among inner-outer sleeve.Embodiment 1 is obtained under magnetic stirring
40mg [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite be added to 50ml initial concentration C0=25mg/L's
Malachite green keeps particle to be uniformly dispersed using strength magnetic agitation, with the residue hundred of the malachite green after reaction a period of time
Divide rate, that is, the concentration C and initial concentration C of malachite green after reacting0The ratio between measure [3-2- (N- ethyl phenylamino) ethyoxyl]
ZnPc/attapulgite photocatalytic activity.Specific method is that 2ml solution is taken after 10min, to test, in order to survey
The concentration of malachite green is tried, [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite particle is removed in centrifugal filtration, in purple
Outer visible Spectra Analysis on Edge Recycling instrument tests its UV absorption intensity at 617nm, to analyze the photocatalytic degradation of malachite green solution
Rate, i.e. Fig. 3.After 60min, [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite degrading malachite green is dense
Degree, prepared [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite photochemical catalyst have apparent photocatalysis
Effect can be used as a kind of good photochemical catalyst.
It is enlightenment with the embodiment of the present invention, according to above-mentioned description, relevant staff can be without departing from this
In the range of item inventive technique thought, the change and modification of multiplicity are carried out.The technical scope of the present invention is not limited to
On content, it is necessary to the technical scope thereof is determined according to the scope of the claim.
Claims (4)
1. a kind of [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite composite photo-catalyst preparation, feature
It is：It is combined by [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc and attapulgite, [3-2- (N- ethyl phenylamino) second
Oxygroup] ZnPc structural formula it is as follows：
2. [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite composite photo-catalyst system described in claim 1
Preparation Method, it is characterized in that：Include the following steps：
(1) pretreatment of attapulgite
Concave-convex clay rod is weighed, is put into three-necked flask, the concentrated nitric acid of 50-70wt%, 120~150 DEG C of heating stirrings 8 are added
~10h, cools down after reaction, is washed with water to neutrality；
(2) preparation of phthalocyanine presoma
3- nitro phthalic nitrile and 2- (N-ethylaniline base) ethyl alcohol are poured into flask, stirred at room temperature for 24 hours, it is cold after reaction
But, it pours into ice water, filters, be washed to neutrality with distillation, crude product is recrystallized, obtain phthalocyanine presoma；
(3) preparation of [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc
Just by phthalocyanine presoma, acetic acid dihydrate zinc, the 11 carbon -7- alkene of catalyst 1,8- diazabicylo [5,4,0] and solvent
Reaction vessel is added in amylalcohol, under nitrogen protection heating stirring, reflux condensation mode, 140 DEG C of reaction 6h, cooling and standings to room temperature, takes out
Filter is washed, and drying obtains crude product, is purified by column chromatography；
(4) [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite composite photo-catalyst preparation
[3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc and attapulgite are added in ethanol solution, ultrasound 2~4h of load,
Obtain [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite composite photo-catalyst.
3. [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite composite photocatalyst according to claim 2
The preparation method of agent, it is characterized in that：It is purified in the step (2) by re-crystallizing in ethyl acetate, the step (3)
The volume ratio of eluent petroleum ether and ethyl acetate is 5:1.
4. [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite composite photo-catalyst as claimed in claim 2
Preparation method, it is characterized in that：[3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc and attapulgite in the step (4)
Mass ratio is 4:1.
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