CN111905769A - Three-dimensional composite catalyst and preparation process and application thereof - Google Patents
Three-dimensional composite catalyst and preparation process and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 239000011165 3D composite Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 37
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 29
- 239000002351 wastewater Substances 0.000 claims abstract description 27
- 230000015556 catabolic process Effects 0.000 claims abstract description 26
- 238000006731 degradation reaction Methods 0.000 claims abstract description 26
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 19
- 231100000719 pollutant Toxicity 0.000 claims abstract description 19
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 18
- -1 graphite alkene Chemical class 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 21
- 239000002105 nanoparticle Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
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- 239000003242 anti bacterial agent Substances 0.000 claims description 8
- 229940088710 antibiotic agent Drugs 0.000 claims description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims description 6
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
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- 238000001816 cooling Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- 101100069231 Caenorhabditis elegans gkow-1 gene Proteins 0.000 claims 1
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- 230000000694 effects Effects 0.000 abstract description 11
- 229910002804 graphite Inorganic materials 0.000 abstract description 8
- 239000010439 graphite Substances 0.000 abstract description 8
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 230000003115 biocidal effect Effects 0.000 abstract description 6
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- 230000009471 action Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000005253 cladding Methods 0.000 abstract description 4
- 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 description 16
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- 239000012028 Fenton's reagent Substances 0.000 description 3
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 description 2
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- 238000001228 spectrum Methods 0.000 description 2
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 2
- 229960004306 sulfadiazine Drugs 0.000 description 2
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B01J35/60—
-
- 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
-
- 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
Abstract
The invention discloses a three-dimensional composite catalyst, a preparation process and application thereof, wherein the three-dimensional composite catalyst has sponge @ MoS2The three-dimensional netted composite structure of @ GO, including the molybdenum disulfide and the outer graphite alkene of inlayer, outer graphite alkene has the guard action for inside cladding molybdenum disulfide is more stable in waste water, and the loss is more difficult, has all shown good catalytic activity to dyestuff molecule, organic pollutant and antibiotic. Due to the excellent sponge adsorption and degradation activity of the composite material, the degradation efficiency of the composite material to pollutants within 15min is as high as 93.3%, and excellent recycling property, stability, high hydrophobicity, high adsorption property, low cost and no toxicity are realizedAnd the like. The material has relatively simple preparation process, excellent material performance and reusability, and has extremely high cost advantage and market popularization value when being applied to the treatment of wastewater containing organic pollutants, dye molecule pollutants and antibiotic pollutants.
Description
Technical Field
The invention relates to the field of pollutant treatment, in particular to a three-dimensional composite material catalyst for removing pollutants in industrial wastewater, mainly dye molecules, organic pollutants and antibiotics, and a preparation process and application thereof.
Background
Various organic pollutants and dye molecules exist in industrial wastewater of printing, dyeing, textile industry and the like, and the modern pharmaceutical industry also generates a large amount of harmful wastewater containing antibiotics, the pollutants have different degrees of toxicity and are difficult to degrade by self through biological channels, and the pollutants further cause more serious and difficult-to-twist consequences on the vegetation once discharged into the soil. And once the wastewater containing the pollutants is discharged into a natural water body, a large amount of precious water resources can be polluted, extremely serious loss can be caused, the pollution can harm the living environment of people, and the non-negligible threat can be caused to the healthy life and sustainable development of human beings.
Therefore, the treatment of the organic pollutants and dye molecules to degrade the organic pollutants and dye molecules to reach the standard and then the emission of the organic pollutants and dye molecules has very important significance for maintaining the normal operation of an ecosystem and the sustainable development of human society. At present, the traditional fenton degradation technology is applied to the degradation of such pollutants in such wastewater. The principle of treating papermaking wastewater by Fenton degradation technology is based on H2O2Is a homogeneous catalytic oxidation method which takes ferrous salt as an oxidant and takes ferrous salt as a catalyst. Hydroxyl radical produced in the reactionThe free radicals can oxidize organic matters in the wastewater, thereby reducing the chromaticity and value of the wastewater. However, the fenton reagent adopted in the conventional fenton degradation technology has a certain degradation effect on organic pollutants and dyes in the wastewater, but has serious self-limitation, so that the application in the environmental field is also limited. The main limitations are that the degradation treatment performance is general, the consumption of Fenton reagent is large, the Fenton reagent is disposable and cannot be recycled, the cost of the reagent is high, and the reagent has certain toxicity.
The invention provides a three-dimensional composite material with excellent recycling property, stability, high hydrophobicity, high adsorption property, low cost, no toxicity and the like, and the three-dimensional composite material is applied to the treatment of wastewater containing organic pollutants, dye molecule pollutants and antibiotic pollutants.
Disclosure of Invention
The invention aims to overcome the defects of the traditional technology, provides a three-dimensional composite material with excellent recycling property, stability, high hydrophobicity, high adsorption property, low cost, no toxicity and the like, and is applied to the treatment of wastewater containing organic pollutants, dye molecule pollutants and antibiotic pollutants.
The aim of the invention is achieved by the following technical measures:
a three-dimensional composite catalyst characterized by: comprising a porous substrate having a microscopic three-dimensional porous network structure, the three-dimensional porous network structure of which the inner layer is coated with MoS2Nanoparticles, three-dimensional porous network structure of said porous substrate and MoS2The outer layer surface of the nano-particles is coated with a graphene oxide layer.
The porous substrate is sponge, activated carbon or porous ceramic made of melamine.
A preparation process of a three-dimensional composite catalyst is characterized by comprising the following steps: the method comprises the following steps:
s1, preparation of MoS2Nanoparticles of MoS2Dispersing the nano particles by using absolute ethyl alcohol to prepare MoS with the concentration of 1mg/mL2An alcohol solution;
s2, preparing graphene, dispersing the graphene with absolute ethyl alcohol, and preparing a 1mg/mL GO alcohol solution;
s3, washing the porous substrate, and immersing the porous substrate in MoS2Taking out the alcoholic solution and drying to obtain the loaded MoS2The porous substrate of (a);
s4, dipping the product obtained in the step S3 in a GO alcohol solution, taking out and drying to obtain an inner layer of MoS2And (3) preparing the three-dimensional composite catalyst by using the nano particles and a porous substrate with the outer layer being a graphene oxide layer.
Wherein MoS is prepared in S12The nanoparticle comprises the following steps:
s1-1, weighing 1-2 parts by weight of ammonium molybdate tetrahydrate, and dissolving the ammonium molybdate tetrahydrate in 30 parts by weight of deionized water;
s1-2, adding 0.5-0.8 part by weight of thioacetamide into the solution obtained in the step S1-1, and stirring for 30 minutes;
s1-3, putting the solution obtained in the step S1-2 into a hydrothermal kettle, and heating for reaction for 24 hours;
s1-4, centrifuging the product obtained in the step S1-3, cleaning the product with deionized water and absolute ethyl alcohol, and drying the product after final alcohol cleaning to obtain MoS2And (3) nanoparticles.
Wherein the hydrothermal kettle is provided with a polytetrafluoroethylene lining.
Wherein the reaction temperature in the hydrothermal kettle in S1-3 is 180-240 ℃, and preferably 200 ℃.
Wherein the preparation of graphene in S2 comprises the following steps:
s2-1, weighing 1-3 parts by weight of natural graphite powder and 0.5-2 parts by weight of sodium nitrate, adding into a mixing container, placing the mixing container in an ice water bath, slowly adding 40-80 parts by weight of concentrated sulfuric acid into the mixing container, and reacting under mechanical stirring;
s2-2, gradually adding 5-8 parts by weight of potassium permanganate into the mixing container within 3 hours of reaction;
s2-3, after continuously reacting for 10 hours in ice water bath, transferring the mixing container to an oil bath pan, heating to 80 ℃, slowly adding 80 parts by weight of deionized water, raising the temperature to 98 ℃ and continuing to react
S2-4, slowly adding 280 parts by weight of deionized water and 80 parts by weight of hydrogen peroxide into a mixing container in sequence;
and S2-5, cooling the mixing container to room temperature, washing the product twice with a 5% hydrochloric acid solution, and then washing with deionized water and absolute ethyl alcohol to obtain the graphene.
Wherein, the drying modes in S3 and S4 are all drying in an oven at 200 ℃ for 5-20 hours.
The three-dimensional composite material catalyst prepared by the invention has sponge @ MoS2The three-dimensional netted composite structure of @ GO, including the molybdenum disulfide and the outer graphite alkene of inlayer, outer graphite alkene has the guard action for inside cladding molybdenum disulfide is more stable in waste water, and the loss of being more difficult to realizes excellent cycle recycling nature, stability, high hydrophobicity, high adsorption efficiency, performance such as low cost and non-toxicity.
Use of a three-dimensional composite catalyst as described above, characterized in that: the method is used for degradation treatment of wastewater containing one or more pollutants of dye molecules, organic pollutants or antibiotics.
A method for treating wastewater by using the three-dimensional composite catalyst comprises the following steps:
adding the three-dimensional composite catalyst and ferrous sulfate into wastewater to be treated to form a mixed system;
adjusting the pH value of the mixed system to 4;
adsorbing the mixed system for 10 minutes to reach an adsorption-desorption equilibrium state;
and step four, adding hydrogen peroxide into the mixed system, driving a catalytic reaction, and finishing degradation treatment.
Wherein, the concentration of the ferrous sulfate in the first step is 1-3mg/mL, preferably, the concentration is 2 mg/mL.
Wherein, dilute sulphuric acid is used for adjusting the pH value in the step two.
Wherein, the hydrogen peroxide in the fourth step is used in the concentration of 30 percent.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the advantages that:
the invention discloses a three-dimensional composite catalyst, a preparation process and application thereof, wherein the three-dimensional composite catalyst has sponge @ MoS2The three-dimensional netted composite structure of @ GO, including the molybdenum disulfide and the outer graphite alkene of inlayer, outer graphite alkene has the guard action for inside cladding molybdenum disulfide is more stable in waste water, and the loss is more difficult, has all shown good catalytic activity to dyestuff molecule, organic pollutant and antibiotic. Due to the excellent sponge adsorption and degradation activity of the composite material, the degradation efficiency of the composite material on pollutants within 15min is as high as 93.3%, and excellent properties such as recycling property, stability, high hydrophobicity, high adsorption property, low cost, no toxicity and the like are realized. The material has relatively simple preparation process, excellent material performance and reusability, and has extremely high cost advantage and market popularization value when being applied to the treatment of wastewater containing organic pollutants, dye molecule pollutants and antibiotic pollutants.
The invention is further described with reference to the following figures and detailed description.
Drawings
FIG. 1 shows a sponge @ MoS constructed according to the present invention2A method route of a @ GO (SMG) three-dimensional composite catalyst and a topography of a Scanning Electron Microscope (SEM).
FIG. 2 shows the sponge @ MoS constructed by the present invention2X-ray diffraction (XRD) analysis patterns performed on @ go (smg) three-dimensional composites.
FIG. 3 shows a sponge @ MoS constructed in accordance with the present invention2@ GO (SMG) elemental X-ray photoelectron spectroscopy (XPS) on three-dimensional composites.
Fig. 4 shows the valence of Mo in the SMG material of fig. 3.
FIG. 5 shows the degradation effect of the three-dimensional composite catalyst on rhodamine B (RhB) under different pH conditions in the first embodiment of the invention.
FIG. 6 shows the degradation effect of the three-dimensional composite catalyst and different Fenton systems on rhodamine B (RhB) in the first embodiment of the invention.
FIG. 7 shows sponge @ MoS in the present invention2The removal effect of the @ GO (SMG) three-dimensional composite catalyst on organic pollutants and antibiotics.
Detailed Description
Example 1: as shown in the attached figure 1, the three-dimensional composite material catalyst comprises a porous substrate with a microscopic three-dimensional porous net structure, wherein the inner layer of the three-dimensional porous net structure of the porous substrate is coated with MoS2Nanoparticles, three-dimensional porous network structure of said porous substrate and MoS2The outer layer surface of the nano-particles is coated with a graphene oxide layer.
In this embodiment, the porous substrate is a sponge made of melamine, and the material prepared from the sponge is labeled sponge @ MoS2@ GO three-dimensional network composite catalyst.
Materials having a microscopic three-dimensional porous network structure, such as activated carbon or porous ceramics, may also be used.
As shown in FIG. 1, the produced sponge @ MoS can be measured by Scanning Electron Microscopy (SEM) and X-ray diffraction (XRD)2The appearance and performance of the @ GO three-dimensional composite catalyst are characterized, and the porous network structure and the excellent hydrophobic performance of the catalyst can be observed.
As shown in FIG. 2, elemental X-ray photoelectron spectroscopy (XPS) spectra were used to identify sponge @ MoS in the present invention2The surface components and chemical states of the catalyst of the @ GO three-dimensional reticular composite material are displayed. As can be seen from the XPS full spectrum of the attached figure 2, the material has peaks of Mo and S elements, and also has a large amount of C and O elements, which indicates that the SMG composite material only has four elements, namely C, O, Mo and S, and also indicates that MoS is contained2Successful loading of the material. Fig. 3 separately analyzes the valence states of the Mo element in the SMG material, and finds that the Mo element does not only exhibit one valence state in the SMG composite material. Binding energies at 229.35 eV and 232.80 eV correspond to Mo4+And the binding energies at 231.7 eV and 235.9 eV are Mo6+The peak appearance. Shows that Mo element in the SMG composite material is mainly Mo4+Mainly contains a small amount of Mo6+And (4) peak generation. This is due to the presence of unsaturated S atoms on the surface of SMG, making Mo4+Much surface exposed, and a small amount of Mo4+Is oxidized into Mo in the process of coating graphene oxide6+。
Example 2: a preparation process of a three-dimensional composite catalyst is characterized by comprising the following steps: the method comprises the following steps:
s1, preparation of MoS2Nanoparticles of MoS2Dispersing the nano particles by using absolute ethyl alcohol to prepare MoS with the concentration of 1mg/mL2An alcohol solution;
s2, preparing graphene, dispersing the graphene with absolute ethyl alcohol, and preparing a 1mg/mL GO alcohol solution;
s3, washing the porous substrate, and immersing the porous substrate in MoS2Taking out the alcoholic solution and drying to obtain the loaded MoS2The porous substrate of (a);
s4, dipping the product obtained in the step S3 in a GO alcohol solution, taking out and drying to obtain an inner layer of MoS2And (3) preparing the three-dimensional composite catalyst by using the nano particles and a porous substrate with the outer layer being a graphene oxide layer.
Wherein MoS is prepared in S12The nanoparticle comprises the following steps:
s1-1, weighing 1-2 parts by weight of ammonium molybdate tetrahydrate, and dissolving the ammonium molybdate tetrahydrate in 30 parts by weight of deionized water;
s1-2, adding 0.5-0.8 part by weight of thioacetamide into the solution obtained in the step S1-1, and stirring for 30 minutes;
s1-3, putting the solution obtained in the step S1-2 into a hydrothermal kettle, and heating for reaction for 24 hours;
s1-4, centrifuging the product obtained in the step S1-3, cleaning the product with deionized water and absolute ethyl alcohol, and drying the product after final alcohol cleaning to obtain MoS2And (3) nanoparticles.
Wherein the hydrothermal kettle is provided with a polytetrafluoroethylene lining.
Wherein the reaction temperature in the hydrothermal kettle in S1-3 is 180-240 ℃, and preferably 200 ℃.
Wherein the preparation of graphene in S2 comprises the following steps:
s2-1, weighing 1-3 parts by weight of natural graphite powder and 0.5-2 parts by weight of sodium nitrate, adding into a mixing container, placing the mixing container in an ice water bath, slowly adding 40-80 parts by weight of concentrated sulfuric acid into the mixing container, and reacting under mechanical stirring;
s2-2, gradually adding 5-8 parts by weight of potassium permanganate into the mixing container within 3 hours of reaction;
s2-3, after continuously reacting for 10 hours in ice water bath, transferring the mixing container to an oil bath pan, heating to 80 ℃, slowly adding 80 parts by weight of deionized water, raising the temperature to 98 ℃ and continuing to react
S2-4, slowly adding 280 parts by weight of deionized water and 80 parts by weight of hydrogen peroxide into a mixing container in sequence;
and S2-5, cooling the mixing container to room temperature, washing the product twice with a 5% hydrochloric acid solution, and then washing with deionized water and absolute ethyl alcohol to obtain the graphene.
Wherein, the drying modes in S3 and S4 are all drying in an oven at 200 ℃ for 20 hours.
The three-dimensional composite material catalyst prepared by the invention has sponge @ MoS2The three-dimensional netted composite structure of @ GO, including the molybdenum disulfide and the outer graphite alkene of inlayer, outer graphite alkene has the guard action for inside cladding molybdenum disulfide is more stable in waste water, and the loss of being more difficult to realizes excellent cycle recycling nature, stability, high hydrophobicity, high adsorption efficiency, performance such as low cost and non-toxicity.
Example 3: use of a three-dimensional composite catalyst as described above, characterized in that: the method is used for degradation treatment of wastewater containing one or more pollutants of dye molecules, organic pollutants or antibiotics.
Example 4: a method for treating wastewater by using the three-dimensional composite catalyst comprises the following steps:
adding the three-dimensional composite catalyst and ferrous sulfate into wastewater to be treated to form a mixed system;
adjusting the pH value of the mixed system to 4;
adsorbing the mixed system for 10 minutes to reach an adsorption-desorption equilibrium state;
and step four, adding hydrogen peroxide into the mixed system, driving a catalytic reaction, and finishing degradation treatment.
Wherein, the concentration of the ferrous sulfate in the first step is 1-3mg/mL, preferably, the concentration is 2 mg/mL.
Wherein, dilute sulphuric acid is used for adjusting the pH value in the step two.
Wherein, the hydrogen peroxide in the fourth step is used in the concentration of 30 percent.
The invention is further illustrated by two sets of experiments.
Sponge @ MoS in the invention2The @ GO three-dimensional reticular composite catalyst is used for carrying out degradation experiments on rhodamine B (RhB). The experiment adopts the method for treating wastewater by using the three-dimensional composite catalyst, and the comparative experiment is carried out according to the following three groups of conditions:
the first group is rhodamine B dye solution with the concentration of 20mg/L and the concentration of 2mg/L Fe, wherein the concentration of the rhodamine B dye solution is 100mL2+1mL,H2O24μL,pH=4;
The second group is rhodamine B dye solution with the concentration of 20mg/L, the concentration of 20mg/L and the concentration of 2mg/L Fe2+1mL,H2O24μL,pH=5;
The third group is 100mL of rhodamine B dye solution with the concentration of 20mg/L, Fe with the concentration of 20mg/L and 2mg/L2+1mL,H2O24μL,pH=6。
The experimental result is shown in fig. 5, when the pH value is 4, the SMG composite material-promoted Fenton reaction has the best removal rate for rhodamine B, and the removal rate of 93.3 percent is realized within 15 min. In the traditional Fenton reaction, the reaction activity is greatly reduced when the pH is more than 5, and in the product of the invention, when the pH is 5, the Fenton reaction promoted by the SMG still has a better removal rate for rhodamine B, the removal rate is 89.1% in 15min, but the removal efficiency is not as good as that of pH 4 in the first 1 min. Even when the pH of the system is 6, 68.9 percent of removal rate is still achieved.
As shown in FIG. 6, the degradation experiment of different Fenton systems on rhodamine B (RhB) and the inventionIn comparison, the Fenton system used to demonstrate the superior performance of the catalyst of the present invention on dye degradation. The results show that SMG/Fe2+-H2O2The system has the best degradation effect on dye rhodamine B, and the introduction of the SMG catalyst material improves the degradation effect of the system from 0% to 83.74%, thereby greatly promoting Fe3+To Fe2+The transformation of (3).
Sponge @ MoS in the invention2The @ GO three-dimensional reticular composite catalyst is used for degradation experiments of organic pollutants such as phenol, 4-chlorophenol, sulfadiazine and norfloxacin and antibiotics. The experiment adopts the method for treating wastewater by using the three-dimensional composite catalyst, and the experiment is carried out according to the following four groups of conditions:
(1) 100mL of 20mg/L phenol solution and 2mg/L Fe2+1mL,H2O24μL,pH=4;
(2) 100mL of 4-chlorophenol solution with the concentration of 20mg/L and Fe with the concentration of 2mg/L2+1mL,H2O24μL,pH=4;
(3) 100mL sulfadiazine solution with the concentration of 20mg/L and Fe with the concentration of 2mg/L2+1mL,H2O24μL,pH=4;
(4) 100mL of norfloxacin solution with the concentration of 20mg/L and Fe with the concentration of 2mg/L2+1mL,H2O24μL,pH=4;
The experimental results are shown in FIG. 7, and the results show that sponge @ MoS2The @ GO three-dimensional mesh composite catalyst shows excellent catalytic activity, shows a good degradation effect in 15min on various dyes, organic pollutants and antibiotics, and has the best degradation effect on rhodamine B.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A three-dimensional composite catalyst characterized by: comprising a porous substrate having a microscopic three-dimensional porous network structure, the three-dimensional porous network structure of which the inner layer is coated with MoS2Nanoparticles, three-dimensional porous network structure of said porous substrate and MoS2The outer layer surface of the nano-particles is coated with a graphene oxide layer.
2. The three-dimensional composite catalyst according to claim 1, wherein: the porous substrate is sponge, activated carbon or porous ceramic made of melamine.
3. A preparation process of a three-dimensional composite catalyst is characterized by comprising the following steps: the method comprises the following steps:
s1, preparation of MoS2Nanoparticles of MoS2Dispersing the nano particles by using absolute ethyl alcohol to prepare MoS with the concentration of 1mg/mL2An alcohol solution;
s2, preparing graphene, dispersing the graphene with absolute ethyl alcohol, and preparing a 1mg/mL GO alcohol solution;
s3, washing the porous substrate, and immersing the porous substrate in MoS2Taking out the alcoholic solution and drying to obtain a porous substrate loaded with MoS 2;
s4, dipping the product obtained in the step S3 in a GO alcohol solution, taking out and drying to obtain an inner layer of MoS2And (3) preparing the three-dimensional composite catalyst by using the nano particles and a porous substrate with the outer layer being a graphene oxide layer.
4. The process according to claim 3, wherein the three-dimensional composite catalyst is prepared by the following steps:
preparation of MoS in the S12The nanoparticle comprises the following steps:
s1-1, weighing 1-2 parts by weight of ammonium molybdate tetrahydrate, and dissolving the ammonium molybdate tetrahydrate in 30 parts by weight of deionized water;
s1-2, adding 0.5-0.8 part by weight of thioacetamide into the solution obtained in the step S1-1, and stirring for 30 minutes;
s1-3, putting the solution obtained in the step S1-2 into a hydrothermal kettle, and heating for reaction for 24 hours;
s1-4, centrifuging the product obtained in the step S1-3, cleaning the product with deionized water and absolute ethyl alcohol, and drying the product after final alcohol cleaning to obtain MoS2And (3) nanoparticles.
5. The process according to claim 4, wherein the three-dimensional composite catalyst is prepared by the following steps:
the hydrothermal kettle is provided with a polytetrafluoroethylene lining.
6. The process according to claim 4, wherein the three-dimensional composite catalyst is prepared by the following steps:
the reaction temperature in the hydrothermal kettle in S1-3 is 180 ℃ and 240 ℃.
7. The process according to claim 3, wherein the three-dimensional composite catalyst is prepared by the following steps:
the preparation of graphene in the step S2 comprises the following steps:
s2-1, weighing 1-3 parts by weight of natural graphite powder and 0.5-2 parts by weight of sodium nitrate, adding into a mixing container, placing the mixing container in an ice water bath, slowly adding 40-80 parts by weight of concentrated sulfuric acid into the mixing container, and reacting under mechanical stirring;
s2-2, gradually adding 5-8 parts by weight of potassium permanganate into the mixing container within 3 hours of reaction;
s2-3, after continuously reacting for 10 hours in ice water bath, transferring the mixing container to an oil bath pan, heating to 80 ℃, slowly adding 80 parts by weight of deionized water, raising the temperature to 98 ℃ and continuing to react
S2-4, slowly adding 280 parts by weight of deionized water and 80 parts by weight of hydrogen peroxide into a mixing container in sequence;
and S2-5, cooling the mixing container to room temperature, washing the product twice with a 5% hydrochloric acid solution, and then washing with deionized water and absolute ethyl alcohol to obtain the graphene.
8. Use of a three-dimensional composite catalyst as described above, characterized in that: the method is used for degradation treatment of wastewater containing one or more pollutants of dye molecules, organic pollutants or antibiotics.
9. A method for treating wastewater by using the three-dimensional composite catalyst comprises the following steps:
adding the three-dimensional composite catalyst and ferrous sulfate into wastewater to be treated to form a mixed system;
adjusting the pH value of the mixed system to 4;
adsorbing the mixed system for 10 minutes to reach an adsorption-desorption equilibrium state;
and step four, adding hydrogen peroxide into the mixed system, driving a catalytic reaction, and finishing degradation treatment.
10. The method for treating wastewater by using the three-dimensional composite catalyst as claimed in claim 9, wherein the method comprises the following steps:
the concentration of ferrous sulfate in the first step is 1-3 mg/mL;
adjusting the pH value by using dilute sulfuric acid in the step two;
in step four, 30% hydrogen peroxide is used.
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