CN112657531A - 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 33
- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- 239000010949 copper Substances 0.000 title claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- DXKGMXNZSJMWAF-UHFFFAOYSA-N copper;oxido(oxo)iron Chemical compound [Cu+2].[O-][Fe]=O.[O-][Fe]=O DXKGMXNZSJMWAF-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 13
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- -1 copper iron oxide co-modified graphite Chemical class 0.000 claims abstract description 5
- 238000011084 recovery Methods 0.000 claims abstract description 4
- 229960003022 amoxicillin Drugs 0.000 claims description 32
- 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 32
- 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 32
- 239000012071 phase Substances 0.000 claims description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 13
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 230000015556 catabolic process Effects 0.000 claims description 10
- 238000006731 degradation reaction Methods 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 8
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 6
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 6
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 150000004687 hexahydrates Chemical class 0.000 claims description 5
- 239000000696 magnetic material Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 229940032296 ferric chloride Drugs 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
- 239000008247 solid mixture Substances 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003242 anti bacterial agent Substances 0.000 claims 1
- 229940088710 antibiotic agent Drugs 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 7
- 239000000463 material Substances 0.000 abstract description 3
- 238000004729 solvothermal method Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 238000012719 thermal polymerization Methods 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000002638 heterogeneous catalyst Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 229910016516 CuFe2O4 Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000005273 aeration Methods 0.000 description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 5
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- CJTCBBYSPFAVFL-UHFFFAOYSA-N iridium ruthenium Chemical compound [Ru].[Ir] CJTCBBYSPFAVFL-UHFFFAOYSA-N 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-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
- 239000002585 base Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- CTQZMNHRQCCAJE-UHFFFAOYSA-N copper;iron(2+);oxygen(2-) Chemical class [O-2].[O-2].[Fe+2].[Cu+2] CTQZMNHRQCCAJE-UHFFFAOYSA-N 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process 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
- 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
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 230000001590 oxidative effect Effects 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
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Images
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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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Abstract
A preparation method and application of a simple substance copper and copper iron oxide co-modified graphite phase carbon nitride magnetic catalyst belong to the technical field of electrochemical water treatment. The invention utilizes dicyandiamide to carry out thermal polymerization reaction at high temperature to prepare graphite-phase carbon nitride, and the prepared graphite-phase carbon nitride is taken as a substrate material, and simple substance copper and copper-iron oxide are jointly modified on the graphite-phase carbon nitride by a solvothermal method, so that the heterogeneous catalyst with good dispersion effect is obtained. The method has the advantages of low price of required materials, convenient acquisition, convenient recovery of the catalyst, wide application pH, overcoming the defects of narrow pH range, easy generation of iron mud, difficult reutilization 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 simple substance copper and copper-iron oxide co-modified graphite-phase carbon nitride magnetic catalyst.
Background
The electro-Fenton technique is an advanced oxidation technique combining electrochemical advanced oxidation and Fenton oxidation, and hydrogen peroxide (H) can be generated through a cathode2O2) With ferrous ions (Fe)2+) Reacts to form hydroxyl free radical (OH, E) with strong oxidation capacity02.87V v/s SHE). OH is an oxidizing agent next to fluorine which can degrade organic pollutants in water without selectivity, but the conventional electro-Fenton technology has a narrow reaction pH range (pH 2E)4) Producing iron mud, Fe2+The defects of non-reutilization and the like limit the application of the method in the field of wastewater treatment. Solid catalysts can be used to replace Fe due to their low sensitivity to pH2+Activation of H2O2A heterogeneous electro-fenton system is formed. The copper-based solid phase catalyst can provide monovalent copper ions (Cu)+) Under neutral conditions with H2O2Reaction to form OH, Cu+Has the characteristics of Fe similarity2+Can form a heterogeneous electro-Fenton-like system, and Cu+The catalytic rate is higher than that of Fe2+(kCu+/H2O2＝1.0×104M-1s-1,kFe2+/H2O2＝76M-1s-1). However, the copper-based catalyst is difficult to recover because of its lack of magnetic properties. 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. Elemental copper-modified copper-iron oxide (Cu-CuFe) has been reported2O4) Can promote Fenton reaction and accelerate the degradation of organic pollutants. Cu-CuFe2O4Can be directly synthesized by a solvothermal method, and the preparation method is simple. However, magnetic metal nanoparticles are easy to agglomerate, so that the preparation of a magnetic solid-phase catalyst for a heterogeneous electro-fenton-like system to oxidatively degrade organic pollutants is urgently needed.
Graphite phase carbon nitride (g-C)3N4) Is a layered compound containing a 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-C3N4The preparation method has the advantages of good mechanical property, acid and alkali resistance, environmental friendliness, low preparation cost and the like. These advantages may result in g-C3N4Is used as a base material.
The invention adopts a solvothermal method to prepare elemental copper (Cu)0) And copper iron oxide (CuFe)2O4) The catalyst is modified to the self-prepared graphite-phase carbon nitride together, so that the catalyst is conveniently recovered while organic pollutants are well degraded under a neutral condition.
Disclosure of Invention
The invention aims to provide a preparation method and application of a simple substance copper and copper-iron oxide co-modified graphite-phase carbon nitride magnetic material.
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, placing the crucible containing dicyandiamide in a high-temperature atmosphere furnace, and introducing N2Removing air in the furnace chamber (N)2The flow rate is 10-15L/min, the aeration time is 0.5h), and the N is stopped from being introduced when the air is completely removed2Heating from room temperature to pyrolysis temperature of 550 ℃ at a heating rate of 10 ℃/min, pyrolyzing for 3h, taking out the solid mixture after the temperature is reduced to the room temperature, and fully grinding to obtain graphite-phase carbon nitride;
(2) dispersing graphite-phase carbon nitride in ethylene glycol and ultrasonically dispersing for 60min, and marking as a dispersion liquid A;
(3) ferric chloride hexahydrate (FeCl) is weighed in sequence3·6H2O), copper chloride dihydrate (CuCl)2·2H2O), sodium acetate (NaAC) and polyvinylpyrrolidone (PVP, molecular weight 40000) are put into glycol and fully stirred to obtain uniform mixed solution which is marked as solution B;
(4) pouring the solution B obtained in the step (3) into the dispersion liquid A obtained in the step (2), and carrying out continuous ultrasonic treatment for 4 hours to obtain a dispersion liquid B; wherein each 0.5g of graphite phase carbon nitride corresponds to 0.2703-1.0812 g of ferric chloride hexahydrate (FeCl)3·6H2O), 0.0853-0.3412 g of copper chloride dihydrate (CuCl)2·2H2O), 2.4g sodium acetate (NaAC), 0.6g polyvinylpyrrolidone (PVP), Fe3+And Cu2+In a 2:1 molar ratio, preferably with a mass of hexahydrate and ferric chloride of 0.8109g, use of copper chloride dihydrateIn an amount of 0.2557 g;
(5) and pouring the dispersion liquid B into a reaction kettle, and then placing the reaction kettle in a forced air drying oven to react for 8 hours at the temperature of 200 ℃. After naturally cooling to room temperature, sequentially cleaning the graphite-phase carbon nitride magnetic material by using ultrapure water and ethanol to obtain the elemental copper and copper-iron oxide co-modified graphite-phase carbon nitride magnetic material (Cu-CuFe)2O4/g-C3N4)。
The simple substance copper and copper-iron oxide co-modified graphite-phase carbon nitride magnetic catalyst obtained by the preparation method is applied to a heterogeneous electro-Fenton-like system and is used for removing antibiotic Amoxicillin (AMX).
The advantages of the invention are:
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 can be well removed within the range of the initial pH of 3-9.
2. Is convenient for recovery. The prepared elemental copper and copper-iron oxide co-modified graphite-phase carbon nitride magnetic catalyst is solid powder, has strong magnetism, can be quickly separated under the action of a magnetic field, and is convenient to recover.
Drawings
FIG. 1 shows examples 1, 2, 3, 4 and 1, different hexahydrates and ferric trichloride (FeCl)3·6H2O), copper chloride dihydrate (CuCl)2·2H2O) amount of Cu-CuFe2O4/g-C3N4(Fe3+And Cu2+In a molar ratio of 0.12:0.06, 0.04:0.02, 0.08:0.04, 0.16:0.08) and g-C, respectively3N4Is applied to a heterogeneous electro-Fenton-like system and is used for the degradation diagram of Amoxicillin (AMX).
FIG. 2 is a Cu-CuFe of example 5 and comparative example 22O4/g-C3N4And a degradation profile for Amoxicillin (AMX) applied at different initial pH conditions in the absence of any catalyst.
FIG. 3(a) is Cu-CuFe in example 12O4/g-C3N4SEM picture of (b) isComparative example 1 g-C3N4SEM image of (d).
FIG. 4 shows Cu-CuFe in example 12O4/g-C3N4And g-C in comparative example 13N4XRD pattern of (a).
FIG. 5(a) shows Cu-CuFe in example 12O4/g-C3N4The magnetic strength is shown in FIG. 5(b) as g-C in comparative example 13N4The strength of magnetism of (2).
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Example 1:
(1) weighing 5g of dicyandiamide in a 20mL crucible, placing the crucible containing dicyandiamide in a high-temperature atmosphere furnace, and introducing N2Air in the furnace chamber is removed, (N)2The flow rate is 10-15L/min, the aeration time is 0.5h), and the N is stopped from being introduced when the air is completely removed2Heating from room temperature to pyrolysis temperature of 550 ℃ at a heating rate of 10 ℃/min, pyrolyzing for 3h, cooling to room temperature, taking out the solid mixture, and fully grinding to obtain graphite-phase carbon nitride (g-C)3N4)；
(2) 25mL of ethylene glycol and 0.5g g-C were weighed out separately3N4Putting the mixture into a 100mL beaker, and putting the beaker into ultrasound for ultrasonic dispersion for 60min, and marking as a dispersion A;
(3) 0.8109g of hexahydrate and ferric chloride (FeCl) were weighed in turn3·6H2O), 0.2557g of copper chloride dihydrate (CuCl)2·2H2O), 2.4g sodium acetate (NaAC) and 0.6g polyvinylpyrrolidone (PVP, MW 40000) in 25mL ethylene glycol, stirred well to give a homogeneous mixed solution, denoted as solution B, Fe3+And Cu2+In a molar ratio of 0.12: 0.06;
(4) and (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 to obtain a dispersion liquid B.
(5) Pouring the dispersion liquid B into a 100mL reaction kettle, then placing the reaction kettle in a forced air drying oven, and reacting for 8 hours at the temperature of 200 ℃. After naturally reaching the room temperatureSequentially cleaning the graphite-phase carbon nitride with ultrapure water and ethanol to obtain elemental copper and copper-iron oxide co-modified graphite-phase carbon nitride (Cu-CuFe)2O4/g-C3N4)。
Mixing the Cu-CuFe prepared in the above step2O4/g-C3N4The catalyst is applied to an electro-Fenton oxidation system to degrade AMX. The initial concentration of AMX is 100mg/L, and the anode is a titanium-coated ruthenium-iridium anode (2 x 5 cm)2) The cathode is a graphite felt cathode (2 multiplied by 5 cm) jointly modified by multi-walled carbon nanotubes and carbon black2) Aeration rate of 0.6L/min and current density of 12mA/cm2Volume of solution 300mL, Cu-CuFe2O4/g-C3N4The amount added was 0.2g/L, and the initial pH was 7.0. The AMX removal is shown as a curve (a) in figure 1, the reaction is carried out for 50min, the AMX removal rate can reach 99.3 percent, and the Cu-CuFe2O4/g-C3N4The SEM image of (A) is shown in FIG. 3(a), Cu-CuFe2O4/g-C3N4The XRD pattern of (A) is shown in FIG. 4, Cu-CuFe2O4/g-C3N4The magnetic strength of (2) is as shown in FIG. 5(a), and the catalyst can be separated by attraction with an external magnet.
Example 2:
this example differs from the preparation process of example 1 in that FeCl is added in step (3)3·6H2Mass of O0.2703 g, CuCl2·2H2Mass of O0.0853 g, Fe3+And Cu2+The molar ratio of (A) to (B) is 0.04:0.02, and the other preparation steps are the same. The prepared catalyst is applied to a heterogeneous electro-Fenton system to carry out oxidative degradation on AMX under the degradation condition shown as embodiment 1, the removal condition of the AMX is shown as a curve (b) in figure 1, the reaction is carried out for 50min, and the removal rate of the AMX can reach 74.5 percent
Example 3:
this example differs from the preparation process of example 1 in that FeCl is added in step (3)3·6H2Mass of O0.5406 g, CuCl2·2H2Mass of O0.1705 g, Fe3+And Cu2+The molar ratio of (A) to (B) was 0.08:0.04, and the other preparation steps were the same. Will prepareThe catalyst is applied to a heterogeneous electro-Fenton system to oxidize and degrade AMX, the degradation condition is as shown in embodiment 1, the removal condition of AMX is as shown in a curve (c) in figure 1, the reaction is carried out for 50min, and the removal rate of AMX can reach 90.5 percent
Example 4:
this example differs from the preparation process of example 1 in that FeCl is added in step (3)3·6H2Mass of O1.0812 g, CuCl2·2H2Mass of O0.3412 g, Fe3+And Cu2+The molar ratio of (A) to (B) was 0.16:0.08, and the other preparation steps were the same. The prepared catalyst is applied to a heterogeneous electro-Fenton system to oxidize and degrade AMX under the degradation condition shown as an embodiment 1, the removal condition of the AMX is shown as a curve (d) in figure 1, the reaction is carried out for 50min, and the removal rate of the AMX can reach 96.0 percent
Example 5:
this example was prepared in the same manner as example 1. The prepared catalyst is applied to a heterogeneous electro-Fenton system, AMX is degraded in an oxidation mode, the initial degradation pH range 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 in a 20mL crucible, placing the crucible containing dicyandiamide in a high-temperature atmosphere furnace, and introducing N2Air in the furnace chamber is removed, (N)2The flow rate is 10-15L/min, the aeration time is 0.5h), and the N is stopped from being introduced when the air is completely removed2Heating from room temperature to pyrolysis temperature of 550 ℃ at a heating rate of 10 ℃/min, pyrolyzing for 3h, cooling to room temperature, taking out the solid mixture, and fully grinding to obtain graphite-phase carbon nitride (g-C)3N4)；
G to C to be prepared3N4The method is applied to a heterogeneous electro-Fenton system, AMX is oxidatively degraded under the same degradation condition as that of example 1, the removal condition of AMX is shown as a curve (e) in figure 1, the reaction is carried out for 50min, the removal rate of AMX can reach 62.8%, and g-C3N4The SEM image of (a) is shown in FIG. 3(b), g-C3N4The XRD pattern of (a) is shown in FIG. 4(b), g-C3N4The magnetic strength of (2) is as shown in FIG. 5(b), and the catalyst cannot be separated by external magnetic attraction.
Comparative example 2:
ruthenium iridium (2X 5 cm) is coated with titanium without adding any catalyst2) Graphite felt (2 x 5 cm) modified by multi-wall carbon nano-tube and carbon black as anode2) Serving as a cathode, electrochemically oxidizing and degrading amoxicillin, wherein the aeration amount is 0.6L/min, and the current density is 12mA/cm2And the volume of the solution is 300mL, the initial pH is 3.0-9.0, and AMX is oxidatively degraded. The removal of AMX was performed for 50min as shown in fig. 3, and the removal rates of AMX 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 65.2% at an initial pH of 9.0, respectively.
As can be seen by comparing examples 1 and 5 with comparative examples 1 and 2, g to C3N4Through Cu-CuFe2O4The modification can realize good degradation of AMX under any pH condition.
The results of the above examples and comparative examples show that varying FeCl3·6H2O and CuCl2·2H2The usage amount of O can significantly influence Cu-CuFe2O4/g-C3N4And in fact catalytic is Cu-CuFe2O4The catalyst can be applied to a wide 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, which is prepared by the invention, has high-efficiency catalytic capability while ensuring easy separation.
Claims (7)
1. A preparation method of a simple substance copper and copper iron oxide co-modified graphite phase carbon nitride magnetic catalyst is characterized by comprising the following steps:
(1) placing dicyandiamide in a crucible, placing the crucible containing dicyandiamide in a high-temperature atmosphere furnace, and introducing N2Exhausting air in the hearth, and stopping introducing N when the air is completely exhausted2Heating at a temperature of 10 ℃/minRaising the temperature from room temperature to the pyrolysis temperature of 550 ℃, pyrolyzing for 3h, taking out the solid mixture after the temperature is reduced to the room temperature, and fully grinding to obtain graphite-phase carbon nitride;
(2) dispersing graphite-phase carbon nitride in ethylene glycol and ultrasonically dispersing for 60min, and marking as a dispersion liquid A;
(3) ferric chloride hexahydrate (FeCl) is weighed in sequence3·6H2O), copper chloride dihydrate (CuCl)2·2H2O), sodium acetate (NaAC) and polyvinylpyrrolidone (PVP) are put into glycol and fully stirred to obtain a uniform mixed solution which is marked as solution B;
(4) pouring the solution B obtained in the step (3) into the dispersion liquid A obtained in the step (2), and carrying out continuous ultrasonic treatment for 4 hours to obtain a dispersion liquid B; wherein each 0.5g of graphite phase carbon nitride corresponds to 0.2703-1.0812 g of ferric chloride hexahydrate (FeCl)3·6H2O), 0.0853-0.3412 g of copper chloride dihydrate (CuCl)2·2H2O), 2.4g sodium acetate (NaAC), 0.6g polyvinylpyrrolidone (PVP), Fe3+And Cu2+In a 2:1 molar ratio, preferably the mass of hexahydrate and ferric chloride is 0.8109g, and the amount of copper chloride dihydrate is 0.2557 g;
(5) and pouring the dispersion liquid B into a reaction kettle, and then placing the reaction kettle in a forced air drying oven to react for 8 hours at the temperature of 200 ℃. After naturally cooling to room temperature, sequentially cleaning the graphite-phase carbon nitride magnetic material by using ultrapure water and ethanol to obtain the elemental copper and copper-iron oxide co-modified graphite-phase carbon nitride magnetic material (Cu-CuFe)2O4/g-C3N4)。
2. The method according to claim 1, wherein the mass of the graphite-phase carbon nitride in the step (4) is 0.5g, the mass of hexahydrate and ferric chloride is 0.8109g, and the mass of copper chloride dihydrate is 0.2557 g.
3. Elemental copper and copper iron oxide co-modified graphitic carbon nitride prepared according to the method of any one of claims 1-2.
4. Use of elemental copper and copper iron oxide co-modified graphitic carbon nitride prepared according to the method of any one of claims 1-2 as a solid phase catalyst in heterogeneous electro-fenton-like systems.
5. Use according to claim 4 for the degradation of waste water of amoxycillin antibiotics.
6. Use according to claim 4, for separation and recovery under magnetic field.
7. The use according to claim 4, wherein the initial pH of the reaction is 3 to 9.
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