CN113289656A - Preparation method and application of nitrogen-doped non-metal catalyst - Google Patents
Preparation method and application of nitrogen-doped non-metal catalyst Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003054 catalyst Substances 0.000 title claims description 54
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- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical compound CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 description 1
- VNBLTKHUCJLFSB-UHFFFAOYSA-N n-(trimethoxysilylmethyl)aniline Chemical compound CO[Si](OC)(OC)CNC1=CC=CC=C1 VNBLTKHUCJLFSB-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 1
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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Abstract
The invention relates to a preparation method and application of a nitrogen-doped non-metallic catalyst. The invention adopts a hydrothermal one-pot method to prepare a nitrogen-doped non-metallic catalyst, and comprises the following specific steps: soaking nano silicon dioxide in an alcohol or ketone solution containing an amino silane coupling agent, making the surface of the nano silicon dioxide have positive charges through surface grafting, drying, grinding and dispersing in water; mixing the graphene oxide dispersion liquid and the nano silicon dioxide dispersion liquid, heating and uniformly stirring; placing the mixed dispersion liquid into a container with a polytetrafluoroethylene lining, adding ammonia water, and reacting under the conditions of high pressure, high temperature and uniform stirring; then cooling, washing and drying to remove the contained water. The preparation method is simple and easy to implement, has low cost and energy consumption, and can effectively activate persulfate to degrade organic pollutants.
Description
Technical Field
The invention relates to the field of environmental pollution treatment, in particular to a preparation method and application of a nitrogen-doped non-metal catalyst.
Background
The advanced oxidation technology is also called as deep oxidation technology, has the characteristics of high efficiency, economy and the like, and is widely applied to environmental pollution treatment. The persulfate can be catalytically activated to generate sulfate radicals, has high oxidation potential and strong oxidizing property, can react with a plurality of pollutants to achieve the aim of purification, so the persulfate-based advanced oxidation technology has wide application prospect in the aspect of pollutant removal and degradation.
There are many catalytic pathways for activating persulfate oxidation, such as photocatalysis, high temperatures, microwaves, and metal or non-metal catalysts. The metal catalyst is commonly used in industrial production, and the preparation of the metal catalyst usually needs hydrothermal reaction, high-temperature pyrolysis (450-. Patent CN 109647413B discloses a supported metal catalyst CuOMO @ Fe3O4The organic pollutants can be degraded, but the reaction condition requires that the pH value is in a range of 7-9, so that the problems of metal leaching and the like are easily caused. Patent CN 110170328A discloses a cobalt manganate/N-doped graphene composite catalyst for enhancing the activity of nitrogen-doped graphene, which achieves better catalytic effect, but the metal catalyst cannot be recycled, thus increasing the operation cost, being not beneficial to industrial application, and more seriously causing serious environmental pollution to atmosphere, water and soil if the metal permeates into the natural world.
The non-metallic catalyst is mostly made of carbon materials such as carbon nano tube, graphene and the like, and the graphene material has high specific surface area, good conductivity and surface defectsSites are of great interest to help activate persulfates. In order to further enhance the catalytic activity, researches show that the active sites of the graphene materials can be improved by doping nitrogen atoms in the graphene materials. Zheng late prepares a nitrogen-doped graphene activated persulfate to degrade phenol, the obtained non-radical reaction is the main reaction path in the reaction process, and the TOC after the reaction is reduced by 53 percent, but the nitrogen-doped graphene is easy to have the defects of agglomeration, poor stability and the like in the preparation process, so the exposure rate of active sites is greatly reduced, and a better degradation effect cannot be achieved. In addition, the preparation conditions of some non-metal catalysts are also relatively high, for example, in patent CN111620327A, a method for preparing nitrogen-doped graphene by using ion beams is disclosed, which needs to be performed under vacuum condition during the nitrogen doping process, and the ion beam equipment used in the nitrogen doping process makes the preparation process complicated and expensive. The patent No. CN111804322A discloses a preparation method of a nitrogen-doped graphene loaded carbon nitride composite material for activating persulfate, the composite material has a good removing effect on partial pollutants, but a semiconductor polymer g-C used in the preparation process3N4Greatly improving the preparation cost and being not beneficial to large-scale production and application. Therefore, it is a research focus to find a simple and economical method for preparing efficient graphene catalysts. In addition, the active potential density is increased, the utilization efficiency of the oxidant is improved, and the electron transfer efficiency is still the research direction of the high-efficiency catalyst at present when the reaction is accelerated.
Disclosure of Invention
The invention aims to provide a preparation method and application of a nitrogen-doped non-metal catalyst, the preparation process of the catalyst is simple and easy to implement, the catalyst is used for treating organic pollutants by a persulfate advanced oxidation technology, the utilization rate of an oxidant is high, the repeatability is good, secondary pollution is avoided, and pollutants can be effectively degraded.
In order to realize the purpose, the invention is realized by the following technical scheme:
a nitrogen-doped non-metallic catalyst is prepared from graphene or reduced graphene oxide micro-sheets and nano silicon dioxide through nitrogen doping.
A preparation method of a nitrogen-doped non-metallic catalyst comprises the following steps:
step 1: soaking nano silicon dioxide in an alcohol or ketone solution containing an amino silane coupling agent, making the surface of the nano silicon dioxide have positive charges through surface grafting, drying, grinding and dispersing in water;
step 2: mixing the graphene oxide dispersion liquid and the nano silicon dioxide dispersion liquid, heating and uniformly stirring;
and step 3: placing the mixed dispersion liquid into a container with a polytetrafluoroethylene lining, adding ammonia water, and reacting under the conditions of high pressure, high temperature and uniform stirring; and then cooling, washing and drying to remove the contained water to obtain the nitrogen-doped non-metal catalyst.
Further, the silane coupling agent containing amino in the step 1 is Y-R-Si-X3Wherein R is alkyl, X is methoxy or ethoxy, and Y is aminoethyl, aminopropyl or anilino.
Further, in the step 1, the alcohol is ethanol, and the ketone is acetone.
Further, the mass ratio of the graphene oxide dispersion liquid to the nano silicon dioxide dispersion liquid in the step 2 is 1: 4-3: 1.
Further, the heating temperature in the step 2 is 50-90 ℃.
Further, the volume ratio of the mixed dispersion liquid to the ammonia water in the step 3 is 12: 1-1: 1.
Further, in the step 3, the reaction temperature is 120-190 ℃, the reaction time is 15-20 hours, and the rotation speed of uniform stirring is 50-100 r/min.
The invention also provides application of the nitrogen-doped non-metal catalyst in high-efficiency activation of persulfate to removal of pollutants.
Compared with the prior art, the invention has the following beneficial effects:
(1) the nitrogen-doped non-metal catalyst provided by the invention is a composite catalyst without any metal element, has no problems of metal leaching and the like in the process of efficiently activating persulfate, and is more environment-friendly.
(2) The nano silicon dioxide in the catalyst mainly plays a role in intercalation regulation, the surface of the treated silicon dioxide is positively charged and uniformly dispersed on the surface and between layers of the graphene oxide through electrostatic adsorption, and the catalyst after hydrothermal reduction has a higher specific surface area. Therefore, the graphene can be prevented from agglomerating, the exposure rate of active sites is reduced, and the catalyst can be prevented from swelling in an aqueous solution, changing the structure and being difficult to recycle.
(3) The catalyst is prepared by a hydrothermal one-pot method, and compared with the traditional thermal reduction method which needs 500 ℃, the temperature is controlled below 200 ℃, so that the preparation process is simple and easy to implement, the preparation condition is mild, and the production energy consumption and the cost are greatly reduced.
(4) The catalyst enables nitrogen-containing substances to react to form active sites containing N during hydrothermal reaction, the nitrogen mainly exists in the form of pyrrole nitrogen, pyridine nitrogen and graphite nitrogen, reduced graphene oxide prepared through hydrothermal high pressure has high electron transfer rate, electron transfer of oxidant activation reaction can be accelerated, the utilization rate of the oxidant and the degradation rate of pollutants are high, and the dynamic reaction rate of catalytic reaction can reach 4.65 multiplied by 10-1min-1。
Drawings
Fig. 1 is an SEM image of a nitrogen-doped graphene-nanosilica catalyst;
FIG. 2 is an infrared spectroscopic analysis of a nitrogen doped graphene-nanosilica catalyst;
fig. 3 is a high resolution XPS plot of N1s for nitrogen doped graphene/nanosilica catalysts;
FIG. 4 shows the effect of the catalyst of example 1 of the present invention on the removal of phenol;
FIG. 5 shows the generation of OH and SO during the treatment of a phenol solution by the catalyst of example 1 of the present invention4-electron paramagnetic resonance boph map;
FIG. 6 shows the production of the catalyst in the treatment of a phenol solution according to example 1 of the present invention1O2Electron paramagnetic resonance map of (a);
FIG. 7 shows the effect of the catalyst of example 1 of the present invention on the removal of humic acid;
FIG. 8 shows the production of OH and SO during the treatment of humic acid solution by the catalyst of example 1 of the present invention4-electron paramagnetic resonance boph map;
FIG. 9 shows the generation of a catalyst during the treatment of humic acid solution according to example 1 of the present invention1O2Electron paramagnetic resonance bopp diagram.
Detailed Description
The following examples are given in the detailed description and the specific operation on the premise of the technical solutions of the present invention, but do not limit the protection scope of the patent of the present invention, and all technical solutions obtained by using equivalent alternatives or equivalent variations should fall within the protection scope of the present invention.
Example 1
The embodiment provides a preparation method of a nitrogen-doped non-metal catalyst, which comprises the following specific steps: preparing graphene oxide by using a Hummers method, and uniformly dispersing the obtained graphene oxide dispersion liquid in water by using ultrasound; soaking the nano-scale silicon dioxide in an ethanol solution containing 3-Aminopropyltriethoxysilane (APTES), making the surface of the nano-scale silicon dioxide have positive charges through surface grafting, then drying, grinding and dispersing in water; mixing 3mg/ml graphene oxide dispersion liquid and nano silicon dioxide according to the mass ratio of 1:1, placing the mixture in a water bath kettle, heating the mixture in a water bath at the temperature of 80 ℃, and stirring and dispersing the mixture for 5 hours; then adding ammonia water with the same volume as the dispersion liquid, mixing, pouring into a high-pressure reaction kettle, carrying out continuous hydrothermal reaction for 18h under the conditions that the temperature is 150 ℃ and the rotating speed is 100r/min, washing and drying to finally obtain the nitrogen-doped graphene-nano silicon dioxide catalyst.
The characterization of the scanning electron microscope in this embodiment is shown in fig. 1, and the catalyst is obtained by observing the catalyst through a JSM-7001F scanning electron microscope of JEOL corporation, and it can be known from the figure that the catalyst is a three-dimensional space structure formed by combining lamellar reduced graphene, and the surface of the graphene is loaded with nano silicon dioxide, so that the micro-nano structure is beneficial to forming a rough surface and improving the exposure degree of active sites. The composition and surface chemical characteristics of the nitrogen-doped graphene/nano-silica catalyst were analyzed by infrared spectroscopy: (FTIR, see FIG. 2) and X-ray photoelectron spectroscopy (XPS, see FIG. 3). FIG. 2 shows N @ SiO23425, 2917, 1581, 1107cm for @ rGO material-1The wavelength corresponds to the vibration peaks of silicon hydroxyl, alkyl chain, N-H, Si-O-Si and C-N, so that nitrogen atoms can be successfully doped on the graphene composite material after ammonia doping; fig. 3 is a N1s high resolution XPS plot of a nitrogen-doped graphene/nanosilica composite, showing that nitrogen atoms are predominantly in the pyrrole nitrogen form, except for the presence of pyridine nitrogen (11.59%) and graphite nitrogen (15.94%).
Example 2
The catalyst prepared in example 1 was used to perform an experiment for removing small organic phenol, 0.2g/L of catalyst and 0.3g/L of PMS were added to a 20mg/L phenol solution, a control group was prepared by separately adding 0.3g/L of PMS peroxymonosulfate, sampling was performed at intervals, the obtained water sample was filtered with a 0.45 μm filter membrane to remove impurities, and changes in the phenol concentration in the reaction system were analyzed by HPLC. As shown in fig. 4, phenol can be completely degraded within 10min, verifying the high efficiency of the catalyst. The solution was subjected to electron paramagnetic resonance experiments by electron paramagnetic spectrometer (EPR, see FIGS. 5 and 6) at 0,1,5,10 and 20 minutes, respectively, and N @ SiO in FIG. 52@ rGO material generates OH and SO by adopting DMPO trapping agent in the process of catalytically degrading phenol solution by activated persulfate4 —FIG. 6 shows electron paramagnetic resonance wave spectrum generated using TEMP trapping agent1O2The two figures show when phenol, N @ SiO2In the coexistence of the @ rGO composite material and PMS, a large amount of active oxides OH and SO are generated4 —And1O2and at 10 minutes SO4 —Completely reacted, only OH and OH remain in the solution1O2。
Example 3
An experiment for removing the humic acid of the macromolecular organic matter by using the catalyst prepared in the example 1 is carried out, wherein 0.2g/L of the catalyst and 0.3mg/L of PMS are added into 30mg/L of the humic acid solution, samples are taken at intervals, the obtained water sample is filtered by a 0.45-micron filter membrane to remove impurities, and purple light is adoptedAnd analyzing the change of the concentration of the humic acid in the reaction system by an external spectrophotometry. As shown in figure 7, the removal rate of the humic acid in 10min is as high as 85%, and the humic acid is composed of various macromolecular organic matters and cannot be completely degraded like phenol, but can still achieve the purposes of quickly degrading the organic matters and purifying sewage. The solution was subjected to electron paramagnetic resonance experiments by electron paramagnetic spectrometer (EPR, see FIGS. 8 and 9) at 0,1,4,20 and 40 minutes, respectively, and N @ SiO in FIG. 82@ rGO material generates OH and SO by adopting DMPO trapping agent in the process of catalytically degrading humic acid solution by activated persulfate4 —FIG. 9 shows Electron Paramagnetic Resonance (EPR) mapping using TEMP capture agents1O2The electron paramagnetic resonance diagram of (A) shows the molecular weight of humic acid, N @ SiO2In the coexistence of the @ rGO composite material and PMS, a large amount of active oxides OH and SO are generated4 —And1O2. And at 20 minutes SO4 —Completely reacted, only OH and OH remain in the solution1O2。
Example 4
The embodiment provides a preparation method of a nitrogen-doped non-metal catalyst, which comprises the following specific steps: preparing graphene oxide by using a Hummers method, and uniformly dispersing the obtained graphene oxide dispersion liquid in water by using ultrasound; soaking the nano-scale silicon dioxide in acetone solution containing phenylaminomethyltriethoxysilane, grafting the surface of the nano-scale silicon dioxide to make the surface of the nano-scale silicon dioxide have positive charges, drying, grinding and dispersing in water; mixing 5mg/ml graphene oxide dispersion liquid and nano silicon dioxide according to the mass ratio of 1:4, placing the mixture in a water bath kettle, heating the mixture in a water bath at the temperature of 50 ℃, and stirring and dispersing the mixture for 5 hours; and then mixing the mixed dispersion liquid with ammonia water according to the volume ratio of 12:1, pouring the mixture into a high-pressure reaction kettle, carrying out continuous hydrothermal reaction for 15 hours at the temperature of 190 ℃ and the rotating speed of 50r/min, washing and drying to finally obtain the nitrogen-doped graphene-nano silicon dioxide catalyst.
Example 5
The embodiment provides a preparation method of a nitrogen-doped non-metal catalyst, which comprises the following specific steps: preparing graphene oxide by using a Hummers method, and uniformly dispersing the obtained graphene oxide dispersion liquid in water by using ultrasound; soaking the nano-scale silicon dioxide in an ethanol solution containing 3-aminopropyltrimethoxysilane, grafting the surface of the nano-scale silicon dioxide to make the surface of the nano-scale silicon dioxide have positive charges, drying, grinding and dispersing in water; mixing 4mg/ml graphene oxide dispersion liquid and nano silicon dioxide according to the mass ratio of 3:1, placing the mixture in a water bath kettle, heating the mixture in a water bath at 90 ℃, and stirring and dispersing the mixture for 5 hours; and then mixing the mixed dispersion liquid with ammonia water according to the volume ratio of 6:1, pouring the mixture into a high-pressure reaction kettle, carrying out continuous hydrothermal reaction for 20 hours at the temperature of 120 ℃ and the rotating speed of 80r/min, washing and drying to finally obtain the nitrogen-doped graphene-nano silicon dioxide catalyst.
Example 6
The embodiment provides a preparation method of a nitrogen-doped non-metal catalyst, which comprises the following specific steps: preparing graphene oxide by using a Hummers method, and uniformly dispersing the obtained graphene oxide dispersion liquid in water by using ultrasound; soaking the nano-scale silicon dioxide in an ethanol solution containing N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, grafting the surface of the nano-scale silicon dioxide to make the surface of the nano-scale silicon dioxide have positive charges, drying, grinding and dispersing in water; mixing 3mg/ml graphene oxide dispersion liquid and nano silicon dioxide according to the mass ratio of 2:1, placing the mixture in a water bath kettle, heating the mixture in a water bath at 70 ℃, and stirring and dispersing the mixture for 5 hours; and then mixing the mixed dispersion liquid with ammonia water according to the volume ratio of 3:1, pouring the mixture into a high-pressure reaction kettle, carrying out continuous hydrothermal reaction for 16h at the temperature of 180 ℃ and the rotating speed of 60r/min, washing and drying to finally obtain the nitrogen-doped graphene-nano silicon dioxide catalyst.
Example 7
The embodiment provides a preparation method of a nitrogen-doped non-metal catalyst, which comprises the following specific steps: preparing graphene oxide by using a Hummers method, and uniformly dispersing the obtained graphene oxide dispersion liquid in water by using ultrasound; soaking the nano-scale silicon dioxide in acetone solution containing phenylaminomethyltrimethoxysilane, grafting the surface of the nano-scale silicon dioxide to make the surface of the nano-scale silicon dioxide have positive charges, drying, grinding and dispersing in water; mixing 5mg/ml graphene oxide dispersion liquid and nano silicon dioxide according to the mass ratio of 1:1, placing the mixture in a water bath kettle, heating in a water bath at the temperature of 60 ℃, and stirring and dispersing for 5 hours; and then mixing the mixed dispersion liquid with ammonia water according to a volume ratio of 8:1, pouring the mixture into a high-pressure reaction kettle, carrying out continuous hydrothermal reaction for 19 hours at the temperature of 130 ℃ and the rotating speed of 90r/min, washing and drying to finally obtain the nitrogen-doped graphene-nano silicon dioxide catalyst.
Claims (9)
1. The nitrogen-doped non-metallic catalyst is characterized by being prepared from graphene or reduced graphene oxide micro-sheets and nano silicon dioxide through nitrogen doping.
2. The preparation method of the nitrogen-doped non-metal catalyst is characterized by comprising the following steps of:
step 1: soaking nano silicon dioxide in an alcohol or ketone solution containing an amino silane coupling agent, making the surface of the nano silicon dioxide have positive charges through surface grafting, drying, grinding and dispersing in water;
step 2: mixing the graphene oxide dispersion liquid and the nano silicon dioxide dispersion liquid, heating and uniformly stirring;
and step 3: placing the mixed dispersion liquid into a container with a polytetrafluoroethylene lining, adding ammonia water, and reacting under the conditions of high pressure, high temperature and uniform stirring; and then cooling, washing and drying to remove the contained water to obtain the nitrogen-doped non-metal catalyst.
3. The method for preparing nitrogen-doped non-metallic catalyst according to claim 1, wherein the silane coupling agent containing amino group in the step 1 is Y-R-Si-X3Wherein R is alkyl, X is methoxy or ethoxy, and Y is aminoethyl, aminopropyl or anilino.
4. The method according to claim 1, wherein the alcohol in step 1 is ethanol and the ketone is acetone.
5. The method for preparing the nitrogen-doped non-metallic catalyst according to claim 1, wherein the mass ratio of the graphene oxide dispersion liquid to the nano silicon dioxide dispersion liquid in the step 2 is 1: 4-3: 1.
6. The method for preparing the nitrogen-doped non-metallic catalyst according to claim 1, wherein the heating temperature in the step 2 is 50-90 ℃.
7. The method for preparing the nitrogen-doped non-metallic catalyst according to claim 1, wherein the volume ratio of the mixed dispersion liquid and the ammonia water in the step 3 is 12: 1-1: 1.
8. The preparation method of the nitrogen-doped non-metallic catalyst according to claim 1, wherein the reaction temperature in the step 3 is 120-190 ℃, the reaction time is 15-20 hours, and the rotation speed of uniform stirring is 50-100 r/min.
9. Use of a nitrogen-doped non-metallic catalyst for the efficient activation of persulfate to remove contaminants.
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