CN115869983A - Manganese-nitrogen co-doped carbon nanosheet, preparation method and application - Google Patents
Manganese-nitrogen co-doped carbon nanosheet, preparation method and application Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 90
- 239000002135 nanosheet Substances 0.000 title claims abstract description 69
- RBVYPNHAAJQXIW-UHFFFAOYSA-N azanylidynemanganese Chemical compound [N].[Mn] RBVYPNHAAJQXIW-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 36
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 34
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- 238000002386 leaching Methods 0.000 claims abstract description 8
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- 239000011572 manganese Substances 0.000 claims description 14
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- 238000000034 method Methods 0.000 claims description 13
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
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- 238000007710 freezing Methods 0.000 claims description 10
- 230000008014 freezing Effects 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical group O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
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- 238000007792 addition Methods 0.000 claims description 7
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- 238000004108 freeze drying Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 5
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 23
- 229910052751 metal Inorganic materials 0.000 abstract description 10
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- 229910052723 transition metal Inorganic materials 0.000 abstract description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 7
- 238000003763 carbonization Methods 0.000 abstract description 5
- 230000000593 degrading effect Effects 0.000 abstract description 5
- 238000000197 pyrolysis Methods 0.000 abstract description 5
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910018648 Mn—N Inorganic materials 0.000 description 9
- 229910021642 ultra pure water Inorganic materials 0.000 description 9
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- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 7
- 150000003624 transition metals Chemical class 0.000 description 6
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 231100000719 pollutant Toxicity 0.000 description 1
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical group [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 1
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Abstract
The invention belongs to the field of waste water treatment by environmental materials, and provides a manganese-nitrogen co-doped carbon nanosheet, a preparation method and application. The material is formed by one-step carbonization with melamine as a nitrogen source, glucose as a carbon source and manganese chloride as a metal precursor. The primary carbon intermediate of glucose formation is coupled via donor-acceptor interaction with the layered g-C formed during the pyrolysis of melamine 3 N 4 Binding of g-C 3 N 4 As a templateGuiding the carbon layer to form a carbon nano sheet structure along a plane; the melamine provides an abundant nitrogen atom environment, captures transition metal manganese, forms highly dispersed Mn-Nx coordination bonds, fixes nitrogen species on the carbon nano-chip, and provides a plurality of active nitrogen components. The material can improve the speed of degrading organic pollutant phenol by the catalyst, has good cyclicity, reduces the leaching concentration of metal, and does not cause secondary pollution to the environment.
Description
Technical Field
The invention belongs to the field of wastewater treatment by using environmental materials, and particularly relates to a manganese-nitrogen co-doped carbon nanosheet, a preparation method and application thereof.
Background
Phenolic and antibiotic contaminants are now widely detected in wastewater and water environments. Their widespread presence has a serious impact on nature and human health, and even at low concentrations, they have attracted worldwide attention. Thus, the removal of these organic contaminants from water has created an increasing need for efficient treatment techniques. In recent years, peroxymonosulfate (PMS) activation based on Advanced Oxidation Processes (AOPs) has proven to be one of the most effective methods for removing organic contaminants.
The carbon-based material has the advantages of metal intolerance, acid and alkali resistance, large specific surface area, many active sites and the like, and is widely concerned as a novel heterogeneous catalyst for activating PMS. However, the original carbon-based materials (e.g., carbon nanotubes, graphene, diamond, biochar) still have limited active functional groups, structural defects, and a low degree of graphitization. Although various modification methods have been used to improve the catalytic performance of carbon-based materials, manganese-nitrogen co-doped carbon-based materials are currently under relatively few studies.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
The invention aims to solve the problems and provide a manganese-nitrogen co-doped carbon nanosheet, a preparation method and application thereof.
The invention provides a preparation method of manganese and nitrogen co-doped carbon nanosheets, which is characterized by comprising the following steps of: step 1, dissolving a certain amount of manganese chloride and zinc chloride in water, and uniformly mixing to obtain a solution A; step 2, dissolving a certain amount of melamine and glucose in water, and uniformly mixing to obtain a solution B; step 3, slowly dripping the solution A into the solution B to obtain milky white precipitate; step 4, slowly dropping the milky white precipitate into liquid nitrogen for quick freezing to obtain a frozen product; step 5, putting the frozen product into a freeze dryer, freeze-drying at-45 to-55 ℃, grinding and vacuum-drying to obtain white powder; and 6, calcining the white powder at high temperature in an inert atmosphere to obtain a calcined product, grinding and acid leaching, and drying to obtain the manganese-nitrogen co-doped carbon nanosheet.
In the preparation method of the manganese-nitrogen co-doped carbon nanosheet provided by the invention, the preparation method also has the following characteristics: in the step 1, the manganese chloride is manganese chloride tetrahydrate with the mass of 0.197 g-0.394 g, the zinc chloride with the mass of 0.136g and the volume of water of 5ml.
In the preparation method of the manganese-nitrogen co-doped carbon nanosheet provided by the invention, the preparation method also has the following characteristics: in step 2, the mass of melamine is 5g, the mass of glucose is 2g, and the volume of water is 25ml.
In the preparation method of the manganese-nitrogen co-doped carbon nanosheet provided by the invention, the preparation method also has the following characteristics: and 3, slowly dropwise adding the solution A into the solution B, continuously stirring in the dropwise adding process, and continuously stirring for 4 hours after the dropwise adding is finished to obtain milky white precipitate.
In the preparation method of the manganese-nitrogen co-doped carbon nanosheet provided by the invention, the preparation method also has the following characteristics: in step 4, the white precipitate after standing is dropped into liquid nitrogen at a speed of one drop per second for quick freezing.
In the preparation method of the manganese-nitrogen co-doped carbon nanosheet provided by the invention, the preparation method also has the following characteristics: in step 6, the dried product is heated to 800-900 ℃ at a heating rate of 4-6 ℃ in a nitrogen atmosphere and calcined at a high temperature.
In the preparation method of the manganese-nitrogen co-doped carbon nanosheet provided by the invention, the preparation method also has the following characteristics: in the step 6, the calcined product is washed in 0.5M sulfuric acid for 10 hours and dried to obtain the manganese and nitrogen co-doped carbon nanosheet.
The invention also provides a manganese-nitrogen-codoped carbon nanosheet which has the characteristics and is prepared by the preparation method of the manganese-nitrogen-codoped carbon nanosheet.
The invention also provides application of the manganese-nitrogen co-doped carbon nanosheet in activating persulfate to degrade phenol.
In the application of the manganese-nitrogen co-doped carbon nanosheet in activating persulfate to degrade phenol, the manganese-nitrogen co-doped carbon nanosheet also has the following characteristics: wherein, in the degradation liquid, the content of phenol is 0.2g/L, the content of persulfate is 0.2g/L, and the addition amount of the manganese-nitrogen co-doped carbon nanosheet is 0.2g/L.
Action and effects of the invention
According to the manganese-nitrogen co-doped carbon nanosheet, the preparation method and the application thereof, transition metal manganese is successfully anchored on N-doped porous carbon through two steps of synthesis processes of freeze drying and carbonization. The material is formed by one-step carbonization with melamine as a nitrogen source, glucose as a carbon source and manganese chloride as a metal precursor. Melamine in a pyrolysis processForm g-C 3 N 4 The primary carbon intermediate of glucose production interacts with the lamellar g-C via the donor-acceptor interaction 3 N 4 Binding of g to C 3 N 4 Guiding the carbon layer to form a carbon nano sheet structure along a plane by using the carbon layer as a template; secondly, the melamine provides an abundant nitrogen atom environment, captures transition metal manganese, forms highly dispersed Mn-Nx coordination bonds, fixes nitrogen species on the carbon nano-sheet and provides a plurality of active nitrogen components.
The invention takes glucose as a carbon substrate to fix nitrogen atoms, so as to prevent the loss rate of the nitrogen atoms from being too high in the high-temperature heating process, and is beneficial to forming high density and uniform distribution of Mn-Nx coordination bonds in the carbon-based material. As the temperature increases, g-C 3 N 4 Further pyrolysis generates a large amount of nitrogen-containing gas, so that the carbon nano-sheets are curled to form a mesoporous carbon skeleton structure, thereby not only effectively avoiding the overlapping of carbon layers, but also increasing the possibility that nitrogen sites are fixed on the carbon skeleton. The transition metal and nitrogen co-doped carbon-based material can effectively adjust the electronic structure of the original carbon material and improve the catalytic activity; in addition, the doped transition metal exists in the material in the form of M-Nx coordination bonds and is protected by the outer carbon shell, so that the leaching concentration of the metal is reduced, and the durability of the carbon-based material in the catalytic reaction is effectively improved.
Therefore, the carbon-based material is modified through manganese-nitrogen co-doping engineering, the rate of degrading organic pollutant phenol by the catalyst is increased, the good cyclicity is realized, the metal leaching concentration is reduced, and secondary pollution to the environment is avoided.
Drawings
FIG. 1 is a scanning electron microscope schematic view of manganese-nitrogen co-doped carbon nanosheets of example 1 of the present invention;
fig. 2 is a schematic view of a transmission electron mirror of manganese nitrogen co-doped carbon nanosheets of example 1 of the present invention;
FIG. 3 is a graph of the effect of different types of catalysts on phenol removal in the present invention;
FIG. 4 is a graph of the effect of different catalyst loadings on phenol removal in accordance with the present invention;
fig. 5 is a graph showing the recycling effect of the manganese-nitrogen co-doped carbon nanosheet in the present invention.
Detailed Description
In order to make the technical means, creation features, achievement purposes and effects of the present invention easy to understand, the following embodiments and the accompanying drawings are combined to specifically describe a manganese nitrogen co-doped carbon nanosheet, a preparation method and an application thereof.
Unless otherwise specified, each raw material used in the following examples is a commercially available product, and each apparatus used is a commercially available conventional apparatus.
The persulfate is potassium peroxymonosulfate.
The preparation method of the manganese-nitrogen co-doped carbon nanosheet specifically comprises the following steps:
and 6, calcining the white powder at high temperature in a nitrogen atmosphere to obtain a calcined product, grinding and acid leaching, and drying to obtain the manganese-nitrogen co-doped carbon nanosheet.
In the step 1, the mass of the manganese chloride tetrahydrate is 0.197g to 0.394g, the mass of the zinc chloride is 0.136g, and the volume of the ultrapure water is 5ml. In step 2, the mass of melamine is 5g, the mass of glucose is 2g, and the volume of ultrapure water is 25ml. And 4, dripping the white precipitate after standing into liquid nitrogen at the speed of one drop per second for quick freezing.
In the step 6, heating the white powder to 800-900 ℃ at a heating rate of 4-6 ℃ in a nitrogen atmosphere, calcining at a high temperature to obtain a black calcined product, grinding the obtained calcined product, washing the calcined product in 0.5M sulfuric acid for 10 hours, further washing the calcined product for 2-4 times by using deionized water, and washing and drying the washed product to obtain the manganese-nitrogen co-doped carbon nanosheet.
The manganese-nitrogen co-doped carbon nanosheet prepared according to the preparation method is used as a catalyst, persulfate is activated to degrade phenol, and the specific process for degrading phenol is as follows:
s1, preparing a degradation solution containing phenol, manganese and nitrogen co-doped carbon nanosheets and persulfate, and then degrading under a constant temperature condition;
and step S2, filtering 0.9mL of sample through a 0.22-micron membrane filter within a given time, quenching the sample in a glass bottle by using 0.1mL of methanol solution, analyzing the filtered sample by using high performance liquid chromatography to obtain the concentration of the pollutant at the corresponding time, and finishing degradation after 5 minutes.
In the degradation experiment, the concentration of phenol in the degradation liquid is 0.2g/L, the concentration of persulfate is 0.2g/L, the addition amount of the catalyst is 0.2g/L, the pH value is 7.0, and the degradation is carried out at room temperature. Adding sodium hydrogen phosphate buffer solution into the degradation solution to stabilize the pH value of the solution to 7.
< example 1>
In the embodiment, manganese nitrogen co-doped carbon nanosheets are prepared, the mass of manganese chloride tetrahydrate, the mass of zinc chloride, the mass of melamine and the mass of glucose are respectively 0.197g, 0.136g, 5g and 2g, and the specific operation is as follows:
and step 6, heating the white powder to 800-900 ℃ at a heating rate of 4-6 ℃ in a nitrogen atmosphere, calcining at a high temperature to obtain a black calcined product, grinding and washing in 0.5M sulfuric acid for 10 hours, further washing with deionized water for 2-4 times, washing and drying to obtain the manganese-nitrogen co-doped carbon nanosheet marked as Mn-N @ C-1.
< example 2>
The manganese and nitrogen co-doped carbon nanosheet is prepared by the embodiment, the mass of manganese chloride tetrahydrate, the mass of zinc chloride, the mass of melamine and the mass of glucose are respectively 0.394g, 0.136g, 5g and 2g, and the specific operation is as follows:
and step 6, heating the white powder to 800-900 ℃ at a heating rate of 4-6 ℃ in a nitrogen atmosphere, calcining at a high temperature to obtain a black calcined product, grinding and washing in 0.5M sulfuric acid for 10 hours, further washing with deionized water for 2-4 times, washing and drying to obtain the manganese-nitrogen co-doped carbon nanosheet marked as Mn-N @ C-2.
< comparative example 1>
The manganese and nitrogen co-doped carbon nanosheet is prepared according to the comparative example, the mass of manganese chloride tetrahydrate, the mass of zinc chloride, the mass of melamine and the mass of glucose are respectively 0g, 0.136g, 5g and 2g, the rest of operations are the same as those in the example 2, and the nitrogen-doped carbon nanosheet of the comparative example is obtained and is marked as N @ C.
< comparative example 2>
The manganese nitrogen-doped carbon nanosheet is prepared according to the comparative example, the mass of manganese chloride tetrahydrate, the mass of zinc chloride, the mass of melamine and the mass of glucose are respectively 0.197g, 0.136g, 0g and 2g, the rest of operations are the same as those in the example 2, and the nitrogen-doped carbon nanosheet of the comparative sample is obtained and is marked as Mn @ C.
< test example >
Scanning electron microscope detection and transmission electron microscope detection are performed on the manganese-nitrogen co-doped carbon nanosheet prepared in example 1, and the detection results are shown in fig. 1 and fig. 2.
Fig. 1 is a scanning electron microscope schematic view of manganese-nitrogen-co-doped carbon nanosheets in embodiment 1 of the present invention, and fig. 2 is a transmission electron microscope schematic view of manganese-nitrogen-co-doped carbon nanosheets in embodiment 1 of the present invention.
As shown in FIGS. 1 and 2, it is evident that the SEM image and TEM image of Mn-N @ C-1 are mainly based on the layered and sheet structure, and the surface is rich in wrinkles, indicating successful doping of metal manganese, and furthermore the layered structure provides a larger specific surface area (98.94 m) 2 /g), and more active sites, the catalytic effect of the material is improved.
< application example 1>
Manganese-nitrogen co-doped carbon nanosheets prepared in examples 1 and 2 and comparative examples 1 and 2 are used as catalysts, and Persulfate (PMS) is activated to degrade phenol. The specific experimental procedure for the phenol degradation experiment was as follows:
this was performed in a 250mL beaker containing 100mL of ultrapure water, and magnetic stirring was performed at room temperature. In a typical experiment, 100mL of phenol solution (20 mgL) -1 ) To this was added 20mg of catalyst and 20mg of oxidant PMS. The pH was stabilized with phosphate buffered saline (PBS, 20 mM).
Every 1 minute for a given period of time, 0.9mL of sample was taken, filtered through a 0.22 μm membrane filter, and then quenched with 0.1mL of methanol solution in a glass vial for High Performance Liquid Chromatography (HPLC). The corresponding contaminant concentration was obtained, degradation was stopped after 5 minutes, the experiment was terminated, and the measured data was analyzed for 5 minutes, the experimental results are shown in fig. 3.
FIG. 3 is a graph showing the effect of different types of catalysts on phenol removal in the present invention. Where the abscissa indicates the degradation reaction time in min and the ordinate indicates the degradation ratio (i.e. the concentration of phenol present in the solution/the initial concentration of phenol) in%.
As can be seen from FIG. 3, the addition of Mn-N @ C-1 results in a significant catalytic performance, rapid degradation, a phenol degradation rate of about 100% within 5min, and the best degradation effect. The second is Mn-N @ C-2, and the degradation rate is 70.1%. The degradation of N @ C and Mn @ C is slowest, and when the degradation is stopped after 5 minutes, the degradation effects are 46.7% and 23.6%, respectively. The enhancement of phenol degradation in Mn-N @ C-1 further suggests an important role for the introduction of Mn/N co-doping. The formation of Mn-Nx bonds in the carbon-based material has been proved to adjust the electronic structure of the carbon-based material, and further improve the PMS activation performance of the catalyst.
< application example 2>
The influence of different catalyst additions on a phenol degradation experiment is compared by using Mn-N @ C-1 prepared in example 1 as a catalyst, and the catalyst additions in four parallel experiments are respectively 5mg, 10mg, 20mg and 30mg. The degradation experiment was carried out in the same manner as in application example 1, except that the amount of the catalyst to be added was varied. The results of the degradation comparison of the catalysts at different dosages are shown in FIG. 4.
FIG. 4 is a graph showing the effect of different amounts of catalyst added on phenol removal in the present invention. Where the abscissa indicates the degradation reaction time in min and the ordinate indicates the degradation ratio (i.e. the concentration of phenol present in the solution/the initial concentration of phenol) in%.
As shown in FIG. 4, when the amount of the added material was 0.2g/L, the removal rate of phenol was about 100% in 5 minutes, and thereafter the removal rate of phenol was increased as the amount of the added catalyst Mn-N @ C-1 was increased. When the amount of addition was 0.3g/L, the removal rate of phenol almost reached the maximum value. Indicating that the rate of phenol degradation is directly proportional to the amount of catalyst present. As the catalyst level increases, more active sites are provided for PMS activation, thereby producing abundant active oxygen-depleted phenol.
< application example 3>
This application example is a cycle performance test of the manganese-nitrogen-co-doped carbon nanosheet in example 1, and a cycle test was performed 5 times using Mn-n @ c-1 as the catalyst of the manganese-nitrogen-co-doped carbon nanosheet in example 1. The apparatus and the test apparatus used in the experiment were the same as those in application example 1, and the time course was the same as that in application example 1 except for the amount of the added substance and the sampling time.
The experimental procedure is as follows:
50mg of the material prepared in example 1 and 20mg of persulfate were added to 100mL of a 20mg/l phenol solution at 25 ℃ to prepare a degradation solution, and 0.9mL of the solution was filtered through a 0.22 μm membrane filter at 1 minute intervals for 5 minutes and then quenched with 0.1mL of a methanol solution in a glass bottle for High Performance Liquid Chromatography (HPLC). After 5 minutes, the mixture is filtered by a suction filtration device, washed and dried in a vacuum drying oven at 60 ℃ for 12 hours, and the catalyst is recovered. And in the second circulation, the completely dried sample is carried out again under the experimental conditions of the first circulation, and the circulation is repeated until the fifth circulation is finished. The results are shown in FIG. 5.
FIG. 5 is a graph showing the effect of cyclic degradation in application example 3 of the present invention.
As can be seen from FIG. 5, after 5 cycles of experiments, the manganese-nitrogen co-doped carbon nanosheet prepared in example 1 still has good catalytic degradation performance, and the degradation effects within five minutes are respectively 100%, 99.5%, 99.0%, 95.4% and 89.5%, which indicates that Mn-N @ C-1 has good cyclicity.
Effects and effects of the embodiments
According to the manganese-nitrogen co-doped carbon nanosheet, the preparation method and the application, transition metal manganese is successfully anchored on N-doped porous carbon through a two-step synthesis process of freeze drying and carbonization processes. The material is formed by one-step carbonization with melamine as a nitrogen source, glucose as a carbon source and manganese chloride as a metal precursor.The melamine forms g-C during pyrolysis 3 N 4 The primary carbon intermediate of glucose production interacts with the lamellar g-C via the donor-acceptor interaction 3 N 4 Binding of g-C 3 N 4 Guiding the carbon layer to form a carbon nanosheet structure along a plane as a template; secondly, the melamine provides rich nitrogen atom environment, captures transition metal manganese, forms highly dispersed Mn-Nx coordination bonds, fixes nitrogen species on the carbon nano-chip and provides a plurality of active nitrogen components.
The method takes glucose as a carbon substrate to fix nitrogen atoms, so that the loss rate of the nitrogen atoms in the high-temperature heating process is prevented from being too high, and the high-density and uniform distribution of Mn-Nx coordination bonds in the carbon-based material is facilitated. As the temperature increases, g-C 3 N 4 Further pyrolysis generates a large amount of nitrogen-containing gas, so that the carbon nano-sheets are curled to form a mesoporous carbon skeleton structure, thereby not only effectively avoiding the overlapping of carbon layers, but also increasing the possibility that nitrogen sites are fixed on the carbon skeleton.
The transition metal and nitrogen co-doped carbon-based material can effectively adjust the electronic structure of the original carbon material and improve the catalytic activity; in addition, the doped transition metal exists in the material in the form of M-Nx coordination bonds and is protected by the outer carbon shell, so that the leaching concentration of the metal is reduced, and the durability of the carbon-based material in the catalytic reaction is effectively improved.
Therefore, in the embodiment of the invention, the manganese-nitrogen co-doped modified carbon-based material is adopted, so that the speed of the catalyst for degrading organic pollutant phenol is increased, the good cyclicity is realized, the metal leaching concentration is reduced, and secondary pollution to the environment is avoided. For example, in application example 1, when the degradation is carried out for 5min, the degradation ratio reaches about 100%; in application example 2, the degradation effect of manganese nitrogen co-doped carbon nanosheets with different adding amounts is still excellent; in application example 3, the catalyst can still achieve a good catalytic effect after being recycled for 5 times.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention. All the equivalent structures or equivalent processes performed by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. The preparation method of the manganese and nitrogen co-doped carbon nanosheet is characterized by comprising the following steps of:
step 1, dissolving a certain amount of manganese chloride and zinc chloride in water, and uniformly mixing to obtain a solution A;
step 2, dissolving a certain amount of melamine and glucose in water, and uniformly mixing to obtain a solution B;
step 3, slowly dripping the solution A into the solution B to obtain milky white precipitate;
step 4, slowly dropping the milky white precipitate into liquid nitrogen for quick freezing to obtain a frozen product;
step 5, putting the frozen product into a freeze dryer for freeze drying at the temperature of between 45 ℃ below zero and 55 ℃ below zero, and grinding and vacuum drying to obtain white powder;
and 6, calcining the white powder at high temperature in an inert atmosphere to obtain a calcined product, grinding and acid leaching, and drying to obtain the manganese-nitrogen co-doped carbon nanosheet.
2. The preparation method of manganese-nitrogen co-doped carbon nanosheet according to claim 1, wherein:
in the step 1, the manganese chloride is manganese chloride tetrahydrate, the mass of the manganese chloride is 0.197 g-0.394 g, the mass of the zinc chloride is 0.136g, and the volume of the water is 5ml.
3. The preparation method of manganese and nitrogen co-doped carbon nanosheet according to claim 1, wherein:
in step 2, the mass of the melamine is 5g, the mass of the glucose is 2g, and the volume of the water is 25ml.
4. The preparation method of manganese-nitrogen co-doped carbon nanosheet according to claim 1, wherein:
and 3, slowly dropwise adding the solution A into the solution B, continuously stirring in the dropwise adding process, and continuously stirring for 4 hours after dropwise adding is finished to obtain the milky white precipitate.
5. The preparation method of manganese-nitrogen co-doped carbon nanosheet according to claim 1, wherein:
in step 4, the white precipitate after standing is dropped into liquid nitrogen at a speed of one drop per second for quick freezing.
6. The preparation method of manganese-nitrogen co-doped carbon nanosheet according to claim 1, wherein:
in step 6, the dried product is heated to 800-900 ℃ at a heating rate of 4-6 ℃ in a nitrogen atmosphere and is calcined at high temperature.
7. The preparation method of manganese-nitrogen co-doped carbon nanosheet according to claim 1, wherein:
in step 6, washing the calcined product in 0.5M sulfuric acid for 10 hours, and drying to obtain the manganese-nitrogen co-doped carbon nanosheet.
8. Manganese-nitrogen-codoped carbon nanosheet, characterized by being prepared by the preparation method of manganese-nitrogen-codoped carbon nanosheets according to any one of claims 1-7.
9. The application of the manganese and nitrogen co-doped carbon nanosheet in activating persulfate to degrade phenol is characterized in that the manganese and nitrogen co-doped carbon nanosheet is the manganese and nitrogen co-doped carbon nanosheet as defined in claim 8.
10. The application of the manganese-nitrogen co-doped carbon nanosheet in activating persulfate to degrade phenol according to claim 9, wherein:
wherein, in the degradation liquid, the content of phenol is 0.2g/L, the content of persulfate is 0.2g/L, and the addition amount of the manganese-nitrogen co-doped carbon nanosheet is 0.2g/L.
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