CN111632625A - Preparation method and application of Prussian blue quantum dot titanium carbide composite catalyst - Google Patents
Preparation method and application of Prussian blue quantum dot titanium carbide composite catalyst Download PDFInfo
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- CN111632625A CN111632625A CN202010632021.0A CN202010632021A CN111632625A CN 111632625 A CN111632625 A CN 111632625A CN 202010632021 A CN202010632021 A CN 202010632021A CN 111632625 A CN111632625 A CN 111632625A
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- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 229960003351 prussian blue Drugs 0.000 title claims abstract description 36
- 239000013225 prussian blue Substances 0.000 title claims abstract description 36
- 239000002096 quantum dot Substances 0.000 title claims abstract description 33
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 12
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 238000000967 suction filtration Methods 0.000 claims abstract description 6
- 229920001007 Nylon 4 Polymers 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 17
- -1 potassium ferricyanide Chemical compound 0.000 claims description 13
- 230000015556 catabolic process Effects 0.000 claims description 9
- 238000006731 degradation reaction Methods 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000007790 solid phase Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 229940079593 drug Drugs 0.000 abstract description 7
- 239000003814 drug Substances 0.000 abstract description 7
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract 1
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 abstract 1
- 229910052700 potassium Inorganic materials 0.000 abstract 1
- 239000011591 potassium Substances 0.000 abstract 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 10
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- CAVCGVPGBKGDTG-UHFFFAOYSA-N alumanylidynemethyl(alumanylidynemethylalumanylidenemethylidene)alumane Chemical compound [Al]#C[Al]=C=[Al]C#[Al] CAVCGVPGBKGDTG-UHFFFAOYSA-N 0.000 description 3
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 3
- 229960000956 coumarin Drugs 0.000 description 3
- 235000001671 coumarin Nutrition 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- MYLBTCQBKAKUTJ-UHFFFAOYSA-N 7-methyl-6,8-bis(methylsulfanyl)pyrrolo[1,2-a]pyrazine Chemical compound C1=CN=CC2=C(SC)C(C)=C(SC)N21 MYLBTCQBKAKUTJ-UHFFFAOYSA-N 0.000 description 1
- 241000402754 Erythranthe moschata Species 0.000 description 1
- 208000001953 Hypotension Diseases 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229940035676 analgesics Drugs 0.000 description 1
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- 230000005540 biological transmission Effects 0.000 description 1
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- 239000003433 contraceptive agent Substances 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000009432 framing Methods 0.000 description 1
- 239000000118 hair dye Substances 0.000 description 1
- 239000008266 hair spray Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000000147 hypnotic effect Effects 0.000 description 1
- 208000021822 hypotensive Diseases 0.000 description 1
- 230000001077 hypotensive effect Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229960005404 sulfamethoxazole Drugs 0.000 description 1
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
-
- 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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- 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
- B01J2531/845—Cobalt
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention relates to a preparation method and application of a Prussian blue quantum dot titanium carbide composite catalyst, which comprises the following steps: dispersing titanium aluminum carbide in hydrofluoric acid, stirring, and performing suction filtration to obtain first powder; washing the first powder with water, and freeze-drying to obtain Ti3C2Tx(ii) a Taking out the Ti3C2TxDispersing in dimethyl sulfoxide, ultrasonically stripping, and performing suction filtration to obtain second powder; alternately washing the second powder with alcohol and water, and dispersing in 35-45mL of water to obtain a dispersion liquid; adding cobalt chloride into the dispersion liquid, and stirring to obtain a suspension; dropping polypyrrolidone and ferricyanide into the suspensionAnd dissolving the mixed solution of potassium, stirring, filtering, washing and drying to obtain the Prussian blue quantum dot titanium carbide composite catalyst. The composite catalyst has strong catalytic ability, rich active sites and good recycling property, and can catalyze PMS to oxidize and remove various toxic and harmful refractory organic micro-pollutants including medicines and personal care products.
Description
Technical Field
The invention relates to a preparation method and application of a Prussian blue quantum dot titanium carbide composite catalyst.
Background
The drugs and Personal Care Products (PPCPs) are organic pollutants which have high chemical stability, are difficult to remove by conventional processes and have strong three properties, and because the substances are often detected in natural water bodies in recent years, the removal and degradation of the stubborn pollutants gradually become the popular field of research of environmental management workers.
At present, the method for removing trace PPCPs in water mainly comprises conventional processes such as adsorption, flocculation, membrane separation and the like, and emerging processes such as electrooxidation, catalytic oxidation and the like, wherein the conventional processes are very harsh for selecting an adsorbent and a flocculant, and the removal efficiency of common adsorbent flocculants to such pollutants is low, so that the emerging treatment processes represented by advanced oxidation are gradually favored by researchers, the degradation of PPCPs in water by generating radicals with strong oxidizing property through various means is the core content of the advanced oxidation process, the manner of generating radicals comprises not only light, electricity, activated oxidants, ultrasound and the like, wherein the manner of activating oxidants is popular for the research in the field of advanced oxidation due to the green and energy-saving characteristics. The advanced oxidation technology based on sulfate radical is to generate strong oxidizing sulfate radical by activating Peroxymonosulfate (PMS) or Peroxydisulfate (PDS), and the radical can effectively mineralize organic matters in water by hydrogenation, substitution, electron transfer and other modes.
Prussian Blue Antibodies (PBA), a new type of metal framing Material (MOFs), is commonly available as MII 3[MIII(CN)6]2•H2And O represents. Wherein M isIIAnd MIIIRespectively represent divalent and trivalent metal ions, and are alternately connected with an organic ligand-CN-through the metal ions with two valence statesThis special frame material is formed. The strong adjustability, the high specific surface area and the special framework structure ensure that the PBA is commonly used for the preparation of photoelectric materials and the storage of energy and gas. Also due to these advantages, PBA has also in recent years become of great interest for applications in the field of water treatment. Generally, the PBA has insufficient catalytic active sites due to the excessive particle size, and although the growth particle size of the PBA can be controlled to increase the active sites, the aggregation effect is brought at the same time, and the number of the active sites is further reduced.
Chinese patent specification CN110783536A discloses a Prussian blue analogue/MXene composite electrode material and an in-situ preparation method and application thereof, wherein the prepared Prussian blue analogue/MXene composite electrode material has good electrochemical performance, but the preparation process is complex, byproducts are easily introduced in the preparation process, and the product is not suitable for the field of water treatment.
Disclosure of Invention
Aiming at the defects of the prior art, one of the purposes of the invention is to provide a preparation method of a Prussian blue quantum dot titanium carbide composite catalyst so as to obtain PBA QDs/Ti with fully exposed Prussian blue quantum dot active sites3C2TxA composite material; the invention also aims to provide the application of the Prussian blue quantum dot titanium carbide composite catalyst in catalyzing PPCPs in PMS degradation water, and the degradation efficiency is improved.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a preparation method of a Prussian blue quantum dot titanium carbide composite catalyst comprises the following steps:
s1, dispersing titanium aluminum carbide in hydrofluoric acid, stirring for 20-28h, and performing suction filtration to obtain first powder;
s2, washing the first powder obtained in S1 with water, and freeze-drying to obtain Ti3C2Tx；
S3, taking 0.08-0.12g of the Ti3C2TxDispersing the second powder in 45-55mL of dimethyl sulfoxide, ultrasonically stripping for 5-7h, and performing suction filtration to obtain second powder;
s4, alternately washing the second powder obtained in the step S3 with alcohol and water, and dispersing the second powder in 35-45mL of water to obtain a dispersion liquid;
s5, adding 0.0005 to 0.002mol of cobalt chloride into the dispersion liquid obtained in the step S4, and stirring for 10 to 14 hours to obtain suspension;
s6, dripping a mixed solution of polyvinylpyrrolidone and potassium ferricyanide into the suspension obtained in the step S5, stirring for 22-26 hours, filtering to obtain a solid phase substance, and washing and drying the solid phase substance to obtain the Prussian blue quantum dot titanium carbide composite catalyst;
wherein, in the mixed solution, the molar ratio of the polypyrrolidone to the potassium ferricyanide is 1.3-1.4: 1; the molar ratio of the cobalt chloride in the suspension to the potassium ferricyanide in the mixed solution added dropwise is 1.4-1.6: 1.
Further, in S1, the concentration of hydrofluoric acid is 25 to 35wt%, preferably 30 wt%.
Alternatively, 3-5g of titanium aluminum carbide is dispersed in 35-45mL of hydrofluoric acid.
Further, in S2, freeze-drying at-40 deg.C to completely obtain Ti3C2Tx。
Further, in S4, the alcohol is absolute ethanol.
Further, in S5, the amount of cobalt chloride added is 0.0006 to 0.0018mol, preferably 0.0012 mol.
Further, in S6, the molar ratio of the polypyrrolidone to the potassium ferricyanide in the mixed solution is 1.35: 1; the molar ratio of cobalt chloride in the suspension to potassium ferricyanide in the mixed solution added dropwise was 1.5: 1.
Further, in S6, the solid phase is dried at 55 to 65 ℃.
Based on the same inventive concept, the invention also provides the application of the Prussian blue quantum dot titanium carbide composite catalyst prepared by the preparation method in catalyzing PPCPs in PMS degradation water.
Further, adding the Prussian blue quantum dot titanium carbide composite catalyst and PMS into water to be treated, and stirring.
Further, 0.1-0.4g of Prussian blue quantum dot titanium carbide composite catalyst and 0.01-0.03mol of PMS are added into each 1L of water to be treated; preferably, the temperature of the water is controlled to be 10-45 ℃ during the stirring process.
Further, the PPCPs include drugs and personal care products, and further include various antibiotics, synthetic musk, analgesics, hypotensive drugs, contraceptive drugs, hypnotic drugs, weight-loss drugs, hair spray, hair dyes, bactericides and the like.
The invention uses Prussian blue quantum dot titanium carbide composite catalyst (PBA QDs/Ti)3C2Tx) The mechanism of catalyzing PMS to degrade PPCPs in water comprises Ti3C2TxThe surface unsaturated Lewis acid point position and the terminal fluorine have a synergistic effect with Prussian blue, so that a better degradation effect is obtained.
The invention utilizes Ti3C2TxFor the support, the growth of crystal face of PBA in the formation process is inhibited by polyvinylpyrrolidone in TI3C2TxPBA quantum dots with the particle size of about 50 nm are generated on the surface in situ, so that Prussian blue quantum dots are uniformly dispersed on the surface of the PBA quantum dots, and active sites of the Prussian blue quantum dots are fully exposed. Firstly, etching and stripping titanium aluminum carbide by using hydrofluoric acid and dimethyl sulfoxide to obtain an aluminum carbide nanosheet, then adding cobalt chloride to enable the aluminum carbide nanosheet to adsorb cobalt ions until the cobalt ions are saturated, and finally uniformly forming PBA quantum dots on the surface of the aluminum carbide by using polypyrrolidone.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the Prussian blue quantum dot titanium carbide composite catalyst, PBA is uniformly dispersed in Ti3C2TxThe surface can provide more catalytic active sites, and the catalytic performance of the material is improved;
（2）Ti3C2Txthe support can solve the agglomeration problem of the Prussian blue quantum dots and is beneficial to the full play of the catalytic effect of the Prussian blue quantum dots;
（3）Ti3C2Txa large number of unsaturated sites on the surface cooperate with Prussian blue quantum dots,the catalytic efficiency can be greatly improved.
(4) The preparation method has simple process, produces no by-product and is easier to obtain the catalyst product with higher purity.
Drawings
FIG. 1 is a transmission electron microscope image of Prussian blue quantum dot titanium carbide composite catalyst (1.2 PBA QDs/Ti)3C2Tx）。
FIG. 2 is an energy spectrum scan of Prussian blue quantum dot titanium carbide composite catalyst (1.2 PBA QDs/Ti)3C2Tx）。
Fig. 3 is an X-ray diffraction pattern of the prussian blue quantum dot titanium carbide composite catalyst.
Fig. 4 is a synthesis route diagram of the prussian blue quantum dot titanium carbide composite catalyst.
Fig. 5 is a graph showing the effect of coumarin removal.
FIG. 6 shows 1.2PBA QDs/Ti3C2TxThe effect of the composite catalyst cyclic degradation is shown.
Detailed Description
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
Example 1
In this embodiment, the preparation steps of the prussian blue quantum dot titanium carbide composite catalyst are as follows:
weighing 4g titanium aluminum carbide (obtained from Fosmann technologies, Beijing, Ltd., 200 mesh) dispersed in 40 mL hydrofluoric acid (30 wt%) under stirring at 35 deg.C for 24 hours, washing with ultrapure water, and freeze-drying at-40 deg.C to obtain Ti3C2Tx。
Take 0.1 gTi3C2TxDispersing in 50mL of dimethyl sulfoxide, ultrasonically stripping for 6 hours, washing with absolute ethyl alcohol and ultrapure water alternately, and dispersing in 40 mL of ultrapure water to obtain a dispersion liquid.
0.0006mol of cobalt chloride hexahydrate is weighed and added into the dispersion, and stirred at room temperature for 12 hours to obtain a suspension.
Preparing a mixed solution of polyvinylpyrrolidone and potassium ferricyanide, wherein the molar ratio of the polyvinylpyrrolidone to the potassium ferricyanide is 1.35:1, dripping the prepared mixed solution into the suspension to ensure that the molar ratio of the potassium ferricyanide to cobalt chloride in the suspension is 1:1.5, then continuously stirring for 24 hours, filtering, cleaning, and completely drying at 60 ℃ to obtain the Prussian blue quantum dot titanium carbide composite catalyst which is marked as 0.6PBA QDs/Ti3C2Tx。
Example 2
Example 1 was repeated with the only difference that: in this example, the amount of cobalt chloride hexahydrate added was 0.0012 mol.
Marking the obtained Prussian blue quantum dot titanium carbide composite catalyst as 1.2PBA QDs/Ti3C2Tx。
Example 3
Example 1 was repeated with the only difference that: in this example, the amount of cobalt chloride hexahydrate added was 0.0018 mol.
Marking the obtained Prussian blue quantum dot titanium carbide composite catalyst as 1.8PBA QDs/Ti3C2Tx。
As can be seen from FIGS. 1 to 3, the ratio of Ti to Ti is3C2TxThe characteristic peak belonging to Prussian blue is added in an X-ray diffraction pattern of the Prussian blue quantum dot titanium carbide composite catalyst, which indicates that the Prussian blue is successfully loaded on Ti3C2TxThe surface is uniformly distributed.
Example 4
The method for degrading PPCPs in water by using the Prussian blue quantum dot titanium carbide composite catalyst obtained in the embodiment 1-3 to catalyze PMS comprises the following specific steps: an aqueous solution containing coumarin to be treated was prepared as a solution to be treated (pH =6.6), and the volume was 50mL, and the initial sulfamethoxazole concentration was 10. mu.M (where M is mol/L and. mu.M is 10. mu.M)-6mol/L, mM is 10-3mol/L, the same below), adding 10 mg (mass concentration is 0.2 g/L) of corresponding composite catalyst, and then adding 1 mM PMS. Magnetically stirring at room temperature for 20minAnd then, the removal rate of the coumarin reaches more than 90%, and the effect is obviously better than that of other control treatment groups. The catalytic degradation capacity of the catalyst remained above 85% after three cycles (see fig. 5 and 6).
In conclusion, the composite catalyst has strong catalytic capability, rich active sites and good recycling property, and can catalyze PMS to oxidize and remove various toxic and harmful refractory organic micro-pollutants including medicines and personal care products.
The foregoing examples are set forth to illustrate the present invention more clearly and are not to be construed as limiting the scope of the invention, which is defined in the appended claims to which the invention pertains, as modified in all equivalent forms, by those skilled in the art after reading the present invention.
Claims (10)
1. The preparation method of the Prussian blue quantum dot titanium carbide composite catalyst is characterized by comprising the following steps of:
s1, dispersing titanium aluminum carbide in hydrofluoric acid, stirring for 20-28h, and performing suction filtration to obtain first powder;
s2, washing the first powder obtained in S1 with water, and freeze-drying to obtain Ti3C2Tx；
S3, taking 0.08-0.12g of the Ti3C2TxDispersing the second powder in 45-55mL of dimethyl sulfoxide, ultrasonically stripping for 5-7h, and performing suction filtration to obtain second powder;
s4, alternately washing the second powder obtained in the step S3 with alcohol and water, and dispersing the second powder in 35-45mL of water to obtain a dispersion liquid;
s5, adding 0.0005 to 0.002mol of cobalt chloride into the dispersion liquid obtained in the step S4, and stirring for 10 to 14 hours to obtain suspension;
s6, dripping a mixed solution of polyvinylpyrrolidone and potassium ferricyanide into the suspension obtained in the step S5, stirring for 22-26 hours, filtering to obtain a solid phase substance, and washing and drying the solid phase substance to obtain the Prussian blue quantum dot titanium carbide composite catalyst;
wherein, in the mixed solution, the molar ratio of the polypyrrolidone to the potassium ferricyanide is 1.3-1.4: 1; the molar ratio of the cobalt chloride in the suspension to the potassium ferricyanide in the mixed solution added dropwise is 1.4-1.6: 1.
2. The method according to claim 1, wherein the concentration of hydrofluoric acid in S1 is 25-35 wt%.
3. The method according to claim 1, wherein the Ti is completely obtained by freeze-drying at-40 ℃ in S23C2Tx。
4. The method according to claim 1, wherein the alcohol in S4 is absolute ethanol.
5. The method according to claim 1, wherein the cobalt chloride is added in an amount of 0.0006 to 0.0018mol, preferably 0.0012mol, to S5.
6. The method according to claim 1, wherein in S6, the molar ratio of the polyvinylpyrrolidone to the potassium ferricyanide in the mixed solution is 1.35: 1; the molar ratio of cobalt chloride in the suspension to potassium ferricyanide in the mixed solution added dropwise was 1.5: 1.
7. The method according to claim 1, wherein the solid phase is dried at 55 to 65 ℃ in S6.
8. The Prussian blue quantum dot titanium carbide composite catalyst prepared by the preparation method according to any one of claims 1 to 7 is applied to catalysis of PPCPs in PMS degradation water.
9. The application of the catalyst as claimed in claim 8, wherein the Prussian blue quantum dot titanium carbide composite catalyst and the PMS are added into water to be treated and stirred.
10. The use according to claim 9, characterized in that 0.1-0.4g of prussian blue quantum dot titanium carbide composite catalyst and 0.01-0.03mol of pms are added to 1L of water to be treated; preferably, the temperature of the water is controlled to be 10-45 ℃ during the stirring process.
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