CN115285950A - Poly-triazine carbon material and preparation method and application thereof - Google Patents
Poly-triazine carbon material and preparation method and application thereof Download PDFInfo
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- CN115285950A CN115285950A CN202210671809.1A CN202210671809A CN115285950A CN 115285950 A CN115285950 A CN 115285950A CN 202210671809 A CN202210671809 A CN 202210671809A CN 115285950 A CN115285950 A CN 115285950A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/0828—Carbonitrides or oxycarbonitrides of metals, boron or silicon
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- C—CHEMISTRY; METALLURGY
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- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/087—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms
- C01B21/092—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms containing also one or more metal atoms
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4691—Capacitive deionisation
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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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention discloses a preparation method of a polytriazine carbon material, which comprises the following steps: adding a sulfuric acid solution into water, uniformly stirring, adding 2,6-diaminopyridine and transition metal Lewis acid, stirring until the mixture is dissolved, adding formaldehyde, stirring at normal temperature, centrifuging, concentrating, transferring to an autoclave for reaction, heating after the reaction is finished, continuing the reaction, centrifuging, and drying to obtain a semi-finished product; and heating and calcining the semi-finished product under the protection of nitrogen, washing with a hydrochloric acid solution, then adding water, performing Soxhlet extraction, and drying to obtain the polytriazine carbon material. The CDI electrode material can be prepared by the process of the invention, so that the polluted water containing heavy metal ions is treated, and the selective adsorption-desorption of special heavy metal ions is achieved. Compared with the traditional electrode material nitrogen-doped carbon, the process disclosed by the invention can be used for preparing the CDI electrode material which is green, efficient, low-carbon and sustainable, and plays an important role in the aspects of meeting major challenges such as resource shortage, energy crisis and environmental deterioration.
Description
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to a polytriazine carbon material and a preparation method and application thereof.
Background
Heavy metal pollution is one of the most serious environmental problems at present, has attracted high attention of scientists in various countries in the world, and the solution of the problem is urgent. Heavy metals in water usually exist in a cation form, so the heavy metals can be treated by chemical precipitation, electrolysis, solvent extraction, ion exchange, membrane separation or adsorption method, but the adverse factors of secondary pollution, excessive energy consumption and the like are inevitable. Compared with the traditional processing method, in recent years, the Capacitive Deionization (CDI) separation technology attracts a plurality of researchers with the advantages of being green, efficient, low-carbon, sustainable and the like, and plays an important role in the aspects of meeting major challenges such as resource shortage, energy crisis, environmental deterioration and the like.
The CDI is a pure capacitive process, the working mechanism of the CDI is the same as the energy storage mechanism of a super capacitor, the electric adsorption of ions is realized mainly by an Electric Double Layer (EDL) formed on the surface of a working electrode, and the desorption of pollutant ions by an electrode material can be realized by regulating and controlling external voltage.
The CDI recovery technology of heavy metal ions mainly uses nitrogen-doped carbon as an electrode material, and the preparation process is relatively complex. At present, mainly aiming at lead ions (Pb) 2+ ) Selective reporting of abundant, adsorbed Pb 2+ The solvent is needed to remove, the generated solution causes secondary pollution, the practical cost is improved, and the universality is not high. And the concentration of the lead ion solution to be treated is low, so that the lead ion solution cannot be used on a large scale.
Therefore, how to develop a CDI electrode material to treat the polluted water containing heavy metal ions to achieve selective adsorption-desorption of special heavy metal ions is a technical problem that needs to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a polytriazine carbon material, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the structural general formula of the polytriazine carbon material is shown as the formula I:
wherein, M is Zn, co, mn or Fe, and X is F, cl, br, I or At.
The invention also provides a preparation method of the polytriazine carbon material, which comprises the following steps:
(1) Adding a sulfuric acid solution into water, uniformly stirring, adding 2,6-diaminopyridine and a transition metal Lewis acid, stirring until the mixture is dissolved, adding formaldehyde, stirring at normal temperature, centrifuging and concentrating, transferring to a high-pressure kettle for reaction, heating to continue the reaction after the reaction is finished, centrifuging, and drying to obtain a semi-finished product;
(2) Heating and calcining the semi-finished product under the protection of nitrogen, washing with a hydrochloric acid solution, then adding water, performing Soxhlet extraction, and drying to obtain the polytriazine carbon material, wherein the synthetic route of the polytriazine carbon material shown in the formula I is as follows:
the beneficial effects of the invention are: the CDI electrode material can be prepared by the process of the invention, so that the polluted water containing heavy metal ions is treated, and the selective adsorption-desorption of special heavy metal ions is achieved. Compared with the traditional electrode material nitrogen-doped carbon, the process disclosed by the invention can be used for preparing the CDI electrode material, is green, efficient, low-carbon and sustainable, and plays an important role in the aspects of meeting important challenges such as resource shortage, energy crisis and environmental deterioration.
Further, the transition metal Lewis acid in the step (1) is MnCl 2 、CoCl 2 、NiCl、ZnCl 2 Any one of the above.
Further, in the step (1), the volume ratio of the sulfuric acid solution to water to formaldehyde is 0.88.
Further, in the step (1), the sulfuric acid solution is added into the water and stirred at the rotating speed of 400 revolutions per minute for 24 hours.
Further, the stirring speed at normal temperature in the step (1) is 400 rpm, and the stirring time is 24 hours.
Further, the step (1) is centrifugally concentrated to 1/40 of the volume of water.
Further, the step (1) was transferred to an autoclave reaction at 50 ℃ for 2 days.
Further, the temperature in the step (1) is raised to 90 ℃ and the reaction is continued for 3 days.
Further, after the reaction in the step (1) is finished, the temperature is increased to continue the reaction, the centrifugal rotating speed is 10000 r/min, and the centrifugal time is 5 min.
Further, the drying in the step (1) is drying under vacuum condition, the drying temperature is 70 ℃, and the drying time is 8 hours.
Further, the temperature in the step (2) is increased to 900 ℃ for calcining for 5h, and the temperature increasing speed is 5 ℃/min.
Further, the concentration of the hydrochloric acid solution of the above step (2) is 30wt%.
Further, the Soxhlet extraction time in the step (2) is 48h.
Further, the drying in the step (2) is drying under vacuum condition, the drying temperature is 70 ℃, and the drying time is 8 hours.
An application of the polytriazine carbon material or the polytriazine carbon material prepared by the method in capacitive deionization recovery.
Drawings
FIG. 1 is a graph showing the maximum salt adsorption amount of the polytriazine carbon material to various heavy metal chloride salts in example 1;
FIG. 2 is a graph showing the adsorption-desorption curves of the carbon polytriazine material for various heavy metal chloride salts in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the polytriazine carbon material comprises the following steps:
(1) 880 mul of sulfuric acid solution with the concentration of 1mol/L is added into 600mL of water to be evenly stirred, the rotating speed of the stirring is 400 r/min, the stirring time is 24 hours, then 300mg2, 6-diaminopyridine and 1.74g MnCl are added 2 4H 2 Stirring O until dissolving, adding 450 mu L of formaldehyde, stirring at normal temperature, centrifuging and concentrating to 15mL, stirring at the rotating speed of 400 r/min for 24 hours, transferring to a high-pressure kettle for reaction at the reaction temperature of 50 ℃ for 2 days, heating to 90 ℃ after the reaction is finished, continuing the reaction for 3 days, centrifuging at the rotating speed of 10000 r/min for 5 minutes, drying under vacuum conditions at the drying temperature of 70 ℃ for 8 hours to obtain a semi-finished product;
(2) And heating the semi-finished product to 900 ℃ under the protection of nitrogen, calcining for 5 hours at the heating speed of 5 ℃/min, cleaning by using a hydrochloric acid solution with the concentration of 30wt%, then performing Soxhlet extraction in water for 48 hours, drying under the vacuum condition, wherein the drying temperature is 70 ℃, and the drying time is 8 hours, so as to obtain the Mn-doped polytriazine carbon material.
Example 2
The preparation method of the polytriazine carbon material comprises the following steps:
(1) 880 μ L of 1mol/L sulfuric acid solution is added into 600mL water and stirred evenly, the rotation speed of the stirring is 400 r/min, the stirring time is 24 hours, then 300mg2, 6-diaminopyridine and 2.1g CoCl are added 2 6H 2 Stirring O until dissolving, adding 450 mu L of formaldehyde, stirring at normal temperature, centrifuging and concentrating to 15mL, stirring at the rotating speed of 400 r/min for 24 hours, transferring to a high-pressure kettle for reaction at the reaction temperature of 50 ℃ for 2 days, heating to 90 ℃ after the reaction is finished, continuing the reaction for 3 days, centrifuging at the rotating speed of 10000 r/min for 5 minutes, drying under vacuum conditions at the drying temperature of 70 ℃ for 8 hours to obtain a semi-finished product;
(2) Heating the semi-finished product to 900 ℃ under the protection of nitrogen, calcining for 5h at the heating speed of 5 ℃/min, cleaning with a hydrochloric acid solution with the concentration of 30wt%, then placing the semi-finished product into water, performing Soxhlet extraction for 48h, and drying under the vacuum condition, wherein the drying temperature is 70 ℃, and the drying time is 8 hours, so as to obtain the Co-doped polytriazine carbon material.
Example 3
The preparation method of the polytriazine carbon material comprises the following steps:
(1) 880 mul of sulfuric acid solution with the concentration of 1mol/L is added into 600mL of water to be evenly stirred, the rotating speed of the stirring is 400 r/min, the stirring time is 24 hours, then 300mg2, 6-diaminopyridine and 2.1g NiCl are added 2 6H 2 Stirring O until dissolving, adding 450 mu L of formaldehyde, stirring at normal temperature, centrifuging and concentrating to 15mL, stirring at the rotating speed of 400 r/min for 24 hours, transferring to a high-pressure kettle for reaction at the reaction temperature of 50 ℃ for 2 days, heating to 90 ℃ after the reaction is finished, continuing the reaction for 3 days, centrifuging at the rotating speed of 10000 r/min for 5 minutes, drying under vacuum conditions at the drying temperature of 70 ℃ for 8 hours to obtain a semi-finished product;
(2) Heating the semi-finished product to 900 ℃ under the protection of nitrogen, calcining for 5h at the heating speed of 5 ℃/min, cleaning with a hydrochloric acid solution with the concentration of 30wt%, then placing the semi-finished product into water, performing Soxhlet extraction for 48h, and drying under the vacuum condition, wherein the drying temperature is 70 ℃, and the drying time is 8 hours, so as to obtain the Ni-doped polytriazine carbon material.
Example 4
The preparation method of the polytriazine carbon material comprises the following steps:
(1) 880 mul of sulfuric acid solution with the concentration of 1mol/L is added into 600mL of water to be stirred evenly, the rotating speed of the stirring is 400 r/min, the stirring time is 24 hours, then 300mg2, 6-diaminopyridine and 1.2g ZnCl are added 2 Stirring to dissolve, adding 450 μ L of formaldehyde, stirring at normal temperature, centrifuging, concentrating to 15mL, stirring at 400 r/min for 24 hr, transferring to autoclave for reaction at 50 deg.C for 2 days, heating to 90 deg.C, reacting for 3 days, centrifuging, and concentratingThe speed is 10000 r/min, the centrifugation time is 5 min, the drying is carried out under the vacuum condition, the drying temperature is 70 ℃, and the drying time is 8h, thus obtaining a semi-finished product;
(2) Heating the semi-finished product to 900 ℃ under the protection of nitrogen, calcining for 5h at the heating speed of 5 ℃/min, cleaning with a hydrochloric acid solution with the concentration of 30wt%, then placing the semi-finished product into water, performing Soxhlet extraction for 48h, and drying under the vacuum condition, wherein the drying temperature is 70 ℃, and the drying time is 8 hours, so as to obtain the Zn-doped polytriazine carbon material.
Effect test
Preparing a capacitive deionization electrode from the polytriazine carbon material prepared in example 1, placing 60mg of the polytriazine carbon material, 7.5mg of acetylene black and 7.5mg of polyvinylidene fluoride in a mortar, adding 750 mu LN-methyl pyrrolidone, grinding into uniform slurry, uniformly coating the slurry on two pieces of 4X 4cm graphite paper, standing at room temperature for 2h, transferring to an oven at 60 ℃ for drying for 12 hours, assembling a CDI instrument, testing at room temperature at a flow rate of 10mL/min, wherein the adsorption voltage is 1.2V, the adsorption and desorption time is 3600s, the circulating solution is 500mg/L of various heavy metal ion aqueous solutions (referred to NaCl), the concentrations of various metal chloride aqueous solutions are 50-500mg/L, and as a result, the Mn content is found 2+ Has obvious selective adsorption and large adsorption quantity, and is shown in figure 1 and figure 2.
And (4) conclusion: the transition metal doping can further improve the charge distribution of the nitrogen-containing carbon material, increase the concentration of adsorption sites for heavy metal ions, and optimize the electric adsorption environment for the heavy metal ions.
The description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The poly-triazine carbon material is characterized in that the structural general formula of the poly-triazine carbon material is shown as the formula I:
wherein M is Zn, co, mn or Fe, and X is F, cl, br, I or At.
2. A method for producing a polytriazine carbon material as claimed in claim 1, which comprises the steps of:
(1) Adding a sulfuric acid solution into water, uniformly stirring, adding 2,6-diaminopyridine and transition metal Lewis acid, stirring until the mixture is dissolved, adding formaldehyde, stirring at normal temperature, centrifuging, concentrating, transferring to an autoclave for reaction, heating after the reaction is finished, continuing the reaction, centrifuging, and drying to obtain a semi-finished product;
(2) Heating and calcining the semi-finished product under the protection of nitrogen, washing with a hydrochloric acid solution, then adding water, performing Soxhlet extraction, and drying to obtain the polytriazine carbon material, wherein the synthetic route of the polytriazine carbon material shown in the formula I is as follows:
3. the method for producing a polytriazine carbon material according to claim 2, wherein the transition metal Lewis acid of step (1) is MnCl 2 、CoCl 2 、NiCl、ZnCl 2 Any one of the above.
4. The method for producing a polytriazine carbon material as claimed in claim 2, wherein in step (1), the volume ratio of the sulfuric acid solution, water and formaldehyde is 0.88.
5. The method for producing a polytriazine carbon material as claimed in claim 2, wherein said step (1) is performed by centrifugation and concentration to 1/40 of the volume of water.
6. The method for producing a polytriazine carbon material as claimed in claim 2, wherein said step (1) is carried out by transferring to an autoclave reaction at 50 ℃ for 2 days.
7. The method for producing a polytriazine carbon material as claimed in claim 2, wherein said step (1) is carried out for 3 days with the temperature of 90 ℃ being raised.
8. The method for preparing a polytriazine carbon material as claimed in claim 2, wherein the drying in step (1) is performed under vacuum at a temperature of 70 ℃ for 8 hours.
9. The method for preparing a polytriazine carbon material according to claim 2, wherein in the step (2), the temperature is increased to 900 ℃ and the calcination is performed for 5 hours, and the temperature increasing rate is 5 ℃/min.
10. Use of a polytriazine carbon material as defined in claim 1 or as prepared by a process as defined in any one of claims 2 to 9 in a capacitive deionisation recovery.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634019A (en) * | 2012-04-25 | 2012-08-15 | 哈尔滨工程大学 | Hybrid bisphenol copolymer fluorenyl benzoxazine prepolymer and preparation method thereof |
| US20170044444A1 (en) * | 2014-02-13 | 2017-02-16 | Ecolab Usa Inc. | Process for scavenging hydrogen sulfide present in a fluid stream |
| CN110577223A (en) * | 2019-10-28 | 2019-12-17 | 安徽理工大学 | Preparation process of porous carbon nanosphere |
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- 2022-06-14 CN CN202210671809.1A patent/CN115285950A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634019A (en) * | 2012-04-25 | 2012-08-15 | 哈尔滨工程大学 | Hybrid bisphenol copolymer fluorenyl benzoxazine prepolymer and preparation method thereof |
| US20170044444A1 (en) * | 2014-02-13 | 2017-02-16 | Ecolab Usa Inc. | Process for scavenging hydrogen sulfide present in a fluid stream |
| CN110577223A (en) * | 2019-10-28 | 2019-12-17 | 安徽理工大学 | Preparation process of porous carbon nanosphere |
Non-Patent Citations (3)
| Title |
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| ZHU XINGXING ET AL: "Nitrogen-Doped Porous Carbon Nanospheres Activated under Low ZnCl2 Aqueous System: An Electrode for Supercapacitor Applications", LANGMUIR, vol. 36, pages 9284 - 9290 * |
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