CN104085878A - Surface functionalized ordered mesopore nitrogen-doped carbon material and preparation method thereof - Google Patents
Surface functionalized ordered mesopore nitrogen-doped carbon material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a surface functionalized ordered mesopore nitrogen-doped carbon material. The preparation method of the surface functionalized ordered mesopore nitrogen-doped carbon material comprises the following steps: dissolving a carbohydrate raw material in a melamine salt aqueous dispersion system, carrying out hydrothermal reaction at the temperature of 120-200 DEG C while an amphiphilic triblock copolymer is taken as a soft template, filtering, washing and drying hydrothermal reaction products to obtain a porous carbon material, and carrying out high-temperature calcination to obtain a carbohydrate derived ordered mesopore nitrogen-doped carbon material. The invention also discloses a surface functionalized ordered mesopore nitrogen-doped carbon material product obtained by adopting the preparation method. The preparation method of the surface functionalized ordered mesopore nitrogen-doped carbon material has the advantages that a self-assembly process of the carbohydrate and the soft template is completed on the surface of an indissolvable organic salt precursor, the precursor can be copolymerized with a carbon source, so that a carbonized material is automatically transformed, and interaction between the carbohydrate and the soft template is improved, so that large-scale preparation of ordered mesopore and functionalized carbon materials by virtue of the carbohydrate can come true.
Description
Technical field
The invention belongs to porous material preparing technical field, specifically relate to a kind of preparation method and product of surface-functionalized order mesoporous nitrating Carbon Materials.
Background technology
Along with the discovery of the new carbon such as soccerballene, CNT (carbon nano-tube) and Graphene, scientific worker more and more recognizes the critical role of carbon material in scientific development and human progress.Ordered mesoporous carbon material is except the high heat-conductivity conducting performance and chemical stability that have general carbon material and have, also there is suitable aperture (2-50nm), orderly tunnel, hole, larger specific surface area and porosity, be conducive to absorption and the transmission of material, in the numerous areas such as fractionation by adsorption, catalysis, energy storage/conversion, medicine carrying, be widely used.
By scientists effort for many years, main development nanometer casting and two kinds of methods of soft template prepare ordered mesoporous carbon material.Wherein nanometer is cast conventionally taking ordered mesoporous silica dioxide as hard template, obtains ordered mesoporous carbon material through copying after removing template.The pore structure of the meso-porous carbon material that this method obtains and pattern are subject to the restriction of hard template.In addition, also need the material (NH by contaminate environment
4hF
2) remove hard template, method complexity, cost is high, unfriendly to environment, is unfavorable for large-scale production.Comparatively speaking, soft template method is effective more economically.Soft template method is to realize by the micella of the self assembling process formation ordered arrangement of organic macromolecule and carbon source.Its pore structure and hole size can regulate and control by changing synthesis condition, and method is simply effective.
In actual applications, in order to improve the application performance of material, except orderly pore structure and high specific surface area, porosity, scientists is being found effective means preparation always and is being had the carbon material that enriches functional group.But the soft template method of development is mainly taking resol as carbon source at present, preparation-obtained carbon material chemistry condensation degree is high, is unfavorable for follow-up finishing.And the presoma of resol is Industrial products, there is unsustainable property.Hydrothermal carbonization method, is raw material mainly with reproducible carbohydrate greatly, reaction conditions gentleness (<300 DEG C), and operation is simple, is more conducive to mass-producing, ensured sustained development production.And abundant functional group is contained on preparation-obtained product surface, is conducive to finishing.But the carbon material that Direct Hydrothermal method obtains only has very low specific surface area and porosity, limit the application of such carbon material in fractionation by adsorption, catalysis, energy storage/conversion, medicine carrying etc.In addition, in water-heat process, relate to many reactions such as hydrolysis, degraded, affect the self assembling process of carbon source and soft template.In the preparation field of carbon material, find a kind of simple effective method by hydro-thermal carbohydrate and soft template method combination, be a very significant challenge thereby one-step synthesis has the carbon material of order mesoporous and functionalization.
Summary of the invention
The invention provides a kind of utilization from the means that transform indissoluble organic salt; taking carbohydrate as raw material; prepare the novel method of the order mesoporous nitrating carbon material of carbohydrate-derivedization taking amphiphilic diblock copolymer as soft template; the method not only can single stage method the carbon material of synthesizing ordered mesoporous and functionalization; and raw material is cheap and easy to get; method is simple, and sustainability is strong, has the potentiality that mass-producing generates.
The present invention provides a kind of surface-functionalized order mesoporous nitrating Carbon Materials simultaneously, and this material has flourishing hierarchical porous structure, orderly mesopore orbit, the surface of functionalization, there is good absorption property, simultaneously as electrode material for super capacitor, effective.
A preparation method for surface-functionalized order mesoporous nitrating Carbon Materials, comprising:
Taking carbohydrate as raw material, be dissolved in the aqueous dispersion of melamine salt, simultaneously taking amphiphatic triblock copolymer as soft template, 120-200 DEG C of hydro-thermal reaction, be preferably 130-115 DEG C of hydro-thermal reaction, hydro-thermal reaction product after filtration, washing, dry obtain porous carbon materials, then through high-temperature calcination, obtain the order mesoporous nitrating Carbon Materials of carbohydrate-derivedization.
The method of reporting in paper document and patent documentation before comparing, it is presoma that preparation method of the present invention utilizes the organic salt of indissoluble first, under hydrothermal condition, the self assembling process of carbohydrate and soft template is regulated and controled.Because the melamine salt surface of indissoluble has abundant amino, can interact by hydrogen bond and carbon source and soft template, thereby make the self assembling process of micella be limited in the surface of indissoluble organic salt particle, play the effect of structure directing and class template.In addition, thus indissoluble organic salt can also be converted into certainly with carbon source polymerization the functionalization product of copolymerization.
Described carbohydrate is selected from least one in pentose, hexose, oligose.Described pentose is preferably ribose, wood sugar etc.; Described hexose is preferably fructose, glucose, glucosamine, semi-lactosi etc.; Described oligose is preferably sucrose, maltose etc.; More preferably fructose.
Described melamine salt is selected from least one in trimeric cyanamide vitriol, melamine phosphate, trimeric cyanamide oxalate, trimeric cyanamide carboxylate salt, melamine sulfonate etc.; As further preferential, described melamine salt is that following positively charged ion forms with any negatively charged ion combination:
Described amphiphatic triblock copolymer is F127 or P123.
The aqueous dispersion of described melamine salt is prepared by following method: to mineral acid or the organic acid aqueous solution, add trimeric cyanamide, and the 20-26h that refluxes at temperature 80-100 DEG C, reaction generates melamine salt.
Prepare in melamine salt process, the mol ratio of described mineral acid or organic acid and trimeric cyanamide is:
In the time that mineral acid or organic acid are sulfuric acid, phosphoric acid, carboxylic acid, sulfonic acid, the mol ratio of mineral acid or organic acid and trimeric cyanamide is 1-1.5:1, more preferably 1:1.In the time that mineral acid or organic acid are oxalic acid, the mol ratio of mineral acid or organic acid and trimeric cyanamide is 1:1-2; More preferably 1:1 or 1:2.
Described carbohydrate and the material ratio of soft template are: calculate with 1mol carbohydrate, the soft template needing is 100-200g, more preferably 200g.
Described trimeric cyanamide and the mol ratio of carbohydrate are 1:1-6, and more preferably 1:3-6 is further preferably 1:3.
Above-mentioned each material proportion is an important factor of the final hydrothermal product pattern of impact and composition.Can need to select according to difference the material of different ratios.
Described general 1-3 days of hydro-thermal reaction time.Hydro-thermal reaction is generally carried out in airtight reactor.For ensureing the even of material, before hydro-thermal reaction, first feed back is stirred to 10min-10h, ensure the uniform while of mixing of materials, realize the prepolymerization of carbohydrate and melamine salt, save the follow-up reaction times.
Described high-temperature calcination adopts two-section calcining process, specifically comprises:
Dried hydrothermal product first in air 400 DEG C of calcining 2h or in nitrogen atmosphere 550 DEG C of calcining 4h remove soft template, then 900 DEG C of calcining 1h, thus form order mesoporous nitrating Carbon Materials.
The present invention, taking carbohydrate as raw material, prepares the novel method of the order mesoporous nitrating carbon material of carbohydrate-derivedization taking amphiphilic diblock copolymer as soft template.The pattern of the material that obtains and composition can regulate and control by the ratio of choosing different organic difficulty soluble salts and organic salt and carbon source.The method makes the self assembling process of carbohydrate and soft template occur in indissoluble organic salt presoma surface, and presoma can with carbon source copolymerization, thereby be certainly converted into char-forming material, improve the interaction of carbohydrate and soft template, the carbon material of preparing in a large number order mesoporous and functionalization with carbohydrate is become a reality.The method environmental protection, raw material sources are wide, method is simple, sustainability is strong, can realize mass-producing and generate, and have very large using value.
Compared with existing ordered mesoporous carbon material synthetic method, the method raw material sources are extensive, environmental friendliness, and sustainability is strong, can accomplish scale production.The most important thing is that this reveals 3 obvious advantages from conversion method synthesizing ordered mesoporous carbon bill of material: (1) single stage method modification of surfaces functionalization group, does not need the modification of follow-up complexity; (2) resulting materials has novel pattern, does not need to introduce the hard template of specific morphology, the effect that presoma has class template and certainly transforms; (3) pattern of material and functionalization can regulate and control by pattern and the composition of regulation and control presoma, and method is simple.
Brief description of the drawings
The scanning electron microscope (SEM) photograph (SEM) of the order mesoporous nitrating Carbon Materials that Fig. 1 (a) and Fig. 1 (b) prepare for embodiment 1.
The transmission electron microscope picture (TEM) of the order mesoporous nitrating Carbon Materials that Fig. 2 (a) prepares for embodiment 1.
The high power transmission electron microscope picture (HR-TEM) of the order mesoporous nitrating Carbon Materials that Fig. 2 (b) prepares for embodiment 1.
The order mesoporous nitrating Carbon Materials that Fig. 3 (a) and Fig. 3 (b) prepare for embodiment 1 XPS analysis spectrogram: (a) N1s; (b) C1s.
Fig. 4 be the order mesoporous nitrating Carbon Materials for preparing of embodiment 1 as electrode material for super capacitor time measured cyclic voltammetry curve.
Fig. 5 (a) is the scanning electron microscope (SEM) photograph (SEM) of embodiment empty contrast sample.
Fig. 5 (b) is the transmission electron microscope picture (TEM) of embodiment empty contrast sample.
Fig. 6 (a) is the scanning electron microscope (SEM) photograph (SEM) of sample CDCM-3-0 in embodiment.
Fig. 6 (b) is the transmission electron microscope picture (TEM) of sample CDCM-3-0 in embodiment.
The scanning electron microscope (SEM) photograph (SEM) of the order mesoporous nitrating Carbon Materials that Fig. 7 (a) prepares for embodiment 2.
The transmission electron microscope picture (TEM) of the order mesoporous nitrating Carbon Materials that Fig. 7 (b) prepares for embodiment 2.
The scanning electron microscope (SEM) photograph (SEM) of the order mesoporous nitrating Carbon Materials that Fig. 8 (a) prepares for embodiment 3.
The transmission electron microscope picture (TEM) of the order mesoporous nitrating Carbon Materials that Fig. 8 (b) prepares for embodiment 3.
Embodiment
Following embodiment will describe more comprehensively to the present invention.
Embodiment 1: taking trimeric cyanamide vitriol as presoma
In 100mL beaker, add sulfuric acid and the 6g F127 of 50mL0.2M, stirring and dissolving.This mixing solutions is transferred in the three-necked bottle that 1.26g (0.01mol) trimeric cyanamide is housed to 92 DEG C of stirring and refluxing 24h.Add 5.4g (0.03mol) fructose, continue backflow 10min.Obtained solution is transferred in reactor, be placed in 130 DEG C of baking ovens, reaction 3d.After reaction finishes, product is through suction filtration, and distilled water wash repeatedly, obtains corresponding carbon material after being dried.Then material is calcined (concrete steps of two-step approach calcining are: the dried hydrothermal product 400 DEG C of calcining 2h in air of elder generation remove soft template, then calcine 1h at 900 DEG C) through above-mentioned two-step approach and is obtained order mesoporous nitrating Carbon Materials.
The scanning electron microscope (SEM) photograph of the order mesoporous nitrating Carbon Materials that the present embodiment prepares is as shown in Fig. 1 (a) and Fig. 2 (b), there is novel flower-like structure and flourishing hierarchical porous structure by the order mesoporous nitrating Carbon Materials being prepared by the present embodiment shown in Fig. 1 (a) and Fig. 2 (b), on the one hand, as shown in Fig. 1 (a), order mesoporous nitrating Carbon Materials is made up of multiple spherical structures, has hole between spherical structure; Meanwhile, as shown in Fig. 1 (b), each spherical structure is made up of some sheet structures again, has the hole of smaller szie between sheet structure, is conducive to absorption and the transmission of material.
The transmission electron microscope picture (TEM) that Fig. 2 (a) and Fig. 2 (b) are the order mesoporous nitrating Carbon Materials that prepared by the present embodiment and high power transmission electron microscope (HR-TEM) are schemed, known from Fig. 2 (a) and Fig. 2 (b), order mesoporous nitrating Carbon Materials has orderly pore structure.
The XPS analysis that Fig. 3 (a) and Fig. 3 (b) are the order mesoporous nitrating Carbon Materials that prepared by the present embodiment is composed, and Fig. 3 (a) is N1s; Fig. 3 (b) is C1s.Known from Fig. 3 (a) and Fig. 3 (b), the order mesoporous nitrating charcoal material surface that the present embodiment prepares has several functions group, can meet the needs of various occasions.
Fig. 4 is the order mesoporous nitrating Carbon Materials that prepared by the present embodiment measured cyclic voltammetry curve during as electrode material for super capacitor, as can be seen from Figure 4, along with the reduction of sweep velocity, cyclic voltammetry curve has kept the shape of four limit rhombuses, illustrates that this bill of material has revealed the feature of stable double layer capacitor.
Comparative example
According to the method for embodiment 1, the addition of material sample each material used is as shown in table 1, and order of addition(of ingredients) and reaction conditions are constant, prepares blank contrast sample and sample CDCM-3-0:
Table 1
The scanning electron microscope (SEM) photograph (SEM) of blank contrast sample is as shown in Fig. 5 (a), the transmission electron microscope picture (TEM) of blank contrast sample is as shown in Fig. 5 (b), the scanning electron microscope (SEM) photograph (SEM) of sample CDCM-3-0 is as shown in Fig. 6 (a), and the transmission electron microscope picture (TEM) of sample CDCM-3-0 is as shown in Fig. 6 (b); Can find out from scanning electron microscope and the transmission electron microscope picture of Fig. 5 (a)-6 (b), in the situation that not adding trimeric cyanamide (blank contrast sample) or not adding sulfuric acid (sample CDCM-3-0), products therefrom does not have well-regulated pattern, is some unordered pore structures in material; The nitrogen Carbon Materials pattern preparing from the present invention is completely different.
Embodiment 2: taking melamine phosphate as presoma
In 100mL beaker, add phosphoric acid and the 6g F127 of 50mL0.2M, stirring and dissolving.This mixing solutions is transferred in the three-necked bottle that 1.26g (0.01mol) trimeric cyanamide is housed to 92 DEG C of stirring and refluxing 24h.Add 5.4g (0.03mol) fructose, continue backflow 10min.Obtained solution is transferred in reactor, be placed in 130 DEG C of baking ovens, reaction 3d.After reaction finishes, product is through suction filtration, and distilled water wash repeatedly, obtains corresponding carbon material after being dried.Then material is calcined (with embodiment 1) through above-mentioned two-step approach and is obtained order mesoporous nitrating Carbon Materials.Its scanning electron microscope (SEM) photograph (SEM) is as shown in Fig. 7 (a), and transmission electron microscope picture (TEM) is as shown in Fig. 7 (b).
Embodiment 3: taking trimeric cyanamide oxalate as presoma
In 100mL beaker, add oxalic acid and the 6g F127 of 50mL0.1M, stirring and dissolving.This mixing solutions is transferred in the three-necked bottle that 1.26g (0.01mol) trimeric cyanamide is housed to 92 DEG C of stirring and refluxing 24h.Add 5.4g (0.03mol) fructose, continue backflow 10min.Obtained solution is transferred in reactor, be placed in 130 DEG C of baking ovens, reaction 3d.After reaction finishes, product is through suction filtration, and distilled water wash repeatedly, obtains corresponding carbon material after being dried.Then material is calcined (with embodiment 1) through above-mentioned two-step approach and is obtained order mesoporous nitrating Carbon Materials.Its scanning electron microscope (SEM) photograph (SEM) is as shown in Fig. 8 (a), and transmission electron microscope picture (TEM) is as shown in Fig. 8 (b).
The order mesoporous nitrating Carbon Materials that embodiment 2 and embodiment 3 obtain is through scanning electron microscope (SEM) and transmission electron microscope (TEM) and high power transmission electron microscope (HR-TEM) detection, from detection architecture, different from the product pattern obtaining in embodiment 1, the pattern that the product that embodiment 2 obtains contains nanofiber and orderly meso-hole structure, and embodiment 3 products obtained therefroms are the nano particle evenly with order mesoporous structure.Thus, can be by adopting different types of melamine salt to obtain the product of different-shape.
Embodiment 4
The add-on of fructose is 0.04mol, hydrothermal temperature be 140 DEG C of all the other reinforced and processing condition with embodiment 1, obtain order mesoporous nitrating Carbon Materials.
Embodiment 5
The add-on of fructose is 0.06mol, and all the other reinforced and processing condition, with embodiment 1, obtain order mesoporous nitrating Carbon Materials.
Embodiment 6
Fructose replaces with wood sugar, and all the other reinforced and processing condition, with embodiment 1, obtain order mesoporous nitrating Carbon Materials.
Through scanning electron microscope (SEM) and transmission electron microscope (TEM) and high power transmission electron microscope (HR-TEM) detection, embodiment 4-6 all can obtain order mesoporous nitrating Carbon Materials.
Application examples 1: as heavy metal adsorption material
The order mesoporous nitrating Carbon Materials 10mg respectively embodiment 1-6 being prepared joins 10mL molecular volume content and is respectively the Mn of 10mmol/L
2+, Fe
3+, Ni
2+, Co
2+, Cu
2+, Pb
2+nitrate aqueous solution in, stir 24h, filter, get filtrate and carry out plasma body atomic absorption spectrum test and adsorptive capacity calculating, absorption result is as shown in table 2.
Table 2
As seen from the results in Table 1, the order mesoporous nitrating Carbon Materials that embodiment 1-6 prepares is best to the adsorption effect of mn ion and iron ion, simultaneously also better to the adsorption effect of cupric ion and lead ion.
Application examples 2: as electrode material for super capacitor:
The order mesoporous nitrating Carbon Materials that embodiment 1 is obtained loads in nickel foam, and as the anode of ultracapacitor, adopt three-electrode system to test the cyclic voltammetry curve of this anode, detected result as shown in Figure 4, along with the reduction of sweep velocity, cyclic voltammetry curve has kept the shape of four limit rhombuses, illustrates that this bill of material has revealed the feature of stable double layer capacitor, therefore the order mesoporous nitrating Carbon Materials that, the present invention prepares is fine as electrode material for super capacitor effect.
Claims (10)
1. a preparation method for surface-functionalized order mesoporous nitrating Carbon Materials, comprising:
Taking carbohydrate as raw material, be dissolved in the aqueous dispersion of melamine salt, simultaneously taking amphiphatic triblock copolymer as soft template, 120-200 DEG C of hydro-thermal reaction, hydro-thermal reaction product after filtration, washing, the dry porous carbon materials that obtains, through high-temperature calcination, obtain the order mesoporous nitrating Carbon Materials of carbohydrate-derivedization again.
2. the preparation method of surface-functionalized order mesoporous nitrating Carbon Materials according to claim 1, is characterized in that, described carbohydrate is at least one in pentose, hexose, oligose.
3. the preparation method of surface-functionalized order mesoporous nitrating Carbon Materials according to claim 1, it is characterized in that, described melamine salt is at least one in trimeric cyanamide vitriol, melamine phosphate, trimeric cyanamide oxalate, trimeric cyanamide carboxylate salt, melamine sulfonate.
4. the preparation method of surface-functionalized order mesoporous nitrating Carbon Materials according to claim 1, is characterized in that, described amphiphatic triblock copolymer is F127 or P123.
5. the preparation method of surface-functionalized order mesoporous nitrating Carbon Materials according to claim 1, it is characterized in that, the aqueous dispersion of described melamine salt is prepared by following method: to mineral acid or the organic acid aqueous solution, add trimeric cyanamide, the 20-26h that refluxes at temperature 80-100 DEG C, reaction generates melamine salt.
6. the preparation method of surface-functionalized order mesoporous nitrating Carbon Materials according to claim 5, it is characterized in that, prepare in melamine salt process: in the time that mineral acid or organic acid are sulfuric acid, phosphoric acid, carboxylic acid, sulfonic acid, the mol ratio of mineral acid or organic acid and trimeric cyanamide is 1:1; In the time that mineral acid or organic acid are oxalic acid, the mol ratio of mineral acid or organic acid and trimeric cyanamide is 1:1 or 1:2.
7. the preparation method of surface-functionalized order mesoporous nitrating Carbon Materials according to claim 1, is characterized in that, described carbohydrate and the material ratio of soft template are: calculate with 1mol carbohydrate, the soft template needing is 100-200g.
8. the preparation method of surface-functionalized order mesoporous nitrating Carbon Materials according to claim 1, is characterized in that, described trimeric cyanamide and the mol ratio of carbohydrate are 1:1-6.
9. the preparation method of surface-functionalized order mesoporous nitrating Carbon Materials according to claim 1, it is characterized in that, described high-temperature calcination adopts two-section calcining process, specifically comprise: dried hydrothermal product first in air 400 DEG C of calcining 2h or in nitrogen atmosphere 550 DEG C of calcining 4h remove soft template, then 900 DEG C of calcining 1h, form order mesoporous nitrating Carbon Materials.
10. a surface-functionalized order mesoporous nitrating Carbon Materials, is characterized in that, is prepared by preparation method described in the arbitrary claim of claim 1-9.
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