CN105709831B - A kind of silver orthophosphate-conjugated polymer visible light composite photocatalyst - Google Patents
A kind of silver orthophosphate-conjugated polymer visible light composite photocatalyst Download PDFInfo
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- CN105709831B CN105709831B CN201610057303.6A CN201610057303A CN105709831B CN 105709831 B CN105709831 B CN 105709831B CN 201610057303 A CN201610057303 A CN 201610057303A CN 105709831 B CN105709831 B CN 105709831B
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- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 42
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 title claims abstract description 27
- 229920000547 conjugated polymer Polymers 0.000 title abstract description 6
- 239000004642 Polyimide Substances 0.000 claims abstract description 53
- 229920001721 polyimide Polymers 0.000 claims abstract description 49
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 20
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 229920000877 Melamine resin Polymers 0.000 claims description 9
- 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
- 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 8
- 238000005119 centrifugation Methods 0.000 claims description 6
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 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
- 238000005406 washing Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- MGICRVTUCPFQQZ-UHFFFAOYSA-N 4-methyloxane-2,6-dione Chemical class CC1CC(=O)OC(=O)C1 MGICRVTUCPFQQZ-UHFFFAOYSA-N 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
- 239000004332 silver Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 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
- 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 22
- 239000003054 catalyst Substances 0.000 abstract description 16
- 230000015556 catabolic process Effects 0.000 abstract description 15
- 238000006731 degradation reaction Methods 0.000 abstract description 15
- 230000005855 radiation Effects 0.000 abstract description 12
- 239000000975 dye Substances 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 238000002835 absorbance Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- 229910000161 silver phosphate Inorganic materials 0.000 description 13
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 101710134784 Agnoprotein Proteins 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
- 238000002474 experimental method Methods 0.000 description 4
- 150000007974 melamines Chemical class 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
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000004519 manufacturing process Methods 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
- 229920001223 polyethylene glycol Polymers 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
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 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
- 150000001412 amines Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 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
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 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
- 150000004040 pyrrolidinones Chemical class 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
- 239000004065 semiconductor Substances 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
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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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- 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)
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Abstract
The invention discloses a kind of silver orthophosphate conjugated polymer visible light composite photocatalysts.Phosphoric acid Argent grain is attached to formation silver orthophosphate/polyimides visible light composite photocatalyst on the surface of polyimides, and wherein phosphoric acid Argent grain is spherical shape, and grain size is 300~400 nm.The obtained visible light composite photocatalyst of the present invention has preferable absorption in the ultraviolet visible light region of 200 800 nm, and absorbance is more than 0.3；The visible light catalyst has efficient photocatalytic degradation efficiency under excited by visible light to organic dyestuff rhodamine B：To the rhodamine B solution that concentration is 10 mg/L, when the addition of composite catalyst is 1g/L, the degradation rate of rhodamine is more than 80% after radiation of visible light 30 minutes, reaches more than 95% to the degradation rate of rhodamine B after forty minutes in radiation of visible light.
Description
Technical field
The invention belongs to environmental improvement photocatalysis technology fields, and in particular to a kind of silver orthophosphate-conjugated polymer visible ray
Composite photo-catalyst.
Background technology
Environmental pollution caused by facing mankind serious energy crisis and excessively used due to fossil energy at present,
And photocatalysis technology come environment purification or can decompose aquatic products hydrogen using abundant clean solar energy, thus it is subject to global researchers
Extensive concern.Compared with traditional Treatment process, photocatalysis oxidation technique has energy-efficient, easy to operate, simple for process, clear
It is clean it is nontoxic, reduce secondary pollution the advantages that.
Silver orthophosphate（Ag3PO4）There is stronger photochemical catalytic oxidation ability as novel visible catalyst, theoretical calculation
Quantum efficiency is more up to 90%, far above other visible light catalytic materials (<20%) its quantum efficiency, however in practical application
Far below 90%.This is easily reduced into simple substance with silver ion in silver orthophosphate in actual application by the light induced electron that photocatalysis generates
Silver and its photostability are poor related.How to overcome these defects is the key issue for making silver orthophosphate practical.
The conjugated system that conjugated polymer is made of phenyl ring, C=C or C=N etc. with π delocalized electron structures.Although base
In the electronics of conjugated polymer semiconductor is conductance or the research of photoelectric device is achieved and developed on a large scale very much, but it is in visible regime
Research it is relatively fewer.This is because its broad-band gap causes bad to visible absorption performance, photo-generated carrier mobility is low
Cause photocatalytic activity not high.
The content of the invention
It is an object of the invention to provide a kind of silver orthophosphate/polyimides visible light composite photocatalyst and its preparation sides
Method.
The technical solution used in the present invention is：
Silver orthophosphate/polyimides visible light composite photocatalyst, phosphoric acid Argent grain are attached to shape on the surface of polyimides
Into silver orthophosphate/polyimides visible light composite photocatalyst.
Preferably, the silver orthophosphate/polyimides visible light composite photocatalyst, phosphoric acid Argent grain is spherical, grain size
For 300~400 nm.
The preparation method of the silver orthophosphate/polyimides visible light composite photocatalyst, comprises the following steps：
1) appropriate melamine and dianhydride are mixed and ground uniformly, be warming up to 270-350 DEG C, keep the temperature 4-7h；By gained
Solid mass grind into powder, washing are dried to obtain polyimides；
2) ethanol solution of appropriate polyvinylpyrrolidone is added in the citric acid solution of silver nitrate, stirred in the dark
15-20 min；By step 1）Polyimides obtained is added in above-mentioned solution, the speed stirring of 280rpm-320rpm, then is dripped
Add suitable Na2HPO4Solution；Stirring is stood, centrifugation, and washing drying and grinding obtains silver orthophosphate/polyimides visible ray complex light
Catalyst fines；
3) by step 2）Silver orthophosphate obtained/polyimides visible light composite photocatalyst powder is further in gas shield
Silver orthophosphate/polyimides visible light composite photocatalyst is prepared in lower dry 4-6h.
Preferably, step 1）Middle dianhydride is cyclobutanetetracarboxylic dianhydride, penta tetracarboxylic dianhydride of ring, benzophenone tetracarboxylic dianhydride (BTDA)
Or 3- methyl glutaric anhydrides.
Preferably, step 1）In be warming up to 300-350 DEG C at room temperature with the rate of 5-10 DEG C/min, keep the temperature 5-6h.
Wherein step 1）The selection of diene, warming temperature and heating rate can all influence to close in the synthesis step of polyimides
Into the form for going out polyimides, the polyimides sheet object surface that synthesizes under optimum condition is relatively smooth to be conducive to silver orthophosphate
Attachment on its surface.
Preferably, step 1）When middle melamine and dianhydride Hybrid Heating are reacted, melamine is being heated in order to prevent
Excessively distil volatilization at 300-350 DEG C, so needing the device of breathable semi-hermetic.
Preferably, step 1）When middle melamine and dianhydride Hybrid Heating are reacted, mixture is placed in the porcelain boat of capping
In, it is reacted in Muffle furnace.
Preferably, step 2）Middle polyvinylpyrrolidone is PVPK12, PVPK15 or PVPK17.
Preferably, step 2）The ethanol solution of middle polyvinylpyrrolidone is to add polyvinylpyrrolidone in every liter of ethyl alcohol
15-20 g。
Wherein polyvinylpyrrolidone is used as structure directing agent herein, can ensure that silver nitrate is having polyamides Asia
Energy and Na under the conditions of amine is existing2HPO4The preferable silver orthophosphate of reaction generation form is simultaneously attached to polyimide surface, is through excessive
What secondary research and development preferably came out.If replaced with other species surfactant such as polyethylene glycol, phosphoric acid Argent grain can not be formed
Preferably it is attached to the compound of polyimides.In addition, it is optimal for ethyl alcohol for the solvent of polyethylene dissolving pyrrolidones, if with
Other solvents substitute or cause the dissolubility of polyvinylpyrrolidone bad or not environmentally.
Preferably, step 2）The molar ratio of silver nitrate and citric acid is (1.2-1) in the citric acid solution of middle silver nitrate：1.
Citric acid here functions as the effect of complexing agent, is by repeatedly researching and developing preferably out.If with common
The complexing agents such as EDTA substitute citric acid, and obtained silver orthophosphate composite catalyst catalytic activity is relatively low.
Preferably, step 2）Middle added polyimides accounts for the 10%-15% of the quality of silver orthophosphate.
Preferably, step 3）In under nitrogen protection, temperature during vacuum drying is 70-90 DEG C.
The beneficial effects of the invention are as follows：
The Ag that the present invention is prepared3PO4Grain diameter（300~400 nm）More general solwution method（Grain size>1μm）It prepares
Be obviously reduced, be conducive to improve Ag3PO4Specific surface area, increase and the contact area of pollutant；In addition, required addition is another
The quality of one component polyimides is less than Ag3PO4The 15% of quality since polyimides raw material abundance, manufacturing cost are low, has
Beneficial to reduction catalyst cost while composite photo-catalyst performance is improved.The building-up process is environmental-friendly, it is of low cost and
It is easily enlarged metaplasia production.
The obtained visible light composite photocatalyst of the present invention is formed by two kinds of Material claddings of silver orthophosphate and polyimides,
Middle phosphoric acid Argent grain is attached on the surface of polyimides.
The obtained visible light composite photocatalyst of the present invention has preferable in the ultraviolet visible light region of 200-800 nm
It absorbs, absorbance is more than 0.3；The visible-light photocatalyst has height under excited by visible light to organic dyestuff rhodamine B
The photocatalytic degradation efficiency of effect：It is the rhodamine B solution of 10 mg/L to concentration, when the addition of composite catalyst is 1g/L,
The degradation rate of rhodamine is more than 80% after radiation of visible light 30 minutes, to the drop of rhodamine B after radiation of visible light 40 minutes
Solution rate reaches 95 more than %.
Description of the drawings
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 Ag3PO4/ polyimides（b）SEM spectrum；
Fig. 3 is composite photo-catalyst Ag in example 13PO4The UV-Visible absorption collection of illustrative plates of/polyimides；
Fig. 4 utilizes composite photo-catalyst Ag for example 13PO4The result of the test of/polyimides rhodamine B degradation；
Fig. 5 utilizes composite photo-catalyst Ag for example 23PO4The result of the test of/polyimides rhodamine B degradation.
Specific embodiment
With reference to specific embodiment, the invention will be further described, but is not limited thereto.
Embodiment 1
（1）By 0.252 g melamines and 0.392 g cyclobutanetetracarboxylic dianhydride mixed grindings, then mixture is put
In the porcelain boat of capping, it is put into Muffle furnace and is warming up to 350 DEG C with the speed of 10 DEG C/min, keep the temperature 5 h；
（2）By obtained solid block grind into powder, it is washed with deionized repeatedly, is dried to obtain polyimides；
（3）0.20 mol/L AgNO of 50 mL, 0.20 mol/L citric acid solutions and 50 mL are prepared respectively3Solution；
（4）By prepared AgNO3Solution is added in citric acid solution, stirs 15 min in the dark；
（5）Prepare 100 mL, 15 g/L polyvinylpyrrolidones（PVPK15）Ethanol solution, and be added to step（4）
In solution, 20 min are stirred in the dark；
（6）Take step（2）Preparation-obtained 0.50 g of polyimide powder is added in（5）In with 280rpm-320rpm's
15 min of speed strong stirring；
（7）By prepared 100 mL, 0.06 mol/L Na2HPO4Solution is added drop-wise to step with the 1 drop rate of/3 seconds
（6）In solution, 2 h are stirred after being added dropwise, it is still aging；
（8）Centrifugation, is washed 2 times with deionized water and absolute ethyl alcohol, visible ray complex light is dried to obtain at 60 DEG C respectively
Catalyst Ag3PO4/ polyimides；
（9）By step（8）Obtained catalyst pulverizes and further in N2Under protection 80 DEG C in vacuum drying chamber
5 h are heated, make Ag3PO4Polyimide surface is preferably attached to, finally can obtain the visible light composite photocatalyst.
Performance characterization is tested
The composite photo-catalyst prepared in embodiment 1 is subjected to X-ray diffraction, scanning electron microscope and uv-vis spectra respectively
Analysis, it is as a result as follows：
X ray diffracting spectrum is as shown in Figure 1：All diffraction of the visible light composite photocatalyst of embodiment 1 as shown in Figure 1
Peak and standard JCPDS（74-0911）Card is completely the same, it was demonstrated that it is cubic phase silver orthophosphate.By scanning electron microscope to embodiment 1
The pattern for the composite photo-catalyst being prepared is observed, and the results are shown in Figure 2：Wherein Fig. 2 a are prepared for embodiment 1
Ag3PO4, grain size is 300-400 nm；Fig. 2 b are Ag3PO4/ polyimides, visible phosphoric acid Argent grain is attached to polyamides in figure
On the surface of imines.Ultraviolet-visible spectrum analysis is as shown in Figure 3：Composite photo-catalyst is in the ultraviolet of 200-800nm as shown in Figure 3
Visible region has preferable absorption, and absorbance absorbs plain edge edge near 550 nm, show the catalyst pair more than 0.3
Visible ray has apparent influx and translocation effect.
The composite photo-catalyst prepared using embodiment 1 degrades to organic dyestuff rhodamine B under excited by visible light
Experiment, the results are shown in Figure 4.Fig. 4 shows that the composite photo-catalyst has higher degradation efficiency to rhodamine B.It is to concentration
The rhodamine B solution of 10 mg/L, when the addition of composite photo-catalyst is 1g/L, the Luo Dan after radiation of visible light 30 minutes
Bright degradation rate is more than 80%, reaches 95 more than % to the degradation rate of rhodamine B after 40 minutes in radiation of visible light.
Embodiment 2
（1）By 0.252 g melamines and 0.644g benzophenone tetracarboxylic dianhydride (BTDA) mixed grindings, then mixture is put
In the porcelain boat of capping, it is put into Muffle furnace and is warming up to 300 DEG C with the speed of 6 DEG C/min, keep the temperature 5 h；
（2）By obtained solid block grind into powder, it is washed with deionized repeatedly, is dried to obtain polyimides；
（3）0.20 mol/L AgNO of 50 mL, 0.20 mol/L citric acid solutions and 50 mL are prepared respectively3Solution；
（4）By prepared AgNO3Solution is added in citric acid solution, stirs 15 min in the dark；
（5）Prepare 100 mL, 18 g/L polyvinylpyrrolidones（PVPK12）Ethanol solution, and be added to step（4）
In solution, 20 min are stirred in the dark；
（6）Take step（2）Preparation-obtained 0.42 g of polyimide powder is added to（5）In with 280rpm-320rpm
Speed stir 15 min；
（7）By prepared 100 mL, 0.06 mol/L Na2HPO4Solution is added drop-wise to step with the 1 drop rate of/4 seconds
（6）In solution, 2 h are stirred after being added dropwise, it is still aging；
（8）Centrifugation, is washed 2 times with deionized water and absolute ethyl alcohol, visible ray complex light is dried to obtain at 60 DEG C respectively
Catalyst Ag3PO4/ polyimides；
（9）By step（8）Obtained catalyst pulverizes and further in N2Under protection 90 DEG C in vacuum drying chamber
5 h are heated, make Ag3PO4Polyimide surface is preferably attached to, finally can obtain the visible light composite photocatalyst.
The composite photo-catalyst prepared using embodiment 2 degrades to organic dyestuff rhodamine B under excited by visible light
Experiment, the results are shown in Figure 5.Fig. 5 shows that the composite photo-catalyst has higher degradation efficiency to rhodamine B.It is to concentration
The rhodamine B solution of 10 mg/L, when the addition of composite photo-catalyst is 1g/L, the Luo Dan after radiation of visible light 30 minutes
Bright degradation rate is more than 75%, reaches more than 90% to the degradation rate of rhodamine B after 40 minutes in radiation of visible light.
Comparative example 1
（1）By 0.252 g melamines and 0.392 g cyclobutanetetracarboxylic dianhydride mixed grindings, then mixture is put
In the porcelain boat of capping, it is put into Muffle furnace and is warming up to 350 DEG C with the speed of 15 DEG C/min, keep the temperature 5 h；
（2）By obtained solid block grind into powder, it is washed with deionized repeatedly, is dried to obtain polyimides；
（3）0.20 mol/L AgNO of 50 mL, 0.20 mol/L citric acid solutions and 50 mL are prepared respectively3Solution；
（4）By prepared AgNO3Solution is added in citric acid solution, stirs 15 min in the dark；
（5）Prepare 100 mL, 15 g/L polyethylene glycol（PEG-600）Ethanol solution, and be added to step（4）Solution
In, 20 min are stirred in the dark；
（6）Take step（2）Preparation-obtained 0.50 g of polyimide powder is added in（5）Middle 15 min of strong stirring；
（7）By prepared 100 mL, 0.06 mol/L Na2HPO4Solution is added drop-wise to step with the 1 drop rate of/3 seconds
（6）In solution, 2 h are stirred after being added dropwise, it is still aging；
（8）Centrifugation, is washed 2 times with deionized water and absolute ethyl alcohol, visible ray complex light is dried to obtain at 60 DEG C respectively
Catalyst Ag3PO4/ polyimides；
（9）By step（8）Obtained catalyst pulverizes and further in N2Under protection 80 DEG C in vacuum drying chamber
5 h are heated, make Ag3PO4Polyimide surface is preferably attached to, finally can obtain the visible light composite photocatalyst.
The composite photo-catalyst prepared using comparative example 1 degrades to organic dyestuff rhodamine B under excited by visible light
Experiment, to the rhodamine B solution that concentration is 10 mg/L, when the addition of composite photo-catalyst is 1g/L, in radiation of visible light
The degradation rate of rhodamine is only 55% after 30 minutes, and 70 are only reached to the degradation rate of rhodamine B after 40 minutes in radiation of visible light
%。
Comparative example 2
（1）By 0.252 g melamines and 0.644g benzophenone tetracarboxylic dianhydride (BTDA) mixed grindings, then mixture is put
In the porcelain boat of capping, it is put into Muffle furnace and is warming up to 300 DEG C with the speed of 8 DEG C/min, keep the temperature 5 h；
（2）By obtained solid block grind into powder, it is washed with deionized repeatedly, is dried to obtain polyimides；
（3）0.20 mol/L AgNO of 50 mL, 0.20 mol/L EDTA solution and 50 mL are prepared respectively3Solution；
（4）By prepared AgNO3Solution is added in EDTA solution, stirs 15 min in the dark；
（5）Prepare 100 mL, 18 g/L polyvinylpyrrolidones（PVPK12）Ethanol solution, and be added to step（4）
In solution, 20 min are stirred in the dark；
（6）Take step（2）Preparation-obtained 0.42 g of polyimide powder is added in（5）Middle 15 min of strong stirring；
（7）By prepared 100 mL, 0.06 mol/L Na2HPO4Solution is added drop-wise to step with the 1 drop rate of/4 seconds
（6）In solution, 2 h are stirred after being added dropwise, it is still aging；
（8）Centrifugation, is washed 2 times with deionized water and absolute ethyl alcohol, visible ray complex light is dried to obtain at 60 DEG C respectively
Catalyst Ag3PO4/ polyimides；
（9）By step（8）Obtained catalyst pulverizes and further in N2Under protection 80 DEG C in vacuum drying chamber
5 h are heated, make Ag3PO4Polyimide surface is preferably attached to, finally can obtain the visible light composite photocatalyst.
The composite photo-catalyst prepared using comparative example 2 degrades to organic dyestuff rhodamine B under excited by visible light
Experiment, to the rhodamine B solution that concentration is 10 mg/L, when the addition of composite photo-catalyst is 1g/L, in radiation of visible light
The degradation rate of rhodamine is only 50% after 30 minutes, and 65 are only reached to the degradation rate of rhodamine B after 40 minutes in radiation of visible light
%。
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (8)
1. the preparation method of a kind of silver orthophosphate/polyimides visible light composite photocatalyst, which is characterized in that including following step
Suddenly：
1）Appropriate melamine and dianhydride are mixed and ground uniformly, is warming up to 270-350 DEG C, keeps the temperature 4-7h；By obtained solid
Block grind into powder, washing are dried to obtain polyimides；
2）The ethanol solution of appropriate polyvinylpyrrolidone is added in the citric acid solution of silver nitrate, stirs 15- in the dark
20 min；By step 1）Polyimides obtained is added in above-mentioned solution, the speed stirring of 280rpm-320rpm, then is added dropwise
Suitable Na2HPO4Solution；Stirring is stood, centrifugation, and washing drying and grinding obtains silver orthophosphate/polyimides visible ray complex light and urges
Agent powder；
3）By step 2）Silver orthophosphate obtained/polyimides visible light composite photocatalyst powder is further done under gas shield
Dry 4-6h is prepared silver orthophosphate/polyimides visible ray complex light that phosphoric acid Argent grain is attached on polyimide surface and urges
Agent.
2. preparation method according to claim 1, it is characterised in that：Step 1）Middle dianhydride for cyclobutanetetracarboxylic dianhydride,
Penta tetracarboxylic dianhydride of ring, benzophenone tetracarboxylic dianhydride (BTDA) or 3- methyl glutaric anhydrides.
3. preparation method according to claim 1, it is characterised in that：Step 1）In at room temperature with the rate of 5-10 DEG C/min
It carries out being warming up to 300-350 DEG C, keeps the temperature 5-6h.
4. preparation method according to claim 1, it is characterised in that：Step 2）Middle polyvinylpyrrolidone for PVPK12,
PVPK15 or PVPK17.
5. preparation method according to claim 1, it is characterised in that：Step 2）The ethanol solution of middle polyvinylpyrrolidone
To add polyvinylpyrrolidone 15-20 g in every liter of ethyl alcohol.
6. preparation method according to claim 1, it is characterised in that：Step 2）Nitric acid in the citric acid solution of middle silver nitrate
The molar ratio of silver and citric acid is (1.2-1)：1.
7. preparation method according to claim 1, it is characterised in that：Step 2）Middle added polyimides accounts for silver orthophosphate
Quality 10%-15%.
8. preparation method according to claim 1, it is characterised in that：Step 3）In under nitrogen protection, during vacuum drying
Temperature be 70-90 DEG C.
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