CN112657531B - Preparation method and application of elemental copper and copper-iron oxide co-modified graphite phase carbon nitride magnetic catalyst - Google Patents
Preparation method and application of elemental copper and copper-iron oxide co-modified graphite phase carbon nitride magnetic catalyst Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 239000010949 copper Substances 0.000 title claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 18
- -1 copper-iron oxide co-modified graphite Chemical class 0.000 title description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 10
- DXKGMXNZSJMWAF-UHFFFAOYSA-N copper;oxido(oxo)iron Chemical compound [Cu+2].[O-][Fe]=O.[O-][Fe]=O DXKGMXNZSJMWAF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004064 recycling Methods 0.000 claims abstract description 4
- 229960003022 amoxicillin Drugs 0.000 claims description 31
- LSQZJLSUYDQPKJ-NJBDSQKTSA-N amoxicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=C(O)C=C1 LSQZJLSUYDQPKJ-NJBDSQKTSA-N 0.000 claims description 31
- LSQZJLSUYDQPKJ-UHFFFAOYSA-N p-Hydroxyampicillin Natural products O=C1N2C(C(O)=O)C(C)(C)SC2C1NC(=O)C(N)C1=CC=C(O)C=C1 LSQZJLSUYDQPKJ-UHFFFAOYSA-N 0.000 claims description 31
- 239000012071 phase Substances 0.000 claims description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 7
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 150000004687 hexahydrates Chemical class 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 239000008247 solid mixture Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000000696 magnetic material Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 239000003242 anti bacterial agent Substances 0.000 claims description 2
- 229940088710 antibiotic agent Drugs 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 239000002351 wastewater Substances 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 229910002804 graphite Inorganic materials 0.000 abstract description 9
- 239000010439 graphite Substances 0.000 abstract description 9
- 230000007547 defect Effects 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000004729 solvothermal method Methods 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000012719 thermal polymerization Methods 0.000 abstract description 2
- 239000002638 heterogeneous catalyst Substances 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005273 aeration Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 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 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- CVOFKRWYWCSDMA-UHFFFAOYSA-N 2-chloro-n-(2,6-diethylphenyl)-n-(methoxymethyl)acetamide;2,6-dinitro-n,n-dipropyl-4-(trifluoromethyl)aniline Chemical compound CCC1=CC=CC(CC)=C1N(COC)C(=O)CCl.CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O CVOFKRWYWCSDMA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HJPBEXZMTWFZHY-UHFFFAOYSA-N [Ti].[Ru].[Ir] Chemical group [Ti].[Ru].[Ir] HJPBEXZMTWFZHY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- GRLMDYKYQBNMID-UHFFFAOYSA-N copper iron(3+) oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+3].[Fe+3].[Cu+2] GRLMDYKYQBNMID-UHFFFAOYSA-N 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- CJTCBBYSPFAVFL-UHFFFAOYSA-N iridium ruthenium Chemical compound [Ru].[Ir] CJTCBBYSPFAVFL-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- 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
Abstract
A preparation method and application of a graphite phase carbon nitride magnetic catalyst co-modified by elemental copper and copper iron oxide belong to the technical field of electrochemical water treatment. According to the invention, dicyandiamide is utilized to carry out thermal polymerization reaction under high temperature condition to prepare graphite-phase carbon nitride, and the prepared graphite-phase carbon nitride is taken as a matrix material, and elemental copper and copper iron oxide are jointly modified on the graphite-phase carbon nitride by a solvothermal method to obtain the heterogeneous catalyst with good dispersion effect. The invention has the advantages of low price of the required materials, convenient acquisition, convenient recovery of the catalyst and wide application pH, overcomes the defects of narrow application pH range, easy generation of iron mud, difficult recycling of the catalyst and the like of the traditional electro-Fenton application, and has good application prospect in the aspect of wastewater treatment.
Description
Technical Field
The invention belongs to the technical field of electrochemical water treatment, and relates to a preparation method and application of a graphite phase carbon nitride magnetic catalyst co-modified by elemental copper and copper iron oxide.
Background
electro-Fenton technology is a advanced oxidation technology combining electrochemical advanced oxidation and Fenton oxidation, and hydrogen peroxide (H 2 O 2 ) With ferrous ions (Fe 2+ ) Reacts to form hydroxyl radicals (. OH, E) with strong oxidizing power 0 =2.87V/s SHE). OH is an oxidant next to fluorine that can non-selectively degrade organic contaminants in water, but conventional electro-Fenton technology has a narrow reaction pH range (ph=2-4), producing iron sludge, fe 2+ And the defects of incapability of recycling and the like limit the application of the wastewater treatment device in the field of wastewater treatment. The solid catalyst can be used for replacing Fe due to low sensitivity to pH 2+ Activation of H 2 O 2 Forming a heterogeneous electro-Fenton system. The copper-based solid phase catalyst can provide monovalent copper ions (Cu + ) Under neutral conditions with H 2 O 2 React to form OH, cu + Has a characteristic similar to Fe 2+ Can form heterogeneous electro-Fenton-like system, and Cu + Catalytic rate is higher than Fe 2+ (kCu + /H 2 O 2 ＝1.0×10 4 M -1 s -1 ,kFe 2+ /H 2 O 2 ＝76M -1 s -1 ). However, copper-based catalysts do not haveThe magnetism is difficult to recover. In recent years, heterogeneous magnetic metal catalysts have become a research hotspot due to the advantages of low manufacturing cost, mild operating conditions, easy recovery and the like. There are researches reporting that elemental copper modified copper iron oxide (Cu-CuFe 2 O 4 ) Can promote Fenton reaction and accelerate degradation of organic pollutants. Cu-CuFe 2 O 4 Can be directly synthesized by solvothermal method, and has simple preparation method. However, the magnetic metal nano particles are easy to agglomerate, so that the preparation of a magnetic solid-phase catalyst for a heterogeneous electro-Fenton-like system is urgently needed, and organic pollutants are oxidatively degraded.
Graphite phase carbon nitride (g-C) 3 N 4 ) Is a lamellar compound containing graphite-like structure, and can be prepared by high-temperature thermal polymerization of nitrogen-containing precursors such as melamine, dicyandiamide, urea and the like. g-C 3 N 4 Has the advantages of good mechanical property, acid and alkali resistance, environmental friendliness, low preparation cost and the like. These advantages can be achieved by g-C 3 N 4 Is used as a base material.
The invention adopts solvothermal method to lead the simple substance copper (Cu) 0 ) And copper iron oxide (CuFe 2 O 4 ) The catalyst is modified on the self-prepared graphite phase carbon nitride, so that the catalyst can be conveniently recovered while the organic pollutants are well degraded under the neutral condition.
Disclosure of Invention
The invention aims to provide a preparation method and application of a graphite-phase carbon nitride magnetic material co-modified by elemental copper and copper-iron oxide, wherein the material required by the preparation method is low in cost, convenient and easy to obtain, the preparation method is simple, and the prepared graphite-phase carbon nitride magnetic catalyst co-modified by elemental copper and copper-iron oxide can be applied to a heterogeneous electro-Fenton system, has good catalytic effect and is convenient to recycle, and the defects that the traditional electro-Fenton reaction is narrow in pH range, easy to produce pig iron mud, difficult to recycle and the like are overcome.
The preparation method of the elemental copper and copper iron oxide co-modified graphite phase carbon nitride magnetic catalyst comprises the following steps:
(1) Placing dicyandiamide in a crucible, andplacing the crucible filled with dicyandiamide in a high-temperature atmosphere furnace, and introducing N 2 Removing air in the furnace chamber, (N) 2 The flow speed is 10-15L/min, the aeration time is 0.5 h), and the N is stopped when the air is completely discharged 2 Heating from room temperature to pyrolysis temperature 550 ℃ at a heating rate of 10 ℃/min, pyrolyzing for 3 hours, cooling to room temperature, taking out the solid mixture, and fully grinding to obtain graphite-phase carbon nitride;
(2) Dispersing graphite-phase carbon nitride in ethylene glycol and performing ultrasonic dispersion for 60min, and marking as a dispersion liquid A;
(3) Sequentially weighing ferric trichloride hexahydrate (FeCl) 3 ·6H 2 O), copper chloride dihydrate (CuCl) 2 ·2H 2 O), sodium acetate (NaAC) and polyvinylpyrrolidone (PVP, molecular weight 40000) in ethylene glycol, and stirring thoroughly to obtain a uniform mixed solution, designated as solution B;
(4) Pouring the solution B obtained in the step (3) into the dispersion liquid A obtained in the step (2), and continuing ultrasonic treatment for 4 hours, and marking as a dispersion liquid B; wherein each 0.5g of graphite phase carbon nitride corresponds to 0.2703 to 1.0812g of ferric trichloride hexahydrate (FeCl) 3 ·6H 2 O), 0.0853 to 0.3412g of copper chloride dihydrate (CuCl) 2 ·2H 2 O), 2.4g sodium acetate (NaAC), 0.6g polyvinylpyrrolidone (PVP), fe 3+ With Cu 2+ Preferably the mass of hexahydrate and ferric trichloride is 0.8109g and the amount of cupric chloride dihydrate is 0.2557g;
(5) The dispersion B was poured into a reaction vessel, and then placed in a forced air drying oven to react for 8 hours at 200 ℃. After naturally cooling to room temperature, sequentially cleaning with ultrapure water and ethanol to obtain the elemental copper and copper-iron oxide co-modified graphite phase carbon nitride magnetic material (Cu-CuFe) 2 O 4 /g-C 3 N 4 )。
The application of the elemental copper and copper iron oxide co-modified graphite phase carbon nitride magnetic catalyst obtained by the preparation method in a heterogeneous phase type electro-Fenton system is used for removing Amoxicillin (AMX) antibiotics.
The invention has the advantages that:
compared with the prior art, the invention has the following excellent effects:
1. the application pH of the traditional electro-Fenton reaction is widened, and the amoxicillin is well removed within the range of initial pH of 3-9.
2. Is convenient for recycling. The prepared graphite-phase carbon nitride magnetic catalyst co-modified by elemental copper and copper-iron oxide is solid powder, has strong magnetism, can be rapidly separated under the action of a magnetic field, and is convenient to recycle.
Drawings
FIG. 1 is a schematic diagram of example 1, example 2, example 3, example 4 and comparative example 1, with different hexahydrates and ferric trichloride (FeCl) 3 ·6H 2 O), copper chloride dihydrate (CuCl) 2 ·2H 2 Cu-CuFe prepared by using O) in amount 2 O 4 /g-C 3 N 4 (Fe 3+ With Cu 2+ Molar ratios of 0.12:0.06, 0.04:0.02, 0.08:0.04, 0.16:0.08) and g-C, respectively 3 N 4 Applied to heterogeneous electro-Fenton-like systems and a degradation graph of Amoxicillin (AMX).
FIG. 2 is a Cu-CuFe of example 5 and comparative example 2 2 O 4 /g-C 3 N 4 And a degradation profile for Amoxicillin (AMX) without any catalyst applied at different initial pH conditions.
FIG. 3 (a) shows Cu-CuFe in example 1 2 O 4 /g-C 3 N 4 (b) is g-C in comparative example 1 3 N 4 SEM images of (a).
FIG. 4 is a Cu-CuFe alloy in example 1 2 O 4 /g-C 3 N 4 And g-C in comparative example 1 3 N 4 Is a XRD pattern of (C).
FIG. 5 (a) shows Cu-CuFe in example 1 2 O 4 /g-C 3 N 4 The magnetic strength, FIG. 5 (b) is g-C in comparative example 1 3 N 4 Is a magnetic strength of (a).
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1:
(1) Weighing 5g of dicyandiamidePlacing in a 20mL crucible, placing the crucible filled with dicyandiamide in a high-temperature atmosphere furnace, and introducing N 2 Exhausting air in the hearth (N) 2 The flow speed is 10-15L/min, the aeration time is 0.5 h), and the N is stopped when the air is completely discharged 2 Heating from room temperature to pyrolysis temperature 550 ℃ at a heating rate of 10 ℃/min, pyrolyzing for 3 hours, cooling to room temperature, taking out the solid mixture, and fully grinding to obtain graphite-phase carbon nitride (g-C) 3 N 4 )；
(2) 25mL of ethylene glycol and 0.5-g g-C were weighed separately 3 N 4 In a 100mL beaker, and putting the beaker into ultrasound for ultrasonic dispersion for 60min, and recording the dispersion as a dispersion liquid A;
(3) 0.8109g of iron (FeCl) hexahydrate and trichloride were weighed in order 3 ·6H 2 O), 0.2557g copper chloride dihydrate (CuCl) 2 ·2H 2 O), 2.4g of sodium acetate (NaAC) and 0.6g of polyvinylpyrrolidone (PVP, molecular weight 40000) in 25mL of ethylene glycol, and stirring thoroughly to obtain a uniform mixed solution, designated as solution B, fe 3+ With Cu 2+ The molar ratio of (2) is 0.12:0.06;
(4) Pouring the solution B obtained in the step (3) into the dispersion liquid A obtained in the step (2), and continuing ultrasonic treatment for 4 hours, and marking the solution B as the dispersion liquid B.
(5) The dispersion B was poured into a 100mL reaction vessel, and then placed in a forced air drying oven for reaction at 200℃for 8 hours. After naturally reaching the room temperature, sequentially cleaning the graphite phase carbon nitride with ultrapure water and ethanol to obtain the elemental copper and copper-iron oxide co-modified graphite phase carbon nitride (Cu-CuFe) 2 O 4 /g-C 3 N 4 )。
The Cu-CuFe prepared above is mixed 2 O 4 /g-C 3 N 4 The catalyst is applied to the degradation of AMX by an electro-Fenton oxidation system. AMX initial concentration is 100mg/L, and anode is titanium ruthenium iridium coated anode (2X 5 cm) 2 ) The cathode is a graphite felt cathode (2X 5 cm) 2 ) The aeration rate is 0.6L/min, and the current density is 12mA/cm 2 Solution volume 300mL, cu-CuFe 2 O 4 /g-C 3 N 4 The addition amount was 0.2g/L, and the initial pH was 7.0. The removal of AMX is shown in the graph of FIG. 1(a) As shown, the reaction is carried out for 50min, the AMX removal rate can reach 99.3%, and the Cu-CuFe 2 O 4 /g-C 3 N 4 As shown in FIG. 3 (a), the SEM image of (C) is shown as Cu-CuFe 2 O 4 /g-C 3 N 4 As shown in FIG. 4 (a), the XRD pattern of Cu-CuFe 2 O 4 /g-C 3 N 4 As shown in fig. 5 (a), the catalyst can be separated by external magnet attraction.
Example 2:
the present example differs from example 1 in the preparation process in that FeCl is used in step (3) 3 ·6H 2 O has a mass of 0.2703g and CuCl 2 ·2H 2 O has a mass of 0.0853g, fe 3+ With Cu 2+ The molar ratio of (2) was 0.04:0.02, the other preparation steps being identical. The prepared catalyst is applied to heterogeneous electro-Fenton system, AMX is oxidatively degraded, the degradation condition is as shown in the embodiment 1, the AMX removal condition is as shown in the curve (b) in figure 1, the reaction is carried out for 50min, and the AMX removal rate can reach 74.5%
Example 3:
the present example differs from example 1 in the preparation process in that FeCl is used in step (3) 3 ·6H 2 The mass of O is 0.5406g, cuCl 2 ·2H 2 O has a mass of 0.1705g, fe 3+ With Cu 2+ The molar ratio of (2) was 0.08:0.04, the other preparation steps being identical. The prepared catalyst is applied to heterogeneous electro-Fenton system, AMX is oxidatively degraded, the degradation condition is as shown in embodiment 1, the AMX removal condition is as shown in a curve (c) in figure 1, the reaction is carried out for 50min, and the AMX removal rate can reach 90.5%
Example 4:
the present example differs from example 1 in the preparation process in that FeCl is used in step (3) 3 ·6H 2 The mass of O is 1.0812g, cuCl 2 ·2H 2 O has a mass of 0.3412g, fe 3+ With Cu 2+ The molar ratio of (2) was 0.16:0.08, the other preparation steps being identical. The prepared catalyst is applied to heterogeneous electro-Fenton system, AMX is oxidatively degraded, the degradation condition is as shown in the embodiment 1, the removal condition of AMX is as shown in the curve (d) in figure 1, the reaction is carried out for 50min,the AMX removal rate can reach 96.0 percent
Example 5:
this example was prepared in the same manner as in example 1. The prepared catalyst is applied to a heterogeneous electro-Fenton system, AMX is subjected to oxidative degradation, the initial pH range of degradation is 3.0-9.0, the removal condition of the AMX is shown in figure 2, the reaction is carried out for 50min, and the removal rate of the AMX can reach more than 99.0%.
Comparative example 1:
(1) Weighing 5g of dicyandiamide, placing the dicyandiamide in a 20mL crucible, placing the crucible filled with the dicyandiamide in a high-temperature atmosphere furnace, and introducing N 2 Exhausting air in the hearth (N) 2 The flow speed is 10-15L/min, the aeration time is 0.5 h), and the N is stopped when the air is completely discharged 2 Heating from room temperature to pyrolysis temperature 550 ℃ at a heating rate of 10 ℃/min, pyrolyzing for 3 hours, cooling to room temperature, taking out the solid mixture, and fully grinding to obtain graphite-phase carbon nitride (g-C) 3 N 4 )；
The prepared g-C 3 N 4 The method is applied to heterogeneous electro-Fenton system, the oxidation degradation of AMX is carried out under the same degradation conditions as in example 1, the removal condition of AMX is shown as a curve (e) in FIG. 1, the reaction is carried out for 50min, the AMX removal rate can reach 62.8%, and g-C can be achieved 3 N 4 As shown in FIG. 3 (b), the SEM image of (C) is g-C 3 N 4 The XRD pattern of (a) is shown in FIG. 4 (b), g-C 3 N 4 As shown in fig. 5 (b), the separation of the catalyst cannot be achieved by external magnet attraction.
Comparative example 2:
titanium is used for coating ruthenium iridium (2X 5 cm) 2 ) Graphite felt co-modified with multi-walled carbon nanotubes and carbon black for anode (2X 5cm 2 ) Is used as a cathode, the amoxicillin is degraded by electrochemical oxidation, the aeration quantity is 0.6L/min, and the current density is 12mA/cm 2 The volume of the solution is 300mL, the initial pH is 3.0-9.0, and the AMX is oxidized and degraded. As shown in FIG. 3, the reaction was carried out for 50 minutes, the AMX removal rates were 50.5% at an initial pH of 3.0, 63.2% at an initial pH of 5.5, 62.0% at an initial pH of 7.0, and 9.0 at an initial pH of 9.0The removal rates were 65.2% respectively.
As can be seen from a comparison of example 1, example 5 and comparative example 1, comparative example 2, g-C 3 N 4 Through Cu-CuFe 2 O 4 The modification of (2) can realize good degradation of AMX under any pH condition.
The results of the above examples and comparative examples show that the FeCl is modified 3 ·6H 2 O and CuCl 2 ·2H 2 The usage amount of O can obviously influence Cu-CuFe 2 O 4 /g-C 3 N 4 And in fact the catalytic function is Cu-CuFe 2 O 4 The catalyst can be applied to a wider pH range, and can be attracted under the action of an external magnetic field to realize separation quickly. The graphite phase carbon nitride co-modified by the simple substance copper and the copper-iron oxide prepared by the method has high-efficiency catalytic capability while ensuring easy separation.
Claims (1)
1. The application of the graphite-phase carbon nitride magnetic catalyst co-modified by elemental copper and copper iron oxide is characterized in that the graphite-phase carbon nitride magnetic catalyst is used as a solid phase catalyst and applied to wastewater of degrading amoxicillin antibiotics by a heterogeneous electro-Fenton system, the initial pH value of the reaction is 3-9, the reaction is carried out for 50min, and the AMX removal rate can reach more than 99.0%; separating and recycling under a magnetic field;
wherein the preparation method of the catalyst comprises the following steps:
(1) Placing dicyandiamide in a crucible, placing the crucible filled with dicyandiamide in a high-temperature atmosphere furnace, and introducing N 2 Exhausting air in the hearth, stopping introducing N after the air is completely exhausted 2 Heating from room temperature to pyrolysis temperature 550 ℃ at a heating rate of 10 ℃/min, pyrolyzing 3h, cooling to room temperature, taking out the solid mixture, and fully grinding to obtain graphite-phase carbon nitride;
(2) 25 g mL glycol and 0.5 g-C were weighed separately 3 N 4 In a 100mL beaker, and putting the beaker into ultrasound for ultrasonic dispersion for 60min, and recording the dispersion as a dispersion liquid A;
(3) Sequentially weighing 0.8109g hexahydrate and ferric trichloride (FeCl) 3 ·6H 2 O), 0.2557g copper chloride dihydrate (CuCl) 2 ·2H 2 O), sodium acetate (NaAc) 2.4. 2.4g and polyvinylpyrrolidone (PVP) with molecular weight 40000 0.6. 0.6g in 25mL ethylene glycol, and stirring thoroughly to obtain a uniform mixed solution, designated as solution B, fe 3+ With Cu 2+ The molar ratio of (2) is 0.12:0.06;
(4) Pouring the solution B obtained in the step (3) into the dispersion liquid A obtained in the step (2), and continuing ultrasonic 4 to h, namely the dispersion liquid B;
(5) Pouring the dispersion liquid B into a reaction kettle, then placing the reaction kettle in a blast drying oven, reacting 8h at 200 ℃, naturally cooling to room temperature, and sequentially cleaning the reaction kettle with ultrapure water and ethanol to obtain the elemental copper and copper-iron oxide co-modified graphite-phase carbon nitride magnetic material (Cu-CuFe) 2 O 4 /g-C 3 N 4 ）。
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