CN102583312B - Method for preparing porous carbon spheres doped with nitrogen and phosphorus and application - Google Patents
Method for preparing porous carbon spheres doped with nitrogen and phosphorus and application Download PDFInfo
- Publication number
- CN102583312B CN102583312B CN201210028566.6A CN201210028566A CN102583312B CN 102583312 B CN102583312 B CN 102583312B CN 201210028566 A CN201210028566 A CN 201210028566A CN 102583312 B CN102583312 B CN 102583312B
- Authority
- CN
- China
- Prior art keywords
- porous carbon
- nitrogen
- microsphere
- organophosphazenes
- poly
- 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.)
- Expired - Fee Related
Links
Images
Abstract
The invention belongs to the technical fields of inorganic material chemistry and new energy, and discloses a method for preparing porous carbon spheres doped with nitrogen and phosphorus and an application. Water serves as a solvent, polyphosphazenes microspheres and activating agents are mixed in a mass ratio of (0.2-2):1, concentration of the polyphosphazenes microspheres is maintained at a level of 10-30wt%, stirring is performed completely, the mixture of the polyphosphazenes microspheres and the activating agents is obtained through centrifugal separation, the mixture of the polyphosphazenes microspheres and the activating agents is subjected to carbonization, and finally the porous carbon spheres doped with the nitrogen and the phosphorus are obtained. The activating agents are potassium hydroxide, sodium hydroxide, calcium chloride or zinc chloride. The polyphosphazenes microspheres serve as a carbon precursor in the method, are synthesized directly under the room temperature condition, and has a simple art process and high productivity. Simultaneously, the activating agents are used for processing polyphosphazenes so as to improve specific surface areas and pore structures of the porous carbon spheres greatly and be beneficial to improve hydrogen storage capacity.
Description
Technical field
The invention belongs to inorganic material chemistry and technical field of new energies, be specifically related to preparation method and the application of a kind of nitrogen, phosphorus doping porous carbon ball.
Background technology
Hydrogen is a kind of wide material sources, renewable, the clean energy, is also a kind of important industrial raw material, has become fuel cell, the optimal fuel of hydrogen internal combustion engine.Because hydrogen density is little, easily blast, so the gordian technique of hydrogen energy source utilization is the storage of hydrogen.
The hydrogen storage material of research and development excellent performance is the key that solves hydrogen energy storage problem.In recent years, porous carbon materials is because its low density, high-specific surface area, good chemical stability and the advantages such as adjustability of pore size have become one of important object of Recent Progress in Hydrogen Storage Materials research.Porous carbon materials belongs to physical adsorption to the storage of hydrogen, and the large quality that can realize small volume stores, and therefore the specific surface area of carbon material is higher in theory, and corresponding hydrogen-storage amount also should be larger.Research shows, for desirable porous carbon materials, in order to obtain larger hydrogen-storage amount, need on the one hand higher specific surface area so that more hydrogen adsorption site to be provided, also need in addition the micropore pore volume of larger proportion to improve ratio [Gogotsi Y., the et al. in active adsorption site, Adv. Funct. Mater., 2006,16,2288].Template is a kind of effective method of porous carbon material of preparing, the method is generally by porous templates such as mesoporous silicon oxide, zeolites, carbon matrix precursor is infiltrated in the hole or passage of template, carbonization under certain condition is also removed template and can be obtained porous carbon material, as long as make rational template, just can control pore size and the shape of carbon material.The people such as Yang utilize this path to prepare a kind of specific surface area up to 3200m
2/ g, pore volume is up to 2.41m
3the class zeolite type porous carbon materials of/g, under low-temperature atmosphere-pressure, hydrogen storage ability reaches 2.6wt% [Yang, Z.X., et al., J. Am. Chem. Soc. 2007,129,1673].But the method also has many restrictions, as the removal of template, often need in aggressive solvent, carry out, technique is loaded down with trivial details, and harmful to environment.In addition, for improve porous carbon materials specific surface area, improve its pore structure, conventionally can carry out follow-up activation treatment to carbon material, as carbonic acid gas high-temperature activation, alkali high-temperature activation or water vapour high-temperature activation etc., thereby be conducive to the application of its function.Recently, the people's such as Xia research work shows, CMK-3 is carried out to carbonic acid gas high-temperature activation and can obtain the porous carbon materials [Xia, K.S., et al., Carbon, 2007,45,1989] with higher low temperature hydrogen storage capability.
In the recent period, research can be of value to the improvement of its hydrogen storage property after finding that the carbon skeleton of porous carbon materials is carried out to some elements (nitrogen, phosphorus, boron etc.) doping, and this is verified by room temperature storage hydrogen theory and Preliminary experiment results.Yet, porous carbon materials is carried out to effective element doping, and still can keep its high-specific surface area and specific pore structure and be not easy.Conventionally introduce assorted element way be that carbon material is carried out to pyrochemistry modification as aminating reaction; but this means have just realized at carbon material surface and have introduced assorted element; can not change the elementary composition of carbon skeleton inside; and conventionally can reduce pore volume and the specific surface area of carbon material, concentrated nitric acid is processed the similar problem that also exists.In addition, utilize the precursor that contains assorted element to make carbon source, also can realize the preparation of doping type carbon material.Recently, the people such as Gao Qiuming be take quadrol as presoma, mesoporous silicon oxide is that template has been prepared a kind of order mesoporous nitrogen carbon material, again this order mesoporous nitrogen carbon material is carried out to carbonic acid gas pyroprocessing, obtained the doped meso-porous carbon material of nitrogen with high specific surface area and higher pore volume, the hydrogen [Gao Qiuming, Jiang Jinhua CN 101372325 B] of energy reversible adsorption 2.21 wt% under 80 normal atmosphere of normal temperature.In addition, it is precursor that Gao Qiuming etc. also be take sucrose, furfuryl alcohol, polyacrylonitrile etc., take micro porous molecular sieve as template, adopt the two step method of liquid impregnation and electroless plating combination to synthesize nitrogen-doped porous carbon material, such material can be for hydrogen storage material and electrode material for super capacitor [Gao Qiuming, Wang Huan builds CN 101531357 B].Yet the use of inorganic template still can cause the complicated of porous carbon materials preparation technology in these methods, also can bring the problems such as larger pollution to environment simultaneously.
Summary of the invention
The object of the present invention is to provide preparation method and the application of a kind of nitrogen, phosphorus doping porous carbon ball.
For achieving the above object, the technical scheme that the present invention takes is as follows:
The preparation method of a kind of nitrogen, phosphorus doping porous carbon ball: take water as solvent, by poly (organophosphazenes) microsphere and activator with (0.2～2): 1 mass ratio mixes, keeping the concentration of poly (organophosphazenes) microsphere is 10～30 wt%, fully stir, then centrifugation obtains poly (organophosphazenes) microsphere and activating mixtures, finally, poly (organophosphazenes) microsphere and activating mixtures are carried out to carbonization and obtain nitrogen, phosphorus doping porous carbon ball; Wherein said activator is potassium hydroxide, sodium hydroxide, calcium chloride or zinc chloride.
In the present invention, described poly (organophosphazenes) microsphere can be prepared by prior art, and the present invention is preparation by the following method preferably: under room temperature condition, hexachlorocyclotriphosphazene and comonomer are distributed in organic solvent, then add acid binding agent, in 20～80 ℃ of ultrasonic reaction 1～10 h, reaction finishes rear centrifugation, washing, the dry poly (organophosphazenes) microsphere that obtains, wherein with molar ratio computing, hexachlorocyclotriphosphazene: comonomer: acid binding agent=1:(2.8～3.2): (6～12), the addition of organic solvent guarantees that the concentration of hexachlorocyclotriphosphazene is 0.002～0.02 mol/L, comonomer is 4, 4 '-dioxydiphenyl methane, 4, 4 '-diaminodiphenylsulfone(DDS), 4, 4 '-dihydroxy diphenylsulphone, 4, 4 '-diaminodiphenylmethane, 4, 4 '-diaminodiphenyl oxide, Ursol D or Resorcinol, acid binding agent is triethylamine, organic solvent is ethanol, propyl alcohol, acetonitrile, acetone, tetrahydrofuran (THF), a kind of or its combination in toluene or normal hexane.
Further, the process of described carbonization is: poly (organophosphazenes) microsphere and activating mixtures are placed in to carbide furnace, first logical rare gas element is driven away the air in carbide furnace, then be warming up to 600～1200 ℃, after insulation 2～5h, be naturally cooled to room temperature, then by the hydrochloric acid for black powder obtaining, be washed to neutrality, dry, obtain nitrogen, phosphorus doping porous carbon ball.
Preferably, during intensification, temperature rise rate is 1～20 ℃/min preferably.
Preferably, described rare gas element is high pure nitrogen or high-purity argon gas.
Nitrogen prepared by the inventive method, phosphorus doping porous carbon ball are as the application of hydrogen storage material.
What in the present invention, relate to is dry, all preferably 50～80 ℃ of its temperature, and the time is preferred 12～24h all.
Compared with prior art, beneficial effect of the present invention is embodied in:
(1) carbon matrix precursor that the present invention adopts is poly (organophosphazenes) microsphere, and it can directly synthesize at ambient temperature, and technique is simple, productive rate is high.Poly phosphazene itself is rich in a large amount of non-carbon (comprising nitrogen, phosphorus), and in high temperature cabonization process, these non-carbons have directly caused carbon material to have open pore passage structure with shifting out of gas form, are conducive to the absorption of hydrogen molecule.Meanwhile, adopt activator to process poly phosphazene, significantly improve specific surface area and the pore structure of porous carbon ball, be conducive to the raising of hydrogen-storage amount.
(2) the inventive method provides a path of preparing nitrogen, phosphorus doping porous carbon materials.With respect to methods such as high temperature ammonifications only for porous carbon materials surface doping nitrogen essence, the inventive method has not only realized the nitrogen that adulterates in carbon skeleton, the dual element of phosphorus, and the quantity that has realized doped element is controlled, as passed through, control carbonization technique condition, can realize the controlled of nitrogen in poly phosphazene, phosphoric and shift out, and then it is controlled to realize the content of nitrogen, phosphoric in porous carbon ball.
(3) with by hard template such as silicon-dioxide, zeolites, build porous carbon materials and compare, preparation technology of the present invention is simple, contaminate environment is little, is easy to preparation in batches.Meanwhile, nitrogen, phosphorus doping porous carbon ball good sphericity, specific surface area that the present invention obtains are large, and pore size distribution, within micro-mesoporous scope, has excellent hydrogen storage property.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the prepared poly (organophosphazenes) microsphere of embodiment 1.
Fig. 2 is the transmission electron microscope photo of the prepared poly (organophosphazenes) microsphere of embodiment 1.
Fig. 3 is the stereoscan photograph of the prepared nitrogen of embodiment 1, phosphorus doping porous carbon ball.
Fig. 4 is the transmission electron microscope photo of the prepared nitrogen of embodiment 1, phosphorus doping porous carbon ball.
Fig. 5 is the X-ray energy spectrum analysis of the prepared nitrogen of embodiment 1, phosphorus doping porous carbon ball.
Fig. 6 is the nitrogen suction/desorption isotherm of the prepared nitrogen of embodiment 1, phosphorus doping porous carbon ball.
Fig. 7 is the pore size distribution curve of the prepared nitrogen of embodiment 1, phosphorus doping porous carbon ball.
Fig. 8 is the prepared nitrogen of embodiment 1, phosphorus doping porous carbon ball absolute pressure and hydrogen storage capability relation curve at 77 K temperature.
Fig. 9 is the scanning electron microscope (a) and transmission electron microscope picture (b) of the prepared nitrogen of reference examples 1, phosphorus doping porous carbon ball.
Figure 10 is the nitrogen suction/desorption isotherm of the prepared nitrogen of reference examples 1, phosphorus doping porous carbon ball.
Figure 11 is the pore size distribution curve of the prepared nitrogen of reference examples 1, phosphorus doping porous carbon ball.
Figure 12 is the X-Ray Energy Spectrum Analysis of the prepared nitrogen of reference examples 1, phosphorus doping porous carbon ball.
Figure 13 is the prepared nitrogen of reference examples 1, phosphorus doping porous carbon ball absolute pressure and hydrogen storage capability relation curve at 77 K temperature.
Embodiment
(1), in the dry flask of 150 mL, add 100 mL acetonitriles, take 0.001mol hexachlorocyclotriphosphazene and 0.003mol 4,4 '-dihydroxy diphenylsulphone, after mixing, add wherein 0.01mol triethylamine, sealed flask reacts 2h under 40 ℃ of conditions in ultrasonic cleaner (100W, 40kHz) water-bath immediately.Reaction finishes rear centrifugal, and uses respectively ethanol and the centrifugal product of deionized water wash 3～4 times, finally, by product dry 24h under 80 ℃ of conditions, obtains poly (organophosphazenes) microsphere.
(2), take 0.6g poly (organophosphazenes) microsphere and 0.6g potassium hydroxide, be scattered in 4 mL deionized waters, stir 2h and make activator potassium hydroxide fully be immersed in poly (organophosphazenes) microsphere, then above-mentioned mixing solutions is centrifugal and under 80 ℃ of conditions dry 24h obtain poly (organophosphazenes) microsphere/potassium hydroxide mixture.
(3), the poly (organophosphazenes) microsphere/potassium hydroxide mixture obtaining is placed in to porcelain boat and delivers to carbide furnace, first logical high pure nitrogen 1h drives away the air in carbide furnace, then the temperature rise rate with 5 ℃/min is slowly warming up to 750 ℃, insulation 2h, then be naturally cooled to room temperature, then by the hydrochloric acid for black powder obtaining, be washed to neutrality, under 80 ℃ of conditions, dry 24h, obtains nitrogen, phosphorus doping porous carbon ball.
Fig. 1 has shown the stereoscan photograph of the poly (organophosphazenes) microsphere of preparing under embodiment 1 condition, and result shows that prepared poly (organophosphazenes) microsphere particle diameter is at 400-700 nm, dispersed fine.
Fig. 2 has shown the transmission electron microscope photo of the poly (organophosphazenes) microsphere of preparing under embodiment 1 condition, and result shows that prepared poly (organophosphazenes) microsphere is solid microsphere, smooth surface.
Fig. 3 has shown the nitrogen of preparing under embodiment 1 condition, the stereoscan photograph of phosphorus doping porous carbon ball, and result shows that the median size of gained porous carbon ball is at 500 nm, and monodispersity is good, good sphericity.
Fig. 4 has shown the nitrogen of preparing under embodiment 1 condition, the transmission electron microscope photo of phosphorus doping porous carbon ball, and result shows that gained carbon ball has porousness, and the good sphericity of carbon ball, smooth surface.
Fig. 5 has shown the nitrogen of preparing under embodiment 1 condition, the X-Ray Energy Spectrum Analysis of phosphorus doping porous carbon ball, and result shows that gained carbon ball is rich in nitrogen, phospha element, and nitrogen content is 2.1 wt%, and phosphorus content is 4.5 wt%.
Fig. 6 has shown the nitrogen of preparing under embodiment 1 condition, the nitrogen suction/desorption isotherm of phosphorus doping porous carbon ball, and clearly this type of thermoisopleth belongs to the mixed type of (I) type and (IV) type, shows that gained carbon ball is rich in a large amount of micropore and mesoporous.
Fig. 7 (a) and (b) shown respectively the nitrogen of preparing, micropore and the mesoporous pore size distribution curve of phosphorus doping porous carbon ball under embodiment 1 condition, result shows that the pore size distribution of gained carbon ball is in the micro-mesoporous scope of 0.6～4 nm, shows that with Fig. 6 result is consistent.In addition, specific surface area test shows that the specific surface area of gained carbon ball is 1140 m
2/ g.
Fig. 8 has shown nitrogen, phosphorus doping porous carbon ball absolute pressure and the hydrogen storage capability relation curve at 77 K temperature of preparing under embodiment 1 condition, and clearly under low temperature (77 K) condition of normal pressure, the hydrogen storage capability of (760 mmHg) gained carbon ball is 2.7 wt%.
The performance evaluation of hydrogen storage material in the present invention, adopts static capacity method to measure the adsorptive capacity of hydrogen on nitrogen, phosphorus doping porous carbon ball.Test is carried out on U.S. Mike instrument ASAP2020M, adopts low temperature (77K) normal pressure mode to carry out Chu Qing test.
Reference examples 1
Step (1) and (3) are with embodiment 1, and difference is only to omit step (2), and the poly (organophosphazenes) microsphere that soon prepared by step (1) directly carries out carburising step (3).
Fig. 9 (a) and (b) shown respectively the nitrogen of preparing, scanning electron microscope and the transmission electron microscope picture of phosphorus doping porous carbon ball under reference examples 1 condition, characterization result shows that the median size of gained carbon ball is 480 nm, sphericity is better.
Figure 10 has shown the nitrogen of preparing under reference examples 1 condition, the nitrogen suction/desorption isotherm of phosphorus doping porous carbon ball, and clearly this type of thermoisopleth belongs to typically (I) type, shows that gained carbon ball is only rich in micropore.In addition, specific surface area test shows that the specific surface area of gained carbon ball is 730 m
2/ g.
Figure 11 has shown the nitrogen of preparing under reference examples 1 condition, the pore size distribution curve of phosphorus doping porous carbon ball, and result shows that the pore size distribution of gained carbon ball, in the range of micropores of 0.5～0.8 nm, is consistent with Figure 10 conclusion.
Figure 12 has shown the nitrogen of preparing under reference examples 1 condition, the X-Ray Energy Spectrum Analysis of phosphorus doping porous carbon ball, and result shows that in gained carbon ball, nitrogen content is 2.0 wt%, and phosphorus content is 4.3 wt%.
Figure 13 has shown nitrogen, phosphorus doping porous carbon ball absolute pressure and the hydrogen storage capability relation curve at 77 K temperature of preparing under reference examples 1 condition, and clearly under low temperature (77 K) condition of normal pressure, the hydrogen storage capability of (760 mmHg) gained carbon ball is 2.3 wt%.
Compare with embodiment 1, adopt activator to after poly (organophosphazenes) microsphere processing, significantly improved specific surface area and the pore structure of porous carbon ball, improved hydrogen-storage amount.
(1), in the dry flask of 150 mL, add 50 mL acetone, take 0.001mol hexachlorocyclotriphosphazene and 0.0028mol 4,4 '-diaminodiphenylsulfone(DDS), after mixing, add wherein 0.006mol triethylamine, sealed flask reacts 10h under 20 ℃ of conditions in ultrasonic cleaner (100W, 40kHz) water-bath immediately.Reaction finishes rear centrifugal, and uses respectively ethanol and the centrifugal product of deionized water wash 3～4 times, finally, by product dry 20h under 50 ℃ of conditions, obtains poly (organophosphazenes) microsphere.
(2), take 0.6g poly (organophosphazenes) microsphere and 0.3g sodium hydroxide, be scattered in 2 mL deionized waters, stir 2h and make activator sodium hydroxide fully be immersed in poly (organophosphazenes) microsphere, then above-mentioned mixing solutions is centrifugal and under 50 ℃ of conditions dry 20h obtain poly (organophosphazenes) microsphere/sodium hydroxide mixture.
(3), the poly (organophosphazenes) microsphere/sodium hydroxide mixture obtaining is placed in to porcelain boat and delivers to carbide furnace, first logical high pure nitrogen 1h drives away the air in carbide furnace, then the temperature rise rate with 1 ℃/min is slowly warming up to 600 ℃, insulation 5h, then be naturally cooled to room temperature, then by the hydrochloric acid for black powder obtaining, be washed to neutrality, under 50 ℃ of conditions, dry 20h, obtains nitrogen, phosphorus doping porous carbon ball.
Characterization result shows: the median size of prepared porous carbon ball is 920 nm, and specific surface area is 350 m
2/ g, pore size distribution is in the micro-mesoporous scope of 0.6～5 nm, and in prepared porous carbon ball, nitrogen content is 2.8 wt%, and phosphorus content is 5.7 wt%, and the hydrogen storage capability of this material under 77K condition of normal pressure is 1.6 wt%.
Embodiment 3
(1), in the dry flask of 150 mL, add 500 mL ethanol, take 0.001mol hexachlorocyclotriphosphazene and 0.0032mol Resorcinol, after mixing, add wherein 0.012mol triethylamine, sealed flask immediately, under 80 ℃ of conditions, in ultrasonic cleaner (100W, 40kHz) water-bath, react 1h.Reaction finishes rear centrifugal, and uses respectively ethanol and the centrifugal product of deionized water wash 3～4 times, finally, by product dry 12h under 70 ℃ of conditions, obtains poly (organophosphazenes) microsphere.
(2), take 0.6g poly (organophosphazenes) microsphere and 3g calcium chloride, be scattered in 6 mL deionized waters, stir 2h and make activator calcium chloride fully be immersed in poly (organophosphazenes) microsphere, then above-mentioned mixing solutions is centrifugal and under 70 ℃ of conditions dry 12h obtain poly (organophosphazenes) microsphere/calcium chloride mixture.
(3), the poly (organophosphazenes) microsphere/calcium chloride mixture obtaining is placed in to porcelain boat and delivers to carbide furnace, first logical high pure nitrogen 1h drives away the air in carbide furnace, then the temperature rise rate with 20 ℃/min is slowly warming up to 1200 ℃, insulation 2h, then be naturally cooled to room temperature, then by the hydrochloric acid for black powder obtaining, be washed to neutrality, under 70 ℃ of conditions, dry 12h, obtains nitrogen, phosphorus doping porous carbon ball.
Characterization result shows: the median size of prepared porous carbon ball is 1100 nm, and specific surface area is 870 m
2/ g, pore size distribution is in the micro-mesoporous scope of 0.6～7 nm, and in prepared porous carbon ball, nitrogen content is 0.4 wt%, and phosphorus content is 0.9 wt%, and the hydrogen storage capability of this material under 77K condition of normal pressure is 2.4 wt%.
Embodiment 4
Difference with embodiment 1, is: with 4,4 '-dioxydiphenyl methane, replace 4,4 '-dihydroxy diphenylsulphone, normal hexane/ethanol (volume ratio 1:1) replaces acetonitrile.
Characterization result shows: the median size of prepared porous carbon ball is 780 nm, and specific surface area is 670 m
2/ g, pore size distribution is in the micro-mesoporous scope of 0.6～4 nm, and in prepared porous carbon ball, nitrogen content is 2.0 wt%, and phosphorus content is 4.1 wt%, and the hydrogen storage capability of this material under 77K condition of normal pressure is 2.1 wt%.
Embodiment 5
Difference with embodiment 2, is: by 4,4 '-diaminodiphenylmethane, replace 4,4′ diaminodiphenyl sulfone, with propyl alcohol/toluene (volume ratio 1:1), replace acetone.
Characterization result shows: the median size of prepared porous carbon ball is 1220 nm, and specific surface area is 330 m
2/ g, pore size distribution is in the micro-mesoporous scope of 0.6～5 nm, and in prepared porous carbon ball, nitrogen content is 2.9 wt%, and phosphorus content is 5.9 wt%, and the hydrogen storage capability of this material under 77K condition of normal pressure is 1.4 wt%.
Embodiment 6
Difference with embodiment 2, is: with 4，4′-diaminodipohenyl ether, replace 4,4′ diaminodiphenyl sulfone, with tetrahydrofuran (THF)/ethanol (volume ratio 9:1), replace acetone.
Characterization result shows: the median size of prepared porous carbon ball is 1820 nm, and specific surface area is 280 m
2/ g, pore size distribution is in the micro-mesoporous scope of 0.6～5 nm, and in prepared porous carbon ball, nitrogen content is 3.2 wt%, and phosphorus content is 6.3 wt%, and the hydrogen storage capability of this material under 77K condition of normal pressure is 1.1 wt%.
Embodiment 7
Difference with embodiment 3, is: with Ursol D, replace Resorcinol, zinc chloride replaces calcium chloride.
Characterization result shows: the median size of prepared porous carbon ball is 1250 nm, and specific surface area is 840 m
2/ g, pore size distribution is in the micro-mesoporous scope of 0.6～7 nm, and in prepared porous carbon ball, nitrogen content is 0.7 wt%, and phosphorus content is 1.0 wt%, and the hydrogen storage capability of this material under 77K condition of normal pressure is 2.3 wt%.
Claims (1)
1. a nitrogen, the preparation method of phosphorus doping porous carbon ball, it is characterized in that: take water as solvent, by poly (organophosphazenes) microsphere and activator with (0.2～2): 1 mass ratio mixes, keeping the concentration of poly (organophosphazenes) microsphere is 10～30 wt%, fully stir, then centrifugation obtains poly (organophosphazenes) microsphere and activating mixtures, finally, poly (organophosphazenes) microsphere and activating mixtures are placed in to carbide furnace, first logical rare gas element is driven away the air in carbide furnace, then the temperature rise rate with 1～20 ℃/min is warming up to 600～1200 ℃, after insulation 2～5h, be naturally cooled to room temperature, then by the black powder hydrochloric acid obtaining, be washed to neutrality, dry, obtain nitrogen, phosphorus doping porous carbon ball, wherein said activator is potassium hydroxide, sodium hydroxide, calcium chloride or zinc chloride, described poly (organophosphazenes) microsphere is prepared by the following method: under room temperature condition, hexachlorocyclotriphosphazene and comonomer are distributed in organic solvent, then add acid binding agent, in 20～80 ℃ of ultrasonic reaction 1～10 h, reaction finishes rear centrifugation, washing, the dry poly (organophosphazenes) microsphere that obtains, wherein with molar ratio computing, hexachlorocyclotriphosphazene: comonomer: acid binding agent=1:(2.8～3.2): (6～12), the addition of organic solvent guarantees that the concentration of hexachlorocyclotriphosphazene is 0.002～0.02 mol/L, comonomer is 4, 4 '-dioxydiphenyl methane, 4, 4 '-diaminodiphenylsulfone(DDS), 4, 4 '-dihydroxy diphenylsulphone, 4, 4 '-diaminodiphenylmethane, 4, 4 '-diaminodiphenyl oxide, Ursol D or Resorcinol, acid binding agent is triethylamine, organic solvent is ethanol, propyl alcohol, acetonitrile, acetone, tetrahydrofuran (THF), a kind of or its combination in toluene or normal hexane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210028566.6A CN102583312B (en) | 2012-02-09 | 2012-02-09 | Method for preparing porous carbon spheres doped with nitrogen and phosphorus and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210028566.6A CN102583312B (en) | 2012-02-09 | 2012-02-09 | Method for preparing porous carbon spheres doped with nitrogen and phosphorus and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102583312A CN102583312A (en) | 2012-07-18 |
| CN102583312B true CN102583312B (en) | 2014-01-29 |
Family
ID=46472677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210028566.6A Expired - Fee Related CN102583312B (en) | 2012-02-09 | 2012-02-09 | Method for preparing porous carbon spheres doped with nitrogen and phosphorus and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102583312B (en) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911142B (en) * | 2012-10-24 | 2015-04-22 | 复旦大学 | Method for preparing 5-hydroxymethylfurfural |
| CN103086878B (en) * | 2013-01-14 | 2015-03-25 | 浙江大学 | Preparation method of cyclohexyl compound by aromatic compound catalytic hydrogenation |
| CN103183341B (en) * | 2013-04-02 | 2015-04-29 | 中国矿业大学 | Controllable synthesis method of N-doped graphitized carbon ball with hollow structures |
| CN103714979B (en) * | 2013-12-20 | 2016-05-11 | 北京化工大学 | The preparation method of phosphorus doping porous carbon materials for a kind of ultracapacitor |
| CN104003368B (en) * | 2014-05-06 | 2016-05-11 | 北京理工大学 | A kind of porous phosphorus-nitrogen co-doped material with carbon element and preparation method thereof |
| CN104003367B (en) * | 2014-05-06 | 2016-02-24 | 北京理工大学 | A kind of phosphorus-nitrogen exotic atom doped porous carbon material and synthetic method thereof |
| CN104497316A (en) * | 2014-12-10 | 2015-04-08 | 上海交通大学 | High-nitrogen-content polymeric microsphere and preparation method thereof |
| US20180093893A1 (en) * | 2015-04-02 | 2018-04-05 | Case Western Reserve University | Metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions |
| CN106554004B (en) * | 2015-09-23 | 2018-10-23 | 国家纳米科学中心 | A kind of porous carbon materials and its preparation method and application prepared based on aromatic compound monomer |
| CN105253871B (en) * | 2015-09-25 | 2017-09-15 | 深圳博磊达新能源科技有限公司 | Ultracapacitor nitrogenous carbon material and preparation method thereof, electrode material for super capacitor |
| CN105152160A (en) * | 2015-10-21 | 2015-12-16 | 哈尔滨工业大学 | Preparation method of nitrogen-doped carbon microspheres |
| CN105621390A (en) * | 2015-12-31 | 2016-06-01 | 上海交通大学 | Preparation method of heteroatom-doped carbon hollow microspheres |
| CN105523541B (en) * | 2016-01-29 | 2017-07-18 | 上海交通大学 | Porous carbon tiny balloon of Heteroatom doping and preparation method thereof |
| CN106040121A (en) * | 2016-05-25 | 2016-10-26 | 中国科学院大学 | Method for synthesizing skeleton microsphere material |
| CN106000438A (en) * | 2016-06-03 | 2016-10-12 | 兰州交通大学 | Preparation method and application of nitrogen and phosphorus co-doped porous carbon materials |
| CN106744794B (en) * | 2016-12-07 | 2018-11-30 | 温州大学 | A kind of sheet nitrogen-phosphor codoping porous carbon materials and preparation method thereof and purposes |
| CN106744803B (en) * | 2017-01-23 | 2019-03-08 | 深圳大学 | A kind of method preparing porous carbon and porous carbon |
| CN106882789A (en) * | 2017-04-25 | 2017-06-23 | 上海应用技术大学 | A kind of nitrogen, phosphor codoping porous carbon materials and preparation method thereof |
| CN107126974B (en) * | 2017-06-07 | 2019-11-08 | 北京化工大学常州先进材料研究院 | ZIF-67 modifies Fe3O4The preparation of@PZS core-shell particles and its application of ORR catalyst |
| CN107673323A (en) * | 2017-11-21 | 2018-02-09 | 中原工学院 | A kind of method that self-template prepares hollow carbon balls |
| CN108190855B (en) * | 2018-01-23 | 2021-08-10 | 上海大学 | Doped three-dimensional porous carbon for removing ions in water and preparation method thereof |
| CN109786118B (en) * | 2019-01-05 | 2021-03-26 | 淄博职业学院 | Nitrogen-oxygen doped carbon microsphere with controllable particle size prepared in large scale and preparation method and application thereof |
| CN112467120A (en) * | 2020-12-01 | 2021-03-09 | 桐乡市华璟科技有限公司 | Preparation method of nitrogen-phosphorus-doped porous carbon-coated manganese dioxide cathode material |
| CN112786900B (en) * | 2021-02-03 | 2022-01-28 | 江西理工大学 | Zinc-air cell with embedded Fe2Nitrogen-rich phosphorus carbon spheres of P nanocrystalline and preparation method thereof |
| CN113135569B (en) * | 2021-05-31 | 2022-06-07 | 东北林业大学 | Biomass-derived grade porous carbon electrode material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101372325A (en) * | 2008-04-30 | 2009-02-25 | 中国科学院上海硅酸盐研究所 | Carbon nitride polyporous material and use thereof for hydrogen storage |
| CN101811692A (en) * | 2010-05-05 | 2010-08-25 | 吉林大学 | New method for comprehensive utilization of straw resource |
-
2012
- 2012-02-09 CN CN201210028566.6A patent/CN102583312B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101372325A (en) * | 2008-04-30 | 2009-02-25 | 中国科学院上海硅酸盐研究所 | Carbon nitride polyporous material and use thereof for hydrogen storage |
| CN101811692A (en) * | 2010-05-05 | 2010-08-25 | 吉林大学 | New method for comprehensive utilization of straw resource |
Non-Patent Citations (2)
| Title |
|---|
| 付建伟等.高热稳定性聚膦腈亚微米球的室温快速合成.《应用化学》.2011,第28卷(第8期),第864-868页. |
| 高热稳定性聚膦腈亚微米球的室温快速合成;付建伟等;《应用化学》;20110831;第28卷(第8期);第864-868页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102583312A (en) | 2012-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102583312B (en) | Method for preparing porous carbon spheres doped with nitrogen and phosphorus and application | |
| Huang et al. | Activated carbons prepared by the KOH activation of a hydrochar from garlic peel and their CO2 adsorption performance | |
| Rao et al. | Nitrogen enriched porous carbons from d-glucose with excellent CO2 capture performance | |
| Singh et al. | A facile synthesis of activated porous carbon spheres from d-glucose using a non-corrosive activating agent for efficient carbon dioxide capture | |
| CN106629655B (en) | A kind of preparation method and application of biomass-based N doping porous carbon | |
| Xiao et al. | Phytic acid-induced self-assembled chitosan gel-derived N, P–co-doped porous carbon for high-performance CO2 capture and supercapacitor | |
| CN101434389B (en) | Preparation of super active carbon | |
| CN108380175B (en) | A kind of carbonic acid gas lanthanum-halloysite composite material and its preparation method and application | |
| CN105523541A (en) | Heteroatom doped hollow porous carbon microspheres and preparation method thereof | |
| CN108773844A (en) | A kind of method that micro-calcium addition catalytic activation prepares coal base porous carbon materials | |
| CN101961644B (en) | Chloride-carbonaceous skeleton composite adsorbent and preparation method thereof | |
| CN104130004B (en) | The preparation method of the block porous aluminum oxide nano pottery of high strength | |
| CN109835900A (en) | A kind of preparation method of the coal base porous carbon based on potassium carbonate cyclic activation and the preparation method of biomass-based porous carbon | |
| CN105854801A (en) | Nitrogen-doped porous carbon material and preparation method and application thereof | |
| Cheng et al. | Nitrogen-doped microporous carbon material decorated with metal nanoparticles derived from solid Zn/Co zeolitic imidazolate framework with high selectivity for CO2 separation | |
| Chen et al. | Synthesis, characterization, and selective CO2 capture performance of a new type of activated carbon-geopolymer composite adsorbent | |
| CN107487766A (en) | A kind of three-dimensional porous carbon material of Heteroatom doping and preparation method thereof | |
| CN111874889A (en) | Cellular three-dimensional network structure hierarchical pore carbon material and preparation method thereof | |
| Bai et al. | Sulfur-Doped porous carbon Adsorbent: A promising solution for effective and selective CO2 capture | |
| CN104857980A (en) | Preparation method of hexagonal boron nitride ceramic material stable silver carbonate semiconductor | |
| CN106076260A (en) | A kind of room temperature fast preparation method of metallic organic framework oxidized graphite composite material | |
| Cho et al. | Surface functionalization and CO2 uptake on carbon molecular sieves: experimental observation and theoretical study | |
| Bian et al. | Optimized mesopores enable enhanced capacitance of electrochemical capacitors using ultrahigh surface area carbon derived from waste feathers | |
| CN109292774B (en) | Preparation method and application of pomegranate-shaped porous carbon microsphere material | |
| Wang et al. | Facile synthesis of MOF-5-derived porous carbon with adjustable pore size for CO2 capture |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140129 Termination date: 20150209 |
|
| EXPY | Termination of patent right or utility model |