CN102583312A - 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
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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 materials chemistry and technical field of new energies, be specifically related to the preparation method and the application of a kind of nitrogen, phosphorus doping porous carbon ball.
Background technology
Hydrogen be a kind of wide material sources, renewable, the cleaning the energy, also be a kind of important industrial raw material, become fuel cell, the optimal fuel of hydrogen internal combustion engine.Because hydrogen density is little, blast easily, 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 the Hydrogen Energy storage problem.In recent years, porous carbon materials is because its low density, high-specific surface area, good chemicalstability 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, can realize that the big quality of small volume stores, and therefore the specific surface area of carbon material is high more in theory, and corresponding hydrogen-storage amount also should be big more.Research shows, for the ideal porous carbon materials, in order to obtain bigger hydrogen-storage amount; One side needs higher specific surface area so that more hydrogen adsorption site to be provided, and also needs the micropore pore volume of larger proportion to improve ratio [Gogotsi Y., the et al. in active adsorption site in addition; Adv. Funct. Mater.; 2006,16,2288].Template is a kind of preparation porous carbon material efficient ways; This 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 is under certain condition also removed template and can be obtained porous carbon material, as long as make rational template, just can control the pore size and the shape of carbon material.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, hydrogen storage ability reaches 2.6wt% [Yang, Z.X., et al., J. Am. Chem. Soc. 2007,129,1673] under the low-temperature atmosphere-pressure.But this method also has many restrictions, often need in aggressive solvent, carry out like the removal of template, and technology is loaded down with trivial details, and harmful to environment.In addition, for the specific surface area that improves porous carbon materials, improve its pore structure, can carry out follow-up activation treatment to carbon material usually,, use thereby help its function like carbonic acid gas high-temperature activation, alkali high-temperature activation or water vapour high-temperature activation etc.Recently, people's such as Xia research work shows, CMK-3 is carried out the porous carbon materials [Xia, K.S., et al., Carbon, 2007,45,1989] that the carbonic acid gas high-temperature activation can obtain to have higher low temperature hydrogen storage capability.
In the recent period, discover that carbon skeleton to porous carbon materials carries out can being of value to the improvement of its hydrogen storage property after some elements (nitrogen, phosphorus, boron etc.) mix, this by room temperature storage hydrogen theoretical and Preliminary experiment results verify.Yet, porous carbon materials is carried out effective elements mixes, and still can keep its high-specific surface area and specific pore structure and be not easy.Usually introduce assorted element way be that carbon material is carried out pyrochemistry modification such as aminating reaction; But this means have just realized introducing assorted element at carbon material surface; Can not change the elementary composition of carbon skeleton inside; And can reduce the pore volume and the specific surface area of carbon material usually, concentrated nitric acid is handled and is also had similar problem.In addition, utilize the precursor that contains assorted element to make carbon source, also can realize the preparation of doped carbon material.Recently; People such as Gao Qiuming are presoma with the quadrol; Mesoporous silicon oxide is that template has prepared a kind of order mesoporous nitrogen carbon material, more this order mesoporous nitrogen carbon material is carried out the carbonic acid gas pyroprocessing, has obtained to have the doped meso-porous carbon material of nitrogen of high specific surface area and higher pore volume; 80 normal atmosphere of normal temperature are the hydrogen [Gao Qiuming, Jiang Jinhua CN 101372325 B] of ability reversible adsorption 2.21 wt% down.In addition; Gao Qiuming etc. are precursor with sucrose, furfuryl alcohol, polyacrylonitrile etc. also; With the micro porous molecular sieve is template; Adopt liquid impregnation and electroless plating bonded two step method to synthesize nitrogen-doped porous carbon material, said material can be used 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 problems such as bigger pollution simultaneously to environment.
Summary of the invention
The object of the present invention is to provide the preparation method and the application of a kind of nitrogen, phosphorus doping porous carbon ball.
For realizing above-mentioned purpose, the technical scheme that the present invention takes is following:
The preparation method of a kind of nitrogen, phosphorus doping porous carbon ball: with water is solvent; With poly (organophosphazenes) microsphere and acvator with (0.2～2): 1 mass ratio mixes; Keeping the concentration of poly (organophosphazenes) microsphere is 10～30 wt%, fully stirs, and spinning gets poly (organophosphazenes) microsphere and activating mixtures then; At last, poly (organophosphazenes) microsphere and activating mixtures are carried out carbonization and promptly obtain nitrogen, phosphorus doping porous carbon ball; Wherein said acvator is Pottasium Hydroxide, sodium hydroxide, calcium chloride or zinc chloride.
Among the present invention, said poly (organophosphazenes) microsphere can be by prior art for preparing, and the present invention is preferably by following method preparation: under the room temperature condition hexachlorocyclotriphosphazene and comonomer are distributed in the organic solvent, add acid binding agent again, in 20～80 ℃ of ultrasonic reaction 1～10 h; Spinning after reaction finishes, washing, drying obtain poly (organophosphazenes) microsphere, wherein with molar ratio computing, and 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 '-MDA, 4, Ursol D or Resorcinol; Acid binding agent is a triethylamine, and organic solvent is a kind of or its combination in ethanol, propyl alcohol, acetonitrile, acetone, THF, toluene or the normal hexane.
Further; The process of said carbonization is: poly (organophosphazenes) microsphere and activating mixtures are placed carbide furnace, and earlier logical rare gas element is driven away the air in the carbide furnace, is warming up to 600～1200 ℃ then; Naturally be cooled to room temperature behind insulation 2～5h; Then that the black powder that obtains is extremely neutral with hydrochloric acid, washing, drying obtains nitrogen, phosphorus doping porous carbon ball.
Preferably, during intensification, preferred 1～20 ℃/min of temperature rise rate.
Preferably, said rare gas element is high pure nitrogen or high-purity argon gas.
The nitrogen of the inventive method preparation, phosphorus doping porous carbon ball are as the application of hydrogen storage material.
The drying that relates among the present invention, all preferred 50～80 ℃ of its temperature, all preferred 12～24h of time.
Compared with prior art, beneficial effect of the present invention is embodied in:
(1) carbon matrix precursor of the present invention's employing is a poly (organophosphazenes) microsphere, and it can directly synthesize at ambient temperature, and technology is simple, productive rate is high.Poly phosphazene itself is rich in a large amount of non-carbon (comprising nitrogen, phosphorus), and in the high temperature cabonization process, these non-carbons have directly caused carbon material to have open pore passage structure with shifting out of gas form, help the absorption of hydrogen molecule.Simultaneously, adopt acvator that poly phosphazene is handled, significantly improve the specific surface area and the pore structure of porous carbon ball, help the raising of hydrogen-storage amount.
(2) the inventive method provides a path for preparing nitrogen, phosphorus doping porous carbon materials.With respect to methods such as high temperature ammonifications only for the porous carbon materials surface doping nitrogen essence; The inventive method not only realized in carbon skeleton, mixing nitrogen, the dual element of phosphorus; And realized the controllable number of alloying element; As through control carbonization technique condition, can realize that the controlled of nitrogen in the poly phosphazene, phosphoric shift out, and then realize that the content of nitrogen, phosphoric in the porous carbon ball is controlled.
(3) with make up porous carbon materials by hard template such as silicon-dioxide, zeolites and compare, preparation technology of the present invention is simple, contaminate environment is little, is easy to batch preparations.Simultaneously, nitrogen, phosphorus doping porous carbon ball good sphericity, specific surface area that the present invention obtains are big, and pore size distribution has excellent hydrogen storage property within little mesoporous scope.
Description of drawings
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 prepared nitrogen of embodiment 1, the stereoscan photograph of phosphorus doping porous carbon ball.
Fig. 4 is the prepared nitrogen of embodiment 1, the transmission electron microscope photo of phosphorus doping porous carbon ball.
Fig. 5 is the prepared nitrogen of embodiment 1, the X-ray energy spectrum analysis of phosphorus doping porous carbon ball.
Fig. 6 is the prepared nitrogen of embodiment 1, the nitrogen suction/desorption isotherm of phosphorus doping porous carbon ball.
Fig. 7 is the prepared nitrogen of embodiment 1, the pore size distribution curve of phosphorus doping porous carbon ball.
Fig. 8 is prepared nitrogen, phosphorus doping porous carbon ball absolute pressure and hydrogen storage capability relation curve under 77 K temperature of embodiment 1.
Fig. 9 is the ESEM (a) and the transmission electron microscope picture (b) of the prepared nitrogen of reference examples 1, phosphorus doping porous carbon ball.
Figure 10 is the prepared nitrogen of reference examples 1, the nitrogen suction/desorption isotherm of phosphorus doping porous carbon ball.
Figure 11 is the prepared nitrogen of reference examples 1, the pore size distribution curve of phosphorus doping porous carbon ball.
Figure 12 is the prepared nitrogen of reference examples 1, the X-ray energy spectrum analysis of phosphorus doping porous carbon ball.
Figure 13 is prepared nitrogen, phosphorus doping porous carbon ball absolute pressure and hydrogen storage capability relation curve under 77 K temperature of reference examples 1.
Embodiment
(1), in 150 mL exsiccant flask; Add 100 mL acetonitriles, take by weighing 0.001mol hexachlorocyclotriphosphazene and 0.003mol 4,4 '-dihydroxy diphenylsulphone; Mix the back to wherein adding the 0.01mol triethylamine; Sealed flask immediately, (100W 40kHz) reacts 2h in the water-bath at ultrasonic cleaner under 40 ℃ of conditions.It is centrifugal that reaction finishes the back, and use ethanol and the centrifugal product of deionized water wash respectively 3～4 times, with product dry 24h under 80 ℃ of conditions, obtains poly (organophosphazenes) microsphere at last.
(2), take by weighing 0.6g poly (organophosphazenes) microsphere and 0.6g Pottasium Hydroxide; Be scattered in the 4 mL deionized waters; Stir 2h and make acvator Pottasium Hydroxide fully be immersed in poly (organophosphazenes) microsphere, then with above-mentioned mixing solutions centrifugal and under 80 ℃ of conditions dry 24h get poly (organophosphazenes) microsphere/Pottasium Hydroxide mixture.
(3), the poly (organophosphazenes) microsphere that obtains/Pottasium Hydroxide mixture is placed porcelain boat and delivers to carbide furnace; Earlier logical high pure nitrogen 1h drives away the air in the carbide furnace, and the temperature rise rate with 5 ℃/min slowly is warming up to 750 ℃ then, insulation 2h; Naturally be cooled to room temperature then; Then that the black powder that obtains is extremely neutral with hydrochloric acid, washing, dry 24h under 80 ℃ of conditions obtains nitrogen, phosphorus doping porous carbon ball.
Fig. 1 has shown the stereoscan photograph of the poly (organophosphazenes) microsphere that under embodiment 1 condition, prepares, and the result shows prepared poly (organophosphazenes) microsphere particle diameter at 400-700 nm, and is dispersed fine.
Fig. 2 has shown the transmission electron microscope photo of the poly (organophosphazenes) microsphere that under embodiment 1 condition, prepares, and the result shows that prepared poly (organophosphazenes) microsphere is a solid microsphere, smooth surface.
Fig. 3 has shown the nitrogen that under embodiment 1 condition, prepares, the stereoscan photograph of phosphorus doping porous carbon ball, and the result shows the median size of gained porous carbon ball at 500 nm, and monodispersity is good, good sphericity.
Fig. 4 has shown the nitrogen that under embodiment 1 condition, prepares, the transmission electron microscope photo of phosphorus doping porous carbon ball, and the result shows that gained carbon ball has porousness, and the good sphericity of carbon ball, smooth surface.
Fig. 5 has shown the nitrogen that under embodiment 1 condition, prepares, the X-ray energy spectrum analysis of phosphorus doping porous carbon ball, and the 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 that under embodiment 1 condition, prepares, the nitrogen suction/desorption isotherm of phosphorus doping porous carbon ball, and clearly this type of thermo-isopleth 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 the nitrogen that under embodiment 1 condition, prepares, the micropore and the mesoporous pore size distribution curve of phosphorus doping porous carbon ball respectively, the result shows the little mesoporous scope of the pore size distribution of gained carbon ball at 0.6～4 nm, is consistent with Fig. 6 display result.In addition, the specific surface area of specific surface area test shows gained carbon ball is 1140 m
2/ g.
Fig. 8 has shown that at the nitrogen for preparing under embodiment 1 condition, phosphorus doping porous carbon ball absolute pressure and hydrogen storage capability relation curve under 77 K temperature, clearly the hydrogen storage capability of (760 mmHg) gained carbon ball is 2.7 wt% under low temperature (77 K) condition of normal pressure.
The performance evaluation of hydrogen storage material among the present invention adopts the 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 the Chu Qing test.
Reference examples 1
Step (1) and (3) are with embodiment 1, and difference only is to omit step (2), and the poly (organophosphazenes) microsphere that is about to step (1) preparation directly carries out carburising step (3).
Fig. 9 (a) and (b) shown the nitrogen that under reference examples 1 condition, prepares, the ESEM and the transmission electron microscope picture of phosphorus doping porous carbon ball respectively, characterization result shows that the median size of gained carbon ball is 480 nm, sphericity is better.
Figure 10 has shown the nitrogen that under reference examples 1 condition, prepares, the nitrogen suction/desorption isotherm of phosphorus doping porous carbon ball, and clearly this type of thermo-isopleth belongs to typically (I) type, shows that gained carbon ball only is rich in micropore.In addition, the specific surface area of specific surface area test shows gained carbon ball is 730 m
2/ g.
Figure 11 has shown the nitrogen that under reference examples 1 condition, prepares, the pore size distribution curve of phosphorus doping porous carbon ball, and the result shows the range of micropores of the pore size distribution of gained carbon ball at 0.5～0.8 nm, is consistent with Figure 10 conclusion.
Figure 12 has shown the nitrogen that under reference examples 1 condition, prepares, the X-ray energy spectrum analysis of phosphorus doping porous carbon ball, and the result shows that nitrogen content is 2.0 wt% in the gained carbon ball, and phosphorus content is 4.3 wt%.
Figure 13 has shown that at the nitrogen for preparing under reference examples 1 condition, phosphorus doping porous carbon ball absolute pressure and hydrogen storage capability relation curve under 77 K temperature, clearly the hydrogen storage capability of (760 mmHg) gained carbon ball is 2.3 wt% under low temperature (77 K) condition of normal pressure.
Compare with embodiment 1, adopt acvator, significantly improved the specific surface area and the pore structure of porous carbon ball, improved hydrogen-storage amount after the poly (organophosphazenes) microsphere processing.
Embodiment 2
(1), in 150 mL exsiccant flask; Add 50 mL acetone, take by weighing 0.001mol hexachlorocyclotriphosphazene and 0.0028mol 4,4; Mix the back to wherein adding the 0.006mol triethylamine; Sealed flask immediately, (100W 40kHz) reacts 10h in the water-bath at ultrasonic cleaner under 20 ℃ of conditions.It is centrifugal that reaction finishes the back, and use ethanol and the centrifugal product of deionized water wash respectively 3～4 times, with product dry 20h under 50 ℃ of conditions, obtains poly (organophosphazenes) microsphere at last.
(2), take by weighing 0.6g poly (organophosphazenes) microsphere and 0.3g sodium hydroxide; Be scattered in the 2 mL deionized waters; Stir 2h and make acvator sodium hydroxide fully be immersed in poly (organophosphazenes) microsphere, then with above-mentioned mixing solutions centrifugal and under 50 ℃ of conditions dry 20h get poly (organophosphazenes) microsphere/sodium hydroxide mixture.
(3), the poly (organophosphazenes) microsphere that obtains/sodium hydroxide mixture is placed porcelain boat and delivers to carbide furnace; Earlier logical high pure nitrogen 1h drives away the air in the carbide furnace, and the temperature rise rate with 1 ℃/min slowly is warming up to 600 ℃ then, insulation 5h; Naturally be cooled to room temperature then; Then that the black powder that obtains is extremely neutral with hydrochloric acid, washing, dry 20h under 50 ℃ of conditions 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 are in the little mesoporous scope of 0.6～5 nm, and nitrogen content is 2.8 wt% in the prepared porous carbon ball, and phosphorus content is 5.7 wt%, and the hydrogen storage capability of this material under the 77K condition of normal pressure is 1.6 wt%.
Embodiment 3
(1), in 150 mL exsiccant flask; Add 500 mL ethanol; Take by weighing 0.001mol hexachlorocyclotriphosphazene and 0.0032mol Resorcinol, mix the back to wherein adding 0.012mol triethylamine, sealed flask immediately; (100W 40kHz) reacts 1h in the water-bath at ultrasonic cleaner under 80 ℃ of conditions.It is centrifugal that reaction finishes the back, and use ethanol and the centrifugal product of deionized water wash respectively 3～4 times, with product dry 12h under 70 ℃ of conditions, obtains poly (organophosphazenes) microsphere at last.
(2), take by weighing 0.6g poly (organophosphazenes) microsphere and 3g calcium chloride; Be scattered in the 6 mL deionized waters; Stir 2h and make acvator calcium chloride fully be immersed in poly (organophosphazenes) microsphere, then with above-mentioned mixing solutions centrifugal and under 70 ℃ of conditions dry 12h get poly (organophosphazenes) microsphere/calcium chloride mixture.
(3), the poly (organophosphazenes) microsphere/calcium chloride mixture that obtains is placed porcelain boat and delivers to carbide furnace; Earlier logical high pure nitrogen 1h drives away the air in the carbide furnace, and the temperature rise rate with 20 ℃/min slowly is warming up to 1200 ℃ then, insulation 2h; Naturally be cooled to room temperature then; Then that the black powder that obtains is extremely neutral with hydrochloric acid, washing, dry 12h under 70 ℃ of conditions 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 are in the little mesoporous scope of 0.6～7 nm, and nitrogen content is 0.4 wt% in the prepared porous carbon ball, and phosphorus content is 0.9 wt%, and the hydrogen storage capability of this material under the 77K condition of normal pressure is 2.4 wt%.
Embodiment 4
Difference with embodiment 1 is: with 4,4 '-dioxydiphenyl methane replaces 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 are in the little mesoporous scope of 0.6～4 nm, and nitrogen content is 2.0 wt% in the prepared porous carbon ball, and phosphorus content is 4.1 wt%, and the hydrogen storage capability of this material under the 77K condition of normal pressure is 2.1 wt%.
Embodiment 5
Difference with embodiment 2 is: with 4,4 '-MDA replaces 4,4, with propyl alcohol/toluene (volume ratio 1:1) replacement 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 are in the little mesoporous scope of 0.6～5 nm, and nitrogen content is 2.9 wt% in the prepared porous carbon ball, and phosphorus content is 5.9 wt%, and the hydrogen storage capability of this material under the 77K condition of normal pressure is 1.4 wt%.
Embodiment 6
Difference with embodiment 2 is: replace 4,4 with 4, replace acetone with THF/ethanol (volume ratio 9:1).
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 are in the little mesoporous scope of 0.6～5 nm, and nitrogen content is 3.2 wt% in the prepared porous carbon ball, and phosphorus content is 6.3 wt%, and the hydrogen storage capability of this material under the 77K condition of normal pressure is 1.1 wt%.
Embodiment 7
Difference with embodiment 3 is: replace Resorcinol with Ursol D, 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 are in the little mesoporous scope of 0.6～7 nm, and nitrogen content is 0.7 wt% in the prepared porous carbon ball, and phosphorus content is 1.0 wt%, and the hydrogen storage capability of this material under the 77K condition of normal pressure is 2.3 wt%.
Claims (5)
1. the preparation method of a nitrogen, phosphorus doping porous carbon ball; It is characterized in that: be solvent with water, with poly (organophosphazenes) microsphere and acvator with (0.2～2): 1 mass ratio mixes, and keeping the concentration of poly (organophosphazenes) microsphere is 10～30 wt%; Fully stir; Spinning gets poly (organophosphazenes) microsphere and activating mixtures then, and is last, poly (organophosphazenes) microsphere and activating mixtures carried out carbonization promptly obtain nitrogen, phosphorus doping porous carbon ball; Wherein said acvator is Pottasium Hydroxide, sodium hydroxide, calcium chloride or zinc chloride.
2. preparation method as claimed in claim 1 is characterized in that said poly (organophosphazenes) microsphere prepares by following method: under the room temperature condition hexachlorocyclotriphosphazene and comonomer are distributed in the organic solvent, add acid binding agent again, in 20～80 ℃ of ultrasonic reaction 1～10 h; Spinning after reaction finishes, washing, drying obtain poly (organophosphazenes) microsphere, wherein with molar ratio computing, and 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 '-MDA, 4, Ursol D or Resorcinol; Acid binding agent is a triethylamine, and organic solvent is a kind of or its combination in ethanol, propyl alcohol, acetonitrile, acetone, THF, toluene or the normal hexane.
3. preparation method as claimed in claim 1; The process that it is characterized in that said carbonization is: poly (organophosphazenes) microsphere and activating mixtures are placed carbide furnace, and earlier logical rare gas element is driven away the air in the carbide furnace, is warming up to 600～1200 ℃ then; Naturally be cooled to room temperature behind insulation 2～5h; Then that the black powder that obtains is extremely neutral with hydrochloric acid, washing, drying obtains nitrogen, phosphorus doping porous carbon ball.
4. preparation method as claimed in claim 3 is characterized in that: during intensification, temperature rise rate is 1～20 ℃/min.
5. utilize as nitrogen that any described preparation method of claim 1 ~ 4 prepares, phosphorus doping porous carbon ball as the application of hydrogen storage material.
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| CN109786118A (en) * | 2019-01-05 | 2019-05-21 | 淄博职业学院 | A kind of nitrogen oxygen doping carbosphere of large scale preparation size tunable and its preparation method and application |
| 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 |
| CN112786900A (en) * | 2021-02-03 | 2021-05-11 | 江西理工大学 | Zinc-air cell with embedded Fe2Nitrogen-rich phosphorus carbon spheres of P nanocrystalline and preparation method thereof |
| CN113135569A (en) * | 2021-05-31 | 2021-07-20 | 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 (1)
| 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》 * |
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