CN109607510B - ZIF-based nitrogen-doped porous carbon material and preparation method thereof - Google Patents
ZIF-based nitrogen-doped porous carbon material and preparation method thereof Download PDFInfo
- Publication number
- CN109607510B CN109607510B CN201910035495.4A CN201910035495A CN109607510B CN 109607510 B CN109607510 B CN 109607510B CN 201910035495 A CN201910035495 A CN 201910035495A CN 109607510 B CN109607510 B CN 109607510B
- Authority
- CN
- China
- Prior art keywords
- zif
- solution
- pda
- caco
- carbon material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
Abstract
The invention discloses a ZIF-based nitrogen-doped porous carbon material and a preparation method thereof, wherein solid spherical calcium carbonate is used as a template agent and a pore-expanding agent to load a polydopamine film, and then zeolite imidazole framework crystal ZIF-8 is induced to grow on the surface of the polydopamine film to obtain a nitrogen-containing precursor CaCO3@ PDA @ ZIF-8, and carrying out high-temperature carbonization and water washing treatment to prepare the hollow spherical ZIF-based nitrogen-doped porous carbon material S-NGPC-ZIF-8. The invention is in the high-temperature carbonization process, the composite material CaCO3Calcium carbonate in @ PDA @ ZIF-8 not only plays a role in supporting morphology, but also decomposes CO released at high temperature2The method has the advantages that the method also has a high-efficiency pore-expanding effect, the evaporation of ZIF-8 crystal zinc ions also plays a role in secondary pore-expanding in the pyrolysis process, the problems that the traditional template agent is difficult to remove, the appearance is easy to collapse and the like are solved, and the introduction of a polluting pore-expanding agent is also avoided.
Description
Technical Field
The invention belongs to the technical field of material chemistry, and particularly relates to a ZIF-based nitrogen-doped porous carbon material and a preparation method thereof.
Background
In recent years, hollow spherical carbon materials have attracted attention from researchers for two main reasons: (1) the porous structure of the hollow sphere is beneficial to the diffusion of gas, so that the adsorption rate is improved; (2) the hollow volume in the spherical interior can adapt to the shrinkage change of the volume in the carbonization process, and has certain sintering resistance. The nitrogen-doped porous carbon material is obtained by doping nitrogen elements on the surface or in the porous carbon material, wherein the nitrogen element doping can improve the surface property of the carbon material or change the internal structure of the carbon material, so that the performance of the material on one aspect is improved. Therefore, the preparation of the nitrogen-doped carbon material with higher nitrogen content and suitable pore channel structure is particularly important for improving the adsorption performance of the material. Through the doping of the nitrogenous basic groups, a certain amount of chemical adsorption sites can be provided for the adsorption of acid gas, and the carbon material has a developed microporous structure, can effectively combine the combined action of physical and chemical adsorption, and provides a feasible way for the development of the adsorbent.
The hard template method is a common method for effectively synthesizing a nitrogen-doped porous carbon material, and generally comprises the following steps: (1) immersing a carbon precursor into a template; (2) polymerizing the precursor on a template agent to obtain a nitrogen-containing precursor, and then carbonizing at high temperature to obtain a carbon material with a specific morphology; (3) removing the template agent in the carbon material; (4) adding a pore-expanding agent into the carbon material with the specific morphology, and carrying out high-temperature carbonization pore-expanding to obtain the porous carbon material with the specific morphology.
Calcium carbonate is a common inorganic material, and has the advantages of low price, no toxicity, good biocompatibility and the like. Calcium carbonate products with different appearances can be prepared by utilizing different processing methods and crystallization conditions, and can be used as a template agent to be applied to the preparation of the porous carbon material. Dopamine (dopamine), a biological neurotransmitter, can undergo oxidation-crosslinking reaction under the action of dissolved oxygen in an aqueous solution condition to form a polydopamine composite thin layer (PDA) which is strongly adhered to the surface of a solid material. By means of the cross-linking effect of dopamine, zeolite imidazole framework material (ZIF-8) is further introduced to grow on the surface of the template to obtain a nitrogen-containing precursor. The abundant organic ligands in the zeolite imidazole framework material make the zeolite imidazole framework material very suitable for being used as a carbon source for porous carbon synthesis, and imidazole rings in a ZIF-8 structure provide abundant nitrogen elements for a doped carbon material. Moreover, as ZIF-8 has a zeolite topological structure, the ZIF-8 has very good thermal stability, and the introduction of the ZIF-8 as an additional carbon source can improve the pore volume structure of the carbon material to a certain extent.
The above background disclosure is only for the purpose of assisting understanding of the concept and technical solution of the present invention and does not necessarily belong to the prior art of the present patent application, and should not be used for evaluating the novelty and inventive step of the present application in the case that there is no clear evidence that the above content is disclosed at the filing date of the present patent application.
Disclosure of Invention
The invention aims to solve the technical problems of difficulty in removing a traditional template agent, easiness in shape collapse and introduction of a polluting pore-enlarging agent.
In order to solve the technical problems, the invention adopts the following technical scheme:
a ZIF-based nitrogen-doped porous carbon material is prepared by taking solid spherical calcium carbonate as a template agent and a pore-expanding agent, loading a polydopamine film, and inducing growth of a zeolite imidazole framework crystal ZIF-8 on the surface of the polydopamine film to obtain a nitrogen-containing precursor CaCO3@ PDA @ ZIF-8, and carrying out high-temperature carbonization and water washing treatment to prepare the hollow spherical ZIF-based nitrogen-doped porous carbon material S-NGPC-ZIF-8.
The invention also provides a preparation method of the ZIF-based nitrogen-doped porous carbon material, which comprises the following steps:
(1) synthesis of spherical calcium carbonate:
respectively preparing 490mL of calcium chloride aqueous solution, 490mL of sodium carbonate aqueous solution and 20mL of polyvinylpyrrolidone aqueous solution; under the condition of 35 ℃, the three solutions are sealed and fully stirred uniformly; uniformly dividing the polyvinylpyrrolidone solution into two parts, and respectively adding into CaCl2Solution and Na2CO3In the solution, keeping the temperature at 35 ℃ and stirring in water bath for 30min to fully and uniformly stir; adding CaCl2The solution was quickly poured into stirred Na2CO3Stirring the solution for 1h, and carrying out the whole reaction process in a constant-temperature water bath; separating white precipitate from mother liquor, filtering the obtained product, repeatedly washing with anhydrous ethanol and distilled water, drying in an oven at 80 deg.C for 5 hr, grinding, and collecting sample;
(2)CaCO3preparation of @ PDA composite:
respectively preparing 100-200mL of dopamine salt aqueous solution and 50-100mL of calcium carbonate suspension, fully stirring, pouring the dopamine salt solution into the calcium carbonate suspension, and stirring at the rotating speed of 150--1Reacting for 15 minutes under the condition of (1), and adding the prepared alkaline solution into the dopamine salt mixed solution; keeping the reaction temperature and the rotation speed unchanged, and reacting for 20 hours; filtering the reacted slurry, washing with deionized water and ethanol, and vacuum drying at 80 deg.C for 5 hr to obtain CaCO3@ PDA precursor material;
(3) nitrogen-containing precursor CaCO3Preparation of @ PDA @ ZIF-8
Respectively arranged at a concentration of 3 g.L-1CaCO3Methanol solution of @ PDA (80 mL) with a concentration of 4 g.L-180-150mL of a methanol solution of dimethyl imidazole; adding 0.1-0.5g zinc nitrate hexahydrate crystals to CaCO3Stirring at room temperature for 1h in a @ PDA solution; adding 0.3mL of triethylamine into the dimethyl imidazole solution, and stirring for 30 minutes at room temperature; the uniformly mixed dimethyl imidazole solution is dropwise added into CaCO3@ PDA solution at room temperature at 550 r.min-1Stirring for 1 h; filtering the reacted slurry, washing with ethanol, and vacuum drying at 80 deg.C for 5 hr to obtain CaCO3@ PDA @ ZIF-8 composite material;
(4) preparation of ZIF-based nitrogen-doped porous carbon material S-NGPC-ZIF-8
Weighing CaCO3The sample of @ PDA @ ZIF-8 is placed in a tubular furnace, high-temperature carbonization is carried out at the temperature of 700-.
Preferably, the concentration of the calcium chloride aqueous solution in the step (1) is 0.4 mol.L-1。
Preferably, the concentration of the sodium carbonate aqueous solution in the step (1) is 0.4 mol.L-1。
Preferably, the concentration of the polyvinylpyrrolidone aqueous solution in the step (1) is 2 g.L-1。
Preferably, the concentration of the dopamine salt aqueous solution in the step (2) is 4-6 g.L-1。
Preferably, the concentration of the calcium carbonate suspension in the step (2) is 8 g.L-1。
Preferably, the alkaline solution in step (2) is prepared from 0.75mL of ammonia water, 40-80mL of ethanol and 90-180mL of deionized water.
Preferably, the high temperature carbonization procedure in step (4) comprises the steps of:
(1) and (3) heating process: at 2-10 deg.C/min-1Speed of CaCO3The sample of @ PDA @ ZIF-8 is heated from room temperature to 900 ℃;
(2) and (3) constant temperature process: mixing CaCO3The @ PDA @ ZIF-8 sample is kept at the temperature of 700-;
(3) and (3) cooling: naturally cooling the precursor from 700-900 ℃ to room temperature.
Preferably, the water washing procedure in step (4) comprises the following steps:
(1) the intermediate product CaO @ S-NGPC-ZIF-8 is prepared into 1 g.L-1Stirring the aqueous solution for 30min, and performing suction filtration on the solution through an organic filter membrane;
(2) dissolving the suction filtration product in deionized water, and adding the solution with the concentration of 0.1 mol.L-1Hydrochloric acid solution is stirred for 6 hours, and the solution is washed to be neutral by water;
(3) adding methanol into the neutral solution, stirring for 1h, repeatedly washing with methanol and filtering.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, spherical calcium carbonate is used as a template agent, the spherical calcium carbonate is decomposed into calcium oxide and carbon dioxide after high-temperature carbonization, and the calcium oxide can be removed by using water and dilute hydrochloric acid, so that the problem that the template agent is difficult to remove in the later period is solved;
(2) the spherical calcium carbonate used in the invention decomposes and releases CO in the high-temperature carbonization process2The method has high-efficiency hole expanding effect, and avoids the problem of introducing a hole expanding agent;
(3) the product prepared by the invention has a meso-microporous double-pore structure, and most micropores exist in the form of a superfine microporous structure;
(4) according to the invention, ZIF-8 and dopamine are introduced as a carbon source and a nitrogen source to prepare the porous carbon material with high nitrogen content.
(5) According to the invention, spherical calcium carbonate is used as a template agent to load a polydopamine film, a ZIF-8 crystal is induced and grown on the surface of the polydopamine film to obtain a novel composite material, and the novel hollow spherical nitrogen-doped porous carbon material S-NGPC-ZIF-8 is prepared after high-temperature carbonization, water washing and other treatments. During high-temperature carbonization, composite material CaCO3Calcium carbonate in @ PDA @ ZIF-8 not only plays a role in supporting morphology, but also decomposes CO released at high temperature2The method has the advantages that the efficient pore-expanding effect is achieved, the evaporation of ZIF-8 crystal zinc ions also plays a role in secondary pore-expanding in the pyrolysis process, the problems that the traditional template is difficult to remove, the appearance is easy to collapse and the like are solved, and the introduction of a polluting pore-expanding agent (such as strong base NaOH and the like) is avoided.
Drawings
FIG. 1 is SEM and TEM images of spherical calcium carbonate and S-NGPC-ZIF-8 of example 1 of the present invention;
FIG. 2 is a graph showing the elemental contents of CaO @ S-NPC @ C-ZIF-8 composite material and washed S-NPC @ C-ZIF-8 according to example 1 of the present invention;
FIG. 3 is an XRD pattern of solid spherical calcium carbonate, S-NGPC-ZIF-8 of example 1 of the present invention;
FIG. 4 is a TG plot of S-NGPC-ZIF-8, a cardiospherical calcium carbonate of example 1 of the present invention;
FIG. 5 is N of S-NGPC-ZIF-8 according to example 1 of the present invention2Adsorption-desorption diagram and micropore distribution diagram.
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and accompanying drawings. It should be emphasized that the following description is merely exemplary in nature and is not intended to limit the scope of the invention or its application.
Example 1
A preparation method of a ZIF-based nitrogen-doped porous carbon material comprises the following steps:
(1) respectively configure 0.4 mol.L-1Calcium chloride (CaCl) of2) 490mL of aqueous solution, 0.4 mol. L-1Sodium carbonate (Na)2CO3) 490mL of aqueous solution, 2 g.L-120mL of polyvinylpyrrolidone (PVP) aqueous solution. Under the condition of 35 ℃, the three solutions are sealed and fully stirred uniformly; uniformly dividing polyvinylpyrrolidone (PVP) solution into two parts (10mL), and respectively adding into CaCl2Solution and Na2CO3In the solution, keeping the temperature at 35 ℃ and stirring in water bath for 30min to fully and uniformly stir; adding CaCl2The solution was quickly poured into vigorously stirred Na2CO3In solution at 600 r.min-1The slurry after reaction is filtered, washed by absolute ethyl alcohol and deionized water, the operations are repeated for three times, and vacuum drying is carried out for 5 hours at the temperature of 80 ℃, so as to obtain the solid spherical calcium carbonate product.
(2) The preparation concentration is 4 g.L-1100mL of dopamine salt (DA) aqueous solution with concentration of 8 g.L-150ml of hollow spherical calcium carbonate aqueous solution, namely CaCO with the weight ratio of 1.25DA/1.03The dopamine salt, solid spherical calcium carbonate and weak alkaline solution prepared by 0.75mL ammonia water, 40mL ethanol and 90mL deionized water are respectively sealed and stirred uniformly; adding the prepared dopamine salt aqueous solution into the calcium carbonate aqueous solution, and stirring at the water bath temperature of 25 ℃ and the stirring speed of 200 r-min-1Under the condition of (1), reacting for half h. Adding the prepared weak alkaline solution into the dopamine salt mixed solution, and keeping the reaction temperature and the rotating speed constantAnd reacting for 20 hours. Filtering the reacted slurry, washing with deionized water, and vacuum drying at 80 deg.c for 5 hr to obtain CaCO3@ PDA composite material.
(3) Respectively arranged at a concentration of 3 g.L-1CaCO3@ PDA methanol solution 80mL, concentration 4 g.L-180mL of dimethyl imidazole in methanol. 0.5g of zinc nitrate hexahydrate crystals are added to CaCO3@ PDA solution, stirred at room temperature for 1 h. The uniformly mixed dimethylimidazole solution was added dropwise to the CaCO3@ PDA solution, at room temperature at 550 r.min-1Stirring for 1 h. Filtering the reacted slurry, washing with ethanol, and vacuum drying at 80 deg.C for 5 hr to obtain CaCO3@ PDA @ ZIF-8 composite material.
(4) Weighing CaCO3The @ PDA @ ZIF-8 sample is placed in a tubular furnace, and high-temperature carbonization is carried out under the protection of nitrogen under the following carbonization conditions: at 5 ℃ min-1Speed of CaCO3The sample @ PDA @ ZIF-8 is heated to 700 ℃ from room temperature, is kept for 1h, and is naturally cooled to room temperature. And obtaining an intermediate product CaO @ S-NGPC-ZIF-8, washing with water, and drying to finally obtain the ZIF-based nitrogen-doped porous carbon material S-NGPC-ZIF-8.
The water washing program in step (4) of the invention comprises the following steps:
(1) the intermediate product CaO @ S-NGPC-ZIF-8 is prepared into 1 g.L-1Stirring the aqueous solution for 30min, and performing suction filtration on the solution through an organic filter membrane;
(2) dissolving the suction filtration product in deionized water, and adding hydrochloric acid solution (the concentration is 0.1 mol. L)-1) Stirring for 6h, and washing the solution to be neutral by water;
(3) adding methanol into the neutral solution, stirring for 1h, repeatedly washing with methanol and filtering.
Example 2
A preparation method of a ZIF-based nitrogen-doped porous carbon material comprises the following steps:
the procedure of example 1 was repeated except for the following changes. 0.1g of zinc nitrate hexahydrate crystals are added to CaCO3@ PDA solution, stirred at room temperature for 1 h. 0.3mL of triethylamine was added to the dimethylimidazole solution, and the mixture was stirred at room temperature for 30 min. Dropwise adding the uniformly mixed dimethyl imidazole solution to the solution CaCO3@ PDA solution, at room temperature at 550 r.min-1Stirring for 1 h. Filtering the reacted slurry, washing with ethanol, and vacuum drying at 80 deg.C for 5 hr to obtain CaCO3@ PDA @ ZIF-8 composite material. Weighing a certain mass of CaCO3The @ PDA @ ZIF-8 sample is placed in a tubular furnace, and high-temperature carbonization is carried out under the protection of nitrogen under the following carbonization conditions: at 5 ℃ min-1Speed of CaCO3The sample @ PDA @ ZIF-8 is heated to 800 ℃ from room temperature, is kept at the constant temperature for 2 hours, and is naturally cooled to room temperature. And (3) obtaining an intermediate product CaO @ S-NGPC-ZIF-8, washing the intermediate product CaO @ S-NGPC-ZIF-8 to be neutral by using deionized water (the water washing procedure is the same as that in the example 1), and finally obtaining the ZIF-based nitrogen-doped porous carbon material S-NGPC-ZIF-8.
Example 3
A preparation method of a ZIF-based nitrogen-doped porous carbon material comprises the following steps:
the procedure of example 2 was followed, except for the following changes. Weighing a certain mass of CaCO3The @ PDA sample is placed in a tube furnace, and high-temperature carbonization is carried out under the protection of nitrogen under the following carbonization conditions: at 5 ℃ min-1Speed of CaCO3The sample @ PDA @ ZIF-8 is heated to 900 ℃ from room temperature, is kept for 2 hours at the constant temperature, and is naturally cooled to the room temperature. Obtaining an intermediate product CaO @ S-NGPC-ZIF-8, and washing the intermediate product CaO @ S-NGPC-ZIF-8 to be neutral by using deionized water (the water washing procedure is the same as that of the water washing procedure)
Example 1), and finally obtaining the ZIF-based nitrogen-doped porous carbon material S-NGPC-ZIF-8.
Example analysis
As shown in fig. 1, the nitrogen-doped porous carbon material S-NGPC-ZIF-8 prepared in example 1 of the present invention has a hollow spherical morphology structure, which indicates that the template agent calcium carbonate has been completely decomposed into calcium oxide and removed by water washing, and the morphology does not collapse after water washing.
As shown in FIG. 2, S-NGPC-ZIF-8 prepared in example 1 of the present invention contained up to 25.76% nitrogen. Wherein the contents of calcium element in CaO @ S-NGPC @ C-ZIF-8 and the washed S-NGPC-ZIF-8 are respectively 19.84 percent and 0.19 percent, which shows that the calcium carbonate of the template is completely removed by water washing.
As shown in FIG. 3, the solid spherical calcium carbonate prepared in example 1 of the present invention is a vaterite-type calcium carbonate, and the intermediate product S-The XRD pattern of NGPC-ZIF-8 has no characteristic peak of calcium carbonate, which shows that CaCO3The calcium carbonate in @ PDA @ ZIF-8 has been completely decomposed to calcium oxide. And the XRD of the S-NGPC-ZIF-8 material shows two typical wide diffraction peaks at 23 degrees and 43 degrees respectively, which correspond to the (002) and (100) crystal planes of the graphite carbon respectively. The partially graphitized structure in the S-NGPC-ZIF-8 material is illustrated.
As shown in FIG. 4, the spherical calcium carbonate CaCO prepared in example 1 of the present invention3And CaCO3The decomposition temperatures of @ PDA @ ZIF-8 are respectively 605 ℃ and 645 ℃, wherein CaCO3The weight loss rate of @ PDA @ ZIF-8 is about 52% under the condition that the temperature of a greenhouse is increased to 900 ℃.
FIG. 5 and Table 1 show the N of S-NGPC-ZIF-8 prepared in example 1 of the present invention2Adsorption stripping figure and pore structure data of the material. S-NGPC-ZIF-8 has a mesoporous and microporous structure and a BET of 497.03m2·g-1The proportion of micropores is 76.94%, the pore diameter of micropores calculated by HK model is 0.6853nm, and the micropores belong to superfine micropore structure.
TABLE 1 pore Structure parameters of S-NGPC-ZIF-8
Those skilled in the art will recognize that numerous variations are possible in light of the above description, and therefore the examples and drawings are merely intended to describe one or more specific embodiments.
While there has been described and illustrated what are considered to be example embodiments of the present invention, it will be understood by those skilled in the art that various changes and substitutions may be made therein without departing from the spirit of the invention. In addition, many modifications may be made to adapt a particular situation to the teachings of the present invention without departing from the central concept described herein. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed, but that the invention will include all embodiments and equivalents falling within the scope of the invention.
Claims (7)
1. A preparation method of a ZIF-based nitrogen-doped porous carbon material is characterized by comprising the following steps:
(1) synthesis of spherical calcium carbonate:
respectively preparing 490mL of calcium chloride aqueous solution, 490mL of sodium carbonate aqueous solution and 20mL of polyvinylpyrrolidone aqueous solution; under the condition of 35 ℃, the three solutions are sealed and fully stirred uniformly; uniformly dividing the polyvinylpyrrolidone solution into two parts, and respectively adding into CaCl2Solution and Na2CO3In the solution, keeping the temperature at 35 ℃ and stirring in water bath for 30min to fully and uniformly stir; adding CaCl2The solution was quickly poured into stirred Na2CO3Stirring the solution for 1h, and carrying out the whole reaction process in a constant-temperature water bath; separating white precipitate from mother liquor, filtering the obtained product, repeatedly washing with anhydrous ethanol and distilled water, drying in an oven at 80 deg.C for 5 hr, grinding, and collecting sample;
（2）CaCO3preparation of @ PDA composite:
respectively preparing 100-200mL of dopamine salt aqueous solution and 50-100mL of spherical calcium carbonate suspension, fully stirring, pouring the dopamine salt solution into the spherical calcium carbonate suspension, and stirring at the rotating speed of 150--1Reacting for 15 minutes under the condition of (1), and adding the prepared alkaline solution into the dopamine salt mixed solution; keeping the reaction temperature and the rotation speed unchanged, and reacting for 20 hours; filtering the reacted slurry, washing with deionized water and ethanol, and vacuum drying at 80 deg.C for 5 hr to obtain CaCO3@ PDA precursor material;
(3) nitrogen-containing precursor CaCO3Preparation of @ PDA @ ZIF-8
Respectively arranged at a concentration of 3 g.L-1 CaCO3Methanol solution of @ PDA (80 mL) with a concentration of 4 g.L-180-150mL of a methanol solution of dimethyl imidazole; adding 0.1-0.5g zinc nitrate hexahydrate crystals to CaCO3Stirring at room temperature for 1h in a @ PDA solution; adding 0.3mL of triethylamine into the dimethyl imidazole solution, and stirring for 30 minutes at room temperature; adding the uniformly mixed dimethyl imidazole solution into CaCO dropwise3@ PDA solution, at room temperature at 550 r.min-1Stirring for 1 h; the slurry after the reaction is filtered,washing with ethanol, and vacuum drying at 80 deg.C for 5 hr to obtain CaCO3@ PDA @ ZIF-8 composite material;
(4) preparation of ZIF-based nitrogen-doped porous carbon material S-NGPC-ZIF-8
Weighing CaCO3The sample of @ PDA @ ZIF-8 is placed in a tubular furnace, and subjected to high-temperature carbonization at 900 ℃ of 700 ℃ under the protection of nitrogen, so as to obtain an intermediate product CaO @ S-NGPC-ZIF-8, and the intermediate product CaO @ S-NGPC-ZIF-8 is washed with water and dried, so as to obtain a ZIF-based nitrogen-doped porous carbon material S-NGPC-ZIF-8;
the high-temperature carbonization procedure comprises the following steps:
(1) and (3) heating process: at 2-10 deg.C/min-1Speed of CaCO3The sample of @ PDA @ ZIF-8 is heated from room temperature to 900 ℃;
(2) and (3) constant temperature process: mixing CaCO3The @ PDA @ ZIF-8 sample is kept at the temperature of 700-;
(3) and (3) cooling: naturally cooling the precursor from the temperature of 700-900 ℃ to room temperature;
the water washing procedure comprises the following steps:
(1) the intermediate product CaO @ S-NGPC-ZIF-8 is prepared into 1 g.L-1Stirring the aqueous solution for 30min, and performing suction filtration on the solution through an organic filter membrane;
(2) dissolving the suction filtration product in deionized water, and adding the solution with the concentration of 0.1 mol.L-1Hydrochloric acid solution is stirred for 6 hours, and the solution is washed to be neutral by water;
(3) adding methanol into the neutral solution, stirring for 1h, repeatedly washing with methanol and filtering.
2. The method of manufacturing a ZIF-based nitrogen-doped porous carbon material according to claim 1, wherein the concentration of the aqueous calcium chloride solution in step (1) is 0.4 mol-L-1。
3. The method of manufacturing a ZIF-based nitrogen-doped porous carbon material according to claim 1, wherein the concentration of the aqueous sodium carbonate solution in step (1) is 0.4 mol-L-1。
4. According to claim 1The preparation method of the ZIF-based nitrogen-doped porous carbon material is characterized in that the concentration of the polyvinylpyrrolidone aqueous solution in the step (1) is 2 g.L-1。
5. The method of preparing a ZIF-based nitrogen-doped porous carbon material according to claim 1, wherein: the concentration of the dopamine salt aqueous solution in the step (2) is 4-6 g.L-1。
6. The method of preparing a ZIF-based nitrogen-doped porous carbon material according to claim 1, wherein: the concentration of the spherical calcium carbonate suspension in the step (2) is 8 g.L-1。
7. The method of preparing a ZIF-based nitrogen-doped porous carbon material according to claim 1, wherein: the alkaline solution in the step (2) is prepared from 0.75mL of ammonia water, 40-80mL of ethanol and 90-180mL of deionized water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910035495.4A CN109607510B (en) | 2019-01-15 | 2019-01-15 | ZIF-based nitrogen-doped porous carbon material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910035495.4A CN109607510B (en) | 2019-01-15 | 2019-01-15 | ZIF-based nitrogen-doped porous carbon material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109607510A CN109607510A (en) | 2019-04-12 |
| CN109607510B true CN109607510B (en) | 2022-04-05 |
Family
ID=66017364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910035495.4A Active CN109607510B (en) | 2019-01-15 | 2019-01-15 | ZIF-based nitrogen-doped porous carbon material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109607510B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110152702A (en) * | 2019-04-29 | 2019-08-23 | 同济大学 | Derivative nitrogen carbon nanomaterial of a kind of organic backbone and its preparation method and application |
| CN111785943B (en) * | 2020-07-20 | 2022-06-03 | 江苏理工学院 | Preparation method and application of NPC @ C/S composite material |
| CN112374488B (en) * | 2020-11-17 | 2022-07-19 | 山东大学 | Preparation method of hollow boron-nitrogen co-doped carbon nanospheres with high boron content |
| CN113042087B (en) * | 2021-03-29 | 2023-02-28 | 陕西科技大学 | Preparation method of electrocatalytic double-function nitrogen-doped carbon-loaded carbon-coated cobalt phosphide core-shell nano material |
| CN113462356B (en) * | 2021-06-16 | 2023-11-28 | 盐城工学院 | Preparation method of binary composite wave-absorbing material |
| CN113368826B (en) * | 2021-07-06 | 2023-11-07 | 江阴市锦绣江南环境发展有限公司 | Adsorbent for heavy metal wastewater treatment and preparation method thereof |
| CN113979425B (en) * | 2021-10-21 | 2023-05-23 | 河北中煤旭阳能源有限公司 | Cobalt/nitrogen double-doped carbon nanoribbon and Li-SeS 2 Battery positive electrode material, preparation method thereof and secondary battery |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103072970A (en) * | 2013-02-04 | 2013-05-01 | 河北科技大学 | Spherical hollow mesoporous carbon shell and preparing method thereof |
| CN106495128A (en) * | 2016-11-09 | 2017-03-15 | 江苏理工学院 | A kind of single dispersing N doping hollow carbon nanometer polyhedral and preparation method thereof |
| CN106564873A (en) * | 2016-11-08 | 2017-04-19 | 广西大学 | Novel macro- and micro-porous thin film carbon material and preparation method of same |
| CN106986324A (en) * | 2017-03-10 | 2017-07-28 | 江苏海能动力科技有限公司 | It is a kind of for hollow porous carbon ball electrode material of ultracapacitor and preparation method thereof |
| CN107055510A (en) * | 2017-02-28 | 2017-08-18 | 合肥工业大学 | A kind of preparation method of metal organic complex nanotube and its derivative porous CNT |
| CN107572497A (en) * | 2017-09-26 | 2018-01-12 | 南京理工大学 | The preparation method of N doping grade hole carbon material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110082024A1 (en) * | 2008-06-10 | 2011-04-07 | Hansan Liu | Controllable Synthesis of Porous Carbon Spheres, and Electrochemical Applications Thereof |
-
2019
- 2019-01-15 CN CN201910035495.4A patent/CN109607510B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103072970A (en) * | 2013-02-04 | 2013-05-01 | 河北科技大学 | Spherical hollow mesoporous carbon shell and preparing method thereof |
| CN106564873A (en) * | 2016-11-08 | 2017-04-19 | 广西大学 | Novel macro- and micro-porous thin film carbon material and preparation method of same |
| CN106495128A (en) * | 2016-11-09 | 2017-03-15 | 江苏理工学院 | A kind of single dispersing N doping hollow carbon nanometer polyhedral and preparation method thereof |
| CN107055510A (en) * | 2017-02-28 | 2017-08-18 | 合肥工业大学 | A kind of preparation method of metal organic complex nanotube and its derivative porous CNT |
| CN106986324A (en) * | 2017-03-10 | 2017-07-28 | 江苏海能动力科技有限公司 | It is a kind of for hollow porous carbon ball electrode material of ultracapacitor and preparation method thereof |
| CN107572497A (en) * | 2017-09-26 | 2018-01-12 | 南京理工大学 | The preparation method of N doping grade hole carbon material |
Non-Patent Citations (3)
| Title |
|---|
| Nano-sized ZIF-8 anchored polyelectrolyte-decorated silica for Nitrogen-Rich Hollow Carbon Shell Frameworks toward alkaline and neutral supercapacitors;Li, ZW et al;《CARBON》;20180427;第136卷;第176-186页 * |
| Well-dispersed hollow porous carbon spheres synthesized by direct pyrolysis of core-shell type metal-organic frameworks and their sorption properties;Lee, HJ et al.;《CHEMICAL COMMUNICATIONS》;20140304;第50卷(第34期);第4494页第24-25行，附加材料第2-3页 * |
| 基于高分子-无机纳米粒子制备导电复合材料用于构建电化学传感器;王阳;《中国优秀博硕士学位论文全文数据库（博士） 工程科技I辑》;20180115;第76页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109607510A (en) | 2019-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109607510B (en) | ZIF-based nitrogen-doped porous carbon material and preparation method thereof | |
| CN112038648B (en) | Hollow-structure transition metal cobalt and nitrogen co-doped carbon oxygen reduction catalyst and preparation method and application thereof | |
| CN111943227B (en) | Preparation method of low-defect and low-water-content Prussian white analogue | |
| CN113549223B (en) | Micron MOF-303 and preparation method thereof | |
| CN110898794B (en) | Preparation method of lithium ion sieve | |
| CN109336161B (en) | CeO2 nanotube preparation method, CeO2 nanotube and application | |
| CN111533201B (en) | Biomass water treatment agent based on porous coffee grounds and preparation method thereof | |
| CN107916452B (en) | Preparation method of calcium carbonate whiskers with continuously controllable morphology | |
| CN113736094B (en) | Synthesis method of hierarchical porous ZIF-9 | |
| CN105460916A (en) | Preparation method of hollow carbon nanospheres-assembled mesoporous carbon fiber material | |
| CN110294637A (en) | A kind of modified porous cordierite ceramics material and the preparation method and application thereof | |
| CN109529903A (en) | A method of the nitrogen co-doped carbon material of nickel is prepared by template of hydrotalcite | |
| CN103539121B (en) | Porous carbonate and porous oxide preparation methods | |
| CN106564873B (en) | A kind of big micro-diplopore film carbon material and preparation method thereof | |
| CN108584977B (en) | Method for one-step green synthesis of cobalt-doped SBA-15 mesoporous molecular sieve material | |
| CN108793120B (en) | Preparation of hydrophobic double MOF-based porous carbon material | |
| CN102513069A (en) | Method for producing hierarchically structured porous coordination polymer absorbent material | |
| CN114682215B (en) | Setaria viridis-shaped composite nano-adsorption material with bionic structure and preparation method thereof | |
| CN114956078A (en) | Porous carbon material and preparation method and application thereof | |
| CN106564871B (en) | A kind of crystal whisker-shaped thin film bio carbon material and preparation method thereof | |
| CN109987640B (en) | Preparation of nano α -Fe2O3Method (2) | |
| CN113786839A (en) | ZnO/CuO/GO heterojunction photocatalyst with composite microsphere structure and preparation method and application thereof | |
| CN112915966A (en) | Preparation method and application of polyaniline-based activated carbon | |
| CN113428854B (en) | For CO 2 Adsorbed wood-based porous carbon materials and methods of making the same | |
| CN109879315B (en) | Two-dimensional layered porous hexagonal nano titanium dioxide and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |