CN113000062A - Nitrogen-doped carbon material and preparation method and application thereof - Google Patents
Nitrogen-doped carbon material and preparation method and application thereof Download PDFInfo
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- CN113000062A CN113000062A CN202110242361.7A CN202110242361A CN113000062A CN 113000062 A CN113000062 A CN 113000062A CN 202110242361 A CN202110242361 A CN 202110242361A CN 113000062 A CN113000062 A CN 113000062A
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 43
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 13
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 11
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 8
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims abstract description 8
- 230000000593 degrading effect Effects 0.000 claims abstract description 7
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 230000003213 activating effect Effects 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 238000005554 pickling Methods 0.000 claims abstract description 4
- JTHJPGYVFWJIQZ-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid;iron Chemical compound [Fe].OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 JTHJPGYVFWJIQZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000000356 contaminant Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 239000003054 catalyst Substances 0.000 abstract description 7
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004202 carbamide Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000007605 air drying Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 2
- 229960002135 sulfadimidine Drugs 0.000 description 11
- ASWVTGNCAZCNNR-UHFFFAOYSA-N sulfamethazine Chemical compound CC1=CC(C)=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 ASWVTGNCAZCNNR-UHFFFAOYSA-N 0.000 description 11
- 230000015556 catabolic process Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 description 3
- 229960000623 carbamazepine Drugs 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229960001193 diclofenac sodium Drugs 0.000 description 3
- -1 melamine compound Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- JGMJQSFLQWGYMQ-UHFFFAOYSA-M sodium;2,6-dichloro-n-phenylaniline;acetate Chemical compound [Na+].CC([O-])=O.ClC1=CC=CC(Cl)=C1NC1=CC=CC=C1 JGMJQSFLQWGYMQ-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000001477 organic nitrogen group Chemical group 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910017112 Fe—C Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical class [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229960003742 phenol Drugs 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229960005404 sulfamethoxazole Drugs 0.000 description 1
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- 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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- C02F2101/36—Organic compounds containing halogen
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/38—Organic compounds containing nitrogen
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention provides a preparation method of a nitrogen-doped carbon material taking iron-trimesic acid (Fe-BTC) gel/nitrogen source as a precursor and application of the nitrogen-doped carbon material in degrading organic pollutants by activating Peroxymonosulfate (PMS). Mixing Fe-BTC gel with different nitrogen sources to serve as a precursor, drying and air-drying the mixture, carbonizing the mixture at a high temperature under inert gas, and carrying out acid pickling treatment to obtain the Fe-BTC gel/nitrogen source derived nitrogen-doped carbon material, wherein the material can efficiently activate PMS to degrade organic pollutants. The Fe-BTC gel/nitrogen source derived nitrogen-doped carbon material prepared by the method is used as a catalyst, and compared with the traditional carbon material catalyst, the catalytic activity, stability and catalytic efficiency of the catalyst are obviously improved. The Fe-BTC gel/nitrogen source precursor used for preparing the material can be rapidly synthesized in large quantity at room temperature, ferric nitrate nonahydrate and trimesic acid required for synthesizing the Fe-BTC gel have wide sources and low price, and the compounded nitrogen sources, namely dicyandiamide, melamine and urea, are all readily available nitrogen sources.
Description
Technical Field
The invention relates to the technical field of material engineering and environmental engineering, in particular to a preparation method and application of a nitrogen-doped carbon material.
Background
Environmental problems caused by organically contaminated wastewater containing antibiotics and personal care products are increasingly being valued. After partial organic matters in the wastewater enter a water body through various ways, the wastewater not only pollutes the water environment, but also can be transferred through a food chain and finally spread to human bodies, and potential danger is brought to the ecological environment and the healthy life of people. The invention finds that the advanced oxidation technology based on the Permonosulfate (PMS) has good degradation effect on organic pollutants in the wastewater.
The new advanced oxidation technologies based on sulfate radicals have unique advantages and have therefore been rapidly developed in recent years. Compared with other advanced oxidation technologies for generating hydroxyl radicals, the sulfate radical has stronger oxidation capability, wider pH adaptation range, better selectivity and longer half-life. Traditional advanced oxidation technologies using MOFs as precursors utilize activated persulfate or peroxodisulfate to generate sulfate radicals to degrade organic pollutants. Although the reaction has high degradation efficiency, the problems of metal dissolution, complex preparation process and the like always exist, and the practical application of the technology is restricted. The carbon material can be widely applied to the field of catalysis due to the characteristics of green nonmetal, low price and the like. And because the diameter of the nitrogen atom is similar to that of the carbon atom and the electronegativity is higher than that of carbon, the capability of adsorbing electrons is strong, the original carbon plane electronic structure can be changed by doping the nitrogen atom into the carbon material, and a new active site can be introduced, so that the performance of the carbon material is more excellent.
At present, Metal Organic Frameworks (MOFs) are mostly selected as precursors in the prior art, and commonly used MOFs precursors include ZIF-67, ZIF-8 and the like. The preparation process needs to adopt a toxic solvent methanol for dissolution, has low yield, and also needs a series of complicated processes such as precipitation, centrifugation and the like. Aiming at the problems, the invention prepares a nitrogen source derived nitrogen-doped carbon material which is simple to operate and is used for degrading organic pollutants in wastewater based on Fe-BTC gel.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the Fe-BTC gel/nitrogen source derived nitrogen-doped carbon material which is simple to operate, environment-friendly and low in cost, and the preparation method thereof, and the Fe-BTC gel/nitrogen source derived nitrogen-doped carbon material is simultaneously applied to degrading organic pollutants.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in one aspect, the invention provides a method for preparing a nitrogen-doped carbon material, which comprises the following steps:
(1) preparing an iron-trimesic acid (Fe-BTC) gel/nitrogen source complex from an iron salt, a nitrogen source and trimesic acid (BTC);
(2) and carbonizing the Fe-BTC gel/nitrogen source compound to obtain the nitrogen-doped carbon material.
Further, the step (1) includes: adding ferric nitrate nonahydrate and a nitrogen source into an organic solvent, and fully mixing to prepare a precursor solution A;
dissolving trimesic acid in an organic solvent to prepare a precursor solution B;
and adding the precursor solution A which is fully mixed and uniformly dispersed into the precursor solution B, and slightly stirring to form the Fe-BTC gel/nitrogen source compound.
Further, the step (2) includes: the Fe-BTC gel/nitrogen source complex is dried thoroughly, carbonized at 750 ℃ to 1000 ℃ (e.g., 800 ℃, 850 ℃, 900 ℃ or 950 ℃) in an inert gas atmosphere, and then cooled.
Further, the molar ratio of ferric nitrate nonahydrate to trimesic acid in the step (1) is 1: 1-2: 1.
Further, the molar ratio of the ferric nitrate nonahydrate to the nitrogen source in the step (1) is 1: 5-1: 10.
Further, the organic solvent in the step (1) is ethanol, and 25mL of ethanol is used for dissolving every 2-6mmol of trimesic acid.
Further, the nitrogen source is melamine and/or dicyandiamide.
Further, the step (2) further comprises: and (4) cooling, carrying out acid pickling on the obtained material, cleaning the material to be neutral by using ultrapure water, and drying the material.
Further, the acid used for acid washing is sulfuric acid or hydrochloric acid, and preferably, the concentration of the acid is 0.5 to 2.0 mol/L.
On the other hand, the invention also provides a nitrogen-doped carbon material obtained by using the preparation method.
In another aspect, the invention also provides an application of the nitrogen-doped carbon material in degrading organic pollutants.
Further, the application includes activating Peroxymonosulfate (PMS) with the nitrogen doped carbon material to degrade organic contaminants.
Compared with the prior art, the invention has the following outstanding characteristics and beneficial effects:
(1) the method for preparing the Fe-BTC gel/nitrogen source precursor by adopting the one-step method is simple to operate and environment-friendly. And the raw materials are directly stirred uniformly and then air-dried, so that the raw materials can be further carbonized at high temperature, toxic solvents and centrifugal cleaning are not needed, the yield is high, and the preparation cost and the operation difficulty are reduced.
(2) The Fe-BTC gel/nitrogen source precursor used for preparing the material can be rapidly synthesized in large quantity at room temperature, ferric nitrate nonahydrate and trimesic acid required for synthesizing the Fe-BTC gel have wide sources and low price, and the compounded nitrogen sources, namely dicyandiamide, melamine and urea, are common and easily available nitrogen sources.
Drawings
The drawings are only for purposes of illustrating and explaining the present invention and are not to be construed as limiting the scope of the present invention. Wherein:
FIG. 1 is an SEM image of a nitrogen-doped carbon material (melamine is the carbon source) in an embodiment of the present invention;
FIG. 2 is an SEM image of a nitrogen-doped carbon material (dicyandiamide being a carbon source) according to an embodiment of the present invention;
FIG. 3 is a graph showing the degradation effect of sulfadimidine on nitrogen-doped carbon material in an embodiment of the present invention;
FIG. 4 shows the removal effect of nitrogen-doped carbon material on carbamazepine, diclofenac sodium and rhodamine B in the embodiment of the present invention;
FIG. 5 shows the effect of activating PMS to degrade sulfadimidine by different catalysts in comparative examples of the present invention.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
In the examples of the present invention, the raw materials and instruments used are commercially available unless otherwise specified. The data of the degradation effect are average values of more than two repeated experiments.
Example 1:
in this example, the Fe-BTC gel/nitrogen source derived nitrogen doped carbon material was prepared by mixing Fe-BTC gel and a certain amount of melamine, air-drying at room temperature, and pyrolyzing at high temperature, and was referred to as Fe-C-N (M).
The specific preparation process of Fe-C-N (M) is as follows:
(1) preparation of Fe-BTC gel/Nitrogen Source Complex:
putting 6mmol of ferric nitrate nonahydrate and 48mmol of melamine into a reaction container, adding 25mL of ethanol, and fully mixing to obtain a precursor solution A;
dissolving 4mmol of trimesic acid in 25mL of ethanol to prepare a precursor solution B;
quickly pouring the precursor liquid A which is fully mixed and uniformly dispersed into the precursor liquid B, and slightly stirring to form a Fe-BTC gel/nitrogen source compound;
pouring the obtained Fe-BTC gel/melamine compound into a porcelain boat for paving, and naturally drying at room temperature;
(2) Fe-BTC gel/nitrogen-doped carbon material prepared by taking Fe-BTC gel/melamine compound as a precursor.
Putting the porcelain boat containing the Fe-BTC gel/melamine compound into a tube furnace, and heating to 800 ℃ at a heating rate of 5 ℃/min in an inert gas atmosphere; preserving the heat for 2 hours; naturally cooling to below 100 ℃, taking out the material, and pickling with sulfuric acid solution; then washed with ultrapure water to neutral and dried to obtain Fe-C-N (M), and the SEM picture is shown in figure 1.
The prepared Fe-BTC gel/nitrogen source derived nitrogen-doped carbon material can be used for degrading sulfadimidine, and the specific steps are as follows: 0.25mg of Fe-C-N (M) is added into 50mL of sulfamethazine solution with the concentration of 20mg/L, 0.25mL of PMS solution with the concentration of 50mmol/L is added under the mechanical stirring of 350r/min, 1mL of sample is taken and filtered after certain time intervals (1min, 3min, 5min, 10min, 15min, 20min and 30 min). The remaining concentration of sulfadimidine was determined by high performance liquid chromatography, as shown in fig. 3, the sulfadimidine removal rate was about 99% after 30min of degradation, and it was found that the adsorption removal rate of Fe-C-n (m) to sulfadimidine was only 50% without the addition of peroxymonosulfate, whereas the removal rate was only about 1.69% without the addition of catalyst but with the addition of peroxymonosulfate. In FIG. 3, Fe-C is a material prepared without adding a nitrogen source.
Example 2:
the mol ratio of ferric nitrate nonahydrate to melamine is 1: other preparation conditions were the same as in example 1. The resulting Fe-BTC gel/nitrogen source-derived nitrogen-doped carbon material is referred to as Fe-C-N (M) -10. After 60min degradation, the removal rate of 20mg/L sulfamethazine is more than 90%.
Example 3:
the organic nitrogen source was replaced with dicyandiamide. Other preparation conditions were the same as in example 1. The resulting Fe-BTC gel/nitrogen source-derived nitrogen-doped carbon material is referred to as Fe-C-N (D). The SEM image is shown in figure 2, the degradation effect on sulfadimidine is shown in figure 3, and the removal rate of 20mg/L sulfadimidine is more than 90% after 30min degradation.
Example 4:
the sulfamethoxazole, carbamazepine, phenol, diclofenac sodium and rhodamine B are treated by adopting the same materials and degradation conditions as those in example 1, as shown in figure 4, the removal rate of Fe-C-N (M) to four pollutants is over 90 percent, and the removal rate to carbamazepine and diclofenac sodium is over 99 percent.
Comparative example 1:
the organic nitrogen source was replaced by urea. Other preparation conditions were the same as in example 1. It was found that the mixture did not gel after the addition of urea.
Comparative example 2:
active carbon, multi-walled carbon nanotubes and cobaltosic oxide are respectively used as catalysts, the same degradation conditions as those in example 1 are adopted, only the catalysts are different, as shown in figure 5, the comparison shows that the activated carbon, the multi-walled carbon nanotubes and the cobaltosic oxide activated PMS have obviously lower capability of degrading sulfadimidine than Fe-C-N (M), and the Fe-BTC/nitrogen source derived nitrogen doped carbon material provided by the invention has better effect.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be noted that the above-mentioned embodiments are only illustrative of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a nitrogen-doped carbon material comprises the following steps:
(1) preparing an iron-trimesic acid (Fe-BTC) gel/nitrogen source complex from an iron salt, a nitrogen source and trimesic acid (BTC);
(2) and carbonizing the Fe-BTC gel/nitrogen source compound to obtain the nitrogen-doped carbon material.
2. The production method according to claim 1, wherein the step (1) includes: adding ferric nitrate nonahydrate and a nitrogen source into an organic solvent, and fully mixing to prepare a precursor solution A;
dissolving trimesic acid in an organic solvent to prepare a precursor solution B;
and adding the precursor solution A which is fully mixed and uniformly dispersed into the precursor solution B, and slightly stirring to form the Fe-BTC gel/nitrogen source compound.
3. The production method according to claim 1, wherein the step (2) includes: the Fe-BTC gel/nitrogen source complex is dried thoroughly, carbonized at 750 ℃ to 1000 ℃ (e.g., 800 ℃, 850 ℃, 900 ℃ or 950 ℃) in an inert gas atmosphere, and then cooled.
4. The preparation method according to claim 2, wherein the molar ratio of ferric nitrate nonahydrate to trimesic acid in step (1) is 1: 1-2: 1.
5. The preparation method according to claim 2, wherein the molar ratio of the ferric nitrate nonahydrate to the nitrogen source in the step (1) is 1: 5 to 1: 10.
6. The preparation method according to claim 2, wherein the organic solvent in the step (1) is ethanol, and 25mL of ethanol is used for dissolving every 2-6mmol of trimesic acid.
7. The production method according to claim 1, wherein the nitrogen source is melamine and/or dicyandiamide.
8. The production method according to claim 1, wherein the step (2) further comprises: cooling, performing acid pickling on the obtained material, cleaning the material to be neutral by using ultrapure water, and drying the material; preferably, the acid used for acid washing is sulfuric acid or hydrochloric acid, more preferably, the concentration of the acid is 0.5 to 2.0 mol/L.
9. A nitrogen-doped carbon material obtained by the production method according to any one of claims 1 to 8.
10. Use of the nitrogen-doped carbon material of claim 9 in degrading organic contaminants, preferably, the use comprises activating Peroxymonosulfate (PMS) with the nitrogen-doped carbon material to degrade organic contaminants.
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