CN105709831A - Silver phosphate and conjugated polymer visible light composite photocatalyst - Google Patents
Silver phosphate and conjugated polymer visible light composite photocatalyst Download PDFInfo
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- CN105709831A CN105709831A CN201610057303.6A CN201610057303A CN105709831A CN 105709831 A CN105709831 A CN 105709831A CN 201610057303 A CN201610057303 A CN 201610057303A CN 105709831 A CN105709831 A CN 105709831A
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- visible light
- polyimides
- silver phosphate
- composite photocatalyst
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- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 229910000161 silver phosphate Inorganic materials 0.000 title claims abstract description 51
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 50
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 title claims abstract description 37
- 229940019931 silver phosphate Drugs 0.000 title claims abstract description 37
- 229920000547 conjugated polymer Polymers 0.000 title abstract description 6
- 239000004642 Polyimide Substances 0.000 claims abstract description 56
- 229920001721 polyimide Polymers 0.000 claims abstract description 56
- 239000002245 particle Substances 0.000 claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 12
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 9
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000008187 granular material Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- UZVQOEUTOCRSJN-UHFFFAOYSA-N silver 2-hydroxypropane-1,2,3-tricarboxylic acid nitrate Chemical compound [N+](=O)([O-])[O-].[Ag+].C(CC(O)(C(=O)O)CC(=O)O)(=O)O UZVQOEUTOCRSJN-UHFFFAOYSA-N 0.000 claims description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- AMHXQVUODFNFGR-UHFFFAOYSA-K [Ag+3].[O-]P([O-])([O-])=O Chemical compound [Ag+3].[O-]P([O-])([O-])=O AMHXQVUODFNFGR-UHFFFAOYSA-K 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 abstract description 26
- 229940043267 rhodamine b Drugs 0.000 abstract description 21
- 230000015556 catabolic process Effects 0.000 abstract description 15
- 238000006731 degradation reaction Methods 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 abstract description 11
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 238000002835 absorbance Methods 0.000 abstract description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- 230000005284 excitation Effects 0.000 abstract 1
- 230000005855 radiation Effects 0.000 description 10
- 101710134784 Agnoprotein Proteins 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000000975 dye Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004941 influx Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000005945 translocation Effects 0.000 description 1
- 238000002371 ultraviolet--visible spectrum 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
- B01J31/26—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
- B01J31/02—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
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
-
- 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)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a silver phosphate and conjugated polymer visible light composite photocatalyst. Silver phosphate particles are attached to the surface of polyimide to form a silver phosphate/polyimide visible light composite photocatalyst, wherein the silver phosphate particles are spherical, and the particle size is 300-400 nm. The obtained visible light composite photocatalyst has good absorption performance in a 200-800 nm ultraviolet visible light area, and absorbance exceeds 0.3. The visible light catalyst has efficient photocatalytic degradation efficiency on organic dye rhodamine B under excitation of visible light. As for a rhodamine B solution with the concentration being 10 mg/L, when the addition amount of the composite catalyst is 1g/L, the degradation rate of rhodamine exceeds 80% after being irradiated by visible light for 30 min, and the degradation rate of rhodamine reaches 95% or above after being irradiated by visible light for 40 min.
Description
Technical field
The invention belongs to environmental improvement photocatalysis technology field, be specifically related to a kind of silver phosphate-conjugated polymer visible ray
Composite photo-catalyst.
Background technology
Facing mankind serious energy crisis and excessively uses caused environmental pollution due to fossil energy at present,
And photocatalysis technology can utilize the solar energy of abundant cleaning carry out environment purification or decompose Aquatic product hydrogen, thus by whole world researchers
Extensive concern.Compared with traditional Treatment process, photocatalysis oxidation technique has operation energy-efficient, easy, technique simply, clearly
The advantages such as clean nontoxic, minimizing secondary pollution.
Silver phosphate (Ag3PO4) as novel visible catalyst, there is stronger photochemical catalytic oxidation ability, Theoretical Calculation
Quantum efficiency is more up to 90%, far above other visible light catalytic material (< 20%), but its quantum efficiency in actual application
Far below 90%.This light induced electron easily generated by photocatalysis with silver ion in silver phosphate in actual application is reduced into simple substance
Silver and light stability thereof are poor relevant.How overcoming these defects is the key issue making silver phosphate practical.
Conjugated polymer is had, by phenyl ring, C=C or C=N etc., the conjugated system that π delocalized electron structure is formed.Although base
Conductance or photoelectric device the research of electronics in conjugated polymer quasiconductor achieves and develops on a large scale very much, but it is at visible regime
Research the most relatively fewer.This is that photo-generated carrier mobility is low owing to its broad-band gap causes visible absorption performance the best
Cause photocatalytic activity the highest.
Summary of the invention
It is an object of the invention to provide a kind of silver phosphate/polyimides visible light composite photocatalyst and preparation side thereof
Method.
The technical solution used in the present invention is:
Silver phosphate/polyimides visible light composite photocatalyst, silver phosphate granule is attached on the surface of polyimides form phosphorus
Acid silver/polyimides visible light composite photocatalyst.
Preferably, described silver phosphate/polyimides visible light composite photocatalyst, its silver phosphate granule is spherical, particle diameter
It is 300～400 nm.
The preparation method of described silver phosphate/polyimides visible light composite photocatalyst, comprises the following steps:
1) appropriate tripolycyanamide and dianhydride mixed and grind uniformly, being warming up to 270-350 DEG C, being incubated 4-7h；By gained solid
Block grind into powder, washing is dried to obtain polyimides；
2) ethanol solution of appropriate polyvinylpyrrolidone is joined in the citric acid solution of silver nitrate, in the dark stir 15-
20 min；The polyimides that step 1) prepares is joined in above-mentioned solution, the speed stirring of 280rpm-320rpm, then drip
Appropriate Na2HPO4Solution；Stirring, stand, be centrifuged, washing drying and grinding obtains silver phosphate/polyimides visible ray complex light and urges
Agent powder；
3) by step 2) silver phosphate/polyimides visible light composite photocatalyst powder of preparing is dry under gas shield further
Dry 4-6h, prepares silver phosphate/polyimides visible light composite photocatalyst.
Preferably, in step 1), dianhydride is cyclobutanetetracarboxylic dianhydride, ring penta tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride (BTDA)
Or 3-methylpent dianhydride.
Preferably, in step 1), under room temperature, speed with 5-10 DEG C/min carries out being warming up to 300-350 DEG C, is incubated 5-6h.
Wherein in the synthesis step of step 1) polyimides, the choosing of diene, warming temperature and heating rate all can affect conjunction
Become out the form of polyimides, the most smooth beneficially silver phosphate in polyimides lamellar thing surface synthesized under optimum condition
Attachment on its surface.
Preferably, in step 1) when tripolycyanamide and the reaction of dianhydride Hybrid Heating, in order to prevent tripolycyanamide being heated to
Excessively distil when 300-350 DEG C volatilization, so needing the device of the semi-hermetic that can breathe freely.
Preferably, in step 1) when tripolycyanamide and the reaction of dianhydride Hybrid Heating, mixture is placed in the porcelain boat adding lid
In, react in Muffle furnace.
Preferably, step 2) in polyvinylpyrrolidone be PVPK12, PVPK15 or PVPK17.
Preferably, step 2) in the ethanol solution of polyvinylpyrrolidone be interpolation polyvinylpyrrolidone in every liter of ethanol
15-20 g。
Wherein polyvinylpyrrolidone is here to use as structure directing agent, it is possible to ensure that silver nitrate is having polyamides sub-
Energy and Na under conditions of amine existence2HPO4Reaction generates the preferable silver phosphate of form and is attached to polyimide surface, is through too much
Secondary research and development are the most out.If replaced with other kind surfactant such as Polyethylene Glycol, then cannot form silver phosphate granule
Preferably it is attached to the complex of polyimides.Additionally, the solvent optimum for polyethylene dissolving ketopyrrolidine is ethanol, if used
Other solvent substitutes, or causes the dissolubility of polyvinylpyrrolidone bad, or not environmentally.
Preferably, step 2) in silver nitrate citric acid solution in the mol ratio of silver nitrate and citric acid be (1.2-1): 1.
Citric acid here functions as the effect of chelating agent, through repeatedly researching and developing the most out.If with commonly use
The chelating agent such as EDTA substitute citric acid, and the silver phosphate composite catalyst obtained catalysis activity is relatively low.
Preferably, step 2) in the polyimides that added account for the 10%-15% of quality of silver phosphate.
Preferably, in step 3) under nitrogen protection, temperature during vacuum drying is 70-90 DEG C.
The invention has the beneficial effects as follows:
The Ag that the present invention prepares3PO4Prepared by grain diameter (300～400 nm) more general solwution method (particle diameter > 1 μm) bright
Aobvious reduction, is conducive to improving Ag3PO4Specific surface area, increase and the contact area of pollutant；Additionally, another group of required addition
The quality of part polyimides is less than Ag3PO4The 15% of quality, owing to polyimides raw material abundance, preparation cost are low, is conducive to
Catalyst cost is reduced while improving composite photo-catalyst performance.This building-up process environmental friendliness, with low cost and be prone to
Extension produces.
Visible light composite photocatalyst obtained by the present invention is composited by silver phosphate and polyimides bi-material, its
Middle silver phosphate granule is attached on the surface of polyimides.
Visible light composite photocatalyst obtained by the present invention has preferably in the ultraviolet-visible district of 200-800 nm
Absorbing, absorbance is all more than 0.3；Described visible-light photocatalyst has height to organic dyestuff rhodamine B under excited by visible light
The photocatalytic degradation efficiency of effect: to the rhodamine B solution that concentration is 10 mg/L, when the addition of composite catalyst is 1g/L,
After radiation of visible light 30 minutes, the degradation rate of rhodamine is more than 80%, fall to rhodamine B after radiation of visible light 40 minutes
Solution rate reaches 95 more than %.
Accompanying drawing explanation
Fig. 1 is composite photo-catalyst Ag in example 13PO4The X ray diffracting spectrum of/polyimides；
Fig. 2 is composite photo-catalyst Ag in example 13PO4(a) and Ag3PO4The SEM collection of illustrative plates of/polyimides (b)；
Fig. 3 is composite photo-catalyst Ag in example 13PO4The UV-Visible absorption collection of illustrative plates of/polyimides；
Fig. 4 is that example 1 utilizes composite photo-catalyst Ag3PO4The result of the test of/polyimides rhodamine B degradation；
Fig. 5 is that example 2 utilizes composite photo-catalyst Ag3PO4The result of the test of/polyimides rhodamine B degradation.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described, but is not limited thereto.
Embodiment 1
(1) by 0.252 g tripolycyanamide and 0.392 g cyclobutanetetracarboxylic dianhydride mixed grinding, then mixture is placed in and adds
In the porcelain boat of lid, it is put in Muffle furnace and is warming up to 350 DEG C with the speed of 10 DEG C/min, being incubated 5 h；
(2) by gained solid mass grind into powder, it is washed with deionized repeatedly, is dried to obtain polyimides；
(3) 50 mL 0.20 mol/L citric acid solutions and 50 mL 0.20 mol/L AgNO are prepared respectively3Solution；
(4) AgNO that will prepare3Solution adds in citric acid solution, in the dark stirs 15 min；
(5) prepare the ethanol solution of 100 mL 15 g/L polyvinylpyrrolidone (PVPK15), and join step (4) solution
In, in the dark stir 20 min；
(6) speed with 280rpm-320rpm in step (2) preparation-obtained polyimide powder 0.50 g addition (5) is taken
Strong stirring 15 min；
(7) the 100 mL 0.06 mol/L Na that will prepare2HPO4Solution, is added drop-wise to step (6) with the speed of 1/3 seconds molten
In liquid, after dropping, stir 2 h, still aging；
(8) centrifugal, respectively with deionized water and absolute ethanol washing 2 times, at 60 DEG C, it is dried to obtain visible ray composite photocatalyst
Agent Ag3PO4/ polyimides；
(9) catalyst that step (8) obtains is pulverized and further at N280 DEG C of heating in vacuum drying oven under protection
5 h, make Ag3PO4Preferably it is attached to polyimide surface, final available described visible light composite photocatalyst.
Performance characterization is tested
The composite photo-catalyst of preparation in embodiment 1 is carried out X-ray diffraction, scanning electron microscope and uv-vis spectra respectively divide
Analysis, result is as follows:
X ray diffracting spectrum is as shown in Figure 1: as shown in Figure 1 all of diffraction maximum of the visible light composite photocatalyst of embodiment 1 with
Standard JCPDS(74-0911) card is completely the same, it was demonstrated that and it is Emission in Cubic silver phosphate.By scanning electron microscope prepared by embodiment 1
The pattern of the composite photo-catalyst obtained is observed, result as shown in Figure 2: wherein Fig. 2 a is that embodiment 1 prepares
Ag3PO4, its particle diameter is 300-400 nm；Fig. 2 b is Ag3PO4/ polyimides, in figure, visible silver phosphate granule is attached to polyamides
On the surface of imines.Ultraviolet-visible analysis of spectrum is as shown in Figure 3: composite photo-catalyst is in the ultraviolet of 200-800nm as shown in Figure 3
Visible region has preferably absorption, and absorbance is all more than 0.3, and absorbing light edge, near 550 nm, shows this catalyst pair
Visible ray has obvious influx and translocation effect.
Organic dyestuff rhodamine B is degraded under excited by visible light by the composite photo-catalyst utilizing embodiment 1 to prepare
Experiment, result is as shown in Figure 4.Fig. 4 shows that this composite photo-catalyst has higher degradation efficiency to rhodamine B.To concentration it is
The rhodamine B solution of 10 mg/L, when the addition of composite photo-catalyst is 1g/L, Luo Dan after radiation of visible light 30 minutes
Bright degradation rate, more than 80%, reaches 95 more than % to the degradation rate of rhodamine B after radiation of visible light 40 minutes.
Embodiment 2
(1) by 0.252 g tripolycyanamide and 0.644g benzophenone tetracarboxylic dianhydride (BTDA) mixed grinding, then mixture is placed in and adds
In the porcelain boat of lid, it is put in Muffle furnace and is warming up to 300 DEG C with the speed of 6 DEG C/min, being incubated 5 h；
(2) by gained solid mass grind into powder, it is washed with deionized repeatedly, is dried to obtain polyimides；
(3) 50 mL 0.20 mol/L citric acid solutions and 50 mL 0.20 mol/L AgNO are prepared respectively3Solution；
(4) AgNO that will prepare3Solution joins in citric acid solution, in the dark stirs 15 min；
(5) prepare the ethanol solution of 100 mL 18 g/L polyvinylpyrrolidone (PVPK12), and join step (4) solution
In, in the dark stir 20 min；
(6) take step (2) preparation-obtained polyimide powder 0.42 g and join in (5) speed with 280rpm-320rpm
Degree stirring 15 min；
(7) the 100 mL 0.06 mol/L Na that will prepare2HPO4Solution, is added drop-wise to step (6) with the speed of 1/4 seconds molten
In liquid, after dropping, stir 2 h, still aging；
(8) centrifugal, respectively with deionized water and absolute ethanol washing 2 times, at 60 DEG C, it is dried to obtain visible ray composite photocatalyst
Agent Ag3PO4/ polyimides；
(9) catalyst that step (8) obtains is pulverized and further at N290 DEG C of heating in vacuum drying oven under protection
5 h, make Ag3PO4Preferably it is attached to polyimide surface, final available described visible light composite photocatalyst.
Organic dyestuff rhodamine B is degraded under excited by visible light by the composite photo-catalyst utilizing embodiment 2 to prepare
Experiment, result is as shown in Figure 5.Fig. 5 shows that this composite photo-catalyst has higher degradation efficiency to rhodamine B.To concentration it is
The rhodamine B solution of 10 mg/L, when the addition of composite photo-catalyst is 1g/L, Luo Dan after radiation of visible light 30 minutes
Bright degradation rate, more than 75%, reaches more than 90% to the degradation rate of rhodamine B after radiation of visible light 40 minutes.
Comparative example 1
(1) by 0.252 g tripolycyanamide and 0.392 g cyclobutanetetracarboxylic dianhydride mixed grinding, then mixture is placed in and adds
In the porcelain boat of lid, it is put in Muffle furnace and is warming up to 350 DEG C with the speed of 15 DEG C/min, being incubated 5 h；
(2) by gained solid mass grind into powder, it is washed with deionized repeatedly, is dried to obtain polyimides；
(3) 50 mL 0.20 mol/L citric acid solutions and 50 mL 0.20 mol/L AgNO are prepared respectively3Solution；
(4) AgNO that will prepare3Solution adds in citric acid solution, in the dark stirs 15 min；
(5) prepare the ethanol solution of 100 mL 15 g/L Polyethylene Glycol (PEG-600), and join in step (4) solution,
20 min are stirred in dark place；
(6) take step (2) preparation-obtained polyimide powder 0.50 g and add strong stirring 15 min in (5)；
(7) the 100 mL 0.06 mol/L Na that will prepare2HPO4Solution, is added drop-wise to step (6) with the speed of 1/3 seconds molten
In liquid, after dropping, stir 2 h, still aging；
(8) centrifugal, respectively with deionized water and absolute ethanol washing 2 times, at 60 DEG C, it is dried to obtain visible ray composite photocatalyst
Agent Ag3PO4/ polyimides；
(9) catalyst that step (8) obtains is pulverized and further at N280 DEG C of heating in vacuum drying oven under protection
5 h, make Ag3PO4Preferably it is attached to polyimide surface, final available described visible light composite photocatalyst.
Organic dyestuff rhodamine B is degraded under excited by visible light by the composite photo-catalyst utilizing comparative example 1 to prepare
Experiment, to the rhodamine B solution that concentration is 10 mg/L, when the addition of composite photo-catalyst is 1g/L, at radiation of visible light
After 30 minutes, the degradation rate of rhodamine is only 55%, after radiation of visible light 40 minutes, the degradation rate of rhodamine B is only reached 70
%。
Comparative example 2
(1) by 0.252 g tripolycyanamide and 0.644g benzophenone tetracarboxylic dianhydride (BTDA) mixed grinding, then mixture is placed in and adds
In the porcelain boat of lid, it is put in Muffle furnace and is warming up to 300 DEG C with the speed of 8 DEG C/min, being incubated 5 h；
(2) by gained solid mass grind into powder, it is washed with deionized repeatedly, is dried to obtain polyimides；
(3) 50 mL 0.20 mol/L EDTA solution and 50 mL 0.20 mol/L AgNO are prepared respectively3Solution；
(4) AgNO that will prepare3Solution adds in EDTA solution, in the dark stirs 15 min；
(5) prepare the ethanol solution of 100 mL 18 g/L polyvinylpyrrolidone (PVPK12), and join step (4) solution
In, in the dark stir 20 min；
(6) take step (2) preparation-obtained polyimide powder 0.42 g and add strong stirring 15 min in (5)；
(7) the 100 mL 0.06 mol/L Na that will prepare2HPO4Solution, is added drop-wise to step (6) with the speed of 1/4 seconds molten
In liquid, after dropping, stir 2 h, still aging；
(8) centrifugal, respectively with deionized water and absolute ethanol washing 2 times, at 60 DEG C, it is dried to obtain visible ray composite photocatalyst
Agent Ag3PO4/ polyimides；
(9) catalyst that step (8) obtains is pulverized and further at N280 DEG C of heating in vacuum drying oven under protection
5 h, make Ag3PO4Preferably it is attached to polyimide surface, final available described visible light composite photocatalyst.
Organic dyestuff rhodamine B is degraded under excited by visible light by the composite photo-catalyst utilizing comparative example 2 to prepare
Experiment, to the rhodamine B solution that concentration is 10 mg/L, when the addition of composite photo-catalyst is 1g/L, at radiation of visible light
After 30 minutes, the degradation rate of rhodamine is only 50%, after radiation of visible light 40 minutes, the degradation rate of rhodamine B is only reached 65
%。
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify,
All should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (10)
1. silver phosphate/polyimides visible light composite photocatalyst, it is characterised in that: silver phosphate granule is attached to polyimides
Silver phosphate/polyimides visible light composite photocatalyst is formed on surface.
Silver phosphate the most according to claim 1/polyimides visible light composite photocatalyst, it is characterised in that: silver phosphate
Granule is spherical, and particle diameter is 300～400 nm.
3. the preparation method of the silver phosphate described in claim 1/polyimides visible light composite photocatalyst, it is characterised in that
Comprise the following steps:
1) appropriate tripolycyanamide and dianhydride mixed and grind uniformly, being warming up to 270-350 DEG C, being incubated 4-7h；By gained solid
Block grind into powder, washing is dried to obtain polyimides；
2) ethanol solution of appropriate polyvinylpyrrolidone is joined in the citric acid solution of silver nitrate, in the dark stir 15-
20 min；The polyimides that step 1) prepares is joined in above-mentioned solution, the speed stirring of 280rpm-320rpm, then drip
Appropriate Na2HPO4Solution；Stirring, stand, be centrifuged, washing drying and grinding obtains silver phosphate/Polyimides visible ray complex light is urged
Agent powder；
3) by step 2) silver phosphate/polyimides visible light composite photocatalyst powder of preparing is dry under gas shield further
Dry 4-6h, prepares silver phosphate/polyimides visible light composite photocatalyst.
Preparation method the most according to claim 3, it is characterised in that: in step 1) dianhydride be cyclobutanetetracarboxylic dianhydride,
Ring penta tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride (BTDA) or 3-methylpent dianhydride.
Preparation method the most according to claim 3, it is characterised in that: with the speed of 5-10 DEG C/min under room temperature in step 1)
Carry out being warming up to 300-350 DEG C, be incubated 5-6h.
Preparation method the most according to claim 3, it is characterised in that: step 2) in polyvinylpyrrolidone be PVPK12,
PVPK15 or PVPK17.
Preparation method the most according to claim 3, it is characterised in that: step 2) in the ethanol solution of polyvinylpyrrolidone
For every liter of ethanol adds polyvinylpyrrolidone 15-20 g.
Preparation method the most according to claim 3, it is characterised in that: step 2) in silver nitrate citric acid solution in nitric acid
The mol ratio of silver and citric acid is (1.2-1): 1.
Preparation method the most according to claim 3, it is characterised in that: step 2) in the polyimides that added account for silver phosphate
The 10%-15% of quality.
Preparation method the most according to claim 3, it is characterised in that: in step 3) under nitrogen protection, during vacuum drying
Temperature be 70-90 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107824207A (en) * | 2017-07-28 | 2018-03-23 | 湖南大学 | A kind of preparation method for the silver phosphate composite photocatalyst for handling water body Malachite Green |
| CN108246364A (en) * | 2018-03-05 | 2018-07-06 | 常州大学 | A kind of preparation method for aoxidizing Ag doping crystalline state polyimides compounded visible light photocatalyst |
| CN109622046A (en) * | 2018-12-29 | 2019-04-16 | 东华大学 | A kind of preparation method of fabric/poly- nitrogen/polypyrrole/bismuth phosphate catalysis material |
| CN110201722A (en) * | 2019-06-13 | 2019-09-06 | 广东石油化工学院 | The silver phosphate composite photocatalyst and its preparation method and application of rose red b in a kind of processing high-salt wastewater |
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| JP2009078211A (en) * | 2007-09-26 | 2009-04-16 | National Institute For Materials Science | Photocatalyst |
| CN103623870A (en) * | 2013-12-11 | 2014-03-12 | 河北科技大学 | Method for preparing silver phosphate/polyvinyl chloride-based conjugated-polyene visible-light catalyst |
| CN104277219A (en) * | 2014-10-11 | 2015-01-14 | 南京大学 | Photocatalytic material polyimide, as well as preparation method and applications thereof |
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2016
- 2016-01-27 CN CN201610057303.6A patent/CN105709831B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009078211A (en) * | 2007-09-26 | 2009-04-16 | National Institute For Materials Science | Photocatalyst |
| CN103623870A (en) * | 2013-12-11 | 2014-03-12 | 河北科技大学 | Method for preparing silver phosphate/polyvinyl chloride-based conjugated-polyene visible-light catalyst |
| CN104277219A (en) * | 2014-10-11 | 2015-01-14 | 南京大学 | Photocatalytic material polyimide, as well as preparation method and applications thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107824207A (en) * | 2017-07-28 | 2018-03-23 | 湖南大学 | A kind of preparation method for the silver phosphate composite photocatalyst for handling water body Malachite Green |
| CN107824207B (en) * | 2017-07-28 | 2020-05-15 | 湖南大学 | Preparation method of silver phosphate composite photocatalyst for treating malachite green in water body |
| CN108246364A (en) * | 2018-03-05 | 2018-07-06 | 常州大学 | A kind of preparation method for aoxidizing Ag doping crystalline state polyimides compounded visible light photocatalyst |
| CN108246364B (en) * | 2018-03-05 | 2020-05-26 | 常州大学 | Preparation method of silver oxide doped crystalline polyimide composite visible light photocatalyst |
| CN109622046A (en) * | 2018-12-29 | 2019-04-16 | 东华大学 | A kind of preparation method of fabric/poly- nitrogen/polypyrrole/bismuth phosphate catalysis material |
| CN110201722A (en) * | 2019-06-13 | 2019-09-06 | 广东石油化工学院 | The silver phosphate composite photocatalyst and its preparation method and application of rose red b in a kind of processing high-salt wastewater |
| CN110201722B (en) * | 2019-06-13 | 2022-04-15 | 广东石油化工学院 | Silver phosphate composite photocatalyst for treating rose bengal B in high-salinity wastewater and preparation method and application thereof |
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