CN115445642B - Coated bifunctional catalyst and preparation method and application thereof - Google Patents
Coated bifunctional catalyst and preparation method and application thereof Download PDFInfo
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- CN115445642B CN115445642B CN202211136167.1A CN202211136167A CN115445642B CN 115445642 B CN115445642 B CN 115445642B CN 202211136167 A CN202211136167 A CN 202211136167A CN 115445642 B CN115445642 B CN 115445642B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 135
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000013179 MIL-101(Fe) Substances 0.000 claims abstract description 81
- 239000000463 material Substances 0.000 claims abstract description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004098 Tetracycline Substances 0.000 claims description 33
- 235000019364 tetracycline Nutrition 0.000 claims description 33
- 150000003522 tetracyclines Chemical class 0.000 claims description 33
- 229960002180 tetracycline Drugs 0.000 claims description 32
- 229930101283 tetracycline Natural products 0.000 claims description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 26
- 101710134784 Agnoprotein Proteins 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 18
- 238000004729 solvothermal method Methods 0.000 claims description 17
- 230000002195 synergetic effect Effects 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical class S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 238000013032 photocatalytic reaction Methods 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229940040944 tetracyclines Drugs 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 36
- 238000004064 recycling Methods 0.000 abstract description 21
- 238000000034 method Methods 0.000 abstract description 10
- 238000001556 precipitation Methods 0.000 abstract description 4
- 239000011941 photocatalyst Substances 0.000 abstract description 3
- 238000005538 encapsulation Methods 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 47
- 230000001699 photocatalysis Effects 0.000 description 22
- 230000000694 effects Effects 0.000 description 19
- 238000012360 testing method Methods 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 13
- 239000013078 crystal Substances 0.000 description 11
- 238000005286 illumination Methods 0.000 description 8
- 238000011056 performance test Methods 0.000 description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000001994 activation Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000013082 iron-based metal-organic framework Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 1
- 229940019931 silver phosphate Drugs 0.000 description 1
- 229910000161 silver phosphate Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- 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
- B01J33/00—Protection of catalysts, e.g. by coating
-
- 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
- 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
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
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- Environmental & Geological Engineering (AREA)
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- Catalysts (AREA)
Abstract
The invention provides a coated bifunctional catalyst and a preparation method thereof, belonging to the technical field of catalytic materials, wherein the coated bifunctional catalyst is MIL-101 (Fe) coated Ag 3 PO 4 Materials according to the invention are obtained by combining Ag 3 PO 4 Encapsulation constructs heterojunction photocatalyst in MIL-101 (Fe) material, thereby solving the problem of Ag 3 PO 4 The catalyst has limited catalytic activity and the recycling stability of the catalyst is difficult to maintain. The invention also provides a preparation method of the coated double-function catalyst, which is used for preparing MIL-101 (Fe) coated Ag 3 PO 4 In the material, ag is prepared by precipitation method 3 PO 4 And forming MIL-101 (Fe) on the surface of the catalyst to form the coated heterojunction catalyst. Thus can reduce Ag 3 PO 4 Contact with water, reduce Ag 3 PO 4 And photo-generate electronsRapid transfer is also achieved through the heterojunction interface, thereby reducing the Ag contact 3 PO 4 Ag in lattice + Can effectively inhibit Ag 3 PO 4 Is not too sensitive to light.
Description
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a coated bifunctional catalyst, and a preparation method and application thereof.
Background
The semiconductor photocatalysis technology has the advantages of high reaction efficiency, high reaction rate, easy regulation and control of reaction conditions, wide sources of catalyst raw materials, rich preparation method and the like, and has great application prospect in the field of organic pollution wastewater treatment because inexhaustible sunlight in nature can be used as excitation energy.
Silver phosphate (Ag) 3 PO 4 ) The catalyst is a visible light response catalyst which has been paid attention in recent years, and mainly because of the low valence band position, the generated photo-generated holes have strong oxidizing ability. However, the strong oxidizing ability is exhibited by the existence of a photo-generated electron sacrificial agent, such as an electron capturing agent AgNO, which is added into the reaction system 3 . Otherwise, photo-generated electrons are more easily formed by Ag 3 PO 4 Ag in lattice + The reduction reaction is carried out by capturing, so that the dissociated Ag is gradually generated + Conversion to Ag 0 And is deposited on the catalyst surface. On the one hand, ag 0 Is formed such that Ag 3 PO 4 Is damaged by the structure of Ag 3 PO 4 Performance as a semiconductor is suppressed; ag, on the other hand 0 In Ag 3 PO 4 The deposition of the surface hinders the light absorption efficiency of the catalyst and reduces the light quantum yield, which in turn reduces the photocatalytic activity, a phenomenon known asPhoto-etching effects are also found in single catalyst systems such as cadmium sulfide. Therefore, it is necessary to take effective measures to cope with this.
It can be seen that there is a need for improvements and improvements in the art.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a coated bifunctional catalyst and a preparation method thereof, which aims to solve the problems of Ag 3 PO 4 The catalyst has limited catalytic activity and the recycling stability of the catalyst is difficult to maintain.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a coated double-function catalyst, which is MIL-101 (Fe) coated Ag 3 PO 4 Material, the MIL-101 (Fe) coats Ag 3 PO 4 MIL-101 (Fe) and Ag in the material 3 PO 4 The mass ratio of (2) is 1 (0.05).
In the coated bifunctional catalyst, MIL-101 (Fe) and Ag 3 PO 4 The mass ratio of (2) is 0.5:1.
In addition, the invention also provides a preparation method of the coated bifunctional catalyst, which comprises the following steps:
step S001, preparing AgNO 3 Solution and NaH 2 PO 4 Solution and NaH 2 PO 4 AgNO addition to solution 3 Fully stirring the solution to obtain solution A;
step S002, centrifuging the solution A, and cleaning, drying, grinding and sieving the centrifuged solid particles to obtain Ag 3 PO 4 ；
Step S003, ag to be prepared 3 PO 4 Ultrasonic dispersing in N, N-dimethylformamide organic solution to obtain dispersion B;
step S004, feCl 3 ·6H 2 O and terephthalic acid are ultrasonically dispersed in an N, N-dimethylformamide organic solvent to obtain a dispersion liquid C;
step S005, mixing the dispersion liquid B and the dispersion liquid C, and performing ultrasonic treatment to obtain a dispersion liquid D;
s006, transferring the dispersion liquid D into a polytetrafluoroethylene lining stainless steel autoclave for solvothermal reaction to obtain liquid E;
step S007, centrifuging the E solution, and cleaning, drying, grinding and sieving the centrifuged solid particles to obtain MIL-101 (Fe) coated Ag 3 PO 4 A material.
Further, in step S001, agNO 3 AgNO in solution 3 The concentration of (C) is 0.0225mol/mL; naH (NaH) 2 PO 4 NaH in solution 2 PO 4 Is 0.035mol/mL, naH 2 PO 4 AgNO addition to solution 3 The speed in the solution was 10mL/min.
Further, in step S001, the stirring time is 1.5h.
Further, in step S002, the rate of adding solution B to solution A was 10mL/min.
Further, in step S002, ag 3 PO 4 The fineness of (3) is 60-120 meshes; in step S007, MIL-101 (Fe) is coated with Ag 3 PO 4 The fineness of the material is 60-120 meshes.
Further, in the step S006, the solvothermal reaction time is 10-20 h, and the reaction temperature is 100-200 ℃.
Further, in step S005, the ultrasonic power is 450W to 700W, and the ultrasonic treatment time is 1h.
The invention also provides application of the coated bifunctional catalyst, in particular application of the coated bifunctional catalyst to treatment of tetracycline-containing organic pollution wastewater.
Further, the coated bifunctional catalyst is used for treating the organic pollution wastewater containing the tetracycline through any one of photocatalytic reaction, activated persulfate Fenton catalytic reaction or photo-Fenton-like synergistic catalytic reaction.
The beneficial effects are that:
the invention provides a coated double-function catalyst, which is MIL-101 (Fe) coating Ag 3 PO 4 Materials according to the invention are obtained by combining Ag 3 PO 4 The heterojunction photocatalyst is packed in MIL-101 (Fe) material, which is favorable for separation of photo-generated electrons and holes, and can obtain more abundant and effective active substances, so that the coated bifunctional catalyst can show excellent photocatalytic degradation activity, activated persulfate Fenton catalytic degradation activity, photo-Fenton-like synergistic catalytic degradation activity and recycling stability, thereby solving the problems of Ag 3 PO 4 The catalyst has limited catalytic activity and the stability of the catalyst is difficult to maintain.
The invention also provides a preparation method of the coated double-function catalyst, which is used for preparing MIL-101 (Fe) coated Ag 3 PO 4 In the material, ag is prepared by precipitation method 3 PO 4 Then through solvothermal reaction on Ag 3 PO 4 The surface realizes the formation of MIL-101 (Fe), thereby forming the coated heterojunction catalyst. Thus can reduce Ag 3 PO 4 Contact with water, reduce Ag 3 PO 4 And photo-generated electrons are rapidly transferred through the heterojunction interface, thereby reducing Ag alignment 3 PO 4 Ag in lattice + Can effectively inhibit Ag 3 PO 4 Is not too sensitive to light.
Description of the drawings:
FIG. 1 shows a coated bifunctional catalyst (MIL-101 (Fe) -coated Ag) prepared in example 1 of the present invention 3 PO 4 Material) is provided.
FIG. 2 is an X-ray diffraction (XRD) pattern of the coated bifunctional catalyst prepared in example 1 of the present invention.
FIG. 3 is a graph showing the ultraviolet-visible absorption spectrum (UV-vis) of the coated bifunctional catalyst prepared in example 1 of the present invention.
FIG. 4 is a graph showing photocatalytic degradation activity of the coated bifunctional catalyst prepared in example 1 of the present invention on tetracycline.
FIG. 5 is a graph showing the Fenton catalytic degradation activity of the activated persulfate of tetracycline by the coated bifunctional catalyst prepared in example 1 of the present invention.
FIG. 6 is a graph showing the photo-Fenton-like synergistic catalytic degradation activity of the coated bifunctional catalyst prepared in example 1 of the present invention on tetracycline (light source 300W xenon lamp, wavelength of light lambda. Gtoreq.420 nm).
FIG. 7 is a photo-Fenton-like co-catalytic degradation activity graph (natural sunlight as a light source, sunny days and outdoor temperature of 27+ -1deg.C) of the coated bifunctional catalyst prepared in example 1 of the present invention on tetracycline.
FIG. 8 is a graph showing the photo-Fenton-like synergistic catalytic degradation activity of the coated bifunctional catalyst prepared in example 1 of the present invention under 5 cycles.
Detailed Description
The invention provides a coated bifunctional catalyst, a preparation method and application thereof, and aims to make the purposes, technical schemes and effects of the invention clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The invention provides a coated double-function catalyst, which is MIL-101 (Fe) coated Ag 3 PO 4 Material, the MIL-101 (Fe) coats Ag 3 PO 4 MIL-101 (Fe) and Ag in the material 3 PO 4 The mass ratio of (2) is 1 (0.05).
The coated dual-function catalyst provided by the invention has the advantages that the design of a coated structure can reduce Ag 3 PO 4 Contact interface with aqueous solution to inhibit Ag 3 PO 4 Is dissociated to make Ag 3 PO 4 Can be protected against Ag 3 PO 4 Has an important role in the aspect of photo-etching. MIL-101 (Fe) belongs to an iron-based metal organic framework material. Since MIL-101 (Fe) has stronger coordination bond energy, more stable skeleton structure, rich Fe-O cluster sites and wider spectral response range, and the valence band and conduction band of MIL-101 (Fe) are higher than Ag 3 PO 4 Thus Ag (silver) 3 PO 4 Encapsulation in MILs-101 (Fe) facilitates the formation of heterojunction photocatalysts. While heterojunction interfaces are beneficialThe transfer of photo-generated electrons is accelerated, so that the efficient separation of photo-generated electrons and holes is promoted, and richer and more effective active substances can be obtained. Therefore, the coated bifunctional catalyst provided by the invention can show excellent photocatalytic degradation activity and recycling stability, thereby solving the problem of Ag 3 PO 4 The catalyst has limited catalytic activity, and the catalyst is difficult to maintain in recycling stability (the problem of low catalytic removal efficiency when the catalyst is recycled).
In addition, unsaturated Fe sites existing in the MIL-101 (Fe) crystal structure can be used as activation sites of persulfate, and the active sites on the MIL-101 (Fe) surface can capture photo-generated electrons to strengthen the activation process of persulfate. Meanwhile, under the illumination condition, the photo-generated electrons of the catalyst system are continuously generated, SO that persulfate is continuously and efficiently activated to form active free radical SO with stronger oxidizing capability and longer service life 4 ·- . Furthermore, MIL-101 (Fe) further promotes the efficient separation of photo-generated electrons and photo-generated holes, so that Fenton-like process and photocatalysis process are synergistically promoted, and efficient catalytic degradation of organic matters is realized. Therefore, the coated bifunctional catalyst provided by the invention also has excellent activity of catalyzing and degrading the persulfates Fenton and photo-Fenton-like synergistic catalysis and can well couple and apply the photocatalysis technology and the persulfate activation technology to the field of organic wastewater catalytic oxidation treatment.
In the coated bifunctional catalyst provided by the invention, MIL-101 (Fe) and Ag 3 PO 4 The mass ratio of (2) can influence the catalytic activity and the recycling stability of the catalyst, and in the catalyst, ag 3 PO 4 When the mass ratio of Ag is relatively large 3 PO 4 The excellent catalytic activity of the catalyst ensures that the catalytic activity of the whole catalyst is good, but the inhibition of the photo-corrosiveness is limited, so that the recycling stability of the catalyst is poor, and the catalytic activity is greatly reduced after the catalyst is recycled for a plurality of times; when the mass of MIL-101 (Fe) is relatively large, MIL-101 (Fe) is excessively coated on Ag 3 PO 4 The light absorption performance of the catalyst is also affected and the light is reducedThe yields of electron and hole pairs correspondingly deteriorate the catalytic activity and the recycling stability of the catalyst. Preferably, the MIL-101 (Fe) and Ag 3 PO 4 The mass ratio of (2) is 0.5:1.
In addition, the invention also provides a preparation method of the coated bifunctional catalyst, which comprises the following steps:
step S001, preparing AgNO 3 Solution and NaH 2 PO 4 Solution and NaH 2 PO 4 AgNO addition to solution 3 Fully stirring the solution to obtain solution A;
step S002, centrifuging the solution A in the step S001, cleaning solid particles obtained by centrifugation by deionized water, and drying, grinding and sieving to obtain Ag 3 PO 4 ；
Step S003, ag to be prepared 3 PO 4 Ultrasonic dispersing in N, N-dimethylformamide organic solution to obtain dispersion B;
step S004, feCl 3 ·6H 2 Ultrasonic dispersing O and terephthalic acid in N, N-dimethylformamide organic solvent to obtain dispersion liquid C, wherein FeCl 3 ·6H 2 The mass ratio of O to terephthalic acid is 1:0.615;
step S005, mixing the dispersion liquid B and the dispersion liquid C, and performing ultrasonic treatment to obtain a dispersion liquid D;
s006, transferring the dispersion liquid D into a polytetrafluoroethylene lining stainless steel autoclave for solvothermal reaction to obtain liquid E;
step S007, centrifuging the E solution, cleaning the reaction product obtained by centrifugation by using ethanol and deionized water, and drying, grinding and sieving the reaction product after the cleaning is finished to obtain MIL-101 (Fe) coated Ag 3 PO 4 A material.
Due to Ag 3 PO 4 Has slight solubility (solubility of 0.2 g/L) in aqueous solution, so Ag in aqueous solution 3 PO 4 Has a certain dissociation degree, and can dissociate Ag + And the dissociated Ag in the aqueous solution + The catalytic reaction system production is more easily capturedGenerated photo-generated electrons are converted into Ag 0 Further strengthen Ag 3 PO 4 To dissociate Ag 3 PO 4 The structure of (C) is gradually destroyed, the recycling efficiency is extremely poor, and Ag 0 After generation at Ag 3 PO 4 The deposition on the surface also affects the light absorption performance of the catalyst, so that the catalytic activity of the material is greatly reduced, and therefore, the method firstly prepares Ag by a precipitation method 3 PO 4 Then through solvothermal reaction on Ag 3 PO 4 The surface realizes the formation of MIL-101 (Fe), thereby forming the coated heterojunction catalyst. On the one hand, can reduce Ag 3 PO 4 Contact with water, reduce Ag 3 PO 4 The dissociation degree of the (C) and the other photo-generated electrons can be rapidly transferred through the heterojunction interface, thereby reducing the Ag concentration 3 PO 4 Ag in lattice + Can effectively inhibit Ag 3 PO 4 Is not too sensitive to light.
Further, in step S001, agNO is prepared 3 The starting material for the solution included 0.9mmol AgNO 3 And 40mL deionized water to prepare NaH 2 PO 4 The starting material for the solution included 1.4mmol NaH 2 PO 4 ·12H 2 O and 40mL deionized water, naH 2 PO 4 AgNO addition to solution 3 The speed in the solution was 10mL/min. In step S001, the NaH 2 PO 4 ·12H 2 The dosage of O can ensure AgNO 3 Ag in (a) + And (5) fully precipitating. NaH (NaH) 2 PO 4 The solution is used as a precipitator to be dripped into the AgNO3 solution, and if the dripping speed is too high, the rapid precipitation condition can occur, and Ag 3 PO 4 The crystal nucleus is easy to agglomerate, and correspondingly, ag can be caused 3 PO 4 When the crystal agglomeration is serious, ag 3 PO 4 The heterojunction interface area formed by contact with MIL-101 (Fe) is small, the photo-generated electrons and holes cannot be separated efficiently, and accordingly the catalytic activity and the recycling stability of the catalyst are deteriorated. Preferably, in step S001, naH 2 PO 4 AgNO addition to solution 3 The speed in the solution was 10mL/min.
Further, in step S001, the duration of the stirring reaction can affect Ag 3 PO 4 Crystallinity of the crystals. Since nucleation of crystals requires a certain process, the stirring time is short, the growth degree of the crystal nuclei is limited, and Ag can be caused 3 PO 4 The crystallinity of the crystal is reduced. While Ag is 3 PO 4 When the crystallinity of the crystal is low, the light absorption intensity of the catalyst is weakened, the yield of photo-generated electron-hole pairs is reduced, and the catalytic activity of the catalyst is correspondingly deteriorated; however, when the stirring reaction time is long, the crystallinity of the crystal can be improved, but the degree of improvement of the crystallinity of the crystal is limited. Preferably, in step S002, the reaction time is stirred for 1.5h.
Further, in step S002, the drying time is 20 hours and the drying temperature is 60℃to make Ag 3 PO 4 The moisture in the material is sufficiently removed before grinding.
From the foregoing, ag 3 PO 4 The finer the particles, the larger the specific surface area of the material, but the easier the agglomeration; while Ag is 3 PO 4 When the particles are large, the specific surface area of the material is small, and the heterojunction interface area formed by contact with MIL-101 (Fe) is small, so that the catalytic activity and the use stability of the catalyst are deteriorated, and therefore, in step S002, the catalyst is used for Ag 3 PO 4 The sieving process can further improve the agglomeration of the material. Preferably Ag 3 PO 4 The fineness of the sieved powder is 60 to 120 meshes, and the mesh number of Ag is in the range 3 PO 4 The method is used for preparing the coated type double-function catalyst, and the prepared coated type double-function catalyst has optimal catalytic activity and recycling stability.
Further, in step S005, the ultrasonic power is 450W-700W and the ultrasonic treatment time is 1h, so that MIL-101 (Fe) coated Ag is prepared 3 PO 4 The raw material components of the material (catalyst) are uniformly dispersed, and when the solvothermal reaction is carried out, the raw materials can fully react, which is favorable for crystal nucleation and growth, so that the prepared MIL-101 (Fe) cladding Ag 3 PO 4 The crystallinity of the material is improved, so that the catalytic activity of the catalyst is improved, and the recycling stability of the catalyst is improved.
Further, in step S006, the temperature of the solvothermal reaction cannot be too high, when the reaction temperature is too high, potential safety hazards exist, the MIL-101 (Fe) material structure is easy to collapse, other derivatives are easy to form, and MIL-101 (Fe) may not be produced; and the reaction temperature is too low and the reaction time is too short, the MIL-101 (Fe) coated Ag is prepared 3 PO 4 The poor crystallinity of the material correspondingly deteriorates the catalytic activity and the recycling stability of the catalyst. Preferably, in step S006, the solvothermal reaction is carried out at a temperature of 100-200 ℃ for a reaction time of 10-20 h.
In the invention, raw materials for preparing MIL-101 (Fe) and Ag 3 PO 4 Dispersing in organic solvent, and then solvothermal reacting in a mixture, so as not to affect the nucleation and crystallization process of MIL-101 (Fe), and the MIL-101 (Fe) can be coated with Ag 3 PO 4 The crystallinity of the material is improved, so that the catalytic activity of the catalyst is improved, and the recycling stability of the catalyst is improved.
Further, in step S007, MIL-101 (Fe) is coated with Ag 3 PO 4 The fineness of the material is 60-120 meshes. When the fineness of the coated bifunctional catalyst prepared by the invention is in the range, the catalytic activity and the recycling stability of the coated bifunctional catalyst are optimal.
Further, in step S007, the drying temperature is 60℃and the drying time is 20 hours, so that MIL-101 (Fe) coats Ag 3 PO 4 The water and organic solvent components in the material are substantially removed prior to milling.
The invention also provides application of the coated bifunctional catalyst, in particular to treatment of organic pollution wastewater containing tetracycline by photocatalytic reaction, activated persulfate Fenton catalytic reaction or photo-Fenton-like synergistic catalytic reaction of the coated bifunctional catalyst.
In order to further illustrate the coated bifunctional catalyst provided by the invention, and the preparation method and application thereof, the following examples are provided:
example 1
The invention provides a coating typeThe coated bifunctional catalyst is MIL-101 (Fe) coated Ag 3 PO 4 Material, the MIL-101 (Fe) coats Ag 3 PO 4 MIL-101 (Fe) and Ag in the material 3 PO 4 The mass ratio of (2) is 0.5:1.
In addition, the invention also provides a preparation method of the coated bifunctional catalyst, which comprises the following steps:
step S001, 0.9mmol AgNO 3 Dissolving in 40mL deionized water, and magnetically stirring to obtain AgNO 3 Solution, 1.4mmol NaH 2 PO 4 ·12H 2 O is dissolved in 40mL deionized water, and NaH is obtained under magnetic stirring 2 PO 4 Solution, then NaH 2 PO 4 AgNO addition to solution 3 In the solution, after a yellow-green solution is gradually formed, fully stirring and reacting for a period of time to obtain solution A, wherein NaH 2 PO 4 AgNO addition to solution 3 The speed in the solution is 10mL/min, and the stirring reaction time is 1.5h;
step S002, centrifuging the solution A, and cleaning solid particles obtained by centrifugation by deionized water to clean unreacted NaH 2 PO 4 After the cleaning is finished, the Ag is prepared by drying, grinding and sieving 3 PO 4 Wherein the drying time is 20h, the drying temperature is 60 ℃, and Ag 3 PO 4 The fineness of (3) is 80 meshes;
step S003, taking 0.2g of prepared Ag 3 PO 4 Ultrasonic dispersing in 30mL of N, N-dimethylformamide (the analytical grade of the Schlemn science) organic solution to obtain a dispersion B;
step S004, mixing 0.1160g of FeCl 3 ·6H 2 O and 0.0713g of terephthalic acid are ultrasonically dispersed in 30mL of N, N-dimethylformamide organic solvent to obtain a dispersion liquid C,
step S005, mixing the dispersion liquid B and the dispersion liquid C, and performing ultrasonic treatment to obtain a dispersion liquid D, wherein the ultrasonic treatment power is 500W, and the ultrasonic treatment time is 1h;
step S006, transferring the dispersion liquid D into a polytetrafluoroethylene lining stainless steel autoclave for solvothermal reaction to obtain a liquid E, wherein the solvothermal reaction time is 12 hours, and the reaction temperature is 110 ℃;
step S007, centrifuging the E solution, cleaning the reaction product obtained by centrifugation by using ethanol and deionized water, and drying, grinding and sieving the reaction product after the cleaning is finished to obtain MIL-101 (Fe) coated Ag 3 PO 4 The material has a drying temperature of 60 ℃ and a drying time of 20 hours, and MIL-101 (Fe) coats Ag 3 PO 4 The fineness of the material is 60-120 meshes.
Example 2
The invention provides a coated double-function catalyst, which is MIL-101 (Fe) coated Ag 3 PO 4 Material, the MIL-101 (Fe) coats Ag 3 PO 4 MIL-101 (Fe) and Ag in the material 3 PO 4 The mass ratio of (2) is 0.05:1.
In addition, the present invention also provides a preparation method of the coated bifunctional catalyst, which is substantially the same as that provided in example 1, except that in step S005, feCl 3 ·6H 2 The amount of O was 0.0116g, and the amount of terephthalic acid was 0.0071g.
Example 3
The invention provides a coated double-function catalyst, which is MIL-101 (Fe) coated Ag 3 PO 4 Material, the MIL-101 (Fe) coats Ag 3 PO 4 MIL-101 (Fe) and Ag in the material 3 PO 4 The mass ratio of (2) is 1:1.
In addition, the present invention also provides a preparation method of the coated bifunctional catalyst, which is substantially the same as that provided in example 1, except that in step S005, feCl 3 ·6H 2 The amount of O was 0.232g and the amount of terephthalic acid was 0.1426g.
Example 4
The invention provides a coated double-function catalyst, which is MIL-101 (Fe) coated Ag 3 PO 4 Material, the MIL-101 (Fe) is coatedAg 3 PO 4 MIL-101 (Fe) and Ag in the material 3 PO 4 The mass ratio of (2) to (1).
In addition, the present invention also provides a preparation method of the coated bifunctional catalyst, which is substantially the same as that provided in example 1, except that in step S005, feCl 3 ·6H 2 The amount of O was 0.4639g and the amount of terephthalic acid was 0.2851g.
Example 5
The invention provides a coated double-function catalyst, which is MIL-101 (Fe) coated Ag 3 PO 4 Material, the MIL-101 (Fe) coats Ag 3 PO 4 MIL-101 (Fe) and Ag in the material 3 PO 4 The mass ratio of (2) is 0.5:1.
In addition, the invention also provides a preparation method of the coated bifunctional catalyst, which is basically the same as the preparation method provided in the embodiment 1, except that in the step S006, the ultrasonic power is 700W.
Example 6
The invention provides a coated double-function catalyst, which is MIL-101 (Fe) coated Ag 3 PO 4 Material, the MIL-101 (Fe) coats Ag 3 PO 4 MIL-101 (Fe) and Ag in the material 3 PO 4 The mass ratio of (2) is 0.5:1.
In addition, the invention also provides a preparation method of the coated bifunctional catalyst, which is basically the same as the preparation method provided in the embodiment 1, except that in the step S007, the solvothermal reaction time is 18h.
Example 7
The invention provides a coated double-function catalyst, which is MIL-101 (Fe) coated Ag 3 PO 4 Material, the MIL-101 (Fe) coats Ag 3 PO 4 MIL-101 (Fe) and Ag in the material 3 PO 4 The mass ratio of (2) is 0.5:1.
In addition, the invention also provides a preparation method of the coated bifunctional catalyst, which is basically the same as the preparation method provided in the embodiment 1, except that in the step S007, the solvothermal reaction temperature is 150 ℃.
Example 8
The invention provides a coated double-function catalyst, which is MIL-101 (Fe) coated Ag 3 PO 4 Material, the MIL-101 (Fe) coats Ag 3 PO 4 MIL-101 (Fe) and Ag in the material 3 PO 4 The mass ratio of (2) is 0.5:1.
In addition, the invention also provides a preparation method of the coated bifunctional catalyst, which is basically the same as the preparation method provided in the embodiment 1, except that in the step S007, the solvothermal reaction temperature is 180 ℃.
Comparative example 1
Provides an Ag 3 PO 4 Materials, described Ag 3 PO 4 The material was obtained by the preparation method in example 1, ag 3 PO 4 The fineness of the material is 60-120 meshes.
Comparative example 2
The MIL-101 (Fe) material is provided, and the preparation method of the MIL-101 (Fe) material comprises the following steps:
step S001, mixing 0.1160g FeCl 3 ·6H 2 O and 0.0713g of terephthalic acid are ultrasonically dispersed in an N, N-dimethylformamide organic solvent to obtain a dispersion liquid F, wherein the ultrasonic dispersion power is 500W, and the ultrasonic dispersion time is 1h;
step S002, transferring the dispersion liquid F into a polytetrafluoroethylene lining stainless steel autoclave for solvothermal reaction, wherein the solvothermal reaction time is 12 hours, and the reaction temperature is 110 ℃;
step S003, the reaction product obtained in the step S002 is processed by a centrifugal machine, and the reaction product obtained by the centrifugal machine is thoroughly cleaned by ethanol and deionized water;
and step S004, after the reaction product in the step S003 is cleaned, drying, grinding and sieving are carried out to obtain the MIL-101 (Fe) material, wherein the fineness of the MIL-101 (Fe) material is 60-120 meshes.
The following are performance tests:
(1) The coated bifunctional catalyst prepared in example 1 was subjected to scanning electron microscopy morphology analysis, X-ray diffraction analysis and UV-vis spectroscopic analysis, and the test results are shown in fig. 1, 2 and 3, respectively. Wherein, as can be known from the appearance pattern of the coated bifunctional catalyst in FIG. 1, ag in the material 3 PO 4 Presents an irregular nano polyhedral structure, MIL-101 (Fe) is deposited on Ag 3 PO 4 The surface forms a cladding structure; from the XRD pattern of FIG. 2, it can be seen that the high intensity peaks in the pattern correspond mainly to Ag 3 PO 4 The weak broad spectrum peak at about 24℃indicates MIL-101 (Fe), indicating that MIL-101 (Fe) is composed of Ag 3 PO 4 A material; as can be seen from the UV-vis spectrum of FIG. 3, MIL-101 (Fe) coated Ag 3 PO 4 The material exhibits good photoresponsive ability over the entire spectral range.
(2) The photocatalytic activity of the coated bifunctional catalyst prepared in example 1 was tested under the following conditions:
in 1L of solution containing 10mg/L of tetracycline, 0.2g of coated bifunctional catalyst is added, dark adsorption reaction is carried out for 70min, so that the tetracycline reaches adsorption-desorption equilibrium on the surface of the catalyst, then illumination is started, a 300W xenon lamp is used as a light source, a 420nm filter sheet (providing a spectrum with the wavelength lambda of more than or equal to 420 nm) is equipped, photocatalysis reaction is carried out for 120min, supernatant is taken at certain intervals, an organic filter film with the wavelength lambda of 0.46 micron is used for filtering, and the concentration of the tetracycline in the reaction solution is tested (the testing condition of the concentration of the tetracycline is high performance liquid chromatography (HPLC; agilent 1260, USA), the testing wavelength of 357nm, 0.1% formic acid (90%) and acetonitrile (10%) are used as mobile phases). And drawing a photocatalytic degradation activity graph of the coated bifunctional catalyst on the tetracycline based on the tetracycline concentration value obtained by the test, wherein the removal rate of the tetracycline is 96.84% after 70min dark adsorption and 120min illumination, as shown in fig. 4, so that the coated bifunctional catalyst has good photocatalytic activity.
(3) The coated bifunctional catalyst prepared in example 1 was tested for the Fenton catalytic activity of the activated persulfate under the following conditions:
in 1L containing 10mg/L tetracycline solution, adding 0.2g coated bifunctional catalyst, and adding 0.5mmol sodium peroxodisulfate, taking supernatant at intervals, filtering with 0.45 μm organic filter membrane, testing the concentration of tetracycline in the reaction. The activity of the coated bifunctional catalyst on the activated persulfate Fenton catalytic degradation of the tetracycline is plotted based on the tetracycline concentration value obtained by the test, and as shown in fig. 5, the removal rate of the tetracycline is 97.56% after 160min reaction. In addition, when 0.6g of the coated bifunctional catalyst was added, after 100 minutes, the tetracycline was completely removed.
(4) The photo-Fenton-like synergistic catalytic degradation activity of the coated bifunctional catalyst prepared in example 1 was tested under the following conditions:
adding 0.2g of the coated bifunctional catalyst into 1L of solution containing 10mg/L of tetracycline, adding 0.5mmol of sodium peroxodisulfate, reacting for 70min in dark condition, then turning on illumination, wherein a 300W xenon lamp is used as a light source, a 420nm filter sheet (providing a spectrum with the wavelength lambda of more than or equal to 420 nm) is arranged, supernatant is taken at certain time intervals, and the concentration of the tetracycline in the reaction is tested by filtering with a 0.45-micrometer organic filter film. And drawing a photo-Fenton-like catalytic degradation activity diagram of the coated bifunctional catalyst on the tetracycline based on the tetracycline concentration value obtained by the test, and turning on illumination for 30min after a photo-Fenton-like synergistic catalytic reaction for 70min as shown in fig. 6, so that the tetracycline is completely removed.
(5) The photo-Fenton-like synergistic catalytic degradation activity of the coated bifunctional catalyst prepared in example 1 was tested under the following conditions (natural sunlight is used as the light source for the photocatalytic reaction):
adding 0.2g of the coated bifunctional catalyst and 0.5mmol of sodium peroxodisulfate into 1L of solution containing 10mg/L of tetracycline, reacting for 70min under dark condition, then starting illumination, taking supernatant at certain time intervals when the light source is natural sunlight (sunny day, outdoor temperature is about 27+/-1 ℃), filtering by using an organic filter membrane of 0.45 microns, and testing the concentration of the tetracycline in the reaction solution. And drawing a photo-Fenton-like synergistic catalytic degradation activity diagram of the coated bifunctional catalyst on the tetracycline based on the tetracycline concentration value obtained by the test, and turning on illumination for 5min after a photo-Fenton-like synergistic catalytic reaction for 70min as shown in fig. 7, so that the tetracycline is completely removed. In addition, the invention draws a photo-Fenton-like synergistic catalytic degradation activity diagram of the coated bifunctional catalyst under 5 cycles (after each cycle is finished, the catalyst is centrifugally recovered and dried in a vacuum drying oven at 60 ℃ for 24 hours), as shown in fig. 8, after a photo-Fenton-like synergistic catalytic reaction for 70min, illumination is started for 45min, so that tetracycline can be completely removed, thus showing that the coated bifunctional catalyst has good recycling stability, and the catalytic activity of the catalyst can be kept at a higher level after the catalyst is repeatedly used.
(6) For Ag prepared in comparative example 1 3 PO 4 The photocatalytic activity of the material and the MILs-101 (Fe) material prepared in comparative example 2 were tested under the same conditions as those in performance test (2), and the photocatalytic removal efficiency of the material obtained by the test and the photocatalytic removal efficiency value after recycling the material 5 times are shown in table 1 below.
Table 1:
(7) The photocatalytic activity of the coated bifunctional catalysts prepared in examples 2, 3 and 4 was tested. The obtained catalyst was tested for photocatalytic removal efficiency, and photocatalytic removal efficiency values after 5 times of catalyst recycling are shown in table 2 below (test conditions not listed in table 2 are the same as those in the performance test (2)).
Table 2:
(8) The photocatalytic activity of the coated bifunctional catalyst prepared in example 5 was tested under the same conditions as those in the performance test (2), and the photocatalytic removal efficiency of the catalyst obtained by the test and the photocatalytic removal efficiency value after 5 times of catalyst recycling are shown in the following table 3.
Table 3:
(9) The photocatalytic activity of the coated bifunctional catalyst prepared in example 6 was tested under the same conditions as those in the performance test (2), and the photocatalytic removal efficiency of the catalyst obtained by the test and the photocatalytic removal efficiency value after 5 times of catalyst recycling are shown in the following table 4.
Table 4:
(10) The photocatalytic activity of the coated bifunctional catalysts prepared in examples 7 and 8 was tested under the same conditions as those in the performance test (2), and the photocatalytic removal efficiency of the catalysts obtained by the test and the photocatalytic removal efficiency values after 5 times of catalyst recycling are shown in the following table 5.
Table 5:
it will be understood that equivalents and modifications will occur to those skilled in the art in light of the present invention and their spirit, and all such modifications and substitutions are intended to be included within the scope of the present invention as defined in the following claims.
Claims (3)
1. A preparation method of a coated bifunctional catalyst is characterized in that the coated bifunctional catalyst is MIL-101 (Fe) coated Ag 3 PO 4 Material, the MIL-101 (Fe) coats Ag 3 PO 4 MIL-101 (Fe) and Ag in the material 3 PO 4 The mass ratio of (2) is 0.5:1, and the preparation method comprises the following steps: step S001, 0.9mmol AgNO 3 Dissolving in 40mL deionized water, and magnetically stirring to obtain AgNO 3 Solution, 1.4mmol NaH 2 PO 4 ·12H 2 O is dissolved in 40mL deionized water, and NaH is obtained under magnetic stirring 2 PO 4 Solution, then NaH 2 PO 4 AgNO addition to solution 3 In the solution, after a yellow-green solution is gradually formed, fully stirring and reacting for a period of time to obtain solution A, wherein NaH 2 PO 4 AgNO addition to solution 3 The speed in the solution is 10mL/min, and the stirring reaction time is 1.5h;
step S002, centrifuging the solution A, and cleaning solid particles obtained by centrifugation by deionized water to clean unreacted NaH 2 PO 4 After the cleaning is finished, the Ag is prepared by drying, grinding and sieving 3 PO 4 Wherein the drying time is 20h, the drying temperature is 60 ℃, and Ag 3 PO 4 The fineness of (3) is 80 meshes; step S003, taking 0.2g of prepared Ag 3 PO 4 Ultrasonic dispersing in 30mL of N, N-dimethylformamide organic solution to obtain a dispersion liquid B;
step S004, mixing 0.1160g of FeCl 3 ·6H 2 O and 0.0713g of terephthalic acid are ultrasonically dispersed in 30mL of N, N-dimethylformamide organic solvent to obtain a dispersion liquid C;
step S005, mixing the dispersion liquid B and the dispersion liquid C, and performing ultrasonic treatment to obtain a dispersion liquid D, wherein the ultrasonic treatment power is 500W, and the ultrasonic treatment time is 1h;
step S006, transferring the dispersion liquid D into a polytetrafluoroethylene lining stainless steel autoclave for solvothermal reaction to obtain a liquid E, wherein the solvothermal reaction time is 12 hours, and the reaction temperature is 110 ℃;
step S007, centrifuging the E solution, cleaning the reaction product obtained by centrifugation by using ethanol and deionized water, and drying, grinding and sieving the reaction product after the cleaning is finished to obtain MIL-101 (Fe) coated Ag 3 PO 4 The material has a drying temperature ofDrying at 60deg.C for 20 hr, wherein MIL-101 (Fe) coats Ag 3 PO 4 The fineness of the material is 60-120 meshes.
2. The use of a coated bifunctional catalyst, characterized in that the coated bifunctional catalyst prepared by the process for preparing a coated bifunctional catalyst as defined in claim 1 is used for treating organic contaminated wastewater containing tetracyclines.
3. The use of the coated bifunctional catalyst of claim 2, wherein the coated bifunctional catalyst is used for treating the tetracycline-containing organic contaminated wastewater by any one of a photocatalytic reaction, an activated persulfate Fenton-like catalytic reaction, and a photo-Fenton-like synergistic catalytic reaction, respectively.
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