CN114700071A - CN @ MnO composite catalytic material and preparation method and application thereof - Google Patents
CN @ MnO composite catalytic material and preparation method and application thereof Download PDFInfo
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- CN114700071A CN114700071A CN202210505929.4A CN202210505929A CN114700071A CN 114700071 A CN114700071 A CN 114700071A CN 202210505929 A CN202210505929 A CN 202210505929A CN 114700071 A CN114700071 A CN 114700071A
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002105 nanoparticle Substances 0.000 claims abstract description 34
- 238000001354 calcination Methods 0.000 claims abstract description 23
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- LTEALMDLAOASIE-UHFFFAOYSA-N 3-n-methylpyrazine-2,3-diamine Chemical compound CNC1=NC=CN=C1N LTEALMDLAOASIE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
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- 238000000034 method Methods 0.000 claims description 23
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- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 15
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 15
- 239000012286 potassium permanganate Substances 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
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- 239000000706 filtrate Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 238000005949 ozonolysis reaction Methods 0.000 claims description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 abstract description 81
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000593 degrading effect Effects 0.000 abstract description 8
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- 238000006731 degradation reaction Methods 0.000 abstract description 4
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- 239000003054 catalyst Substances 0.000 description 26
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 21
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- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B01J35/23—
-
- B01J35/394—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/306—Pesticides
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a CN @ MnO composite catalytic material and a preparation method and application thereof. The CN @ MnO composite catalytic material takes MnO as a core and is wrapped by nitrogen-doped carbon. The manganese dioxide nanoparticle is obtained by one-step reaction of manganese dioxide nanoparticles and 2-amino-3-methylaminopyrazine through a calcining mode. The CN @ MnO composite catalytic material prepared by the invention has better effect on degrading organic pollutants by catalyzing ozone than nitrogen-doped carbon coated manganese dioxide composite materials and commercial manganese monoxide materials, and can be applied to the degradation of organic pollutants in tap water or town sewage by catalyzing ozone and efficiently degrading the organic pollutants. In addition, the manganese dioxide nanoparticles and the 2-amino-3-methylaminopyrazine which has reducibility and can provide carbon and nitrogen elements are mixed and calcined, so that the reduction of manganese dioxide into manganese monoxide and the wrapping of nitrogen-doped carbon on the manganese monoxide are completed in one step, and the preparation process of the composite catalytic material is simplified.
Description
Technical Field
The invention relates to a nanometer material and a chemical catalytic decomposition technology, in particular to a CN @ MnO composite catalytic material for catalyzing ozone to efficiently degrade organic pollutants, and a preparation method and application thereof.
Background
The constant input of new pollutants into the environment leads to a rapid accumulation of pollutants in the water and potential, irreversible damage to humans by means of the food chain. Antibiotics in the water environment mainly come from urban sewage, hospital sewage, regenerated wastewater and wastewater discharged by the pharmaceutical industry, and most of the antibiotics are organic pollutants which are difficult to biodegrade. Therefore, the development of a technology capable of effectively removing or decomposing organic pollutants in tap water or town wastewater to eliminate the harm of the pollutants to human bodies or various organisms has become a problem to be solved urgently. At present, the main methods for degrading and treating novel organic pollutants in water bodies include conventional water treatment technologies, activated carbon adsorption methods, chemical oxidation methods, membrane separation methods and the like.
The ozone oxidation method belongs to a chemical oxidation method, and is a common and effective treatment method for removing new organic pollutants in water. But the ozone oxidation method alone is selective and only degrades and removes some organic matters which are easy to be oxidized by ozone. And most of novel organic pollutants in the water body can be efficiently degraded by catalyzing ozone to generate free radicals such as hydroxyl free radicals by using the catalyst.
The nitrogen-doped carbon-combined metal oxide catalyst is a catalyst for catalyzing ozone to oxidize organic pollutants in recent years due to good catalytic degradation effect, but the metal oxide has the problems of metal dissolution, poisoning inactivation and the like. Therefore, it is necessary to find a catalyst which can catalyze ozone to degrade organic pollutants efficiently.
Disclosure of Invention
The invention aims to provide a simple and easy-to-operate synthesis method of a nitrogen-doped carbon-coated manganese monoxide nanoparticle (CN @ MnO) composite catalytic material.
In a first aspect, the invention provides a CN @ MnO composite catalytic material, which takes MnO as a core and is wrapped with nitrogen-doped carbon.
Preferably, the CN @ MnO composite catalytic material is spherical, and the particle size is 20 nm-50 nm.
Preferably, the CN @ MnO composite catalytic material is obtained by a one-step reaction of manganese dioxide nanoparticles and 2-amino-3-methylaminopyrazine through a calcination mode.
In a second aspect, the present invention provides a preparation method of the above CN @ MnO composite catalytic material, which comprises the following steps:
step one, adding manganese dioxide nanoparticles into a 2-amino-3-methylaminopyrazine dissolving solution to obtain a suspension.
And step two, drying the suspension, grinding the obtained solid, and calcining to obtain the CN @ MnO composite catalytic material.
Preferably, in step one, the ratio of the amounts of manganese dioxide and 2-amino-3-methylaminopyrazine species is 1: 4.
Preferably, in the first step, the mass concentration of the 2-amino-3-methylaminopyrazine solution is 0.02-0.08 g/mL.
Preferably, in the first step, the manganese dioxide nanoparticles are added into the 2-amino-3-methylaminopyrazine dissolving solution and then are mixed by ultrasound.
Preferably, in the second step, the suspension is dried by a water bath.
Preferably, the conditions of the calcination in step two are: heating to 450 ℃ per minute at 3 ℃ under the protection of argon, calcining for 3 hours, and then naturally cooling.
Preferably, the manganese dioxide nanoparticles are obtained by the following steps: mixing a sodium thiosulfate solution and a potassium permanganate solution, carrying out solid-liquid separation after reaction, washing a solid component with water until the filtrate is neutral, drying the solid component, and then feeding the solid component into a tubular furnace for calcination.
Preferably, the reaction of the sodium thiosulfate solution and the potassium permanganate solution is carried out under magnetic stirring at a constant temperature of 60 ℃.
Preferably, the sodium thiosulfate solution is mixed into the potassium permanganate solution in a dropwise manner; before mixing, the sodium thiosulfate solution and the potassium permanganate solution are respectively heated by an ultrasonic cleaning bath at 60 ℃.
Preferably, after the sodium thiosulfate solution is completely dripped, the obtained suspension is continuously aged in a water bath at 60 ℃; and naturally cooling the suspension after the water bath aging is finished to room temperature, and then realizing solid-liquid separation in a centrifugal or filtering mode. The centrifugal separation condition is 12000r/min, 5min, washing for many times; the filtration was carried out by vacuum filtration using a filter membrane of 0.45 μm and washing with water several times.
Preferably, the water bath aging time of the suspension is 2 h.
Preferably, the molar concentrations of the sodium thiosulfate solution and the potassium permanganate solution are respectively 0.376mol/L and 0.2 mol/L; the volume ratio of the sodium thiosulfate solution to the potassium permanganate solution is 1: 5.
Preferably, the calcining conditions of the solid component obtained after the reaction and solid-liquid separation of the sodium thiosulfate solution and the potassium permanganate solution are as follows: heating to 400 ℃ per minute at 5 ℃ under the protection of nitrogen, calcining for 4 hours, and then naturally cooling.
In a third aspect, the invention provides the use of the aforementioned CN @ MnO composite catalytic material for catalyzing the ozonolysis of organic pollutants in water.
Preferably, the water body is tap water or town sewage.
Compared with the prior art, the invention has the following advantages:
1. the nitrogen-doped carbon-coated manganese monoxide nanoparticle (CN @ MnO) composite catalytic material prepared by the invention has better effect on catalyzing ozone to degrade organic pollutants than nitrogen-doped carbon-coated manganese dioxideComposite material (CN @ MnO)2) And a commercial manganese monoxide material, which can be applied to the degradation of organic pollutants in the catalytic ozone high-efficiency degradation tap water or town sewage.
2. According to the invention, manganese dioxide nanoparticles and 2-amino-3-methylaminopyrazine which has reducibility and can provide carbon and nitrogen are mixed and calcined, so that the reduction of manganese dioxide into manganese monoxide and the wrapping of nitrogen-doped carbon on manganese monoxide are completed in one step, and the preparation process of the composite catalytic material is simplified.
3. The nitrogen-doped carbon-coated manganese monoxide nanoparticle (CN @ MnO) composite catalytic material prepared by the invention has stable properties in an oxidation system, and MnO cannot be oxidized into MnO2The MnO is not separated from the nitrogen-doped carbon even when the oxides with higher manganese valence are used.
4. The nitrogen-doped carbon-coated manganese monoxide nanoparticle (CN @ MnO) composite catalytic material prepared by the invention has the advantages of uniform particles, small particle size, good dispersibility and good repeatability effect.
5. The preparation method of the composite catalytic material provided by the invention has the characteristics of simple process and mild conditions, and the obtained product has good reusability.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of a CN @ MnO composite catalytic material prepared in example 1 of the present invention;
FIG. 2 is a graph comparing the effectiveness of CN @ MnO composite catalytic material provided by the present invention and other materials as catalysts for degrading ATZ organic pollutants;
FIG. 3 is a comparison graph of outlet ozone concentration in the process of degrading organic pollutants ATZ by using the CN @ MnO composite catalytic material provided by the invention and other materials as catalysts.
FIG. 4 is a comparison graph of X-ray diffraction (XRD) before and after reaction of the CN @ MnO composite catalytic material provided by the invention as a catalyst in the process of degrading organic pollutants by ATZ.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. It is intended that all simple modifications or alterations to the methods, procedures or conditions of the present invention, which are within the scope of the present invention and not specifically indicated herein, be resorted to, falling within the scope of the invention, and that all technical means which are within the scope of the appended claims are readily available to those skilled in the art.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
A CN @ MnO composite catalytic material takes MnO as a core, is wrapped by nitrogen-doped carbon, is spherical, and has a particle size of 20-50 nm.
The preparation method of the CN @ MnO composite catalytic material comprises the following steps:
step one, dripping a sodium thiosulfate solution into a potassium permanganate solution which is continuously stirred at a constant temperature of 60 ℃ by magnetic force, aging in a water bath at 60 ℃ for 2 hours after finishing dripping, and carrying out solid-liquid separation after full reaction. The concentration of the sodium thiosulfate solution is 0.376mol/L, and the volume of the sodium thiosulfate solution is 100 mL; the concentration of the potassium permanganate solution is 0.2mol/L, and the volume is 500 mL. The solid-liquid separation method is centrifugal separation (centrifugal separation condition: 12000r/min, 5min) or vacuum filtration separation (0.45 μm filter membrane);
step two, washing the solid component obtained by separation in the step one with water until the filtrate reaches a neutral pH value, drying the solid component at 110 ℃, and then feeding the dried solid component into a tubular furnace for calcination; and calcining to obtain the dry solid material manganese dioxide nano particles. The calcining condition is that the solid material is heated to 400 ℃ per minute at 5 ℃ under the protection of high-purity nitrogen and is calcined for 4 hours, and then the temperature is naturally reduced.
Step three, adding the manganese dioxide nano particles obtained in the step two into a 2-amino-3-methylaminopyrazine dissolving solution, and ultrasonically mixing uniformly for 30 minutes; the mass concentration of the 2-amino-3-methylaminopyrazine dissolved solution is 0.05 g/mL; the mass ratio of manganese dioxide nanoparticles to 2-amino-3-methylaminopyrazine in the resulting suspension was 1: 4. And (3) drying the suspension subjected to ultrasonic treatment in a water bath at the temperature of 80 ℃, grinding the dried solid, and then feeding the ground solid into a tubular furnace for calcination to obtain the nitrogen-doped carbon-coated manganese monoxide nano particle (CN @ MnO) catalytic material. The calcination condition is that the temperature is raised to 450 ℃ per minute under the protection of high-purity argon for 3 hours after calcination, and then the temperature is naturally reduced.
Example 2
This example differs from example 1 in that: the mass concentration of the 2-amino-3-methylaminopyrazine dissolving solution in the third step is 0.02-0.08 g/mL.
Example 3
A method for catalyzing ozone to efficiently degrade organic pollutants in wastewater comprises the following specific processes: adding the CN @ MnO composite catalytic material described in the embodiment 1 or 2 into the water body to be treated, and continuously introducing ozone. The water body to be treated is tap water or town sewage.
The effect of the CN @ MnO composite catalytic material provided by the invention on catalytic decomposition of organic pollutants is verified by the following tests:
test one: the test is a preparation test of a CN @ MnO composite catalytic material, and is specifically carried out according to the following steps:
9.332g of anhydrous sodium thiosulfate is dissolved in 100mL of deionized water, 15.803g of potassium permanganate is dissolved in 500mL of deionized water, the mixture is placed in an ultrasonic cleaning bath (working power: 40kHz, 200W), the temperature is kept constant at 60 ℃ for a period of time, the potassium permanganate solution is moved into a magnetic stirring water bath kettle at 60 ℃, the stirring is continuously carried out at the rotating speed of 120 revolutions per minute until the sodium thiosulfate solution is dropwise added, the stirring is stopped, and the water bath at 60 ℃ is aged for 2 hours. After the reaction is finished, performing solid-liquid separation by a centrifugal separation method (centrifugal separation conditions: 12000r/min, 5min), washing the solid component for 4 times until the filtrate is neutral, then sending the solid component into a drying oven, drying at 110 ℃ for 12h, sending the dried solid into a tubular furnace, heating to 400 ℃ by a heating program of 5 ℃/min under the protection of high-purity nitrogen, calcining for 4h, and naturally cooling to room temperature to obtain the nano-grade manganese dioxide. Preparing 10 groups of solutions of 0.5g of 2-amino-3-methylaminopyrazine dissolved in 10mL of water, adding 0.09g of prepared manganese dioxide nanoparticles into each group of solutions, performing ultrasonic treatment for 30 minutes, putting the solutions in a water bath kettle at 80 ℃ for water bath evaporation to dryness, then feeding the dried solutions into a tubular furnace for calcination, wherein the calcination conditions are that the temperature is increased to 450 ℃ at 3 ℃/min under the protection of high-purity argon, and the temperature is naturally reduced to room temperature after the calcination for 3 hours, so that the CN @ MnO composite catalytic material can be obtained. The XRD pattern of the CN @ MnO composite catalytic material is shown in figure 1; FIG. 1 shows that the prepared CN @ MnO composite catalytic material has higher crystallinity.
And (2) test II: the test is a test of applying CN @ MnO composite catalytic material simulation to catalyzing ozone to efficiently degrade organic pollutants Atrazine (ATZ). ATZ is dissolved in 1L of deionized water to enable the concentration to be 5 mu m/L, the obtained solution is filled into an ozone catalytic reaction device, and then the CN @ MnO composite catalytic material prepared in the first test is put into the solution of the ozone catalytic reaction device, the catalyst dosage is 0.03g/L, and the total dosage is 30 mg. And (3) continuously aerating and introducing ozone into the reactor, and detecting the concentration of the ozone at the outlet of the reactor. The concentration of ATZ in the simulated wastewater was monitored at intervals as experimental groups.
Three control groups are arranged, and the difference between the control group 1, the control group 2 and the control group 3 and the test group is that the CN @ MnO composite catalytic material is replaced by the non-input catalyst, the commercial MnO nano-particles are input, and the CN @ MnO nano-particles are input2Nanoparticles (in MnO)2The nano-particles are used as cores and are obtained by coating nitrogen-doped carbon).
The results of the test group and three control groups for degrading ATZ are shown in fig. 2 and 3.
In FIG. 2,: |, represents the remaining concentration of ATZ as to the remaining concentration of ATZ as ATZ in the catalyst without catalyst (control 1) of the catalyst (control 1), the catalyst), and/or) of the rest) of ATZ, and ● of ATZ, and of the commercial MnO nanoparticles of commercial MnO as used in the commercial MnO as the same catalyst (control 2), and |, (control 2), and of the same catalyst), and of the same concentration of the same catalyst, of commercial MnO nanoparticles of MnO, and of the same catalyst, and of the same concentration of the same catalyst, of the commercial MnO, of the same catalyst, of the same concentration of the same catalyst, of the commercial MnO nanoparticles (control 2) of the same concentration of the same catalyst, and of the same concentration of the same2Residual concentration of ATZ at nanoparticles (control 3) represents residual concentration of ATZ at the time of addition of the CN @ MnO composite catalytic material prepared in experiment one.
Fig. 2 shows that after a reaction time of 30 minutes, 60.4% of ATZ was oxidized by ozone in the control 1 without catalyst: in control 2, using commercial MnO nanoparticles, 66.5% of the ATZ was oxidized by catalytic ozone; using CN @ MnO2In control 3 of nanoparticles, catalytic ozone oxidized 88.0% of ATZ; in the experimental group using the CN @ MnO composite catalytic material prepared in test one, ATZ was almost completely decomposed and over 99.5% of ATZ had been catalytically oxidized within 5 minutes.
In FIG. 3,: (ii) represents the ozone outlet concentration without catalyst addition (control group 1), and ● represents the same catalyst concentrationThe outlet concentration of ozone for the commercial MnO nanoparticles (control 2) is represented by the tangle-solidup representing CN @ MnO of the same catalyst concentration2Ozone exit concentrations at nanoparticles (control 3) represent ozone exit concentrations when the CN @ MnO composite catalytic material prepared in experiment one was added.
FIG. 3 shows that the CN @ MnO composite catalytic material can play a role in catalyzing and decomposing ozone to generate free radicals, and through ICP-OES test, the elution amount of manganese ions in simulated wastewater after reaction is only 0.007mg/L and is extremely low, which indicates that the CN @ MnO composite catalytic material has high stability.
FIG. 4 shows that the X-ray diffraction lines before and after the reaction of the CN @ MnO composite catalytic material as a catalyst in the process of degrading organic pollutants ATZ are basically consistent, the original MnO diffraction peaks exist, and no new diffraction peak is generated, which indicates that the CN @ MnO composite catalytic material has high stability, and MnO is not oxidized or reduced into other valence manganese-containing substances.
Claims (10)
1. A CN @ MnO composite catalytic material is characterized in that: MnO is taken as a core and nitrogen-doped carbon is wrapped.
2. The CN @ MnO composite catalytic material as set forth in claim 1, wherein: is spherical and has a particle size of 20-50 nm.
3. A CN @ MnO composite catalytic material as claimed in claim 1 or 2, wherein: the manganese dioxide nanoparticle is obtained by one-step reaction of manganese dioxide nanoparticles and 2-amino-3-methylaminopyrazine through a calcining mode.
4. The method of claim 1, wherein the CN @ MnO composite catalytic material is prepared by: the method comprises the following steps:
step one, adding manganese dioxide nanoparticles into a 2-amino-3-methylaminopyrazine dissolving solution to obtain a suspension;
and step two, drying the suspension, grinding the obtained solid, and calcining to obtain the CN @ MnO composite catalytic material.
5. The method of claim 4, wherein: in the first step, the ratio of the amounts of manganese dioxide and 2-amino-3-methylaminopyrazine substances is 1: 4.
6. The method of claim 4, wherein: in the first step, the mass concentration of the 2-amino-3-methylaminopyrazine solution is 0.02-0.08 g/mL; adding the manganese dioxide nano-particles into the 2-amino-3-methylaminopyrazine dissolved solution, and then uniformly mixing by ultrasonic.
7. The method of claim 4, wherein: drying the suspension in the step two through a water bath; the calcining conditions in the second step are as follows: heating to 450 ℃ per minute at 3 ℃ under the protection of argon, calcining for 3 hours, and then naturally cooling.
8. The method of claim 4, wherein: the obtaining process of the manganese dioxide nano-particles comprises the following steps: mixing a sodium thiosulfate solution and a potassium permanganate solution, carrying out solid-liquid separation after reaction, washing a solid component with water until the filtrate is neutral, drying the solid component, and then feeding the solid component into a tubular furnace for calcination.
9. The method of claim 8, wherein: the molar concentrations of the sodium thiosulfate solution and the potassium permanganate solution are respectively 0.376mol/L and 0.2 mol/L; the volume ratio of the sodium thiosulfate solution to the potassium permanganate solution is 1: 5.
10. The use of a CN @ MnO composite catalytic material, as set forth in claim 1, for catalyzing the ozonolysis of organic pollutants in water.
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| CN109647474A (en) * | 2018-11-12 | 2019-04-19 | 华中科技大学 | A kind of nitrogen-doped carbon material, its preparation and application |
| CN111495407A (en) * | 2020-04-03 | 2020-08-07 | 三峡大学 | Method for preparing Co/MnO/nitrogen doped carbon composite electrocatalyst |
| CN111834639A (en) * | 2020-07-29 | 2020-10-27 | 郑州大学 | Composite catalyst for cathode of metal-air battery and preparation method thereof |
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| CN109647474A (en) * | 2018-11-12 | 2019-04-19 | 华中科技大学 | A kind of nitrogen-doped carbon material, its preparation and application |
| CN111495407A (en) * | 2020-04-03 | 2020-08-07 | 三峡大学 | Method for preparing Co/MnO/nitrogen doped carbon composite electrocatalyst |
| CN111834639A (en) * | 2020-07-29 | 2020-10-27 | 郑州大学 | Composite catalyst for cathode of metal-air battery and preparation method thereof |
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