CN107572497A - The preparation method of N doping grade hole carbon material - Google Patents
The preparation method of N doping grade hole carbon material Download PDFInfo
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- CN107572497A CN107572497A CN201710883296.XA CN201710883296A CN107572497A CN 107572497 A CN107572497 A CN 107572497A CN 201710883296 A CN201710883296 A CN 201710883296A CN 107572497 A CN107572497 A CN 107572497A
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Abstract
The invention discloses a kind of preparation method of N doping grade hole carbon material.Methods described is based on template, the characteristics of polymerisation forms poly-dopamine easily occurs in weakly alkaline Tris solution using dopamine molecule, dopamine is aggregated in nano level Zinc oxide powder surface, obtain preliminary nano zine oxide poly-dopamine composite construction；In ensuing carbonisation, poly-dopamine layer as carbon matrix precursor forms Nitrogen-rich porous carbon, internal nano zine oxide, by carbon reduction decomposition, is Nitrogen-rich porous carbon pore-creating, the zinc oxide template for finally further sloughing residual forms the grade hole carbon material of N doping under high temperature action.Present invention process is easy, easy to operate, and yield is high, and the porous carbon materials specific surface area of preparation reaches 1359m2g‑1, pore volume reaches 3.11cm3g‑1, rational microporous mesoporous grade pore structure is formed, has good application prospect in the even adsorbing domain of the electrochemical field including ultracapacitor.
Description
Technical field
The invention belongs to the preparation field of carbon material, and in particular to a kind of preparation method of N doping grade hole carbon material.
Background technology
According to bore dia, porous material is divided into three kinds：Micropore (aperture is less than 2nm), mesoporous (aperture is between 2-50nm)
With macropore (aperture is more than 50nm).Porous carbon materials refer to the carbon materials with Different Pore Structures.In recent years, including carbon nanometer
Miscellaneous carbon material including pipe, NACF, activated carbon etc. is constantly found.These carbon materials although possess compared with
Big specific surface area, but still have respective deficiency.Such as the hole of normal activated carbon and carbon fiber is formed mainly based on micropore,
It is unfavorable for mass transfer in actual applications.Number cells purpose increases the specific surface area and avtive spot that can significantly improve material, still
It is still greatly the blind hole or dead hole of randomness in micropore.Excessive micropore is then unfavorable for mass transfer, in electrochemical applications
The middle resistance that can increase material, and obstruction electron transmission (Nanoscale, 2014,6,12120-12129；Desalination 367
(2015)60–68).Mesoporous and macropore advantageously reduces resistance to mass tranfer, improves mass-transfer efficiency.Therefore suitable aperture point is possessed
Cloth, rational pore structure composition, is one of carbon material condition to be possessed in application field.
The porous carbon materials synthetic method of main flow is activation method and template at this stage.The carbon material that activation method prepares
Mostly unordered porous carbon materials, and the size in pass and aperture is difficult to regulate and control.The porous carbon materials that template is prepared then can gram
The drawbacks of carbon material physical dimension is not easily-controllable is taken, realizes the controllability of structure, and the carbon material prepared often has big ratio table
Area, high porosity, narrow pore-size distribution and pore structure order (J.Am.Chem.Soc.2000,122,10712-
10713；Adv.Funct.Mater.2007,17,1828–1836；Angew.Chem.Int.Ed.2008,47,3696–3717).
In order to further improve application performance of the porous carbon materials in fields such as electrochemistry, absorption, energy storage, in recent years, use
Such as the hetero atom such as N, P, S or doped porous carbon material containing heteroatom group are increasingly becoming new focus.In numerous heteroatoms
In, nitrogen is most application prospect.Because no matter its atom size, or valency electricity band is all much like with carbon, nitrogen substitution carbon
Process will not cause significant change to material structure.By taking the application of electrochemistry and capacitor area as an example, the introducing of nitrogen can strengthen
The power supply subcharacter of material, substantially improve the chemical property of carbon material, include the electric conductivity of material, electron transmission ability and
The wetability of material.This also improves the utilization rate of script carbon material internal gutter and structure to a certain extent.Nitrogen at this stage
The method of doping mainly has two kinds of (Journal of Physical Chemistry C, 2012,116 (50):26385-
26395；Acs Nano,2012,6(11):9541-50；Angew.Chem.2010,122,2619–2623；Energy
Environ.Sci.,2011,4,1892-1899).A kind of is the post processing of carbon material, under high temperature action, with nitrogen, ammonia
Material surface is modified Deng nitrogenous gas or grafting nitrogen-containing group.Another kind be in the synthesis of carbon material introduce nitrogen or
Person is directly carbonized to nitrogenous carbon source.Traditional method for preparing nitrogenous porous carbon generally requires a variety of chemical reagent, makes
Technique is relative complex, is easily introduced impurity.Pollution is also easily caused during using template, sloughing template.Therefore,
Need to find a kind of simple and efficient, beneficial to safety in production and the green method for preparing nitrogenous porous carbon.
The content of the invention
It is an object of the invention to provide a kind of simple and efficient, is easy to produce, green, contains micropore-mesopore structure
N doping grade hole carbon material preparation method.
Realize that the technical scheme of the object of the invention is as follows：
The preparation method of N doping grade hole carbon material, based on template, using dopamine molecule in weakly alkaline Tris
The characteristics of polymerisation forms poly-dopamine easily occurs in solution, dopamine is aggregated in nano level Zinc oxide powder surface,
Obtain preliminary nano zine oxide-poly-dopamine composite construction；In ensuing carbonisation, as the poly- more of carbon matrix precursor
Bar amine layer forms Nitrogen-rich porous carbon, and internal nano zine oxide, by carbon reduction decomposition, is made under high temperature action for Nitrogen-rich porous carbon
Hole, the zinc oxide template for finally further sloughing residual form the grade hole carbon material of N doping, comprised the following steps that：
(1) by nano zine oxide ultrasonic disperse in water, uniform nano zinc oxide suspension is formed；
(2) dopamine and Tris reagents are added in nano zinc oxide suspension, stirred at room temperature, polymerize more than 24h,
After reaction terminates, it is filtered under diminished pressure, water and washes of absolute alcohol, dries, obtain nano zine oxide-poly-dopamine compound；
(3) under inert atmosphere, nano zine oxide-poly-dopamine compound is carbonized in 700~900 DEG C, after carbonization terminates,
Residual nano zine oxide is sloughed in pickling, is washed, and drying, obtains N doping grade hole carbon material.
Preferably, in step (1), the size of described nano zine oxide is 15~20nm.
Preferably, in step (2), the mass ratio of described dopamine, nano zine oxide and Tris is 5：10：12, wherein
The quality of nano zine oxide can be reduced suitably.
Preferably, in step (3), described inert atmosphere is nitrogen or argon gas.
Preferably, in step (3), described carbonization time 3~5 hours, heating rate is 3~5 DEG C/min.
Preferably, in step (3), the acid solution of described washing is 10% hydrochloric acid solution.
Compared with prior art, the present invention has advantages below：
(1) using the zinc oxide of nanoscale as template, it is polymerize to form nitrogenous carbon matrix precursor with dopamine, follow-up pyrocarbon
During change, the zinc oxide in presoma is reduced by carbon, and zinc source is finally gasified, and further etches carbon material, forms micropore, significantly
The specific surface area and avtive spot of material, while the effect of template zinc oxide are improved, while forms the big mesoporous of more than 10nm,
Ultimately form rational micropore-mesopore grade pore structure, big specific surface area, up to 1359m2g-1, and big pore volume, reach
3.11cm3g-1；
(2) in composition, because the introducing of dopamine, obtained Carbon Materials have high nitrogen content, the parent of material is increased
Water-based and electric conductivity, beneficial to its application in electrochemistry, be advantageous to electron transmission and mass transfer and preparation method is easy, safety collar
Protect, will all have good application prospect in the electrochemical field including ultracapacitor and adsorbing domain.
Brief description of the drawings
Fig. 1 is the ESEM and transmission electron microscope picture of the N doping grade hole carbon material obtained by embodiment 1.
Fig. 2 is nitrogen adsorption-desorption isotherm of the N doping grade hole carbon material obtained by embodiment 1.
Fig. 3 is the graph of pore diameter distribution of the N doping grade hole carbon material obtained by embodiment 1.
Embodiment
With reference to embodiment and accompanying drawing, the invention will be further described.
Embodiment 1
The first step, precise nano-zinc oxide powder 1g, in being added in the beaker equipped with 1L deionized waters.By beaker
Ultrasonic 1h in supersonic cleaning machine is placed in so that nano zine oxide is uniformly dispersed, forms white suspension.
Second step, 0.5g dopamines reagent is weighed at room temperature and adds above-mentioned white suspension and stirs to dissolving.Connect down
To add 1.21gTris reagents, and it is continuously stirred at room temperature 24h.Period is observed that suspension color is black by leucismus.
3rd step, above-mentioned solution decompression is filtrated to get zinc oxide-poly-dopamine compound, and with deionized water and anhydrous
Ethanol cleans twice, is dried in vacuum drying oven stand-by.
4th step, dry material is placed under nitrogen atmosphere, rises to 900 DEG C with 3 DEG C/min heating rate, keep 3
Room temperature is naturally cooling to after hour, sample is taken out and sloughs remaining template with 10% HCl solution, washing obtains nitrogen several times
Doping level hole carbon material.
Obtained N doping grade hole carbon material specific surface area is 1359m2/ g, pore volume 3.11cm3/ g, nitrogen content are
5.4%.Fig. 1 is the ESEM and transmission electron microscope picture of the N doping grade hole carbon material obtained by embodiment 1.Can be with from figure
The obvious nanoscale pattern for observing material.Fig. 2 and Fig. 3 is the nitrogen of the N doping grade hole carbon material prepared by embodiment 1
Adsorption-desorption isothermal and graph of pore diameter distribution.The pore-size distribution result that stagnant ring and Fig. 3 are significantly returned in Fig. 2 has also confirmed material
The presence of micropore-mesopore in material.
Embodiment 2
The first step, precise nano-zinc oxide powder 1g, in being added in the beaker equipped with 1L deionized waters.By beaker
Ultrasonic 1h in supersonic cleaning machine is placed in so that nano zine oxide is uniformly dispersed, forms white suspension.
Second step, 0.5g dopamines reagent is weighed at room temperature and adds above-mentioned white suspension and stirs to dissolving.Connect down
To add 1.21gTris reagents, and it is continuously stirred at room temperature 24h.Period is observed that suspension color is black by leucismus.
3rd step, above-mentioned solution decompression is filtrated to get zinc oxide-poly-dopamine compound, and with deionized water and anhydrous
Ethanol cleans twice, is dried in vacuum drying oven stand-by.
4th step, dry material is placed under nitrogen atmosphere, rises to 800 DEG C with 3 DEG C/min heating rate, keep 3
Room temperature is naturally cooling to after hour, sample is taken out and sloughs remaining template with 10% HCl solution, washing obtains nitrogen several times
Doping level hole carbon material.
Obtained N doping grade hole carbon material specific surface area is 922m2/ g, pore volume 2.27cm3/ g, nitrogen content 7.0%.
Embodiment 3
The first step, precise nano-zinc oxide powder 1g, in being added in the beaker equipped with 1L deionized waters.By beaker
Ultrasonic 1h in supersonic cleaning machine is placed in so that nano zine oxide is uniformly dispersed, forms white suspension.
Second step, 0.5g dopamines reagent is weighed at room temperature and adds above-mentioned white suspension and stirs to dissolving.Connect down
To add 1.21gTris reagents, and it is continuously stirred at room temperature 24h.Period is observed that suspension color is black by leucismus.
3rd step, above-mentioned solution decompression is filtrated to get zinc oxide-poly-dopamine compound, and with deionized water and anhydrous
Ethanol cleans twice, is dried in vacuum drying oven stand-by.
4th step, dry material is placed under nitrogen atmosphere, rises to 700 DEG C with 3 DEG C/min heating rate, keep 3
Room temperature is naturally cooling to after hour, sample is taken out and sloughs remaining template with 10% HCl solution, washing obtains nitrogen several times
Doping level hole carbon material.
Obtained N doping grade hole carbon material specific surface area is 747m2/ g, pore volume 1.66cm3/ g, nitrogen content 9.2%.
Claims (7)
1. the preparation method of N doping grade hole carbon material, it is characterised in that comprise the following steps that：
(1) by nano zine oxide ultrasonic disperse in water, uniform nano zinc oxide suspension is formed；
(2) dopamine and Tris reagents are added in nano zinc oxide suspension, stirred at room temperature, polymerize more than 24h, reaction
After end, it is filtered under diminished pressure, water and washes of absolute alcohol, dries, obtain nano zine oxide-poly-dopamine compound；
(3) under inert atmosphere, by nano zine oxide-poly-dopamine compound in 700~900 DEG C of carbonizations, after carbonization terminates, pickling
Residual nano zine oxide is sloughed, is washed, drying, obtains N doping grade hole carbon material.
2. preparation method according to claim 1, it is characterised in that in step (1), the size of described nano zine oxide
For 15~20nm.
3. preparation method according to claim 1, it is characterised in that described dopamine, nano oxidized in step (2)
Zinc and Tris mass ratio are 5：10：12, the wherein quality of nano zine oxide can be reduced suitably.
4. preparation method according to claim 1, it is characterised in that in step (3), described inert atmosphere be nitrogen or
Argon gas.
5. preparation method according to claim 1, it is characterised in that in step (3), described carbonization time 3~5 is small
When, heating rate is 3~5 DEG C/min.
6. preparation method according to claim 1, it is characterised in that in step (3), the acid solution of described washing is
10% hydrochloric acid solution.
7. N doping grade hole carbon material made from preparation method according to any one of claims 1 to 6.
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| CN109607510A (en) * | 2019-01-15 | 2019-04-12 | 广西大学 | ZIF base nitrogen-doped porous carbon material and preparation method thereof |
| CN109950566A (en) * | 2019-04-15 | 2019-06-28 | 南京大学 | A kind of high-performance oxygen reduction catalyst and its preparation method based on function of surface enhancing |
| CN110085438A (en) * | 2019-04-21 | 2019-08-02 | 北京工业大学 | A kind of preparation method of nitrogen oxygen codope porous carbon |
| CN110697680A (en) * | 2019-10-18 | 2020-01-17 | 龙岩学院 | Heteroatom-doped porous carbon material with high specific surface area and preparation method thereof |
| CN110813241A (en) * | 2019-12-17 | 2020-02-21 | 国网山东综合能源服务有限公司 | Nitrogen-oxygen co-doped porous carbon material and preparation method and application thereof |
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| CN113148973A (en) * | 2021-03-29 | 2021-07-23 | 中南大学 | Nitrogen-doped porous carbon electrode material for adsorbing hexavalent chromium, and preparation and application methods thereof |
| CN113381015A (en) * | 2021-06-18 | 2021-09-10 | 郑州大学 | Nitrogen-doped hollow amorphous carbon shell material, preparation method and application |
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| CN109607510B (en) * | 2019-01-15 | 2022-04-05 | 广西大学 | ZIF-based nitrogen-doped porous carbon material and preparation method thereof |
| CN109607510A (en) * | 2019-01-15 | 2019-04-12 | 广西大学 | ZIF base nitrogen-doped porous carbon material and preparation method thereof |
| CN109950566A (en) * | 2019-04-15 | 2019-06-28 | 南京大学 | A kind of high-performance oxygen reduction catalyst and its preparation method based on function of surface enhancing |
| CN110085438A (en) * | 2019-04-21 | 2019-08-02 | 北京工业大学 | A kind of preparation method of nitrogen oxygen codope porous carbon |
| CN110697680A (en) * | 2019-10-18 | 2020-01-17 | 龙岩学院 | Heteroatom-doped porous carbon material with high specific surface area and preparation method thereof |
| CN110813241A (en) * | 2019-12-17 | 2020-02-21 | 国网山东综合能源服务有限公司 | Nitrogen-oxygen co-doped porous carbon material and preparation method and application thereof |
| CN112216517A (en) * | 2020-09-03 | 2021-01-12 | 中国汽车技术研究中心有限公司 | Composite energy storage material, preparation method thereof, electrode material and energy storage device |
| CN112707555A (en) * | 2020-12-07 | 2021-04-27 | 北京师范大学 | Multistage series filtration system composed of porous ceramic filters and preparation method |
| CN112844351A (en) * | 2021-01-08 | 2021-05-28 | 杭州神起科技有限公司 | Flower-shaped Fe-doped TiO2Preparation method and application of porous carbon-loaded composite material |
| CN112830471A (en) * | 2021-01-11 | 2021-05-25 | 大连理工大学盘锦产业技术研究院 | Preparation method of two-dimensional nitrogen-doped porous carbon material for supercapacitor |
| CN113148973A (en) * | 2021-03-29 | 2021-07-23 | 中南大学 | Nitrogen-doped porous carbon electrode material for adsorbing hexavalent chromium, and preparation and application methods thereof |
| CN113381015A (en) * | 2021-06-18 | 2021-09-10 | 郑州大学 | Nitrogen-doped hollow amorphous carbon shell material, preparation method and application |
| CN114212768A (en) * | 2021-12-08 | 2022-03-22 | 上海应用技术大学 | Preparation method of nitrogen-doped two-dimensional flaky hexagonal hollow carbon material with open pores on surface |
| CN114212768B (en) * | 2021-12-08 | 2023-04-28 | 上海应用技术大学 | Preparation method of nitrogen-doped two-dimensional flaky hexagonal hollow carbon material with surface open pores |
| CN115863544A (en) * | 2023-02-24 | 2023-03-28 | 江苏正力新能电池技术有限公司 | Positive pole piece and preparation method and application thereof |
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