CN108940376B - Surface organic complexing copper sulfide Fenton catalyst and synthetic method and application thereof - Google Patents
Surface organic complexing copper sulfide Fenton catalyst and synthetic method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 230000000536 complexating effect Effects 0.000 title claims abstract description 18
- 238000010189 synthetic method Methods 0.000 title claims abstract description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 20
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 20
- 229910001868 water Inorganic materials 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 16
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 14
- 231100000719 pollutant Toxicity 0.000 claims abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000012265 solid product Substances 0.000 claims abstract description 3
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 5
- 229960003405 ciprofloxacin Drugs 0.000 claims description 5
- CXOFVDLJLONNDW-UHFFFAOYSA-N Phenytoin Chemical compound N1C(=O)NC(=O)C1(C=1C=CC=CC=1)C1=CC=CC=C1 CXOFVDLJLONNDW-UHFFFAOYSA-N 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 4
- 229960002036 phenytoin Drugs 0.000 claims description 4
- CQPFMGBJSMSXLP-ZAGWXBKKSA-M Acid orange 7 Chemical compound OC1=C(C2=CC=CC=C2C=C1)/N=N/C1=CC=C(C=C1)S(=O)(=O)[O-].[Na+] CQPFMGBJSMSXLP-ZAGWXBKKSA-M 0.000 claims description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 3
- 229940043267 rhodamine b Drugs 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 229940106691 bisphenol a Drugs 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 14
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 230000015556 catabolic process Effects 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 3
- -1 hydroxyl free radical Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 102000014150 Interferons Human genes 0.000 description 1
- 108010050904 Interferons Proteins 0.000 description 1
- 229910014291 N—Cu Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002124 endocrine Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229940079322 interferon Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000002186 photoelectron spectrum Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004065 wastewater treatment 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
-
- 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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a surface organic complexing copper sulfide Fenton catalyst and a synthetic method and application thereof, wherein the synthetic method of the catalyst comprises the following steps: dissolving a copper source into water to form a solution A; adding CTAB and thiourea into ethylene glycol at the same time, and stirring until the CTAB and the thiourea are dissolved to prepare a solution B; uniformly mixing the solution A and the solution B to form a mixed solution; placing the mixed solution at 120-160 ℃ for hydrothermal reaction; and after natural cooling, filtering, washing and drying the solid product to obtain the surface organic complexing copper sulfide Fenton catalyst. The surface of the catalyst has more active defect sites, and the active components of the catalyst are greatly exposed on the surface of the catalyst and have the effects of resisting pollutants and H2O2The contact is easy, and the obvious influence of steric hindrance effect and capillary phenomenon is avoided; the pH value does not need to be adjusted to harsh conditions in the reaction process, and the degradation effect on the organic pollutants difficult to biodegrade is good under the condition of neutral room temperature.
Description
Technical Field
The invention belongs to the field of water treatment, and particularly relates to a surface organic complexing copper sulfide Fenton catalyst, and a synthesis method and application thereof.
Background
The principle of Fenton catalytic water purification technology is hydrogen peroxide (H)2O2) Decomposed under the action of catalyst to generate hydroxyl free radical (OH) with strong oxidizability to react with organic pollutant, and finally the organic pollutant is oxidized and decomposed into CO2、H2O, inorganic salt and the like.
Compared with the classical homogeneous Fenton catalytic technology, the heterogeneous Fenton catalytic technology has the advantages that the catalyst is easy to separate and recycle, easy to combine with other wastewater treatment technologies, free of iron mud and the like. Compared with advanced oxidation technologies such as photocatalysis, catalytic ozonation and the like, the multiphase Fenton catalytic technology has the advantages of easiness in operation, low cost, low requirements on instruments and equipment and the like.
However, most of the current heterogeneous Fenton catalysts rely on oxidation and reduction of a single active site to complete the catalytic reaction, and the heterogeneous Fenton catalysts still have low activity, poor stability and low hydrogen peroxide (H)2O2) Utilization rate and the like. The development of a novel high-efficiency multiphase Fenton catalytic water treatment technology to overcome the problems is imminent.
Disclosure of Invention
The invention aims to provide a synthetic method of a surface organic complexing copper sulfide Fenton catalyst. Cetyl Trimethyl Ammonium Bromide (CTAB) is used as template agent, and copper compound (specifically CuSO) is used4、CuCl2、Cu(NO3)2Etc.) as copper source, reacting the copper source and thiourea to generate a catalyst active component-CuS, and synthesizing the target catalyst through hydrothermal reaction.
Another object of the present invention is to provide the surface organic complex copper sulfide Fenton prepared by the methodThe catalyst utilizes the complexation characteristic of CTAB to complex the CTAB and the surface of CuS, and constructs a stronger metal-organic coordination structure, thereby realizing the rapid transfer and transfer of electrons in the Fenton reaction and improving the activity of the catalyst in the Fenton reaction; the catalyst is in a flower shape, and the surface of the catalyst is in a porous structure, so that the active sites on the surface of the catalyst are obviously increased, and pollutants and H are generated2O2Can be fully contacted with the active site, thereby improving the reactivity of the Fenton reaction.
Still another object of the present invention is to provide an application of the above surface organic complex copper sulfide fenton catalyst in catalytic degradation of endocrine interferon bisphenol a (bpa), pharmaceutical Ciprofloxacin (CIP), Phenytoin (PHI), dye-based substances acid orange 7(AO7), rhodamine b (rhb), and other organic pollutants, wherein the catalytic degradation activity and efficiency are significantly higher than those of conventional heterogeneous fenton catalysts.
The purpose of the invention is realized by the following technical scheme:
a synthetic method of a surface organic complexing copper sulfide Fenton catalyst comprises the following steps:
(1) dissolving a copper source into water to form a solution A;
the copper source is CuSO4、CuCl2Or Cu (NO)3)2One or more of (1);
(2) adding CTAB and thiourea into ethylene glycol at the same time, and stirring until the CTAB and the thiourea are dissolved to prepare a solution B;
(3) mixing the solution A and the solution B, controlling the molar ratio of copper ions, CTAB and thiourea to be 1.0 (0.1-2.0) to 1.0-3.0, and stirring for more than 50 minutes to form a mixed solution;
the molar ratio of the copper ions, CTAB and thiourea in the step (3) is preferably 1:1: 2; the stirring speed is 400-600 revolutions per minute, specifically 450 revolutions per minute;
(4) pouring the mixed solution into a high-pressure reaction kettle, and performing hydrothermal reaction at 120-160 ℃ for 12-18 hours;
the temperature of the hydrothermal reaction in the step (4) is preferably 130 ℃, and the reaction time is preferably 15 hours;
(5) taking out the autoclave, naturally cooling, filtering the obtained solid product, alternately washing with deionized water and absolute ethyl alcohol, and drying to obtain the surface organic complexing copper sulfide Fenton catalyst;
the drying temperature is 50-100 ℃, and preferably 70 ℃.
The surface organic complexing copper sulfide Fenton catalyst CTAB-CuS-thu prepared by the method is black solid powder; the microstructure is a flower-shaped nanofiber particle with a porous surface and a shape like a flower formed by a piece of curled petals. The catalyst active component CuS is greatly exposed on the surface of the catalyst, so that pollutants and H2O2Can fully contact with active sites on the surface of the catalyst, thereby realizing a high-efficiency degradation process.
The surface organic complexing copper sulfide Fenton catalyst and H2O2The combined use is used for treating organic pollutants in water, and specifically comprises the following steps:
putting the surface organic complex copper sulfide Fenton catalyst into water containing organic pollutants, maintaining natural pH value, continuously stirring for more than 10 minutes to ensure that the pollutants and the catalyst reach adsorption balance, and then adding H2O2The concentration of the organic pollutants reaches more than 10mM, and the organic pollutants are degraded after reacting for 5 to 50 minutes according to different types of the pollutants;
in the water containing the organic pollutants, the concentration of the organic pollutants is 0.1-100 ppm;
in the method, a surface organic complexing copper sulfide Fenton catalyst is added until the concentration of the catalyst in water reaches more than 1 g/L;
the organic pollutants comprise bisphenol A, ciprofloxacin, phenytoin, acid orange 7, rhodamine B and the like;
the surface organic complexing copper sulfide Fenton catalyst and H2O2When used in combination in water, OH and O are generated2Applications other than environmental remediation are also possible in the end.
Compared with the prior art, the invention has the following advantages and effects:
(1) the surface organic complexing copper sulfide Fenton catalyst does not need to adjust the pH value (pH value) of a system to 2-3 in the reaction process, and has a good effect on degradation of organic pollutants difficult to biodegrade under the condition of neutral room temperature.
(2) The surface of the catalyst has more active defect sites, and the active components of the catalyst are greatly exposed on the surface of the catalyst and have the effects of resisting pollutants and H2O2Is not obviously influenced by steric hindrance effect and capillary phenomenon.
(3) The catalyst of the invention does not produce solid foreign matters such as iron mud and the like in the reaction process, and does not need a foreign matter removing device.
(4) The catalyst of the invention can efficiently activate H in the process of degrading pollutants2O2So that a large amount of OH with strong degradation activity is generated, and the OH can not selectively attack pollutants, and finally the catalytic degradation of the pollutants is realized.
(5) The invention has good stability in the process of removing organic pollutants.
(6) The catalyst of the invention belongs to a solid catalyst, is convenient to separate from water and is convenient to recycle.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of CTAB-CuS-thu prepared in example.
FIG. 2 is a Scanning Electron Microscope (SEM) image of CTAB-CuS-thu prepared in example.
FIG. 3 shows the Cu 2p X Photoelectron Spectrum (XPS) of CTAB-CuS-thu prepared in the example.
FIG. 4 is a graph of the degradation curves of CTAB-CuS-thu prepared in the examples for four different contaminants.
FIG. 5 shows the spectrum of the CTAB-CuS-thu repeat activity evaluation obtained in the example.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Examples
The invention discloses a synthetic method of a surface organic complexing copper sulfide Fenton catalyst CTAB-CuS-thu, which comprises the following steps:
(1) 0.97g of Cu (NO)3)2·3H2O was dissolved in 20mL of water to form solution A.
(2) 0.61g of thiourea and 0.15g of CTAB were added to 160mL of ethylene glycol, and the mixture was stirred until dissolved to prepare a solution B.
(3) After mixing A and B for several minutes, solution C was formed.
(4) And putting the mixed solution C into a 200mL high-pressure reaction kettle, putting the whole into a 130 ℃ oven, and reacting for 15 hours.
(5) And after natural cooling, alternately washing with water and ethanol for five times, and drying in a 70 ℃ drying oven to obtain the product.
Evidence of structural characterization of the products obtained in the examples:
FIGS. 1 and 2 are TEM and SEM images of CTAB-CuS-thu prepared in example. As can be seen from the figure, CTAB-CuS-thu is a disordered flower-shaped mesoporous nanofiber particle, the surface of the CTAB-CuS-thu has a petal-shaped hierarchical structure, and the particle size of the CTAB-CuS-thu is 500-1000 nanometers. The CTAB-CuS-thu has a specific surface area, determined by BET, of about 14.8778m2(ii) in terms of/g. The Cu content of CTAB-CuS-thu was 65.26 wt% by XPS analysis, where Cu+The content in the catalyst was 48.18 wt%, Cu2+The content in the catalyst was 17.08 wt%. Indicating that the active component of the catalyst exhibits multiple valence states.
FIG. 3 shows Cu 2p of CTAB-CuS-thu3/2XPS spectra. As is apparent from the figure, in CTAB-CuS-thu, Cu 2p3/2Belong to lower-valence and higher-valence copper species at binding energies of 932.48eV and 933.68eV, respectively. And the atomic ratio of monovalent copper to divalent copper is 2.82: 1. As the catalyst also contains carbon element and nitrogen element, and the valence state forms of Cu in the catalyst are very various, we can further conclude that C-N-Cu bridging bonds formed by C species, N species and Cu species exist in CTAB-CuS-thu, so that the electron transfer rate is greatly improved, and the catalytic degradation activity is enhanced.
Application experiments:
adding 0.05g of the above synthesized catalyst into 50mL of 10 or 15mg/L pollutant solution, maintaining natural pH value (about 7.0), keeping the temperature at 35 ℃, continuously stirring for 10 minutes until the pollutant and the catalyst reach adsorption equilibrium, and adding 15mM H2O2The fenton reaction was started and samples were taken at different time points to measure the concentration of contaminants.
FIG. 4 is a graph of CTAB-CuS-thu degradation curves for different contaminants. Among them, the effect of degradation by RhB and CIP was the best. In the CTAB-CuS-thu Fenton system, RhB is degraded almost completely within 5 minutes, while CPI is degraded up to 100% within 50 minutes. The results fully show that the surface organic complex copper sulfide Fenton catalyst has very remarkable catalytic activity.
FIG. 5 shows a CTAB-CuS-thu repetitive activity evaluation spectrum. From the figure, the removal rate of the catalyst to pollutants still reaches 100 percent after the CTAB-CuS-thu is subjected to 6 times of cycle experiments; in addition, the release amount of copper in the catalyst is very small in the whole reaction and is lower than 0.4mg/L, which indicates that the catalyst has good adaptability and stability to various pollutants.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. Surface organic complexing copper sulfide Fenton catalyst and H2O2The application of the combination in treating organic pollutants in water is characterized in that:
the synthetic method of the surface organic complexing copper sulfide Fenton catalyst comprises the following steps:
(1) dissolving a copper source into water to form a solution A;
(2) adding CTAB and thiourea into ethylene glycol at the same time, and stirring until the CTAB and the thiourea are dissolved to prepare a solution B;
(3) mixing the solution A and the solution B, controlling the molar ratio of copper ions, CTAB and thiourea to be 1.0 (0.1-2.0) to 1.0-3.0, and stirring for more than 50 minutes to form a mixed solution;
(4) pouring the mixed solution into a high-pressure reaction kettle, and placing the mixture at 130 ℃ for hydrothermal reaction for 15 hours;
(5) and taking out the autoclave, naturally cooling, filtering the obtained solid product, alternately washing with deionized water and absolute ethyl alcohol, and drying to obtain the surface organic complexing copper sulfide Fenton catalyst.
2. Use according to claim 1, characterized in that: the copper source in the step (1) is CuSO4、CuCl2Or Cu (NO)3)2More than one of them.
3. Use according to claim 1, characterized in that: in the step (3), the molar ratio of the copper ions, CTAB and thiourea is 1:1: 2.
4. Use according to claim 1, characterized in that: and (5) drying at the temperature of 50-100 ℃.
5. Use according to claim 1, characterized in that it comprises the following steps:
putting the surface organic complex copper sulfide Fenton catalyst into water containing organic pollutants, maintaining natural pH value, continuously stirring for more than 10 minutes to ensure that the pollutants and the catalyst reach adsorption balance, and then adding H2O2The concentration of the organic pollutants is more than 10mM, the reaction lasts for 5 to 50 minutes, and the organic pollutants are degraded.
6. Use according to claim 1, characterized in that:
in the water containing the organic pollutants, the concentration of the organic pollutants is 0.1-100 ppm;
and putting the surface organic complexing copper sulfide Fenton catalyst until the concentration of the catalyst in water reaches more than 1 g/L.
7. Use according to claim 1, characterized in that: the organic pollutants comprise bisphenol A, ciprofloxacin, phenytoin, acid orange 7 and rhodamine B.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201810823312.0A CN108940376B (en) | 2018-07-25 | 2018-07-25 | Surface organic complexing copper sulfide Fenton catalyst and synthetic method and application thereof |
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| CN110180556B (en) * | 2019-05-28 | 2022-03-11 | 广州大学 | Modified vanadium tetrasulfide Fenton catalyst and preparation method and application thereof |
| CN110950344B (en) * | 2019-11-25 | 2023-02-17 | 四川建筑职业技术学院 | Silicon dioxide modified material for producing self-cleaning glass and preparation method thereof |
| CN113611833A (en) * | 2021-07-30 | 2021-11-05 | 广东工业大学 | Application of cation intercalation modified CuS @ CTAB electrode material in zinc ion battery |
| CN114156443A (en) * | 2021-10-11 | 2022-03-08 | 广东省国研科技研究中心有限公司 | Preparation method of positive electrode active material CuS/CTAB of magnesium ion battery |
| CN115025789B (en) * | 2022-06-14 | 2024-03-12 | 三峡大学 | In-situ preparation method and application of high-activity copper sulfide biochar catalyst CuSx@BC |
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