CN108579806A - A kind of preparation method and applications of acid imide-urea polymer - Google Patents
A kind of preparation method and applications of acid imide-urea polymer Download PDFInfo
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- CN108579806A CN108579806A CN201810270469.5A CN201810270469A CN108579806A CN 108579806 A CN108579806 A CN 108579806A CN 201810270469 A CN201810270469 A CN 201810270469A CN 108579806 A CN108579806 A CN 108579806A
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- acid imide
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- 239000004202 carbamide Substances 0.000 title claims abstract description 51
- 229920000642 polymer Polymers 0.000 title claims abstract description 42
- 239000002253 acid Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 tetracarboxylic acid dianhydride Chemical class 0.000 claims abstract description 9
- 239000011941 photocatalyst Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 84
- 239000010865 sewage Substances 0.000 claims description 36
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 30
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 150000002460 imidazoles Chemical class 0.000 claims description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 6
- 229940057499 anhydrous zinc acetate Drugs 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 3
- 238000011109 contamination Methods 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 150000003949 imides Chemical class 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 238000001228 spectrum Methods 0.000 abstract description 5
- 238000005286 illumination Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000008346 aqueous phase Substances 0.000 abstract 1
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 230000000192 social effect Effects 0.000 abstract 1
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 13
- 230000001699 photocatalysis Effects 0.000 description 11
- 238000007146 photocatalysis Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229940106691 bisphenol a Drugs 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002524 electron diffraction data Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 210000002700 urine Anatomy 0.000 description 2
- 229960000314 zinc acetate Drugs 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KSSNXJHPEFVKHY-UHFFFAOYSA-N phenol;hydrate Chemical compound O.OC1=CC=CC=C1 KSSNXJHPEFVKHY-UHFFFAOYSA-N 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/345—Phenols
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of preparation method and applications of acid imide urea polymer, belong to technical field of nano material.Preparation method is：It using the single step reaction of tetracarboxylic acid dianhydride and urea dehydration polymerization at high temperature, is collected by filtration, is dried in vacuo, prepares acid imide urea polymer.Acid imide urea polymer photocatalyst structure stabilization produced by the present invention, good crystallinity, spectrum efficiency are high, aqueous phase dispersibility protrudes, widely used, have important social effect and application value.The material can rapidly and efficiently degradation treatment organic pollution under visible light illumination, there is the great value of environmental protection；The material can also under light illumination efficiently, last decomposition water, discharge oxygen, have great industrial value and medical value.
Description
Technical field
The present invention relates to a kind of preparation method and applications of acid imide-urea polymer more particularly to one kind to be used for
Acid imide-urea polymer of photocatalysis Decomposition aquatic products oxygen and contaminant degradation, belongs to technical field of nano material.
Background technology
Acid imide (perylenediimides, hereinafter referred to as PDI) is that a kind of plane with super large conjugated system is rigid
Property organic molecule.Due to the conjugation delocalization structure that intramolecular is larger, PDI has visible light strong absorption, is forming half
After conductor level structure, absorption region can be widened to 400~750nm, substantially cover whole visible spectrums.Therefore, PDI
It is widely used in organic photoelectric field.The big π systems of PDI molecules so that its is intermolecular there are the effect of strong pi-pi accumulation,
Again plus the effect of end position amido bond, the guarantee that the polymer based on PDI provides active force is constructed to introduce covalent bond.
Energy crisis and environmental pollution are that two mankind nowadays social developments face, compel highly necessary to solve the problems, such as.Profit
With PDI to the strong absorption of visible light, develops it and decompose answering for aquatic production oxygen, hydrogen etc. in mimic photosynthesis effect
It is especially necessary with just seeming.Meanwhile using the stronger oxidisability of PDI, water pollutant can be handled under light illumination, it is real
Existing environmental contaminants purification.
Invention content
The purpose of the present invention is to propose to a kind of preparations of acid imide-urea polymer (hereinafter referred to as PUP) photochemical catalyst
Method and its application are chemically reacted by a simple step, prepare hydrophilic, high activity photochemical catalyst, to utilize the material
Visible light-responded performance, clean energy resource production and the technical fields such as sewage disposal can be widely used in.
The preparation method of acid imide proposed by the present invention-urea polymer photochemical catalyst, includes the following steps：
(1) at 120-150 DEG C, tetracarboxylic acid dianhydride and urea, tetracarboxylic acid dianhydride and urine are put into reaction system
The stoichiometric ratio of element is 1 ︰ 1, and using imidazoles as solvent, the amount of solvent is 10 times of four dioctyl phthalate, at the same be added catalyst without
Water zinc acetate, the stoichiometric ratios such as the addition of catalyst anhydrous zinc acetate and urea；
(2) reaction system of above-mentioned steps (1) is sufficiently stirred, reacts 5-8 hours, keeps the raw material in reaction system abundant
Reaction, subsequent natural cooling；
(3) dilute hydrochloric acid is added into the reaction system of above-mentioned steps (2), the volume fraction of dilute hydrochloric acid in the reaction system is
5%-20% is stirred well to imidazoles and is completely dissolved；
(4) reaction system of above-mentioned steps (3) is filtered, collects solid, solid is fully washed with deionized water；
(5) solid of above-mentioned steps (4) is dried in vacuo, vacuum drying temperature is 50~80 DEG C, and drying time is
4-12 hours；
(6) solid obtained to step (5) is washed colourless to filtrate with dimethyl sulfoxide (DMSO)；
(7) solid that above-mentioned steps (6) obtain is washed with ethyl alcohol；
(8) solid of above-mentioned steps (7) is dried in vacuo, vacuum drying temperature is 50~80 DEG C, and drying time is
4-12 hours, obtain acid imide-urea polymer photocatalyst product.
The application of acid imide-urea polymer photochemical catalyst prepared by the method for the present invention, is applied to sewage disposal,
Application process includes the following steps：
(1) acid imide-urea polymer photochemical catalyst is added in the sewage that organic contamination generates, the photochemical catalyst
Addition mass volume ratio is 0.5~5g/L；
(2) it is sufficiently stirred, keeps the photochemical catalyst evenly dispersed in sewage；
(3) sewage for the light source irradiation above-mentioned steps (2) for being 300-850nm with wavelength, irradiation time are that sewage reaches row
Put standard.
Clean energy resource life is used it in the application of acid imide-urea polymer photochemical catalyst prepared by the method for the present invention
Production, application process include the following steps：
(1) acid imide-urea polymer photochemical catalyst, acid imide-urea polymer photochemical catalyst are added in water
Addition mass volume ratio be according to 0.05~2g/L；
(2) sacrifice agent is added in the reaction system of above-mentioned steps (1), the addition of sacrifice agent is the 10 of photochemical catalyst2-
105Times, the sacrifice agent is silver nitrate or ferrous nitrate；
(3) reaction system for the light source irradiation above-mentioned steps (2) for being 300-850nm with wavelength, output oxygen.
The preparation method and applications of acid imide proposed by the present invention-urea polymer photochemical catalyst, its advantage is that：
1, PUP photochemical catalysts prepared by the method for the present invention, compared to general organic photochemical catalyst, compound with regular structure, crystallization
It is orientated single, crystallinity height, therefore has better photo-generated carrier separating effect, has superior photocatalysis performance.And
And photocatalysis has the characteristics that safe and environment-friendly, efficient, keeps the application prospect of PUP photochemical catalysts prepared by the present invention boundless.
2, the method for the present invention is prepared for PUP photochemical catalysts, and preparation method by simple step chemical reaction process
It is easy to operate, it is easy to repeat, solves the problems such as cumbersome preparing for organic photochemical catalyst, low output, provided for commercial applications
Good technical foundation and material guarantee.
3, PUP photochemical catalysts prepared by the method for the present invention, have the excellent properties such as stable structure, visible light-responded performance,
Performance protrudes, therefore has extensive use in the fields such as sewage disposal and clean energy resource generation, under visible light illumination for having
The degradation treatment of machine pollutant acts on, therefore has regulation effect for environmental contaminants；It, can be to water by radiation of visible light
It is decomposed, discharges oxygen, therefore can be used for producing clean energy resource.
Description of the drawings
Fig. 1 is the electron scanning micrograph of the PUP photochemical catalysts prepared in embodiment 1.
Fig. 2 is the high resolution transmission electron microscopy photo of the PUP photochemical catalysts prepared in embodiment 1.
Fig. 3 is the selective electron diffraction pattern of the PUP photochemical catalysts prepared in embodiment 1.
Fig. 4 is the high resolution transmission electron microscopy photo of the PUP photochemical catalysts prepared in embodiment 2.
Fig. 5 is the high resolution transmission electron microscopy photo of the PUP photochemical catalysts prepared in embodiment 2.
Fig. 6 is the selective electron diffraction pattern of the PUP photochemical catalysts prepared in embodiment 2.
Fig. 7 is the Photocatalytic Degradation of Phenol sewage of PUP photochemical catalysts in embodiment 3.
Fig. 8 is the photocatalytic degradation bisphenol-A sewage of PUP photochemical catalysts in embodiment 4.
Fig. 9 is the photocatalytic degradation 2,4- Dichlorophenol sewage of PUP photochemical catalysts in embodiment 5.
Figure 10 is in embodiment 6 using ferrous nitrate as the photocatalysis oxygen production of the PUP photochemical catalysts of sacrifice agent.
Figure 11 is in embodiment 7 using silver nitrate as the photocatalysis oxygen production of the PUP photochemical catalysts of sacrifice agent.
Figure 12 is in embodiment 8 using silver nitrate as the photocatalysis oxygen production of the PUP photochemical catalysts of sacrifice agent.
Figure 13 is in embodiment 9 using silver nitrate as the photocatalysis oxygen production of the PUP photochemical catalysts of sacrifice agent.
Specific implementation mode
The preparation method of acid imide proposed by the present invention-urea polymer photochemical catalyst, includes the following steps：
(1) at 120-150 DEG C, tetracarboxylic acid dianhydride and urea, tetracarboxylic acid dianhydride and urine are put into reaction system
The stoichiometric ratio of element is 1 ︰ 1, and using imidazoles as solvent, the amount of solvent is 10 times of four dioctyl phthalate, at the same be added catalyst without
Water zinc acetate, the stoichiometric ratios such as the addition of catalyst anhydrous zinc acetate and urea；
(2) reaction system of above-mentioned steps (1) is sufficiently stirred, reacts 5-8 hours, keeps the raw material in reaction system abundant
Reaction, subsequent natural cooling；
(3) dilute hydrochloric acid is added into the reaction system of above-mentioned steps (2), the volume fraction of dilute hydrochloric acid in the reaction system is
5%-20% is stirred well to imidazoles and is completely dissolved；
(4) reaction system of above-mentioned steps (3) is filtered, collects solid, solid is fully washed with deionized water；
(5) solid of above-mentioned steps (4) is dried in vacuo, vacuum drying temperature is 50~80 DEG C, and drying time is
4-12 hours；
(6) solid obtained to step (5) is washed colourless to filtrate with dimethyl sulfoxide (DMSO) (DMSO)；
(7) solid that above-mentioned steps (6) obtain is washed with ethyl alcohol；
(8) solid of above-mentioned steps (7) is dried in vacuo, vacuum drying temperature is 50~80 DEG C, herein without vacuum
Degree requires, general vacuum drying oven, and drying time is 4-12 hours, obtains acid imide-urea polymer photochemical catalyst production
Product.
Acid imide-urea polymer photochemical catalyst prepared by the method for the present invention, can be applied to sewage disposal, answer
Included the following steps with process：
(1) acid imide-urea polymer photochemical catalyst is added in the sewage that organic contamination generates, the photochemical catalyst
Addition mass volume ratio is 0.5~5g/L；
(2) it is sufficiently stirred, keeps the photochemical catalyst evenly dispersed in sewage；
(3) sewage for the light source irradiation above-mentioned steps (2) for being 300-850nm with wavelength, irradiation time are that sewage reaches row
Put standard.
Acid imide-urea polymer photochemical catalyst prepared by the method for the present invention, can also be applied to clean energy resource
Production, application process include the following steps：
(1) acid imide-urea polymer photochemical catalyst, acid imide-urea polymer photochemical catalyst are added in water
Addition mass volume ratio be according to 0.05~2g/L；
(2) sacrifice agent is added in the reaction system of above-mentioned steps (1), the addition of sacrifice agent is the 10 of photochemical catalyst2-
105Times, the sacrifice agent is silver nitrate or ferrous nitrate；
(3) reaction system for the light source irradiation above-mentioned steps (2) for being 300-850nm with wavelength, output oxygen.
The method of the present invention is illustrated by specific embodiment below in conjunction with the accompanying drawings, but the invention is not limited in
This, any modifications, equivalent replacements and improvementsmade within the spirit and principles of the invention, etc. should be included in the present invention
Protection domain within.
The materials, reagents and the like used in the following examples is commercially available.
Embodiment 1 prepares acid imide-urea polymer photochemical catalyst：
(1) at 120-150 DEG C, tetracarboxylic acid dianhydride 784.64mg and urea 120.12mg is put into, is molten with 5g imidazoles
The input amount of agent, catalyst anhydrous zinc acetate is 366.96mg；
(2) reaction system of above-mentioned steps (1) is sufficiently stirred, reacts more than 6 hours, the raw material in reaction system is made to fill
Divide reaction, subsequent natural cooling；
(3) dilute hydrochloric acid is added into reaction system after cooling, dilute hydrochloric acid volume fraction is 10%, is stirred well to imidazoles
It is completely dissolved；
(4) reaction system is filtered, collects solid, solid is fully washed with deionized water；
(5) solid of above-mentioned steps (4) is dried in vacuo, vacuum drying temperature is 60 DEG C, and drying time is 8 small
When, obtain PUP photochemical catalyst crude products.
(6) solid being collected into step (5) is washed colourless to filtrate with dimethyl sulfoxide (DMSO) (DMSO)；
(7) (6) obtained solid is washed with ethyl alcohol；
(8) solid of above-mentioned steps (7) is dried in vacuo, vacuum drying temperature is 60 DEG C, and drying time is 8 small
When, obtain PUP photocatalyst products.
According to Fig. 1 observables, the sample in Fig. 1 shows lamella packed structures, excellent when showing material internal molecular crystalline
Gesture is orientated；In high resolution transmission electron microscopy photo shown in Fig. 2, it is observed that the crystallization situation of material, it was demonstrated that poly-
Close π-π interactions strong and regular inside object；High-resolution electronic selected area diffraction patterns shown in Fig. 3 prove that the material is excellent
Crystal property；High resolution transmission electron microscopy photo shown in Fig. 4 then shows the crystal grain diameter in material internal crystallite area
In 20nm or so, be conducive to the transmission and separation of photo-generated carrier, guarantee is provided for the performance of PUP photochemical catalysts.
Embodiment 2 prepares acid imide-urea polymer organic semiconductor photochemical catalyst：
(1) at 120-150 DEG C, tetracarboxylic acid dianhydride 1569.28mg and urea 240.24mg is put into, is with 10g imidazoles
The input amount of solvent, catalyst anhydrous zinc acetate is 733.92mg；
(2) reaction system of above-mentioned steps (1) is sufficiently stirred, reacts more than 6 hours, the raw material in reaction system is made to fill
Divide reaction, subsequent natural cooling；
(3) dilute hydrochloric acid is added into reaction system after cooling, dilute hydrochloric acid volume fraction is 20%, is stirred well to imidazoles
It is completely dissolved；
(4) reaction system is filtered, collects solid, solid is fully washed with deionized water；
(5) solid of above-mentioned steps (4) is dried in vacuo, vacuum drying temperature is 80 DEG C, and drying time is 10 small
When, obtain PUP photochemical catalyst crude products.
(6) solid being collected into step (5) is washed colourless to filtrate with dimethyl sulfoxide (DMSO) (DMSO)；
(7) (6) obtained solid is washed with ethyl alcohol；
(8) solid of above-mentioned steps (7) is dried in vacuo, vacuum drying temperature is 80 DEG C, and drying time is 10 small
When, obtain PUP photocatalyst products.
According in high resolution transmission electron microscopy photo shown in fig. 5, it is observed that the crystallization situation of material, it was demonstrated that
The crystallite area of polymeric inner strong and regular π-π interaction and a diameter of 20nm；High-resolution electronic constituency shown in fig. 6
Diffraction pattern proves the advantageous crystalline performance of the polymer material, is conducive to the transmission and separation of photo-generated carrier, is urged for PUP light
The performance of agent provides guarantee.
Embodiment 3, the acid imide-urea polymer photochemical catalyst for preparing the present invention are dirty for Photocatalytic Degradation of Phenol
Water：
(1) in 50mL, 25mgPUP photochemical catalysts are added in the sewage that phenol concentration is 5ppm；
(2) it is sufficiently stirred, makes to be uniformly dispersed in sewage in PUP photochemical catalysts；
(3) sewage for the light source irradiation above-mentioned steps (2) for being 350-800nm with wavelength, irradiation time are that sewage reaches row
The standard of putting is limited.
Sewage degradation treatment effect is as shown in Figure 7.
The present invention is prepared acid imide-urea polymer photochemical catalyst for photocatalytic degradation bisphenol-A dirt by embodiment 4
Water：
(1) in 50mL, 25mgPUP photochemical catalysts are added in the sewage that bisphenol A concentration is 5ppm；
(2) it is sufficiently stirred, makes to be uniformly dispersed in sewage in PUP photochemical catalysts；
(3) sewage for the light source irradiation above-mentioned steps (2) for being 350-800nm with wavelength, irradiation time are that sewage reaches row
The standard of putting is limited.
Sewage degradation treatment effect is as shown in Figure 8.
The present invention is prepared acid imide-urea polymer photochemical catalyst for photocatalytic degradation 2,4- dichloros by embodiment 5
Phenol sewage：
(1) 25mgPUP photochemical catalysts are added in 50mL, the sewage of a concentration of 5ppm of 2,4- Dichlorophenols；
(2) it is sufficiently stirred, makes to be uniformly dispersed in sewage in PUP photochemical catalysts；
(3) sewage for the light source irradiation above-mentioned steps (2) for being 350-800nm with wavelength, irradiation time are that sewage reaches row
The standard of putting is limited.
Sewage degradation treatment effect is as shown in Figure 9.
The present invention is prepared acid imide-urea polymer photochemical catalyst for photocatalysis oxygen production by embodiment 6：
(1) PUP photochemical catalysts are added in 100mL water, the addition quality of PUP photochemical catalysts is 50mg, and it is molten to obtain first
Liquid；
(2) ferrous nitrate is added in above-mentioned first solution, ferrous nitrate dosage is 20mL, 0.05molL-1Solution；
(3) 300-850nm continuous spectrums are used to irradiate reaction system.
As shown in Figure 10, using ferrous nitrate as sacrifice agent, oxygen output is 600 μm of olg in 6 hours-1。
The present invention is prepared acid imide-urea polymer photochemical catalyst for photocatalysis oxygen production by embodiment 7：
(1) PUP photochemical catalysts are added in 100mL water, the addition quality of PUP photochemical catalysts is 50mg, and it is molten to obtain first
Liquid；
(2) silver nitrate is added in above-mentioned first solution, silver nitrate dosage is 10mL, 0.05molL-1Solution；
(3) 300-850nm continuous spectrums are used to irradiate reaction system.
If Figure 11 shows, using silver nitrate as sacrifice agent, oxygen output is 1100 μm of ollg in 6 hours-1。
The present invention is prepared acid imide-urea polymer photochemical catalyst for photocatalysis oxygen production by embodiment 8：
(1) PUP photochemical catalysts are added in 100mL water, the addition quality of PUP photochemical catalysts is 50mg, and it is molten to obtain first
Liquid；
(2) silver nitrate is added in above-mentioned first solution, silver nitrate dosage is 10mL, 0.05molL-1Solution；
(3) 300-850nm continuous spectrums are used to irradiate reaction system.
If Figure 12 shows, using silver nitrate as sacrifice agent, oxygen output is about 4000 μm of ollg in 24 hours-1。
The present invention is prepared acid imide-urea polymer photochemical catalyst for the life of photocatalysis circulating oxygen by embodiment 9
Production：
(1) PUP photochemical catalysts are added in 100mL water, the addition quality of PUP photochemical catalysts is 50mg, and it is molten to obtain first
Liquid；
(2) silver nitrate is added in above-mentioned first solution, silver nitrate dosage is 10mL, 0.05molL-1Solution；
(3) 300-850nm continuous spectrums are used to irradiate reaction system.
(4) every 6h, system is emptied, repeats step (3), is recycled 3 times；
If Figure 13 shows, using silver nitrate as sacrifice agent, oxygen output can be stably held in 1100 μm of ollg in 6 hours-1
Left and right.
Claims (3)
1. a kind of preparation method of acid imide-urea polymer photochemical catalyst, it is characterised in that this method comprises the following steps：
(1) tetracarboxylic acid dianhydride and urea are put at 120-150 DEG C, into reaction system, tetracarboxylic acid dianhydride and urea
Stoichiometric ratio is 1 ︰ 1, and using imidazoles as solvent, the amount of solvent is 10 times of four dioctyl phthalate, while the anhydrous second of catalyst is added
Sour zinc, the stoichiometric ratios such as the addition of catalyst anhydrous zinc acetate and urea；
(2) reaction system of above-mentioned steps (1) is sufficiently stirred, reacts 5-8 hours, keeps the raw material in reaction system fully anti-
It answers, subsequent natural cooling；
(3) dilute hydrochloric acid is added into the reaction system of above-mentioned steps (2), the volume fraction of dilute hydrochloric acid in the reaction system is 5%-
20%, it is stirred well to imidazoles and is completely dissolved；
(4) reaction system of above-mentioned steps (3) is filtered, collects solid, solid is fully washed with deionized water；
(5) solid of above-mentioned steps (4) is dried in vacuo, vacuum drying temperature is 50~80 DEG C, drying time 4-12
Hour；
(6) solid obtained to step (5) is washed colourless to filtrate with dimethyl sulfoxide (DMSO)；
(7) solid that above-mentioned steps (6) obtain is washed with ethyl alcohol；
(8) solid of above-mentioned steps (7) is dried in vacuo, vacuum drying temperature is 50~80 DEG C, drying time 4-12
Hour, obtain acid imide-urea polymer photocatalyst product.
2. a kind of application of the acid imide-urea polymer photochemical catalyst prepared such as claim 1, it is characterised in that by acyl
In sewage disposal, application process includes the following steps imines-urea polymer photocatalyst applications：
(1) acid imide-urea polymer photochemical catalyst, the addition of the photochemical catalyst are added in the sewage that organic contamination generates
Mass volume ratio is 0.5~5g/L；
(2) it is sufficiently stirred, keeps the photochemical catalyst evenly dispersed in sewage；
(3) sewage for the light source irradiation above-mentioned steps (2) for being 300-850nm with wavelength, irradiation time are that sewage reaches discharge mark
It is accurate.
3. a kind of application of the acid imide-urea polymer photochemical catalyst prepared such as claim 1, it is characterised in that by acyl
Imines-urea polymer photocatalyst applications are produced in clean energy resource, and application process includes the following steps：
(1) acid imide-urea polymer photochemical catalyst is added in water, acid imide-urea polymer photochemical catalyst adds
It is according to 0.05~2g/L to enter mass volume ratio；
(2) sacrifice agent is added in the reaction system of above-mentioned steps (1), the addition of sacrifice agent is the 10 of photochemical catalyst2-105
Times, the sacrifice agent is silver nitrate or ferrous nitrate；
(3) reaction system for the light source irradiation above-mentioned steps (2) for being 300-850nm with wavelength, output oxygen.
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| CN114797973A (en) * | 2022-04-12 | 2022-07-29 | 南京师范大学 | Urea PDI polymer/MoS 2 Catalyst preparation method and application |
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Application publication date: 20180928 |