CN109607510A - ZIF base nitrogen-doped porous carbon material and preparation method thereof - Google Patents
ZIF base nitrogen-doped porous carbon material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of ZIF base nitrogen-doped porous carbon materials and preparation method thereof, using real spherical calcium carbonate as template and expanding agent, load poly-dopamine film, then grow zeolite imidazole skeleton crystal ZIF-8 in its spatial induction, obtain nitrogenous precursor CaCO3The ZIF base nitrogen-doped porous carbon material S-NGPC-ZIF-8 of hollow sphere is made after high temperature cabonization, washing process in@[email protected] present invention is during high temperature cabonization, composite material CaCO3Calcium carbonate in@PDA@ZIF-8 not only acts as pattern supporting role, the CO of pyrolytic release2Also there is efficient reaming effect, and the evaporation of ZIF-8 crystal zinc ion also functions to the effect of second reaming in pyrolytic process, the method not only solve conventional template agent it is difficult remove, the problems such as pattern easily collapses, it is thus also avoided that the introducing of pollution expanding agent.
Description
Technical field
The invention belongs to material chemistry technical fields, and in particular to a kind of ZIF base nitrogen-doped porous carbon material and its preparation
Method.
Background technique
The carbon material of hollow sphere has obtained the extensive concern of scholar in recent years, mainly has following two reason: (1) hollow
Spherical porous structure is conducive to the diffusion of gas, to promote the rate of adsorption；(2) the hollow volume of spherical inner is suitable for carbon
The contraction change of volume during change has certain anti-caking power.Nitrogen-doped porous carbon material refers to nitrogen-doping
The carbon material obtained after into the surface or inside of porous carbon materials, wherein nitrogen-doping often improves carbon material surface property
Or change carbon material internal structure, and then improve the performance of material in one aspect.Therefore, preparation have both higher nitrogen content and
Be suitable for cellular structure nitrogen-doped carbon material, to improve material absorption property with regard to particularly important.Pass through nitrogen-containing basic group
Doping, can provide a certain amount of chemisorption position, and have both the microcellular structure of carbon material prosperity for acid gas adsorption, can have
Effect combines the collective effect of physical and chemical adsorption, provides feasible way for the exploitation of adsorbent.
Hard template method is a kind of common method for being effectively synthesized nitrogen-doped porous carbon material, generally there is following steps structure
At: (1) carbon matrix precursor is immersed in template；(2) it allows presoma to polymerize on template and obtains nitrogenous precursor, then lead to
It crosses high temperature cabonization and obtains the carbon material of specific morphology；(3) template in carbon material is removed；(4) add in specific morphology carbon material
Enter expanding agent, carry out high temperature cabonization reaming, the porous carbon materials with special appearance are made.
Calcium carbonate is a kind of common inorganic material, has many advantages, such as cheap, nontoxic, good biocompatibility.
The calcium carbonate products of different-shape can be prepared using processing method, the difference of crystallization condition, can be used as template be applied to it is more
In the preparation of hole carbon material.Dopamine (dopamine) is a kind of biological neural mediator, and under aqueous conditions, it can be molten
Oxidation-cross-linking reaction occurs under the action of solution oxygen, forms the compound thin layer of poly-dopamine that strength is attached to solid material surface
(PDA).By means of the crosslinked action of dopamine, it is further introduced into zeolite imidazole skeleton material (ZIF-8) and is grown in template surface
Obtain nitrogenous precursor.Organic ligand abundant makes it be highly suitable as porous carbon synthesis in zeolite imidazole skeleton material
Carbon source, and the imidazole ring in ZIF-8 structure provides nitrogen abundant for doping carbon material.And since ZIF-8 has
Zeolite topological, so it with extraordinary thermal stability, the introducing as Additional carbon sources can also change to a certain extent
The hole of kind carbon material holds structure.
The disclosure of background above technology contents is only used for auxiliary and understands design and technical solution of the invention, not necessarily
The prior art for belonging to present patent application, no tangible proof show above content present patent application the applying date
In disclosed situation, above-mentioned background technique should not be taken to the novelty and creativeness of evaluation the application.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of ZIF base nitrogen-doped porous carbon material and preparation method thereof, with
Solve the problems, such as that the difficult removal of conventional template agent, pattern easily collapse, introduce pollution expanding agent.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of ZIF base nitrogen-doped porous carbon material loads poly-dopamine using real spherical calcium carbonate as template and expanding agent
Film, then zeolite imidazole skeleton crystal ZIF-8 is grown in its spatial induction, obtain nitrogenous precursor CaCO3@PDA@ZIF-8, warp
After crossing high temperature cabonization, washing process, the ZIF base nitrogen-doped porous carbon material S-NGPC-ZIF-8 of hollow sphere is made.
The present invention also provides a kind of preparation methods of ZIF base nitrogen-doped porous carbon material, comprising the following steps:
(1) synthesis of spherical calcium carbonate:
Calcium chloride water 490mL, aqueous sodium carbonate 490mL, aqueous povidone solution 20mL is respectively configured；
Under the conditions of 35 DEG C of temperature, three kinds of solution sealings are stirred；Polyvinylpyrrolidonesolution solution is uniformly divided into two parts, point
CaCl is not added to it2Solution and Na2CO3In solution, 35 DEG C of stirring in water bath 30min is kept to stir it；By CaCl2
Solution is quickly poured into the Na of stirring2CO3In solution, it is kept stirring 1h, entire reaction process carries out in water bath with thermostatic control；It will be white
Color precipitating is separated from mother liquor, and products therefrom after dehydrated alcohol and distilled water wash repeatedly, is put into 80 DEG C of baking ovens through filtering
Dry 5h, collects sample after grinding；
(2)CaCO3The preparation of@PDA composite material:
Dopamine saline solution 100-200mL, calcium carbonate suspension 50-100mL are prepared respectively, it, will after being sufficiently stirred
DOPA amine salt solution pours into calcium carbonate suspension, in speed of agitator 150-300rmin-1Under conditions of react 15 minutes, will
Prepared alkaline solution is added in above-mentioned dopamine mixed salt solution；It keeps reaction temperature and revolving speed constant, reacts 20h；
Reaction rear slurry is filtered, with deionized water and ethanol washing, is dried in vacuo 5h under the conditions of 80 DEG C, CaCO is made3@
PDA persursor material；
(3) nitrogenous precursor CaCO3The preparation of@PDA@ZIF-8
It is 3gL that concentration, which is respectively configured,-1CaCO3The methanol solution 80mL of@PDA, concentration 4gL-1Methylimidazole
Methanol solution 80-150mL；0.1-0.5g zinc nitrate hexahydrate crystal is added to CaCO3In@PDA solution, 1h is stirred at room temperature；It takes
0.3mL triethylamine adds in methylimidazole solution, is stirred at room temperature 30 minutes；Dropwise by uniformly mixed methylimidazole solution
It is added in CaCO3@PDA solution, at room temperature with 550rmin-1Condition stirs 1h；Slurries after reaction are filtered, are used
Ethanol washing is dried in vacuo 5h at 80 DEG C, and CaCO is made3@PDA@ZIF-8 composite material；
(4) preparation of ZIF base nitrogen-doped porous carbon material S-NGPC-ZIF-8
Weigh CaCO3@PDA@ZIF-8 sample is placed in tube furnace, under nitrogen protection, carries out 700-900 DEG C of pyrocarbon
Change, obtains intermediate product CaO@S-NGPC-ZIF-8, washing, dry, acquisition ZIF base nitrogen-doped porous carbon material S-NGPC-
ZIF-8。
Preferably, the concentration of calcium chloride water described in step (1) is 0.4molL-1。
Preferably, the concentration of aqueous sodium carbonate described in step (1) is 0.4molL-1。
Preferably, the concentration of aqueous povidone solution described in step (1) is 2gL-1。
Preferably, the concentration of dopamine saline solution described in step (2) is 4-6gL-1。
Preferably, the concentration of calcium carbonate suspension described in step (2) is 8gL-1。
Preferably, alkaline solution described in step (2) is by 0.75mL ammonium hydroxide, 40-80mL ethyl alcohol, 90-180mL deionized water
It is formulated.
Preferably, high temperature cabonization program described in step (4) the following steps are included:
(1) temperature-rise period: with 2-10 DEG C of min-1Speed by CaCO3@PDA@ZIF-8 sample rises to 700- from room temperature
900℃；
(2) thermostatic process: by CaCO3@PDA@ZIF-8 sample is in 700-900 DEG C of 1~3h of holding；
(3) temperature-fall period: by presoma from 700-900 DEG C of cooled to room temperature.
Preferably, water wash procedures described in step (4) the following steps are included:
(1) intermediate product CaO@S-NGPC-ZIF-8 is configured to 1gL-1Aqueous solution, stirs 30min, and solution passes through organic
Filter membrane is filtered；
(2) product will be filtered to be dissolved in deionized water, addition concentration is 0.1molL-1Hydrochloric acid solution stirs 6h, uses water
Solution is washed to neutrality；
(3) methanol is added in neutral solution is molten, stirs 1h, washs suction filtration repeatedly with methanol.
Compared with the prior art, the present invention has the following beneficial effects:
(1) present invention resolves into calcium oxide and carbon dioxide after high temperature cabonization, uses water using spherical calcium carbonate as template
Calcium oxide can be removed with dilute hydrochloric acid, solves the problems, such as the removal of later period template difficulty；
(2) spherical calcium carbonate used in the present invention decomposes the CO of release during high temperature cabonization2Expand with efficient
Hole effect avoids the problem of introducing expanding agent；
(3) product of preparation of the invention has Jie's micro-diplopore structure, and the most of shape with ultrafine micropore structure of micropore
Formula exists；
(4) invention introduces ZIF-8, dopamines as carbon source and nitrogen source, prepares the porous carbon materials of high nitrogen-containing.
(5) present invention is template using spherical calcium carbonate, loads poly-dopamine film, grows ZIF- by spatial induction
8 crystal obtain advanced composite material (ACM), after the processing such as high temperature cabonization, washing, prepare the N doping of Novel hollow spherical shape
Porous carbon materials S-NGPC-ZIF-8.During high temperature cabonization, composite material CaCO3Calcium carbonate in@PDA@ZIF-8 is not only
Play pattern supporting role, the CO of pyrolytic release2Also there is efficient reaming effect, and the ZIF-8 in pyrolytic process
The evaporation of crystal zinc ion also functions to the effect reaming of second reaming, the method not only solve conventional template agent difficult removal,
The problems such as pattern easily collapses, it is thus also avoided that introduce pollution expanding agent (such as highly basic NaOH).
Detailed description of the invention
Fig. 1 is 1 spherical calcium carbonate of the embodiment of the present invention and SEM and the TEM figure of S-NGPC-ZIF-8；
Fig. 2 is S-NPC@C-ZIF-8 element after 1 composite material CaO@S-NPC@C-ZIF-8 of the embodiment of the present invention and washing
Content analysis figure；
Fig. 3 is the XRD diagram of the solid spherical calcium carbonate of the embodiment of the present invention 1, S-NGPC-ZIF-8；
Fig. 4 is the TG figure of 1 heart spherical calcium carbonate of the embodiment of the present invention, S-NGPC-ZIF-8；
Fig. 5 is the N of 1 S-NGPC-ZIF-8 of the embodiment of the present invention2Adsorption-desorption figure and micropore size distribution map.
Specific embodiment
With reference to embodiment and compares attached drawing invention is further described in detail.It is emphasized that
Following the description is only exemplary, the range and its application being not intended to be limiting of the invention.
Embodiment 1
A kind of preparation method of ZIF base nitrogen-doped porous carbon material, comprising the following steps:
(1) 0.4molL is respectively configured-1Calcium chloride (CaCl2) aqueous solution 490mL, 0.4molL-1Sodium carbonate
(Na2CO3) aqueous solution 490mL, 2gL-1Polyvinylpyrrolidone (PVP) aqueous solution 20mL.Under the conditions of 35 DEG C of temperature, three kinds
Solution sealing stirs；Polyvinylpyrrolidone (PVP) solution is uniformly divided into two parts (10mL), is added separately to
CaCl2Solution and Na2CO3In solution, 35 DEG C of stirring in water bath 30min is kept to stir it；By CaCl2Solution is quick
Pour into the Na being vigorously stirred2CO3In 600rmin in solution-1Speed of agitator under the conditions of, will reaction rear slurry take out
Filter is washed with dehydrated alcohol and deionized water, and in triplicate, solid spherical carbonic acid is made in 80 DEG C of vacuum drying 5h for the above operation
Calcium product.
(2) compound concentration is 4gL-1DOPA amine salt (DA) aqueous solution 100mL, concentration 8gL-1Hollow sphere calcium carbonate
Aqueous solution 50ml, i.e. weight ratio are 1.25DA/1.0CaCO3DOPA amine salt and solid spherical calcium carbonate, and by 0.75mL
Ammonium hydroxide, 40mL ethyl alcohol, the weakly alkaline solution that 90mL deionized water is prepared, three kinds of different solutions seal respectively to stir evenly；It will match
The dopamine saline solution set is added into calcium carbonate aqueous solution, at 25 DEG C of bath temperature, speed of agitator 200rmin-1's
Under the conditions of, react half h.Prepared weakly alkaline solution is added in above-mentioned dopamine mixed salt solution, reaction temperature with turn
Speed remains unchanged, and reacts 20h.Reaction rear slurry is filtered, is washed with deionized, 80 DEG C of vacuum drying 5h, is made
CaCO3@PDA composite material.
(3) it is 3gL that concentration, which is respectively configured,-1CaCO3@PDA methanol solution 80mL, concentration 4gL-1The first of methylimidazole
Alcoholic solution 80mL.0.5g zinc nitrate hexahydrate crystal is added to CaCO3@PDA solution, is stirred at room temperature 1h.By what is be uniformly mixed
Methylimidazole solution is added dropwise to CaCO3In@PDA solution, at room temperature with 550rmin-1Condition stirs 1h.After reacting
Slurries are filtered, with ethanol washing, and CaCO is made in 80 DEG C of vacuum drying 5h3@PDA@ZIF-8 composite material.
(4) CaCO is weighed3@PDA@ZIF-8 sample is placed in tube furnace, under the protection of nitrogen, carries out high temperature cabonization, carbon
Change condition are as follows: with 5 DEG C of min-1Speed by CaCO3@PDA@ZIF-8 sample rises to 700 DEG C, constant temperature 1h from room temperature, then natural
It is cooled to room temperature.Obtain intermediate product CaO@S-NGPC-ZIF-8, washing, dry, final acquisition ZIF base nitrogen-doped porous carbon
Expect S-NGPC-ZIF-8.
Step (4) the of the present invention water wash procedures the following steps are included:
(1) intermediate product CaO@S-NGPC-ZIF-8 is configured to 1gL-1Aqueous solution, stirs 30min, and solution passes through organic
Filter membrane is filtered；
(2) product will be filtered to be dissolved in deionized water, hydrochloric acid solution (concentration 0.1molL is added-1), 6h is stirred, is used
Water washing solution is to neutrality；
(3) methanol is added in neutral solution is molten, stirs 1h, washs suction filtration repeatedly with methanol.
Embodiment 2
A kind of preparation method of ZIF base nitrogen-doped porous carbon material, comprising the following steps:
In addition to following variations, remaining is the same as embodiment 1.0.1g zinc nitrate hexahydrate crystal is added to CaCO3@PDA solution, room
Temperature stirring 1h.0.3mL triethylamine is added into methylimidazole solution, 30min is stirred at room temperature.By uniformly mixed dimethyl miaow
Azoles solution is added dropwise to CaCO3In@PDA solution, at room temperature with 550rmin-1Condition stirs 1h.Reaction rear slurry is carried out
It filters, with ethanol washing, 80 DEG C of vacuum drying 5h, obtained CaCO3@PDA@ZIF-8 composite material.Weigh certain mass
CaCO3@PDA@ZIF-8 sample is placed in tube furnace, under the protection of nitrogen, carries out high temperature cabonization, Carbonization Conditions are as follows: with 5
℃·min-1Speed by CaCO3@PDA@ZIF-8 sample rises to 800 DEG C, constant temperature 2h, then cooled to room temperature from room temperature.It obtains
Intermediate product CaO S-NGPC-ZIF-8 is obtained, is washed with deionized water to neutral (water wash procedures are with embodiment 1), is finally obtained
Obtain ZIF base nitrogen-doped porous carbon material S-NGPC-ZIF-8.
Embodiment 3
A kind of preparation method of ZIF base nitrogen-doped porous carbon material, comprising the following steps:
In addition to following variations, remaining is the same as embodiment 2.Weigh the CaCO of certain mass3@PDA sample is placed in tube furnace,
Under the protection of nitrogen, high temperature cabonization, Carbonization Conditions are as follows: with 5 DEG C of min are carried out-1Speed by CaCO3@PDA@ZIF-8 sample from
Room temperature rises to 900 DEG C, constant temperature 2h, then cooled to room temperature.Intermediate product CaO S-NGPC-ZIF-8 is obtained, deionized water is used
Washed to neutral that (water wash procedures are same
Embodiment 1), it is final to obtain ZIF base nitrogen-doped porous carbon material S-NGPC-ZIF-8.
Instance analysis
As shown in Figure 1, nitrogen-doped porous carbon material S-NGPC-ZIF-8 prepared by the embodiment of the present invention 1, has hollow ball
The appearance structure of shape shows that template calcium carbonate has resolved into calcium oxide completely and has been washed with water removal, and pattern does not occur after wash water
It collapses.
As shown in Fig. 2, its nitrogen content of the S-NGPC-ZIF-8 of the preparation of the embodiment of the present invention 1 is up to 25.76%.Wherein CaO@
Calcium element content in S-NGPC@C-ZIF-8 and S-NGPC-ZIF-8 after washing, respectively 19.84% and 0.19%, show mould
Plate calcium carbonate is washed with water removal completely.
As shown in figure 3, solid spherical calcium carbonate prepared by the embodiment of the present invention 1 is vaterite-type calcium carbonate, and intermediate production
The XRD spectrum of object S-NGPC-ZIF-8 without the characteristic peak of calcium carbonate, shows CaCO3Calcium carbonate in@PDA@ZIF-8 is complete
Resolve into calcium oxide.And to occur two typical diffraction at 23 ° and 43 ° respectively wide by the XRD of S-NGPC-ZIF-8 material
Peak corresponds respectively to (002) and (100) crystal face of graphitic carbon.Illustrate there is part graphitization knot in S-NGPC-ZIF-8 material
Structure.
As shown in figure 4, spherical calcium carbonate CaCO prepared by the embodiment of the present invention 13And CaCO3@PDA@ZIF-8 decomposition temperature
Respectively 605 DEG C and 645 DEG C, wherein CaCO3@PDA@ZIF-8 weight-loss ratio under conditions of greenhouse rises to 900 DEG C is about 52%.
Such as the N that Fig. 5 and table 1 are S-NGPC-ZIF-8 prepared by the embodiment of the present invention 12The hole knot of adsorption/desorption figure and material
Structure data.Know that S-NGPC-ZIF-8 has Jie's micro-diplopore structure, BET 497.03m2·g-1, micropore ratio is 76.94%,
Micropore size under HK model calculates is 0.6853nm, this micropore belongs to ultrafine micropore structure.
The pore structure parameter of 1 S-NGPC-ZIF-8 of table
It would be recognized by those skilled in the art that above description make numerous accommodations be it is possible, so embodiment and attached
Figure is intended merely to describe one or more particular implementations.
It is counted as example embodiment of the invention although having been described and describing, it will be apparent to those skilled in the art that
It can be variously modified and is replaced, without departing from spirit of the invention.Furthermore it is possible to make many modifications with will be special
Condition of pledging love is fitted to religious doctrine of the invention, without departing from invention described herein central concept.So the present invention is unrestricted
In specific embodiment disclosed herein, but the present invention may further include belonging to all embodiments of the scope of the invention and its being equal
Object.
Claims (10)
1. a kind of ZIF base nitrogen-doped porous carbon material, it is characterised in that: using real spherical calcium carbonate as template and expanding agent, bear
Poly-dopamine film is carried, then grows zeolite imidazole skeleton crystal ZIF-8 in its spatial induction, obtains nitrogenous precursor CaCO3@
The ZIF base nitrogen-doped porous carbon material S-NGPC- of hollow sphere is made after high temperature cabonization, washing process in PDA@ZIF-8
ZIF-8。
2. a kind of preparation method of ZIF base nitrogen-doped porous carbon material according to claim 1, which is characterized in that including
Following steps:
(1) synthesis of spherical calcium carbonate:
Calcium chloride water 490mL, aqueous sodium carbonate 490mL, aqueous povidone solution 20mL is respectively configured；35
Under the conditions of DEG C temperature, three kinds of solution sealings are stirred；Polyvinylpyrrolidonesolution solution is uniformly divided into two parts, respectively plus
Enter to CaCl2Solution and Na2CO3In solution, 35 DEG C of stirring in water bath 30min is kept to stir it；By CaCl2Solution
It is quickly poured into the Na of stirring2CO3In solution, it is kept stirring 1h, entire reaction process carries out in water bath with thermostatic control；White is heavy
Shallow lake is separated from mother liquor, and products therefrom after dehydrated alcohol and distilled water wash repeatedly, is put into 80 DEG C of oven dryings through filtering
5h collects sample after grinding；
(2)CaCO3The preparation of@PDA composite material:
Dopamine saline solution 100-200mL, calcium carbonate suspension 50-100mL are prepared respectively, after being sufficiently stirred, by DOPA
Amine salt solution pours into calcium carbonate suspension, in speed of agitator 150-300rmin-1Under conditions of react 15 minutes, will prepare
Good alkaline solution is added in above-mentioned dopamine mixed salt solution；It keeps reaction temperature and revolving speed constant, reacts 20h；It will be anti-
It answers rear slurry to be filtered, with deionized water and ethanol washing, is dried in vacuo 5h under the conditions of 80 DEG C, CaCO is made3Before@PDA
Drive body material；
(3) nitrogenous precursor CaCO3The preparation of@PDA@ZIF-8
It is 3gL that concentration, which is respectively configured,-1CaCO3The methanol solution 80mL of@PDA, concentration 4gL-1The methanol of methylimidazole
Solution 80-150mL；0.1-0.5g zinc nitrate hexahydrate crystal is added to CaCO3In@PDA solution, 1h is stirred at room temperature；Take 0.3mL
Triethylamine adds in methylimidazole solution, is stirred at room temperature 30 minutes；Uniformly mixed methylimidazole solution is added dropwise
Into CaCO3@PDA solution, at room temperature with 550rmin-1Condition stirs 1h；Slurries after reaction are filtered, ethyl alcohol is used
Washing, is dried in vacuo 5h at 80 DEG C, and CaCO is made3@PDA@ZIF-8 composite material；
(4) preparation of ZIF base nitrogen-doped porous carbon material S-NGPC-ZIF-8
Weigh CaCO3@PDA@ZIF-8 sample is placed in tube furnace, under nitrogen protection, is carried out 700-900 DEG C of high temperature cabonization, is obtained
Obtain intermediate product CaO@S-NGPC-ZIF-8, washing, dry, acquisition ZIF base nitrogen-doped porous carbon material S-NGPC-ZIF-8.
3. the preparation method of ZIF base nitrogen-doped porous carbon material according to claim 2, which is characterized in that in step (1)
The concentration of the calcium chloride water is 0.4molL-1。
4. the preparation method of ZIF base nitrogen-doped porous carbon material according to claim 2, which is characterized in that in step (1)
The concentration of the aqueous sodium carbonate is 0.4molL-1。
5. the preparation method of ZIF base nitrogen-doped porous carbon material according to claim 2, which is characterized in that in step (1)
The concentration of the aqueous povidone solution is 2gL-1。
6. the preparation method of ZIF base nitrogen-doped porous carbon material according to claim 2, it is characterised in that: in step (2)
The concentration of the dopamine saline solution is 4-6gL-1。
7. the preparation method of ZIF base nitrogen-doped porous carbon material according to claim 2, it is characterised in that: in step (2)
The concentration of the calcium carbonate suspension is 8gL-1。
8. the preparation method of ZIF base nitrogen-doped porous carbon material according to claim 2, it is characterised in that: in step (2)
The alkaline solution is formulated by 0.75mL ammonium hydroxide, 40-80mL ethyl alcohol, 90-180mL deionized water.
9. the preparation method of ZIF base nitrogen-doped porous carbon material according to claim 2, it is characterised in that: in step (4)
The high temperature cabonization program the following steps are included:
(1) temperature-rise period: with 2-10 DEG C of min-1Speed by CaCO3@PDA@ZIF-8 sample rises to 700-900 DEG C from room temperature；
(2) thermostatic process: by CaCO3@PDA@ZIF-8 sample is in 700-900 DEG C of 1~3h of holding；
(3) temperature-fall period: by presoma from 700-900 DEG C of cooled to room temperature.
10. the preparation method of ZIF base nitrogen-doped porous carbon material according to claim 2, it is characterised in that: step (4)
Described in water wash procedures the following steps are included:
(1) intermediate product CaO@S-NGPC-ZIF-8 is configured to 1gL-1Aqueous solution, stirs 30min, and solution passes through organic filter membrane
It is filtered；
(2) product will be filtered to be dissolved in deionized water, addition concentration is 0.1molL-1Hydrochloric acid solution stirs 6h, is washed with water
Solution is to neutrality；
(3) methanol is added in neutral solution is molten, stirs 1h, washs suction filtration repeatedly with methanol.
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Cited By (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 |
| CN111785943A (en) * | 2020-07-20 | 2020-10-16 | 江苏理工学院 | Preparation method and application of NPC @ C/S composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN111785943A (en) * | 2020-07-20 | 2020-10-16 | 江苏理工学院 | Preparation method and application of NPC @ C/S composite material |
| CN112374488A (en) * | 2020-11-17 | 2021-02-19 | 山东大学 | Preparation method of hollow boron-nitrogen co-doped carbon nanospheres with high boron content |
| 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 |
| CN113042087A (en) * | 2021-03-29 | 2021-06-29 | 陕西科技大学 | Preparation method of electrocatalytic double-function nitrogen-doped carbon-loaded carbon-coated cobalt phosphide core-shell nano material |
| 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 |
| CN113462356A (en) * | 2021-06-16 | 2021-10-01 | 盐城工学院 | Preparation method of binary composite wave-absorbing material |
| CN113462356B (en) * | 2021-06-16 | 2023-11-28 | 盐城工学院 | Preparation method of binary composite wave-absorbing material |
| CN113368826A (en) * | 2021-07-06 | 2021-09-10 | 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 |
| 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 |
| CN113979425A (en) * | 2021-10-21 | 2022-01-28 | 河北中煤旭阳能源有限公司 | Co/N double-doped carbon nanoribbon and Li-SeS2Battery positive electrode material, preparation method thereof and secondary battery |
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