CN116212916A - Cobalt-manganese-based composite catalyst, preparation method thereof and application thereof in degradation of antibiotics by activated peroxymonosulfate - Google Patents
Cobalt-manganese-based composite catalyst, preparation method thereof and application thereof in degradation of antibiotics by activated peroxymonosulfate Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical class [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 title claims abstract description 9
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 8
- 229940088710 antibiotic agent Drugs 0.000 title claims abstract description 8
- 230000015556 catabolic process Effects 0.000 title abstract description 14
- 238000006731 degradation reaction Methods 0.000 title abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000137 annealing Methods 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 11
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims abstract description 10
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims abstract description 10
- 230000003213 activating effect Effects 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 22
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 9
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229960000282 metronidazole Drugs 0.000 abstract description 11
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 abstract description 11
- 239000011148 porous material Substances 0.000 abstract description 10
- 230000004913 activation Effects 0.000 abstract description 9
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 231100000719 pollutant Toxicity 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
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- 238000011068 loading method Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
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- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
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- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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Images
Classifications
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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
- C02F1/722—Oxidation by peroxides
-
- 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
- B01J27/24—Nitrogen compounds
-
- B01J35/61—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention belongs to the technical field of advanced oxidation, and provides a cobalt-manganese-based composite catalyst, a preparation method thereof and application thereof in degradation of antibiotics by activated peroxymonosulfate, which solve the problems of high energy consumption and low pollutant degradation efficiency of the traditional activating agent. The method comprises the following steps: mixing melamine, cyanuric acid and water, and annealing to obtain three-dimensional porous g-C 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the Three-dimensional porous g-C 3 N 4 Is mixed with ethanol solution of cobalt chloride hexahydrate, manganese chloride tetrahydrate and ammonium bicarbonateAnd (3) annealing treatment is carried out to obtain the cobalt-manganese-based composite catalyst. The cobalt-manganese-based composite catalyst prepared by the invention has high specific surface area, rich pore structure and a large number of active sites, and is beneficial to PMS activation and pollutant degradation; the cobalt-manganese-based composite catalyst prepared by the invention is applied to the degradation of metronidazole by activating peroxymonosulfate, and after the reaction is carried out for 30min under the dark condition, the removal rate of the metronidazole in the solution is more than 99%.
Description
Technical Field
The invention relates to the technical field of advanced oxidation, in particular to a cobalt-manganese-based composite catalyst, a preparation method thereof and application thereof in degradation of antibiotics by activated peroxomonosulfate.
Background
Advanced oxidation processes (SR-AOPs) based on sulfate radicals are considered to be effective methods for removing toxic contaminants. In the technology, peroxomonosulfate (PMS) can be activated by ultraviolet radiation, heating or transition metal to generate high-activity substances such as sulfate radical, hydroxyl radical and the like, thereby mineralizing organic pollutants into CO 2 、H 2 Small inorganic molecules such as O. The transition metal activation is free in external energy input, is simple to operate, and is considered as a PMS activation mode with high efficiency and wide application prospect.
Cobalt-based catalyst as an effective PMS activationAgents, are extensively studied and reported. Cobalt manganese bimetallic oxide (CoMnO) x ) Not only can reduce the content of toxic cobalt, but also can inhibit the leaching of metal ions through strong interaction between the two components, thereby enhancing the stability of the composite material. More importantly, two metal ions in the bimetallic compound can influence the internal electronic structure through synergistic effect so as to improve the efficiency of PMS activation. However, due to CoMnO x Poor dispersibility and uncontrollable morphology, the number of reaction centers and electron/hole separation efficiency remain limited. Therefore, how to synthesize a cobalt-manganese based composite catalyst simply and easily can control CoMnO x The dispersibility of the catalyst, the number of the reactive centers of the catalyst and the charge transfer efficiency are increased, and the catalyst has great research significance.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a cobalt-manganese-based composite catalyst, a preparation method thereof and application thereof in degradation of antibiotics by activated peroxymonosulfate.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a cobalt-manganese-based composite catalyst, which comprises the following steps:
(1) Mixing melamine, cyanuric acid and water, and annealing to obtain three-dimensional porous g-C 3 N 4 ;
(2) Three-dimensional porous g-C 3 N 4 Mixing ethanol solution of cobalt chloride hexahydrate, manganese chloride tetrahydrate and ammonium bicarbonate, and carrying out annealing treatment to obtain the cobalt-manganese-based composite catalyst.
Preferably, the mole ratio of melamine to cyanuric acid in the step (1) is 0.8-1.2: 0.8 to 1.2; the mass fraction of melamine in the mixed solution is 1.5-2.5%.
Preferably, the rotational speed of the mixing in the step (1) is 500-800 rpm, and the mixing time is 10-14 h.
Preferably, the temperature of the annealing treatment in the step (1) is 500-600 ℃, and the time of the annealing treatment is 3-5 hours.
Preferably, the three-dimensional porous g-C of step (2) 3 N 4 Three-dimensional porous g-C in ethanol solution of (C) 3 N 4 The mass fraction of (2) is 0.2-1.5%.
Preferably, in the step (2), the mol volume ratio of the cobalt chloride hexahydrate, the manganese chloride tetrahydrate, the ammonium bicarbonate and the ethanol is 0.5-0.8 mmol:0.2 to 0.5mmol:2 to 2.5mmol:100mL.
Preferably, the rotational speed of the mixing in the step (2) is 500-800 rpm, and the mixing time is 10-14 h.
Preferably, the temperature of the annealing treatment in the step (2) is 300-400 ℃, and the time of the annealing treatment is 1-3 hours.
The invention also provides the cobalt-manganese-based composite catalyst obtained by the preparation method.
The invention also provides application of the cobalt-manganese-based composite catalyst in activating peroxymonosulfate to degrade antibiotics.
The beneficial effects of the invention are as follows:
(1) g-C of three-dimensional porous structure 3 N 4 The catalyst has high surface area, can provide a large number of sites for loading metal, and reduces aggregation of active sites; at the same time, g-C 3 N 4 The molecule contains rich N atoms, and a nitrogen lone pair can be used as an electron donor to form a metal-nitrogen (M-N) bond with metal ions, so that electron transfer and redox processes are promoted, and the PMS activation efficiency is improved; in addition, g-C of three-dimensional porous structure 3 N 4 The catalyst also has good structural stability, and can avoid accumulation in the catalytic process, so that the catalyst has long-term catalytic activity; the cobalt-manganese-based composite catalyst prepared by the method has the advantages of low cost of raw materials, simple preparation process, easiness in large-scale production and strong practicability.
(2) The cobalt-manganese-based composite catalyst prepared by the invention has three-dimensional porous g-C 3 N 4 Upper loading of CoMnO x The nanoclusters enable the catalyst to have a high specific surface area, rich pore structures and a large number of active sites, and are beneficial to activation of PMS and degradation of pollutants; preparation of the inventionThe cobalt-manganese-based composite catalyst is applied to the degradation of the metronidazole by activating the peroxomonosulfate, and the removal rate of the metronidazole in the solution is more than 99 percent after the reaction is carried out for 30min under the dark condition.
(3) The cobalt-manganese-based composite catalyst prepared by the invention has good charge migration efficiency, excellent PMS activation efficiency, high-efficiency pollutant degradation capability, good stability and reusability under dark conditions, and can be widely applied to degradation of common organic pollutants.
Drawings
FIG. 1 is a flow chart of a specific preparation of a cobalt manganese based composite catalyst according to the present invention;
FIG. 2 is a representation of a field emission electron scanning microscope of the cobalt manganese based composite catalyst of example 1;
FIG. 3 is a transmission electron microscope characterization of the cobalt manganese based composite catalyst of example 1;
FIG. 4 is a three-dimensional porous g-C of example 1 3 N 4 And a nitrogen adsorption and desorption isotherm map (relative pressure, volume adsorption) of the cobalt-manganese based composite catalyst;
FIG. 5 is a three-dimensional porous g-C of example 1 3 N 4 And pore size distribution map of cobalt manganese based composite catalyst (pore size for porosimeter, pore volume for porolume);
FIG. 6 is a graph showing the effect of the cobalt-manganese based composite catalyst in example 2 on activating peroxymonosulfate to degrade metronidazole.
Detailed Description
The invention provides a preparation method of a cobalt-manganese-based composite catalyst, which comprises the following steps:
(1) Mixing melamine, cyanuric acid and water, and annealing to obtain three-dimensional porous g-C 3 N 4 ;
(2) Three-dimensional porous g-C 3 N 4 Mixing ethanol solution of cobalt chloride hexahydrate, manganese chloride tetrahydrate and ammonium bicarbonate, and carrying out annealing treatment to obtain the cobalt-manganese-based composite catalyst.
In the present invention, the molar ratio of melamine to cyanuric acid in step (1) is preferably 0.8 to 1.2:0.8 to 1.2, more preferably 0.9 to 1.1:0.9 to 1.1, more preferably 0.95 to 1.05:0.95 to 1.05; the mass fraction of melamine in the mixed solution is preferably 1.5 to 2.5%, more preferably 1.8 to 2.2%, and even more preferably 1.8 to 2.2%.
In the present invention, the rotational speed of the mixing in the step (1) is preferably 500 to 800rpm, more preferably 550 to 750rpm, still more preferably 600 to 700rpm; the mixing time is preferably 10 to 14 hours, more preferably 11 to 13 hours, and still more preferably 11.5 to 12.5 hours.
In the present invention, after melamine, cyanuric acid and water are mixed, drying and grinding are sequentially performed, and then annealing treatment is performed.
In the present invention, the drying temperature is preferably 50 to 70 ℃, more preferably 55 to 65 ℃, still more preferably 57 to 63 ℃; the drying time is preferably 10 to 14 hours, more preferably 11 to 13 hours, and still more preferably 11.5 to 12.5 hours.
In the invention, the atmosphere of the annealing treatment in the step (1) is an air atmosphere; the annealing treatment temperature is preferably 500 to 600 ℃, more preferably 520 to 580 ℃, and even more preferably 540 to 560 ℃; the time of the annealing treatment is preferably 3 to 5 hours, more preferably 3.5 to 4.5 hours, and still more preferably 3.8 to 4.2 hours.
In the present invention, the three-dimensional porous g-C of step (2) 3 N 4 Three-dimensional porous g-C in ethanol solution of (C) 3 N 4 The mass fraction of (2) is preferably 0.2 to 1.5%, more preferably 0.4 to 1.3%, and still more preferably 0.6 to 1.1%.
In the present invention, the three-dimensional porous g-C of step (2) 3 N 4 Comprises the following steps: three-dimensional porous g-C 3 N 4 Ultrasonic dispersing in ethanol solution to obtain three-dimensional porous g-C 3 N 4 Is a solution of (a) in ethanol.
In the present invention, the frequency of the ultrasonic wave is preferably 20 to 50kHz, more preferably 25 to 45kHz, still more preferably 28 to 40kHz; the time of the ultrasonic wave is preferably 0.5h or more, more preferably 1h or more, and still more preferably 1.5h or more.
In the present invention, the molar volume ratio of cobalt chloride hexahydrate, manganese chloride tetrahydrate, ammonium bicarbonate and ethanol in the step (2) is preferably 0.5-0.8 mmol:0.2 to 0.5mmol:2 to 2.5mmol:100mL, more preferably 0.6 to 0.7mmol:0.3 to 0.4mmol:2.1 to 2.4mmol:100mL, more preferably 0.63 to 0.67mmol:0.33 to 0.37mmol:2.2 to 2.3mmol:100mL.
In the present invention, the rotational speed of the mixing in the step (2) is preferably 500 to 800rpm, more preferably 550 to 750rpm, still more preferably 600 to 700rpm; the mixing time is preferably 10 to 14 hours, more preferably 11 to 13 hours, and still more preferably 11.5 to 12.5 hours.
In the present invention, the solution mixed in the step (2) is sequentially centrifuged, washed and dried, and then annealed.
In the present invention, the rotational speed of the centrifugation is preferably 6000 to 10000rpm, more preferably 7000 to 9000rpm, and still more preferably 7500 to 8500rpm; the time of the centrifugation is preferably 3 to 7 minutes, more preferably 4 to 6 minutes, and still more preferably 4.5 to 5.5 minutes; the washing is sequentially performed by a first washing agent and a second washing agent, wherein the first washing agent is deionized water, and the second washing agent is absolute ethyl alcohol; the number of times of the first washing is preferably 2 times or more, more preferably 3 times or more, and still more preferably 4 times or more; the number of times of the second washing is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more; the drying temperature is preferably 50 to 70 ℃, more preferably 55 to 65 ℃, and even more preferably 57 to 63 ℃; the drying time is preferably 10 to 14 hours, more preferably 11 to 13 hours, and still more preferably 11.5 to 12.5 hours.
In the present invention, the temperature of the annealing treatment in the step (2) is preferably 300 to 400 ℃, more preferably 320 to 380 ℃, and even more preferably 340 to 360 ℃; the time of the annealing treatment is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours, and still more preferably 1.8 to 2.2 hours.
The invention also provides the cobalt-manganese-based composite catalyst obtained by the preparation method.
The invention also provides application of the cobalt-manganese-based composite catalyst in activating peroxymonosulfate to degrade antibiotics.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Adding 2.0g of melamine and 2.0g of cyanuric acid into 100mL of deionized water, magnetically stirring at 650rpm for 12h, transferring the mixed solution into a glass dish, drying at 60 ℃ for 12h, grinding the dried sample into powder, transferring into a muffle furnace, and annealing at 550 ℃ for 4h in air atmosphere to obtain light yellow three-dimensional porous g-C 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the Taking 0.6g of three-dimensional porous g-C 3 N 4 Ultrasonic dispersing in 100mL ethanol at 35kHz for 1.5h to obtain three-dimensional porous g-C 3 N 4 Then adding 0.8mmol of cobalt chloride hexahydrate, 0.2mmol of manganese chloride tetrahydrate and 2mmol of ammonium bicarbonate, magnetically stirring at 650rpm for 12h, centrifuging the obtained solution at 8000rpm for 5min, washing with deionized water for 2 times, washing with absolute ethanol for 1 time, drying at 60 ℃ for 12h, finally transferring to a muffle furnace, annealing at 350 ℃ for 2h in air atmosphere to obtain the cobalt-manganese-based composite catalyst, wherein the specific preparation flow chart is shown in figure 1.
The cobalt-manganese-based composite catalyst prepared in the embodiment is respectively subjected to field emission electron scanning microscope characterization and transmission electron microscope characterization to obtain a field emission electron scanning microscope characterization diagram of the cobalt-manganese-based composite catalyst, as shown in fig. 2; a transmission electron microscope characterization diagram of the cobalt manganese based composite catalyst is shown in fig. 3. As can be seen from fig. 2, the synthesized cobalt manganese based composite catalyst has a three-dimensional porous structure, which is formed due to the generation of gas during the thermal polymerization. The existence of the porous structure is also clearly observed in fig. 3, and spherical nanoclusters of uniform size, namely cobalt-manganese bimetallic oxide, are also deposited.
The three-dimensional porous g-C prepared in this example 3 N 4 And performing nitrogen adsorption and desorption test on the cobalt-manganese-based composite catalyst to obtain three-dimensional porous g-C 3 N 4 And a nitrogen adsorption and desorption isotherm diagram of the cobalt-manganese based composite catalyst, as shown in fig. 4. As can be seen from the figure, all isotherms are those with H 3 Type IV curve of hysteresis loop, and at 0.9<P/P 0 <1 shows strong adsorption, indicating the existence of mesoporous structure. In addition, with three-dimensional porous g-C 3 N 4 Compared with the cobalt-manganese based composite catalyst, the specific surface area of the cobalt-manganese based composite catalyst is obviously increased to 165.62m 2 ·g -1 The large specific surface area also enables the composite catalyst to have more surface active sites.
The three-dimensional porous g-C prepared in this example 3 N 4 And performing pore size distribution test on the cobalt-manganese-based composite catalyst to obtain three-dimensional porous g-C 3 N 4 And pore size distribution plots for cobalt manganese based composite catalysts, as shown in fig. 5. As can be seen from the figure, the total pore volume of the cobalt-manganese-based composite catalyst sample is larger than that of the three-dimensional porous g-C 3 N 4 . In general, cobalt-manganese-based composite catalysts having a three-dimensional porous structure have a large surface area and a rich pore structure, which will provide more surface reaction sites, facilitate adsorption and degradation of PMS and pollutants, and thus improve catalytic performance.
Example 2
Adding 2.1g melamine and 1.8g cyanuric acid into 100mL deionized water, magnetically stirring at 700rpm for 11.5h, transferring the mixed solution into a glass dish, drying at 58 ℃ for 13.5h, grinding the dried sample into powder, transferring into a muffle furnace, annealing at 530 ℃ for 4.6h in air atmosphere to obtain light yellow three-dimensional porous g-C 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the 0.9g of three-dimensional porous g-C is taken 3 N 4 Dispersing in 100mL ethanol at 28KHz frequency for 1.2 hr to obtain three-dimensional porous g-C 3 N 4 Subsequently adding 0.65mmol of cobalt chloride hexahydrate, 0.35mmol of manganese chloride tetrahydrate and 2.2mmol of ammonium bicarbonate, magnetically stirring at 700rpm for 11.5h, centrifuging the obtained solution at 8500rpm for 5min, and removingWashing with ionized water for 2 times, washing with absolute ethyl alcohol for 2 times, drying at 64 ℃ for 11.5 hours, finally transferring into a muffle furnace, and annealing at 345 ℃ for 1.8 hours in air atmosphere to obtain the cobalt-manganese-based composite catalyst.
50mL of metronidazole solution with the concentration of 20mg/L is taken, the cobalt-manganese-based composite catalyst prepared in the embodiment is added, stirring is carried out for 30min under the dark condition, sampling, filtering and analysis are carried out, then 0.5mL of PMS water solution with the concentration of 1mmol is added, timing is started after the addition is finished, sampling, filtering and analysis are respectively carried out at the time points of 5min,10min,15min,20min,25min and 30min, and an effect diagram of activating peroxomonosulfate to degrade metronidazole of the cobalt-manganese-based composite catalyst in the implementation is obtained, as shown in fig. 6. As can be seen from the figure, the removal rate of the metronidazole in the solution is more than 99% after the reaction is carried out for 30min under the dark condition.
Example 3
Adding 1.9g melamine and 2.2g cyanuric acid into 100mL deionized water, magnetically stirring at 600rpm for 13.5h, transferring the mixed solution into a glass dish, drying at 64 ℃ for 11.5h, grinding the dried sample into powder, transferring into a muffle furnace, annealing at 570 ℃ for 3.6h in air atmosphere to obtain light yellow three-dimensional porous g-C 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the Taking 0.8g of three-dimensional porous g-C 3 N 4 Ultrasonic dispersing in 100mL ethanol at 40kHz for 1 hr to obtain three-dimensional porous g-C 3 N 4 Then 0.5mmol of cobalt chloride hexahydrate, 0.5mmol of manganese chloride tetrahydrate and 2.1mmol of ammonium bicarbonate are added, magnetic stirring is carried out for 13.5 hours at a rotation speed of 600rpm, the obtained solution is centrifuged for 5 minutes at a rotation speed of 7500rpm, the obtained solution is washed 3 times by deionized water, is washed 1 time by absolute ethyl alcohol and is dried for 11.5 hours at 64 ℃, finally the obtained solution is transferred into a muffle furnace, and annealing treatment is carried out for 1.9 hours at 365 ℃ in an air atmosphere, so that the cobalt-manganese based composite catalyst is obtained.
The activation performance of the cobalt-manganese based composite catalyst obtained in this example was tested by the same test method as in example 2, and the removal rate of metronidazole in the solution was greater than 99% after 30min of reaction under dark conditions.
From the above embodimentsIt can be seen that the invention provides a cobalt-manganese-based composite catalyst, which is three-dimensional porous g-C 3 N 4 Upper loading of CoMnO x The nano-cluster ensures that the catalyst has high specific surface area, rich pore structure and a large number of active sites, is favorable for PMS activation and pollutant degradation, and the removal rate of the metronidazole in the solution is more than 99 percent after the cobalt-manganese-based composite catalyst prepared by the invention is applied to the activated peroxomonosulfate to degrade the metronidazole and reacts for 30 minutes in dark condition.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the cobalt-manganese-based composite catalyst is characterized by comprising the following steps of:
(1) Mixing melamine, cyanuric acid and water, and annealing to obtain three-dimensional porous g-C 3 N 4 ;
(2) Three-dimensional porous g-C 3 N 4 Mixing ethanol solution of cobalt chloride hexahydrate, manganese chloride tetrahydrate and ammonium bicarbonate, and carrying out annealing treatment to obtain the cobalt-manganese-based composite catalyst.
2. The process according to claim 1, wherein the molar ratio of melamine to cyanuric acid in step (1) is from 0.8 to 1.2:0.8 to 1.2; the mass fraction of melamine in the mixed solution is 1.5-2.5%.
3. The method according to claim 1 or 2, wherein the rotational speed of the mixing in step (1) is 500 to 800rpm and the mixing time is 10 to 14 hours.
4. The method according to claim 3, wherein the annealing treatment in step (1) is performed at a temperature of 500 to 600 ℃ for a time of 3 to 5 hours.
5. The method of claim 4, wherein the three-dimensional porous g-C of step (2) 3 N 4 Three-dimensional porous g-C in ethanol solution of (C) 3 N 4 The mass fraction of (2) is 0.2-1.5%.
6. The method according to claim 5, wherein the molar volume ratio of cobalt chloride hexahydrate, manganese chloride tetrahydrate, ammonium bicarbonate and ethanol in step (2) is 0.5 to 0.8mmol:0.2 to 0.5mmol:2 to 2.5mmol:100mL.
7. The method according to claim 5 or 6, wherein the rotational speed of the mixing in the step (2) is 500 to 800rpm, and the mixing time is 10 to 14 hours.
8. The method according to claim 7, wherein the annealing treatment in step (2) is performed at a temperature of 300 to 400 ℃ for a time of 1 to 3 hours.
9. The cobalt-manganese based composite catalyst obtained by the production method according to any one of claims 1 to 8.
10. The use of the cobalt-manganese based composite catalyst according to claim 9 for activating peroxymonosulfate to degrade antibiotics.
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