CN104192824A - Preparation method of nitrogen-doped ordered mesoporous carbon material - Google Patents
Preparation method of nitrogen-doped ordered mesoporous carbon material Download PDFInfo
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Abstract
The invention discloses a preparation method of a nitrogen-doped ordered mesoporous carbon material. The preparation method comprises the following steps: performing polymerization reaction on 2,4,6-trichloro-1,3,5-triazine and a polyamine compound in an organic solvent, adding an acid-binding agent to neutralize acid generated during polymerization reaction, so as to promote the polymerization reaction; filtering and drying to obtain a carbon-nitrogen material precursor, and performing high-temperature carbonization under inert atmosphere; cooling to room temperature, removing a template agent by utilizing hydrofluoric acid, to obtain the nitrogen-doped ordered mesoporous carbon material. The polymerization process of the precursor is simple and easily controlled and safe, the nitrogen-doped ordered mesoporous carbon material is good in the integration with a template, the porous structure is controllable, the cost is low, and the equipment is simple and convenient in requirement. The method is high in repeatability, and high in reaction yield; the product is good in uniformity, high in nitrogen content, and regular in structure; the whole process is simple and convenient. The prepared nitrogen-doped ordered mesoporous carbon material has porous ducts with ordered heights, large in specific surface area, the apertures are uniformly distributed, and the nitrogen-doped ordered mesoporous carbon material is high in stability, and has wide application prospects in the field of catalytic and electrode materials, and the like.
Description
Technical field
The present invention relates to ordered mesoporous carbon material preparing technical field, be specifically related to a kind of preparation method of nitrogen doping ordered mesoporous carbon material.
Background technology
In recent years, increasing about the report of carbon-nitrogen material, not only, because the principal element of composition carbon-nitrogen material is carbon and nitrogen and a small amount of hydrogen, environmentally safe, met Green Chemistry requirement; And its Heat stability is good, in reaction, can show outstanding catalytic performance.Ordered mesoporous carbon material is due to its regular duct, and larger specific surface area, the aperture of homogeneous and high stability, in many new and high technologies, as the fields such as fuel cell, support of the catalyst, sensor, membrane sepn have important using value.Wherein, the doped meso-porous carbon material of nitrogen mainly refers to the New Type of Mesoporous carbon material that a class contains nitrogen component, and its purposes is very extensive, is mainly used in hydrogen storage material, electrode materials, catalyzer etc.
The at present doping of nitrogen mainly contains two kinds of modes, and the first is that the carbon material preparing is placed in to nitrogen containing atmosphere pyroprocessing, at carbon material surface grafting nitrogen-containing functional group, but only can change the surface properties of carbon material, cannot change from inside the overall performance of material.Another kind method is in-situ doped, in the building-up process of carbon material, adds nitrogenous precursor, directly introduces nitrogen element.The latter can make N be evenly distributed in whole material, obtains controlled chemical property.Wherein, the doped meso-porous carbon material of nitrogen prepare aspect (Adv.Funct.Mater., 2005, the 17:1648-1652.) reported first such as Vinu in 2005 preparation method of nitrogen doping ordered mesoporous carbon material.They are taking SBA-15 as template, and after tetracol phenixin and quadrol polymerization, making nitrogen content is 16%, and pore size distribution is at the nitrogen doping ordered mesoporous carbon material of 9nm left and right.(the Angew.Chem.Int.Ed. such as Jin in 2009,2009,121 (42): 8024-8027.) reported that again one section using IBN-4 as template, after tetracol phenixin and quadrol polymerization, obtained C/N than the nitrogen doping ordered mesoporous carbon material that is 2.3 high nitrogen content.Mokaya (Chem.Mater., 2005,17 (6): 1553-1560.) is by CVD method, and taking different mesoporous silicons as hard template, acetonitrile is that carbon source has been prepared a series of containing N meso-porous carbon material of nitrogenous rate 8wt%.Park etc. (J.Mater.Chem., 2011,21,10801-10807.) are hard template with mesoporous silicon, and cyanamide is presoma, and wet method is prepared nitrating meso-porous carbon material under without other solvents, and as the applied research of hydrogen storage material.1), the complex process of synthetic presoma is tediously long but still there is many deficiencies in above-mentioned existing technology, is mainly manifested in:, polyreaction is difficult to control, and material is prepared poor repeatability; 2), the amalgamation of presoma and template is poor; 3), reaction yield is lower; Etc..
Summary of the invention
The object of the invention is to provide a kind of preparation method of nitrogen doping ordered mesoporous carbon material, to solve the deficiencies in the prior art.
The present invention is by the following technical solutions:
A preparation method for nitrogen doping ordered mesoporous carbon material, comprises the steps:
Under step 1, room temperature, in tube sealing reaction device or autoclave, multiamino compound and silica type template are dissolved in organic solvent for 1:0.8～1.5 in mass ratio, mix and obtain solution 1; In container containing, 2,4,6-, tri-chloro-1,3,5-triazines are dissolved in organic solvent, mix and obtain solution 2;
Step 2, the solution of step 12 is slowly joined in solution 1, mix, then add tertiary amines acid binding agent, sealing tube sealing reaction device or autoclave, be heated to 100～150 DEG C of stirring reaction 12～24h, obtains oily liquids; Wherein, the mol ratio of 2,4,6-, tri-chloro-1,3,5-triazines and multiamino compound is 2:2.5～3; The mol ratio of tertiary amines acid binding agent and multiamino compound is 2～3:1;
Step 3, the oily liquids that step 2 is obtained are poured in distilled water, produce yellow solid, filter, and washing leaching cake, dry, obtain yellow particle shape solid;
Step 4, yellow particle shape solid abrasive to 100～300 order that step 3 is obtained carry out high temperature cabonization processing under inert atmosphere, obtain black powder;
Step 5, the black powder that step 4 is obtained are poured in hydrofluoric acid aqueous solution, leave standstill 10～24h, filter, and washing leaching cake, dry, obtain described nitrogen doping ordered mesoporous carbon material.
Described in step 1, multiamino compound is the one having in the compound of two or more primary aminos.The described compound with two primary aminos is p-diaminodiphenyl, 4,4'-diaminodiphenylmethane or quadrol.Described silica type template is SBA-15, SBA-3 or MCM-48.Organic solvent in solution 1 and solution 2 is the one in DMF, methyl-sulphoxide or N,N-dimethylacetamide.
Described in step 2, tertiary amines acid binding agent is DIPEA, N, N-di-isopropyl benzylamine or triethylamine.
Described in step 3 and step 5, be dried as dry 10～24h at 60～100 DEG C.
Described in step 4, inert atmosphere is nitrogen, and the speed that passes into of nitrogen is 2～20L/min.Described high temperature cabonization is treated to: be warming up to 200～400 DEG C and keep 2～4h, temperature rise rate is 1～5 DEG C/min, continues to be warming up to 600～800 DEG C and keeps 2～4h, and temperature rise rate is 1～5 DEG C/min, is cooled to afterwards room temperature, and rate of temperature fall is 1～5 DEG C/min.
Described in step 5, hydrofluoric acid aqueous solution is that volume percent is 10～20% hydrofluoric acid aqueous solution.
Beneficial effect of the present invention:
The present invention adopts 2,4,6-, tri-chloro-1,3,5-triazines and multiamino compound to carry out polyreaction, using SBA-15 etc. as template, through carbonization synthetic nitrogen doping ordered mesoporous carbon material.Presoma polymerization process safety simple and easy to control, good with template amalgamation, pore passage structure is controlled, and cost is low, and equipment requirements is easy.The inventive method repeatability is high, and reaction yield is high; Product homogeneity is good, and nitrogen content is higher, compound with regular structure; Whole process operation is easy etc.The nitrogen doping ordered mesoporous carbon material of preparation has the duct of high-sequential, bigger serface, and the aperture of distribution homogeneous, high stability, has broad application prospects in the field such as catalysis and electrode materials.
Brief description of the drawings
Fig. 1 is the product transmission electron microscope picture that embodiment 3 obtains.
Fig. 2 is the product transmission electron microscope picture that embodiment 3 obtains.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is done further and explained.Following embodiment does not limit the present invention in any form, and all employings are equal to replaces or technical scheme that the mode of equivalent transformation obtains, all among protection scope of the present invention.
The present invention adopts 2,4,6-, tri-chloro-1,3,5-triazines and multiamino compound to carry out polyreaction, using SBA-15 etc. as template, through carbonization synthetic nitrogen doping ordered mesoporous carbon material.Dominant mechanism is: in organic solvent, utilize 2,4,6-, tri-chloro-1,3,5-triazines and multiamino compound to carry out polyreaction, add the acid producing with polyreaction in acid binding agent, promote the generation of polyreaction.After filtering drying, obtain carbon-nitrogen material presoma, high temperature cabonization under inert atmosphere.Be cooled to after room temperature, utilize hydrofluoric acid to remove template, obtain nitrogen doping ordered mesoporous carbon material.
A preparation method for nitrogen doping ordered mesoporous carbon material, comprises the steps:
Under step 1, room temperature, in tube sealing reaction device or autoclave, multiamino compound and silica type template are dissolved in organic solvent for 1:0.8～1.5 in mass ratio, mix and obtain solution 1, wherein, multiamino compound is p-diaminodiphenyl, 4, and 4'-diaminodiphenylmethane, quadrol or other have the one in the compound of more than two and two primary amino; The mass ratio of multiamino compound and organic solvent is 1:5～10; Silica type template is SBA-15, SBA-3 or MCM-48 etc.In container containing, 2,4,6-, tri-chloro-1,3,5-triazines are dissolved in organic solvent, mix and obtain solution 2, wherein, the mass ratio of 2,4,6-, tri-chloro-1,3,5-triazines and organic solvent is 1:5～10.Organic solvent in solution 1 and solution 2 is the one in DMF, methyl-sulphoxide or N,N-dimethylacetamide, preferably DMF.
Step 2, the solution of step 12 is slowly joined in solution 1, mix, then add tertiary amines acid binding agent, sealing tube sealing reaction device or autoclave, be heated to 100～150 DEG C of stirring reaction 12～24h, obtains oily liquids; Wherein, the mol ratio of 2,4,6-, tri-chloro-1,3,5-triazines and multiamino compound is 2:2.5～3; The mol ratio of tertiary amines acid binding agent and multiamino compound is 2～3:1; Tertiary amines acid binding agent is DIPEA, N, N-di-isopropyl benzylamine or triethylamine etc., preferably DIPEA.
Step 3, the oily liquids that step 2 is obtained are poured in distilled water, produce yellow solid, filter, and washing leaching cake, at 60～100 DEG C, dry 10～24h, obtains yellow particle shape solid;
Step 4, yellow particle shape solid abrasive to 100～300 order that step 3 is obtained carry out high temperature cabonization processing under nitrogen atmosphere, obtain black powder.The speed that passes into of nitrogen is 2～20L/min.High temperature cabonization is treated to and is warming up to 200～400 DEG C of maintenance 2～4h, and temperature rise rate is 1～5 DEG C/min, continues to be warming up to 600～800 DEG C and keeps 2～4h, and temperature rise rate is 1～5 DEG C/min, is cooled to afterwards room temperature, and rate of temperature fall is 1～5 DEG C/min.
It is in 10～20% hydrofluoric acid aqueous solution that step 5, the black powder that step 4 is obtained are poured volume percent into, leave standstill 10～24h, filter, washing leaching cake, dry 10～24h at 60～100 DEG C, obtain having the black powder shape solid of the hexagonal mesoporous structure of order, be described nitrogen doping ordered mesoporous carbon material.
The template SBA-15 that following examples relate to is Nanjing Xian Feng Nono-material Science & Technology Ltd. product, has the mesoporous silicon based molecular sieve of two-dimentional hexagonal structure, BET specific surface area m
2/ g>=650, aperture 6～10nm; Template MCM-48 is Nanjing Xian Feng Nono-material Science & Technology Ltd. product, has three-dimensional spiral pore network structure, BET specific surface area m
2/ g>=750, aperture 2～3nm; Template SBA-3 is Nanjing Xian Feng Nono-material Science & Technology Ltd. product, has the mesoporous silicon based molecular sieve of two-dimentional hexagonal structure, BET specific surface area m
2/ g>=1000, aperture 2～3nm.
Embodiment 1
A preparation method for nitrogen doping ordered mesoporous carbon material, comprises the following steps:
(1) under room temperature, in tube sealing reaction device, 0.552g p-diaminodiphenyl and 0.5g template SBA-15 are dissolved in the DMF of 5mL, stir and obtain solution 1; Meanwhile, in test tube, by 0.369g 2,4,6-tri-chloro-1,3,5-triazines are dissolved in the DMF of 2mL, obtain settled solution 2;
(2) solution 2 in step (1) is slowly added in solution 1, be uniformly mixed, add 1mL DIPEA, sealing tube sealing reaction device, is heated to 130 DEG C and stirs 12h, makes after abundant polymerization, stops stirring, and obtains oily liquids;
(3) gained oily liquids in step (2) is poured in 200mL distilled water, produced yellow solid, in time at Büchner funnel inner filtration and retain filter cake, with distilled water wash 3 times, at 80 DEG C of baking oven inner drying 12h, obtain presoma, be yellow particle shape solid;
(4) by the yellow particle shape solid obtaining in step (3) porphyrize to 200 order left and right in mortar, put into porcelain boat, at inert atmosphere N
2under, in tube furnace, carry out high temperature cabonization processing and obtain black powder: temperature programming is to be warming up to 400 DEG C and to keep 2h, temperature rise rate is 2 DEG C/min, continues to be warming up to 600 DEG C and keeps 2h, and temperature rise rate is 2 DEG C/min, be cooled to room temperature, rate of temperature fall is 2 DEG C/min.
(5) black powder after gained carbonization in step (4) being poured into volume percent is, in 15% hydrofluoric acid aqueous solution, to leave standstill after 12h, filters, retain filter cake, distilled water wash 3 times, at 80 DEG C of baking oven inner drying 12h, obtains black powder shape solid.
With 2,4,6-, tri-chloro-1,3,5-triazines for benchmark, the 1.5979g presoma that embodiment 1 prepares, yield is 70.8%; The final 1.1234g that reclaims after carbonization, specific surface area is 313m
2/ g, pore size distribution is at 2.5nm, and pore volume is 0.20cm
3/ g, nitrogen content is 9.7%.
Embodiment 2
A preparation method for nitrogen doping ordered mesoporous carbon material, comprises the following steps:
(1) under room temperature, in tube sealing reaction device, 0.552g p-diaminodiphenyl and 0.5g template SBA-15 are dissolved in the DMF of 5mL, stir and obtain solution 1; Meanwhile, in test tube, by 0.369g 2,4,6-tri-chloro-1,3,5-triazines are dissolved in the DMF of 2mL, obtain settled solution 2;
(2) solution 2 in step (1) is slowly added in solution 1, be uniformly mixed, add 1mL DIPEA, sealing tube sealing reaction device, is heated to 130 DEG C and stirs 12h, makes after abundant polymerization, stops stirring, and obtains oily liquids;
(3) gained oily liquids in step (2) is poured in 200mL distilled water, produced yellow solid, in time at Büchner funnel inner filtration and retain filter cake, with distilled water wash 3 times, at 80 DEG C of baking oven inner drying 12h, obtain yellow particle shape solid;
(4) by the yellow particle shape solid obtaining in step (3) porphyrize to 200 order left and right in mortar, put into porcelain boat, at inert atmosphere N
2under, in tube furnace, carry out high temperature cabonization processing and obtain black powder: temperature programming is to be warming up to 400 DEG C and to keep 2h, temperature rise rate is 2 DEG C/min, continues to be warming up to 650 DEG C and keeps 2h, and temperature rise rate is 2 DEG C/min, be cooled to room temperature, rate of temperature fall is 2 DEG C/min.
(5) black powder after gained carbonization in step (4) being poured into volume percent is, in 15% hydrofluoric acid aqueous solution, to leave standstill after 12h, filters, retain filter cake, distilled water wash 3 times, at 80 DEG C of baking oven inner drying 12h, obtains black powder shape solid.
The product that embodiment 2 prepares, specific surface area is 705m
2/ g, pore size distribution is at 3.4nm, and pore volume is 0.60cm
3/ g, nitrogen content is 8.7%.
Embodiment 3
A preparation method for nitrogen doping ordered mesoporous carbon material, comprises the following steps:
(1) under room temperature, in tube sealing reaction device, 0.552g p-diaminodiphenyl and 0.5g template SBA-15 are dissolved in the DMF of 5mL, stir and obtain solution 1; Meanwhile, in test tube, by 0.369g 2,4,6-trichlorine 1,3,5-triazines is dissolved in the DMF of 2mL, obtains settled solution 2;
(2) solution 2 in step (1) is slowly added in solution 1, be uniformly mixed, add 1mL DIPEA, sealing tube sealing reaction device, is heated to 130 DEG C and stirs 12h, makes after abundant polymerization, stops stirring, and obtains oily liquids;
(3) gained oily liquids in step (2) is poured in 200mL distilled water, produced yellow solid, in time at Büchner funnel inner filtration and retain filter cake, with distilled water wash 3 times, at 80 DEG C of baking oven inner drying 12h, obtain yellow particle shape solid;
(4) by the yellow particle shape solid obtaining in step (3) porphyrize to 200 order left and right in mortar, put into porcelain boat, at inert atmosphere N
2under, in tube furnace, carry out high temperature cabonization processing and obtain black powder: temperature programming is to be warming up to 400 DEG C of low temperature and to keep 2h, temperature rise rate is 2 DEG C/min, continues to be warming up to 700 DEG C and keeps 2h, and temperature rise rate is 2 DEG C/min, be cooled to room temperature, rate of temperature fall is 2 DEG C/min.
(5) black powder after gained carbonization in step (4) being poured into volume percent is, in 15% hydrofluoric acid aqueous solution, to leave standstill after 12h, filters, retain filter cake, distilled water wash 3 times, at 80 DEG C of baking oven inner drying 12h, obtains black powder shape solid.
The product that embodiment 3 prepares, specific surface area is 626m
2/ g, pore size distribution is at 5.0nm, and pore volume is 0.78cm
3/ g, nitrogen content is 5.7%.As illustrated in fig. 1 and 2, as seen from the figure, the very regular and distribution homogeneous of the meso-porous carbon material pattern that obtains, all presents orderly hexagonal mesoporous structure to product transmission electron microscope picture; Reflect well the impact of template on pore passage structure.This result shows, in the method, the amalgamation of presoma and template is good, thereby has caused the structure distribution of homogeneous.
Embodiment 4
A preparation method for nitrogen doping ordered mesoporous carbon material, comprises the following steps:
(1) under room temperature, in tube sealing reaction device, 0.552g p-diaminodiphenyl and 0.5g template SBA-15 are dissolved in the DMF of 5mL, stir and obtain solution 1; Meanwhile, in test tube, by 0.369g 2,4,6-triazine-1,3,5-triazines is dissolved in the DMF of 2mL, obtains settled solution 2;
(2) solution 2 in step (1) is slowly added in solution 1, be uniformly mixed, add 1mL DIPEA, sealing tube sealing reaction device, is heated to 130 DEG C and stirs 12h, makes after abundant polymerization, stops stirring, and obtains oily liquids;
(3) gained oily liquids in step (2) is poured in 200mL distilled water, produced yellow solid, in time at Büchner funnel inner filtration and retain filter cake, with distilled water wash 3 times, at 80 DEG C of baking oven inner drying 12h, obtain yellow particle shape solid;
(4) by the yellow particle shape solid obtaining in step (3) porphyrize to 200 order left and right in mortar, put into porcelain boat, at inert atmosphere N
2under, in tube furnace, carry out high temperature cabonization processing and obtain black powder: temperature programming is to be warming up to 400 DEG C of low temperature and to keep 2h, temperature rise rate is 2 DEG C/min, continues to be warming up to 750 DEG C and keeps 2h, and temperature rise rate is 2 DEG C/min, be cooled to room temperature, rate of temperature fall is 2 DEG C/min.
(5) black powder after gained carbonization in step (4) being poured into volume percent is, in 15% hydrofluoric acid aqueous solution, to leave standstill after 12h, filters, retain filter cake, distilled water wash 3 times, at 80 DEG C of baking oven inner drying 12h, obtains black powder shape solid.
The product that embodiment 4 prepares, specific surface area is 789m
2/ g, pore size distribution is at 2.8nm, and pore volume is 0.55cm
3/ g, nitrogen content is 5.8%.
Embodiment 5
A preparation method for nitrogen doping ordered mesoporous carbon material, comprises the following steps:
(1) under room temperature, in tube sealing reaction device, 0.552g p-diaminodiphenyl and 0.5g template SBA-15 are dissolved in the DMF of 5mL, stir and obtain solution 1; Meanwhile, in test tube, by 0.369g 2,4,6-tri-chloro-1,3,5-triazines are dissolved in the DMF of 2mL, obtain settled solution 2;
(2) solution 2 in step (1) is slowly added in solution 1, be uniformly mixed, add 1mL DIPEA, sealing tube sealing reaction device, is heated to 130 DEG C and stirs 12h, makes after abundant polymerization, stops stirring, and obtains oily liquids;
(3) gained oily liquids in step (2) is poured in 200mL distilled water, produced yellow solid, in time at Büchner funnel inner filtration and retain filter cake, with distilled water wash 3 times, at 80 DEG C of baking oven inner drying 12h, obtain yellow particle shape solid;
(4) by the yellow particle shape solid obtaining in step (3) porphyrize to 200 order left and right in mortar, put into porcelain boat, at inert atmosphere N
2under, in tube furnace, carry out high temperature cabonization processing and obtain black powder: temperature programming is to be warming up to 400 DEG C and to keep 2h, temperature rise rate is 2 DEG C/min, continues to be warming up to 800 DEG C and keeps 2h, and temperature rise rate is 2 DEG C/min, be cooled to room temperature, rate of temperature fall is 2 DEG C/min.
(5) black powder after gained carbonization in step (4) being poured into volume percent is, in 15% hydrofluoric acid aqueous solution, to leave standstill after 12h, filters, retain filter cake, distilled water wash 3 times, at 80 DEG C of baking oven inner drying 12h, obtains black powder shape solid.
The product that embodiment 5 prepares, specific surface area is 194m
2/ g, pore size distribution is at 2.9nm, and pore volume is 0.14cm
3/ g, nitrogen content is 5.8%.
Embodiment 6
A preparation method for nitrogen doping ordered mesoporous carbon material, comprises the following steps:
(1), under room temperature, in tube sealing reaction device, by 0.588g 4,4'-diaminodiphenylmethane and 0.5g template SBA-15 are dissolved in the DMF of 5mL, stir and obtain solution 1; Meanwhile, in test tube, by 0.369g 2,4,6-tri-chloro-1,3,5-triazines are dissolved in the DMF of 2mL, obtain settled solution 2;
(2) solution 2 in step (1) is slowly added in solution 1, be uniformly mixed, add 1mL DIPEA, sealing tube sealing reaction device, is heated to 130 DEG C and stirs 12h, makes after abundant polymerization, stops stirring, and obtains oily liquids;
(3) gained oily liquids in step (2) is poured in 200mL distilled water, produced yellow solid, in time at Büchner funnel inner filtration and retain filter cake, with distilled water wash 3 times, at 80 DEG C of baking oven inner drying 12h, obtain yellow particle shape solid;
(4) by the yellow particle shape solid obtaining in step (3) porphyrize to 200 order left and right in mortar, put into porcelain boat, at inert atmosphere N
2under, in tube furnace, carry out high temperature cabonization processing and obtain black powder: temperature programming is, heat up 400 DEG C and keep 2h, temperature rise rate is 2 DEG C/min, continues to be warming up to 750 DEG C and keeps 2h, and temperature rise rate is 2 DEG C/min, is cooled to room temperature, and rate of temperature fall is 2 DEG C/min.
(5) black powder after gained carbonization in step (4) being poured into volume percent is, in 15% hydrofluoric acid aqueous solution, to leave standstill after 12h, filters, retain filter cake, distilled water wash 3 times, at 80 DEG C of baking oven inner drying 12h, obtains black powder shape solid.
The product that embodiment 6 prepares, specific surface area is 843m
2/ g, pore size distribution is at 2.9nm, and pore volume is 0.65cm
3/ g, nitrogen content is 6.8%.
Embodiment 7
A preparation method for nitrogen doping ordered mesoporous carbon material, comprises the following steps:
(1) under room temperature, in tube sealing reaction device, 0.18g quadrol and 0.27g template SBA-15 are dissolved in the DMF of 1.9mL, stir and obtain solution 1; Meanwhile, in test tube, by 0.369g 2,4,6-tri-chloro-1,3,5-triazines are dissolved in the DMF of 2mL, obtain settled solution 2;
(2) solution 2 in step (1) is slowly added in solution 1, be uniformly mixed, add 1mL DIPEA, sealing tube sealing, is heated to 130 DEG C and stirs 12h, makes after abundant polymerization, stops stirring, and obtains oily liquids;
(3) gained oily liquids in step (2) is poured in 200mL distilled water, produced yellow solid, in time at Büchner funnel inner filtration and retain filter cake, with distilled water wash 3 times, at 80 DEG C of baking oven inner drying 12h, obtain yellow particle shape solid;
(4) by the yellow particle shape solid obtaining in step (3) porphyrize to 200 order left and right in mortar, put into porcelain boat, at inert atmosphere N
2under, in tube furnace, carry out high temperature cabonization processing and obtain black powder: temperature programming is to be warming up to 400 DEG C of low temperature and to keep 2h, temperature rise rate is 2 DEG C/min, continues to be warming up to 700 DEG C and keeps 2h, and temperature rise rate is 2 DEG C/min, be cooled to room temperature, rate of temperature fall is 2 DEG C/min.
(5) black powder after gained carbonization in step (4) being poured into volume percent is, in 15% hydrofluoric acid aqueous solution, to leave standstill after 12h, filters, retain filter cake, distilled water wash 3 times, at 80 DEG C of baking oven inner drying 12h, obtains black powder shape solid.
The product that embodiment 7 prepares, specific surface area is 239m
2/ g, pore size distribution is at 4.2nm, and pore volume is 0.37cm
3/ g, nitrogen content is 9.2%.
Embodiment 8
A preparation method for nitrogen doping ordered mesoporous carbon material, comprises the following steps:
(1), under room temperature, in tube sealing reaction device, by 0.588g 4,4'-diaminodiphenylmethane and 0.5g template MCM-48 are dissolved in the DMF of 5mL, stir and obtain solution 1; Meanwhile, in test tube, by 0.369g 2,4,6-tri-chloro-1,3,5-triazines are dissolved in the DMF of 2mL, obtain settled solution 2;
(2) solution 2 in step (1) is slowly added in solution 1, be uniformly mixed, add 1mL DIPEA, sealing tube sealing reaction device, is heated to 130 DEG C and stirs 24h, makes after abundant polymerization, stops stirring, and obtains oily liquids;
(3) gained oily liquids in step (2) is poured in 200mL distilled water, produced yellow solid, in time at Büchner funnel inner filtration and retain filter cake, with distilled water wash 3 times, at 80 DEG C of baking oven inner drying 12h, obtain yellow particle shape solid;
(4) by the yellow particle shape solid obtaining in step (3) porphyrize to 200 order left and right in mortar, put into porcelain boat, at inert atmosphere N
2under, in tube furnace, carry out high temperature cabonization processing and obtain black powder: temperature programming is to be warming up to 400 DEG C of low temperature and to keep 2h, temperature rise rate is 2 DEG C/min, continues to be warming up to 700 DEG C and keeps 2h, and temperature rise rate is 2 DEG C/min, be cooled to room temperature, rate of temperature fall is 2 DEG C/min.
(5) black powder after gained carbonization in step (4) being poured into volume percent is, in 15% hydrofluoric acid aqueous solution, to leave standstill after 12h, filters, retain filter cake, distilled water wash 3 times, at 80 DEG C of baking oven inner drying 12h, obtains black powder shape solid.
The product that embodiment 8 prepares, specific surface area is 763m
2/ g, pore size distribution is at 2.7 nm, and pore volume is 0.35cm
3/ g, nitrogen content is 7.1%.
Embodiment 9
A preparation method for nitrogen doping ordered mesoporous carbon material, comprises the following steps:
(1), under room temperature, in tube sealing reaction device, by 0.5g4,4'-diaminodiphenylmethane and 0.5g template SBA-3 are dissolved in the methyl-sulphoxide of 4mL, stir and obtain solution 1; Meanwhile, in test tube, by 0.369g 2,4,6-tri-chloro-1,3,5-triazines are dissolved in the methyl-sulphoxide of 2mL, obtain settled solution 2;
(2) solution 2 in step (1) is slowly added in solution 1, be uniformly mixed, add 1mL N, N-di-isopropyl benzylamine, sealing tube sealing reaction device, is heated to 100 DEG C and stirs 16h, makes after abundant polymerization, stops stirring, and obtains oily liquids;
(3) gained oily liquids in step (2) is poured in 200mL distilled water, produced yellow solid, in time at Büchner funnel inner filtration and retain filter cake, with distilled water wash 3 times, at 60 DEG C of baking oven inner drying 10h, obtain yellow particle shape solid;
(4) by the yellow particle shape solid obtaining in step (3) porphyrize to 200 order left and right in mortar, put into porcelain boat, at inert atmosphere N
2under, in tube furnace, carry out high temperature cabonization processing and obtain black powder: temperature programming is to be warming up to 200 DEG C and to keep 3h, temperature rise rate is 1 DEG C/min, continues to be warming up to 600 DEG C and keeps 3h, and temperature rise rate is 1 DEG C/min, be cooled to room temperature, rate of temperature fall is 1 DEG C/min.
(5) black powder after gained carbonization in step (4) being poured into volume percent is, in 10% hydrofluoric acid aqueous solution, to leave standstill after 10h, filters, retain filter cake, distilled water wash 3 times, at 60 DEG C of baking oven inner drying 10h, obtains black powder shape solid.
The product that embodiment 9 prepares, specific surface area is 1057m
2/ g, pore size distribution is at 2.3nm, and pore volume is 0.59cm
3/ g, nitrogen content is 6.2%.
Embodiment 10
A preparation method for nitrogen doping ordered mesoporous carbon material, comprises the following steps:
(1), under room temperature, in tube sealing reaction device, by 0.5g4,4'-diaminodiphenylmethane and 0.5g template SBA-3 are dissolved in the N,N-dimethylacetamide of 5mL, stir and obtain solution 1; Meanwhile, in test tube, by 0.369g 2,4,6-tri-chloro-1,3,5-triazines are dissolved in the N,N-dimethylacetamide of 2mL, obtain settled solution 2;
(2) solution 2 in step (1) is slowly added in solution 1, be uniformly mixed, add 1mL triethylamine, sealing tube sealing reaction device, is heated to 150 DEG C and stirs 16h, makes after abundant polymerization, stops stirring, and obtains oily liquids;
(3) gained oily liquids in step (2) is poured in 200mL distilled water, produce yellow solid, in time at Büchner funnel inner filtration and retain filter cake, with distilled water wash 3 times, at 100 DEG C of baking oven inner drying 24h, obtain yellow particle shape solid;
(4) by the yellow particle shape solid obtaining in step (3) porphyrize to 200 order left and right in mortar, put into porcelain boat, at inert atmosphere N
2under, in tube furnace, carry out high temperature cabonization processing and obtain black powder: temperature programming is to be warming up to 300 DEG C and to keep 4h, temperature rise rate is 5 DEG C/min, continues to be warming up to 600 DEG C and keeps 4h, and temperature rise rate is 5 DEG C/min, be cooled to room temperature, rate of temperature fall is 5 DEG C/min.
(5) black powder after gained carbonization in step (4) being poured into volume percent is, in 20% hydrofluoric acid aqueous solution, to leave standstill after 24h, filters, retain filter cake, distilled water wash 3 times, at 100 DEG C of baking oven inner drying 24h, obtains black powder shape solid.
The product that embodiment 10 prepares, specific surface area is 963m
2/ g, pore size distribution is at 2.9nm, and pore volume is 0.52cm
3/ g, nitrogen content is 5.9%.
From embodiment 1～10: prepare the doped meso-porous carbon material of this orderly nitrogen and have the duct of high-sequential, bigger serface, the aperture of distribution homogeneous; Specific surface area is 194～1057m
2/ g, pore size distribution is at 2.3～5.0nm, and pore volume is 0.14～0.78cm
3/ g, nitrogen content is 5.7～9.7%.In addition, preparation method's polymerization process of the present invention is simple and easy to control, and relatively good for the amalgamation of template, pore passage structure is controlled, and cost is low, and equipment requirements is easy.
Claims (10)
1. a preparation method for nitrogen doping ordered mesoporous carbon material, is characterized in that, comprises the steps:
Under step 1, room temperature, in tube sealing reaction device or autoclave, multiamino compound and silica type template are dissolved in organic solvent for 1:0.8～1.5 in mass ratio, mix and obtain solution 1; In container containing, 2,4,6-, tri-chloro-1,3,5-triazines are dissolved in organic solvent, mix and obtain solution 2;
Step 2, the solution of step 12 is slowly joined in solution 1, mix, then add tertiary amines acid binding agent, sealing tube sealing reaction device or autoclave, be heated to 100～150 DEG C of stirring reaction 12～24h, obtains oily liquids; Wherein, the mol ratio of 2,4,6-, tri-chloro-1,3,5-triazines and multiamino compound is 2:2.5～3; The mol ratio of tertiary amines acid binding agent and multiamino compound is 2～3:1;
Step 3, the oily liquids that step 2 is obtained are poured in distilled water, produce yellow solid, filter, and washing leaching cake, dry, obtain yellow particle shape solid;
Step 4, yellow particle shape solid abrasive to 100～300 order that step 3 is obtained carry out high temperature cabonization processing under inert atmosphere, obtain black powder;
Step 5, the black powder that step 4 is obtained are poured in hydrofluoric acid aqueous solution, leave standstill 10～24h, filter, and washing leaching cake, dry, obtain described nitrogen doping ordered mesoporous carbon material.
2. the preparation method of nitrogen according to claim 1 doping ordered mesoporous carbon material, is characterized in that, multiamino compound is the one having in the compound of two or more primary aminos described in step 1.
3. the preparation method of nitrogen according to claim 2 doping ordered mesoporous carbon material, is characterized in that, described in there are two primary aminos compound be p-diaminodiphenyl, 4,4'-diaminodiphenylmethane or quadrol.
4. the preparation method of nitrogen according to claim 1 doping ordered mesoporous carbon material, is characterized in that, silica type template is SBA-15, SBA-3 or MCM-48 described in step 1.
5. the preparation method of nitrogen doping ordered mesoporous carbon material according to claim 1, is characterized in that, the organic solvent in step 1 solution 1 and solution 2 is the one in DMF, methyl-sulphoxide or N,N-dimethylacetamide.
6. the preparation method of nitrogen according to claim 1 doping ordered mesoporous carbon material, is characterized in that, tertiary amines acid binding agent is DIPEA, N described in step 2, N-di-isopropyl benzylamine or triethylamine.
7. the preparation method of nitrogen according to claim 1 doping ordered mesoporous carbon material, is characterized in that, is dried as dry 10～24h at 60～100 DEG C described in step 3 and step 5.
8. the preparation method of nitrogen according to claim 1 doping ordered mesoporous carbon material, is characterized in that, inert atmosphere is nitrogen described in step 4, and the speed that passes into of nitrogen is 2～20L/min.
9. the preparation method of nitrogen doping ordered mesoporous carbon material according to claim 1, it is characterized in that, described in step 4, high temperature cabonization is treated to: be warming up to 200～400 DEG C and keep 2～4h, temperature rise rate is 1～5 DEG C/min, continue to be warming up to 600～800 DEG C and keep 2～4h, temperature rise rate is 1～5 DEG C/min, is cooled to afterwards room temperature, and rate of temperature fall is 1～5 DEG C/min.
10. the preparation method of nitrogen according to claim 1 doping ordered mesoporous carbon material, is characterized in that, hydrofluoric acid aqueous solution is that volume percent is 10～20% hydrofluoric acid aqueous solution described in step 5.
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| CN105152160A (en) * | 2015-10-21 | 2015-12-16 | 哈尔滨工业大学 | Preparation method of nitrogen-doped carbon microspheres |
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