CN117065802A - Preparation method and application of multilayer reduced graphene oxide and CuCo-MOFs composite film - Google Patents
Preparation method and application of multilayer reduced graphene oxide and CuCo-MOFs composite film Download PDFInfo
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 23
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- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims abstract description 5
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 230000003197 catalytic effect Effects 0.000 claims description 21
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 7
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- 238000004108 freeze drying Methods 0.000 claims description 4
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- 239000012190 activator Substances 0.000 claims description 2
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
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- MWKJTNBSKNUMFN-UHFFFAOYSA-N trifluoromethyltrimethylsilane Chemical compound C[Si](C)(C)C(F)(F)F MWKJTNBSKNUMFN-UHFFFAOYSA-N 0.000 description 19
- 239000010410 layer Substances 0.000 description 11
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
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- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 229940063650 terramycin Drugs 0.000 description 1
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- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Nanotechnology (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method and application of a multilayer reduced graphene oxide and CuCo-MOFs composite membrane, and relates to the technical field of composite materials, wherein the specific preparation method comprises the following steps: firstly, washing and drying multilayer reduced graphene oxide by adopting an ethanol solution, dispersing and adding the multilayer reduced graphene oxide into a mixed solution of ultrapure water and N, N-dimethylformamide, carrying out ultrasonic treatment, transferring the mixed solution into a vacuum tank, vacuumizing, adding cobalt acetate tetrahydrate and copper acetate monohydrate into the solution, mixing and stirring uniformly, continuously vacuumizing, adding 2,3,6,7,10, 11-hexahydroxytriphenyl into the solution after vacuumizing, mixing and stirring uniformly, vacuumizing, reacting the vacuumized solution under the condition of heating, collecting a reaction product, filtering, washing and drying to obtain the composite membrane; the multilayer reduced graphene oxide and CuCo-MOFs composite film provided by the invention can generate nano CuCo-MOFs particles in situ between layers of the multilayer reduced graphene oxide nanosheets, so that nanoparticle aggregation is avoided, the mass transfer process can be accelerated, and the degradation efficiency of organic pollution is improved.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a preparation method and application of a multilayer reduced graphene oxide and CuCo-MOFs composite film.
Background
With the acceleration of the progress of human economy and industrialization, the problem of water resource pollution has evolved into a worldwide challenging problem. Therefore, new and efficient water treatment technologies have been widely studied. Based on sulfate radicals (SO 4 ·- ) The advanced oxidation technology is an emerging water treatment technology, has the advantages of high efficiency, economy, environmental protection and the like, has received wide attention in the aspect of organic pollution treatment in recent years, and gradually becomes one of the most efficient technical means in organic wastewater treatment. Therefore, the development of new materials to activate persulfates to degrade organic pollutants has become a research hotspot.
Metal Organic Frameworks (MOFs) have the characteristics of inherent porosity, well-defined pore structure, and large surface area, making them attractive catalytic materials for energy conversion and environmental remediation applications. The coordination effect among metals in the bimetal organic framework is beneficial to the improvement of the catalytic activity; the nano copper-cobalt bimetallic organic frameworks (CuCo-MOFs) prepared by taking copper and cobalt as metal sites and using the organic ligand have excellent persulfate activation performance, but nano CuCo-MOFs particles are difficult to recover after being used, and the nano particles are easy to aggregate, so that the degradation efficiency of the nano particles on organic pollutants is influenced.
Disclosure of Invention
In view of the above, in order to solve the defects of the prior art, the invention provides a preparation method and application of a multilayer reduced graphene oxide and CuCo-MOFs composite film, wherein the composite film can generate nano CuCo-MOFs particles in situ between layers of multilayer reduced graphene oxide (rGO) nanosheets, so that the aggregation of the nano CuCo-MOFs particles is avoided, the mass transfer process can be accelerated, and the degradation efficiency of organic pollution is improved.
The invention discloses a preparation method of a multilayer reduced graphene oxide and CuCo-MOFs composite film, which comprises the following steps:
step S1: washing and drying the multilayer reduced graphene oxide by adopting an ethanol solution, dispersing and adding the multilayer reduced graphene oxide into a mixed solution of ultrapure water and N, N-dimethylformamide, carrying out ultrasonic treatment for 1-3h, and then transferring the solution subjected to ultrasonic treatment into a vacuum tank and vacuumizing for 10-20min;
step S2: adding cobalt acetate tetrahydrate and copper acetate monohydrate into the vacuumized solution obtained in the step S1, uniformly mixing and stirring, and vacuumizing for 5-10min;
step S3: and (2) adding 2,3,6,7,10, 11-hexahydroxy triphenyl into the vacuumized solution obtained in the step (S2), mixing and stirring uniformly, vacuumizing for 5-10min, then heating the vacuumized solution to 60-90 ℃ for reaction for 5-8h, collecting a reaction product, filtering, washing and drying to obtain the composite membrane.
In one embodiment of the present invention, the washing and drying conditions of the ethanol solution of the multilayer reduced graphene oxide in the step S1 are as follows: washing with 50% ethanol water solution, stirring for 1 hr, and freeze drying at-20deg.C, wherein the mass ratio of the multi-layer reduced graphene oxide to ethanol solution is 1:200-250.
In one embodiment of the present invention, the volume ratio of the ultrapure water to the N, N-dimethylformamide in the mixed solution of the ultrapure water and the N, N-dimethylformamide is 1:1-1.5.
One embodiment of the invention is characterized in that the mass ratio of the cobalt acetate tetrahydrate to the copper acetate monohydrate to the 2,3,6,7,10, 11-hexahydroxytriphenyl and the multilayer reduced graphene oxide is 1:0.5-0.7:1-1.5:1-1.5.
One embodiment of the present invention is that the step S3 of collecting the reaction product comprises the steps of: washing with 50% ethanol water solution, stirring for 3 times, and freeze drying at-20deg.C.
In addition, the multilayer reduced graphene oxide and CuCo-MOFs composite film is prepared according to the method.
Meanwhile, the invention also provides an application method of the prepared multilayer reduced graphene oxide and CuCo-MOFs composite membrane, which mainly uses the composite membrane as a persulfate activator for catalyzing and degrading organic pollutants.
Further, the persulfate concentration is in the range of 1 to 10mM.
Further, the persulfate is a combination of one or more of sodium persulfate and potassium persulfate.
The invention has the technical effects that:
(1) The rGO/CuCo-MOFs composite membrane is of a multi-layer nano structure, the CuCo-MOFs is taken as a main active center, the reaction solution is fully introduced into the layers of the multi-layer rGO through vacuumizing operation, then CuCo-MOFs are generated in situ in the interlayer channels of the multi-layer rGO nano sheets, and the CuCo-MOFs and the interlayer rGO nano sheets are tightly structured to form an interlayer nano reaction space, so that mass transfer is accelerated and catalytic efficiency is improved.
(2) The rGO/CuCo-MOFs composite multilayer film is prepared by taking the CuCo-MOFs as the active site and generating in situ among the layers of rGO, and compared with a common mixed preparation method, the active site and rGO are more tightly combined, and the catalytic stability of the film is high; the equipment used is simple, the cost is low, the economic benefit is better, the film forming time after rGO and CuCo-MOFs are compounded is shortened, and the time cost is saved.
(3) The rGO/CuCo-MOFs composite membrane effectively overcomes aggregation of nano CuCo-MOFs particles, improves catalytic efficiency, simplifies catalyst recovery and saves use cost.
(4) The rGO/CuCo-MOFs composite membrane can realize rapid degradation under the condition of high flux, has the advantage of continuously degrading organic matters by flowing, and has wider application range.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a schematic view of a vacuum pumping apparatus according to the present invention;
FIG. 2 is a graph showing XRD analysis results of the composite membrane of the present invention;
FIG. 3 is a diagram of a degradation experiment device in the invention;
FIG. 4 is a graph showing degradation efficiency results in the present invention;
FIG. 5 is a graph showing the degradation stability results in the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the embodiments of the present invention are not limited thereto, wherein the experimental methods used in the following examples are conventional methods unless otherwise specified; materials, reagents and the like used for the preparation are commercially available unless otherwise specified.
Example 1
Dispersing 0.3g of multi-layer rGO into a mixed solution of 100mLDMF and 100mL of ultrapure water, carrying out ultrasonic treatment on the solution for 2h, and vacuumizing the solution for 10min, wherein a vacuumizing device is shown in figure 1, placing the solution with the dispersed multi-layer rGO into a closed container, connecting the closed container with a conventional vacuum pump, vacuumizing for a designated time when the negative pressure condition is stable, and adding 0.2g of Co (Ac) into the obtained solution 2 ·4H 2 O and 0.14g Cu (Ac) 2 ·H 2 O, stirring, and then re-filling the sealed containerVacuumizing for 5min, adding 0.3g of organic ligand 2,3,6,7,10, 11-hexahydroxytriphenyl, vacuumizing the mixed solution again for 5min, reacting the vacuumized solution at 80 ℃ for 6h, cooling, filtering by simple vacuum, washing with 50% ethanol solution for 3 times, and drying to obtain the rGO/CuCo-MOFs composite catalytic film.
Example 2
Dispersing 0.3g of multilayered rGO into a mixed solution of 100 mM LDMF and 100mL of ultrapure water, then sonicating the above solution for 2 hours, then evacuating the above solution for 10 minutes in the same manner as in example 1, and then adding 0.2g of Co (Ac) 2 ·4H 2 O and 0.1g Cu (Ac) 2 ·H 2 O, stirring, vacuumizing the solution for 5min in the same way as in example 1, adding 0.2g of organic ligand 2,3,6,7,10, 11-hexahydroxytriphenyl, vacuumizing the mixed solution for 5min in the same way as in example 1, reacting the vacuumized solution at 80 ℃ for 6h, cooling, filtering by simple vacuum, washing with 50% ethanol solution for 3 times, and drying to obtain the rGO/CuCo-MOFs composite catalytic film.
Example 3
Dispersing 0.3g of multilayered rGO into a mixed solution of 100 mM LDMF and 100mL of ultrapure water, then sonicating the above solution for 2 hours, then evacuating the above solution for 10 minutes in the same manner as in example 1, and then adding 0.2g of Co (Ac) 2 ·4H 2 O and 0.12g Cu (Ac) 2 ·H 2 O, stirring, vacuumizing the solution for 5min in the same way as in example 1, adding 0.24g of organic ligand 2,3,6,7,10, 11-hexahydroxytriphenyl, vacuumizing the mixed solution for 5min in the same way as in example 1, reacting the vacuumized solution at 80 ℃ for 6h, cooling, filtering by simple vacuum, washing with 50% ethanol solution for 3 times, and drying to obtain the rGO/CuCo-MOFs composite catalytic film.
Example 4
The rGO/CuCo-MOFs composite membrane prepared in example 1 was activated with 3mM potassium hydrogen persulfate for degradation of organic contaminants.
To further illustrate the effect of the product, the performance of the product in the present invention will be evaluated in conjunction with examples.
1. Product composition verification
Bimetallic CuCo-MOFs nano-catalysts and rGO films were prepared separately and XRD analysis was performed separately along with the rGO/CuCo-MOFs composite catalytic film prepared in example 1.
The preparation method of the bimetallic CuCo-MOFs nano catalyst comprises the following steps:
0.2g Co(Ac) 2 ·4H 2 o and 0.14g Cu (Ac) 2 ·H 2 O was added to 200mL of DMF aqueous solution; and adding 0.3g of organic ligand 2,3,6,7,10, 11-hexahydroxytriphenyl, placing the solution in an environment of 80 ℃ for reaction for 6 hours, cooling, centrifuging, and washing with 50% ethanol solution for 3 times to obtain the CuCo-MOFs nano catalyst.
The preparation method of the rGO film comprises the following steps:
dispersing 0.3g of multilayer rGO into 200mLDMF water solution, carrying out ultrasonic treatment on the solution for 2h, vacuumizing for 20min in the device shown in FIG. 1, carrying out simple vacuum filtration, washing with 50% ethanol solution for 3 times, and drying to obtain the rGO membrane.
The XRD analysis results are shown in fig. 2.
As can be seen from fig. 2, characteristic peaks of the rGO membrane and the CuCo-MOFs nanomaterial appear on the rGO/CuCo-MOFs composite membrane, while other impurity peaks are not shown, indicating that the composite membrane is composed of rGO and CuCo-MOFs.
2. Application evaluation
Activating potassium hydrogen persulfate by adopting the rGO/CuCo-MOFs composite membrane under the condition of the example 4 for degrading the oxytetracycline hydrochloride, wherein the concentration of the oxytetracycline hydrochloride is 5ppm, and the concentration of the potassium hydrogen persulfate is 3mM; the performance of the rGO/CuCo-MOF membrane for activating potassium hydrogen persulfate to degrade oxytetracycline hydrochloride was evaluated by using a continuous flow filtration device, which is shown in FIG. 3, and comprises the following specific operation steps:
preparing 300mL of a mixed solution of oxytetracycline hydrochloride and potassium hydrogen persulfate in 500mL of a reagent, wherein the concentration of oxytetracycline hydrochloride is 5ppm and the concentration of potassium hydrogen persulfate is 3mM; pushing the mixed solution through rGO/CuCo-MOFs membrane by using compressed air to obtain hydrochloric acidThe terramycin is degraded, and the flux of the mixed solution passing through the membrane is 87.3 L.m -2 ·h -1 The method comprises the steps of carrying out a first treatment on the surface of the Then, 3mL of the filtered solution was collected every 5min until 30min. The absorbance of the removed filtered solution was measured in an ultraviolet-visible spectrophotometer to further calculate the concentration of oxytetracycline hydrochloride in each sample solution.
The catalytic film is replaced by the rGO film prepared in the product composition verification, a blank sample without the catalytic film is arranged at the same time, the rest conditions are unchanged, the degradation test of the oxytetracycline hydrochloride is carried out by adopting the same operation method, the catalytic degradation effect of various catalytic systems on the oxytetracycline hydrochloride is tested, and the result is shown in figure 4. As can be seen from FIG. 4, the rGO/CuCo-MOFs membrane completely degraded oxytetracycline hydrochloride (5 ppm) in the mixed solution at 3mM potassium hydrogen persulfate; the degradation of the oxytetracycline hydrochloride with the concentration is only about 15% after the activation of the potassium hydrogen persulfate by the rGO membrane, thereby proving that the rGO/CuCo-MOFs catalytic membrane prepared by the invention has excellent catalytic performance and the capability of rapidly and thoroughly catalyzing and degrading organic pollutants under the condition of high circulation.
3. Evaluation of application stability
Preparing 300mL of a mixed solution of oxytetracycline hydrochloride and potassium hydrogen persulfate in 500mL of a reagent, wherein the concentration of oxytetracycline hydrochloride is 5ppm and the concentration of potassium hydrogen persulfate is 3mM; the mixed solution is pushed by compressed air to pass through rGO/CuCo-MOFs membrane to degrade the oxytetracycline hydrochloride, and the flow rate of the mixed solution passing through the membrane is 87.3 L.m -2 ·h -1 Left and right; then, 3mL of the filtered solution was collected at regular intervals until 30h. The absorbance of the removed filtered solution was measured in an ultraviolet-visible spectrophotometer to further calculate the concentration of oxytetracycline hydrochloride in each sample solution. The degradation effect of rGO/CuCo-MOFs film on catalytic degradation of oxytetracycline hydrochloride for 30 hours is shown in figure 5. As can be seen from FIG. 5, the rGO/CuCo-MOFs film has good long-term operation stability performance, with complete degradation of oxytetracycline hydrochloride (5 ppm) in the mixed solution within 30h at 3mM persulfate.
In summary, the rGO/CuCo-MOFs composite catalytic membrane material is prepared by combining in-situ growth with stacking self-assembly, nano particles CuCo-MOFs are grown in-situ in nano interlayer channels of a plurality of layers rGO, are closely combined with rGO and uniformly distributed among the layers of the rGO, and form interlayer nano reaction channels, so that the mass transfer process is accelerated, and the degradation effect of organic pollutants is improved. When the catalytic membrane material is used for activating persulfate to degrade the oxytetracycline hydrochloride, the oxytetracycline hydrochloride can be stably, rapidly and thoroughly degraded for a long time, and the cost is saved. Besides good degradation effect on oxytetracycline hydrochloride, the catalyst has excellent degradation capability on nimex Shu Ni, ciprofloxacin and phenol, and has a wide application range, so that the preparation method of the catalytic membrane material is high in catalytic efficiency, simple and convenient to operate and low in cost.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the technical scope of the present invention disclosed in the embodiments of the present invention should be covered by the present invention. Therefore, the protection scope of the present invention should be as defined in the claims.
Claims (9)
1. The preparation method of the multilayer reduced graphene oxide and CuCo-MOFs composite film is characterized by comprising the following steps of:
step S1: washing and drying the multilayer reduced graphene oxide by adopting an ethanol solution, dispersing and adding the multilayer reduced graphene oxide into a mixed solution of ultrapure water and N, N-dimethylformamide to be completely dissolved, carrying out ultrasonic treatment for 1-3h, transferring the solution subjected to ultrasonic treatment into a vacuum tank, and vacuumizing for 10-20min;
step S2: adding cobalt acetate tetrahydrate and copper acetate monohydrate into the vacuumized solution obtained in the step S1, uniformly mixing and stirring, and vacuumizing for 5-10min;
step S3: and (2) adding 2,3,6,7,10, 11-hexahydroxy triphenyl into the vacuumized solution obtained in the step (S2), mixing and stirring uniformly, vacuumizing for 5-10min, then heating the vacuumized solution to 60-90 ℃ for reaction for 5-8h, collecting a reaction product, filtering, washing and drying to obtain the composite membrane.
2. The method for preparing the multilayer reduced graphene oxide and CuCo-MOFs composite film according to claim 1, wherein the method comprises the following steps: the ethanol solution washing and drying conditions of the multilayer reduced graphene oxide in the step S1 are as follows: washing with 50% ethanol water solution, stirring for 1 hr, and freeze drying at-20deg.C, wherein the mass ratio of the multi-layer reduced graphene oxide to ethanol solution is 1:200-250.
3. The method for preparing the multilayer reduced graphene oxide and CuCo-MOFs composite film according to claim 1, wherein the method comprises the following steps: the volume ratio of the ultrapure water to the N, N-dimethylformamide in the mixed solution of the ultrapure water and the N, N-dimethylformamide is 1:1-1.5.
4. The method for preparing the multilayer reduced graphene oxide and CuCo-MOFs composite film according to claim 1, wherein the method comprises the following steps: the mass ratio of the cobalt acetate tetrahydrate to the copper acetate monohydrate to the 2,3,6,7,10, 11-hexahydroxytriphenyl and the multilayer reduced graphene oxide is 1:0.5-0.7:1-1.5:1-1.5.
5. The method for preparing the multilayer reduced graphene oxide and CuCo-MOFs composite film according to claim 1, wherein the method comprises the following steps: the process of collecting reaction products in the step S3 for filtering, washing and drying is as follows: washing with 50% ethanol water solution, stirring for 3 times, and freeze drying at-20deg.C.
6. A multilayer reduced graphene oxide and CuCo-MOFs composite membrane prepared by the preparation method according to any one of claims 1 to 5.
7. The method of using a multilayer reduced graphene oxide and CuCo-MOFs composite membrane according to claim 6, wherein the composite membrane is used as a persulfate activator for catalytic degradation of organic contaminants.
8. The application method of the multilayer reduced graphene oxide and CuCo-MOFs composite film according to claim 7, wherein the application method is characterized in that: the persulfate concentration is in the range of 1-10mM.
9. The application method of the multilayer reduced graphene oxide and CuCo-MOFs composite film according to claim 7, wherein the application method is characterized in that: the persulfate is one or a combination of more of sodium persulfate and potassium persulfate.
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