CN106564868B - A kind of preparation method of nitrogen-doped porous carbon material - Google Patents
A kind of preparation method of nitrogen-doped porous carbon material Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of nitrogen-doped porous carbon material.The present invention for carbon source and nitrogen source, using metal ion as ligand, is based on metal organic coordination theoretical informatics carbonization presoma with poly- 4 vinylpyridine (P4VP).Nitrogen-doped porous carbon material is arrived by high temperature cabonization, salt acid elution to obtain the final product again.Preparation method of the present invention not only has the characteristics that step is simple and convenient to operate, is suitble to large-scale production, but also the nitrogen-doped porous carbon material prepared has the advantages that large specific surface area, pore-size distribution concentration, nitrogen element content are high.Energy stores conversion, catalysis and field of environment protection can be can be widely applied to avoid template step complexity or activation method equipment requirement height, the non-uniform defect of pore-size distribution by preparing porous carbon materials using this method.
Description
Technical field
The invention belongs to technical field of function materials, specifically, are related to a kind of preparation side of nitrogen-doped porous carbon material
Method.
Background technology
For a long time, the novel porous materials with fine pore passage structure are designed and developed, are always material science research
Key areas.Porous material is a kind of by being mutually communicated or closed hole constitutes the material of network structure, because having molecule
The uniform pore passage structure of size, the characteristics such as continuous pore canal system and big specific surface area, absorption, ion exchange, particularly
It is widely used in fields such as catalysis.In recent years, domestic and international scientific worker is developed successively suitable for various different applications
Purpose porous material (for example, silica, aluminium oxide, titanium dioxide, carbon material etc.), and be applied to absorption and detach, be catalyzed,
The fields such as energy electronic, pharmacy and bioengineering.It is porous according to the regulation of International Union of Pure and Applied Chemistry (IUPAC)
Material can be divided into three kinds according to the size of its pore size：Wherein it is less than the poromerics that 2nm is, 2~50nm is mesoporous material
Material, it is large pore material to be more than 50nm, each pore passage structure has its distinctive property.
In numerous porous materials, porous carbon materials due to peculiar property, synthesis material is abundant and is easy to obtain
It takes, therefore there are universal applications in modern science.Porous carbon materials refer to using carbon as basic framework, and have different holes
A kind of material of gap structure.Porous carbon materials have a series of spies such as chemical stability height, acid and alkali-resistance, high temperature resistant, conduction, heat conduction
Point, this kind of material usually have flourishing hole, high specific surface area, high chemical stability, excellent heat-resisting, acid and alkali-resistance and
Unique electronic conductivity matter is one of indispensable important materials in modern industry, is widely used in electrode material (as fired
Expect battery, ultracapacitor etc.), sorbing material, energy storage material and catalyst carrier etc..
The method that porous carbon is prepared in traditional sense can be divided into activation method and template.Activation method includes:(a) chemistry is living
Change, the activation combination of physically activated or physical chemistry；(b) catalytic activation of carbon matrix precursor；(c) carbonization-activation of biomass；(d) high
The carbonization of molecule aeroge；(e) the high molecular polymer mixing carbonization that can be carbonized and be pyrolyzed.It can be quickly square using activation method
Just prepare porous carbon materials, but its often unordered porous carbon materials obtained, it is difficult to control its hole road shape and hole
Diameter；And some specific activators are (such as：Potassium hydroxide, phosphoric acid) there is under high temperature strong corrosivity, improve the material of equipment
Matter requirement, increases production cost.Template:Template is effectively to control pore structure using template, to prepare structure
Orderly, the method for the uniform material in aperture.According to the difference of the template used, template can be divided into following several:(a) soft mode
Plate method is a kind of method of direct synthesizing ordered mesoporous carbon, (such as by carbon matrix precursor：Phenolic resin) and soft template is (mainly
Surfactant) interaction progress self assembly, then surfactant decomposes to obtain porous structure in carbonisation；(b)
Hard template method introduces carbon matrix precursor, by carbon using a kind of material with special pore structure as hard template in its duct
Change and remove hard template and obtains the porous carbon materials with special pore structure；(c) double-template method, (such as using hard template：Porous oxygen
Change aluminium and polystyrene sphere) come control carbon material pattern or macropore formation, while being controlled orderly using soft template
The formation of mesopore orbit, to obtain that there are the porous carbon materials of grade pore passage structure.Pattern can be prepared using template
Controllable porous carbon materials, but complicated preparation process makes it that can only rest on the academic research stage, seriously limits this method
Practical application.
Porous carbon materials have high-specific surface area, big pore volume, connection and uniform duct, adjustable aperture etc. many
Advantage makes it be with a wide range of applications in catalysis, absorption, sensing, electrochemistry etc..In order to further improve porous carbon
Hetero atom N, is usually doped in surface or the structure of porous carbon materials, makes porous carbon materials by the application of material in these areas
The performances of various aspects be upgraded and improved.
Theoretical and numerous experimental study shows that nitrogen is the ideal element for adulterating carbon material.Nitrogen is in the periodic table of elements
Positioned at V A races, with carbon atom ortho position, the radius of atomic radius and carbon atom is close, therefore the doping of nitrogen-atoms can make carbon material
Lattice distortion as small as possible occurs.The lone pair electrons carried on nitrogen-atoms play the role of carrier, when incorporation porous carbon
After material, the charge density of porous carbon materials will be made to increase, forms n-type semiconductor, and then make the electric conductivity of porous carbon materials
Increase.Doping of the nitrogen-atoms in porous carbon materials structure will certainly increase the defective bit of porous carbon materials, in electrochemistry
Or the activity in electrocatalytic reaction increases.Surface nitrogen-doping can then improve the surface hydrophilic performance of porous carbon materials, improve
Its biocompatibility；Surface N doping is but also material improves its absorption property to sour gas with certain alkalinity.Separately
Outer nitrogen-containing functional group makes porous carbon materials be more easy to be combined with metal ion, more uniformly disperses to be conducive to metallic catalyst
On the surface of carbon material.In short, the porous carbon materials of N doping have more excellent properties than pure porous carbon materials, it will significantly
Application range of the extension carbon material in every field.
Invention content
For overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of preparation sides of nitrogen-doped porous carbon material
Method.It is first with poly 4 vinyl pyridine (P4VP) for carbon source and nitrogen source, using metal ion as ligand, is based on metal organic coordination
Theoretical informatics carbonization presoma；Nitrogen-doped porous carbon material can be obtained by high temperature cabonization, salt acid elution again.The system of the present invention
Preparation Method step is simple and convenient to operate, is suitble to large-scale production；And the nitrogen-doped porous carbon material large specific surface area of preparation,
Pore-size distribution is concentrated, nitrogen element content is high.
The specific technical solution of the present invention is implemented by following steps：
The present invention provides a kind of preparation method of nitrogen-doped porous carbon material, is as follows：
(1) P4VP/ ethanol solutions are prepared：Poly 4 vinyl pyridine P4VP and absolute ethyl alcohol are mixed, stirring, is obtained
P4VP/ ethanol solutions；
(2) coordinating metal solution is prepared：Molysite and absolute ethyl alcohol are mixed, stir to get coordinating metal solution；
(3) preparation of carbonization presoma：At room temperature, coordinating metal solution and P4VP/ ethanol solutions are mixed, is formed
Complex precipitates, then through being evaporated under reduced pressure, being dried in vacuo up to carbonization presoma；
(4) it is carbonized：Carbonization presoma is placed in tube furnace and is carbonized, is taken out after cooling and obtains the nitrogen-doped carbon containing Fe；
(5) pickling：It by the nitrogen-doped carbon acid elution containing Fe, is washed with water, filtering, to obtain N doping more for vacuum drying
Hole carbon.
In the present invention, in step (1), a concentration of 0.02~0.2mol/L of P4VP/ ethanol solutions.
In the present invention, in step (2), molysite is iron chloride or ferric sulfate；A concentration of the 0.02 of coordinating metal solution~
0.2mol/L。
In the present invention, in step (3), the Fe in coordinating metal solution3+The molar ratio of ion and P4VP are 1:4~4:1.
In the present invention, in step (4), when carbonization, heating schedule is：800 are warming up to 2~5 DEG C of heating rate~
1200 DEG C, heat preservation 8~for 24 hours.
In the present invention, in step (5), acid is the hydrochloric acid or sulfuric acid of 1~2mol/L.
The nitrogen-doped porous carbon material that the above-mentioned preparation method of the present invention obtains, nitrogen content are 2.7~9.9wt%.It is excellent
Choosing, nitrogen content is 4.7~7.5wt%.
Compared to the prior art, the beneficial effects of the present invention are：The preparation method of the present invention not only have step it is simple,
The characteristics of easy to operate, suitable large-scale production；And the nitrogen-doped porous carbon material prepared has large specific surface area (specific surface
Reach 1211m2/ g), pore-size distribution concentrate, nitrogen element content high (can reach 9.9wt%) the advantages of.Big specific surface area makes
Material has more accessible surfaces；The doping of high nitrogen can be improved the catalytic activity of material, capacitive property and to acid
The absorption property of property gas.Preparing porous carbon materials using this method can be to avoid template step complexity or activation method equipment
It is required that high, the non-uniform defect of pore-size distribution, can be widely applied to energy stores conversion, catalysis and field of environment protection.
Description of the drawings
Fig. 1：(A) technology path of the invention；(B) structural formula of P4VP, P4VP and FeCl3Coordination structure.
Fig. 2：The scanning electron microscope (SEM) photograph of (a, b) NDPC-0.25-800；The projection electron microscope of (c, d) NDPC-0.25-800.
Fig. 3：(a) N of NDPC-0.25-8002Adsorption/desorption curve；(b) the NLDFT pore-size distributions of NDPC-0.25-800
With accumulation pore volume curve.
Fig. 4：(a) the full spike spectrums of the XPS of NDPC-0.25-800；(b) CO of NDPC-0.25-8002Adsorption curve.
Fig. 5：The scanning electron microscope (SEM) photograph of (a, b) NDPC-1-800；The projection electron microscope of (c, d) NDPC-1-800.
Fig. 6：(a) N of NDPC-1-10002Adsorption/desorption curve；(b) the NLDFT pore-size distributions of NDPC-1-1000 and tired
Product pore volume curve.
Fig. 7：(a) the full spike spectrums of the XPS of NDPC-1-1000；(b) CO of NDPC-1-10002Adsorption curve.
Fig. 8：The scanning electron microscope (SEM) photograph of (a, b) NDPC-4-1000；The projection electron microscope of (c, d) NDPC-4-1000.
Fig. 9：(a) N of NDPC-4-10002Adsorption/desorption curve；(b) the NLDFT pore-size distributions of NDPC-4-1000 and tired
Product pore volume curve.
Figure 10：(a) the full spike spectrums of the XPS of NDPC-4-1000；(b) CO of NDPC-4-10002Adsorption curve.
Specific implementation mode
Technical scheme of the present invention is further described with reference to specific sample of implementing, but the protection of the present invention
Range is not limited to following embodiments.
The present invention respectively implements various raw materials used in sample, is commercially available unless otherwise specified.
The nitrogen-doped carbon sample that the present invention respectively implements the containing metal iron prepared in sample is abbreviated as Fe-NDC-X-Y, X generations
Table P4VP and Fe3+Molar ratio；Y is represented as carburizing temperature.
The N doping porous carbon sample that the present invention respectively implements to prepare in sample is abbreviated as NDPC-X-Y, X represent P4VP with
Fe3+Molar ratio；Y is represented as carburizing temperature.
Technical scheme of the present invention is as shown in Figure 1.Figure 1A be the present invention technology path, Figure 1B be P4VP structural formula and
P4VP and Fe3+Coordination structure.
Embodiment 1
(1) P4VP/ ethanol solutions are prepared：At room temperature, 1.05g P4VP are taken to be added in 250ml absolute ethyl alcohols, magnetic
Power stirring makes P4VP dissolve to obtain the P4VP/ ethanol solutions of a concentration of 0.04mol/L, for use.
(2) coordinating metal solution is prepared (with Fe3+For)：Take 2.7g FeCl3It is dissolved in 250ml absolute ethyl alcohols, magnetic force
Stirring makes FeCl3Dissolving obtains the FeCl of a concentration of 0.04mol/L3/ ethanol solution, for use.
(3) preparation of carbonization presoma：Under the conditions of room temperature magnetic agitation, 25ml FeCl are taken3/ ethanol solution is added
Into 100ml P4VP/ ethanol solutions, molar ratio (P4VP：Fe3+=4:1；Reaction for 24 hours, it is heavy to form stable complex
It forms sediment, then is evaporated under reduced pressure through 60 DEG C, 120 DEG C of vacuum drying 12h are carbonized presoma to obtain the final product.
(4) it is carbonized：Carbonization presoma is positioned in quartz boat, quartz boat is then put into tube type resistance furnace, nitrogen is protected
Shield is warming up to 800 DEG C with 5 DEG C of heating rate, keeps the temperature 8h then natural coolings, obtains the nitrogen-doped carbon (Fe-NDC- containing metal
0.25-800)。
(5) pickling：100mg Fe-NDC-0.25-800 are taken to be fitted into the flask of 250ml, with a concentration of 1mol/L of 100ml
HCl wash 3 times, then washed 3 times through deionization, filtering, 80 DEG C of vacuum drying are for 24 hours up to nitrogen-doped porous carbon material (NDPC-
0.25-800)。
The nitrogen-doped carbon material NDPC-O.25-800 of above-mentioned gained.With S-4800 field emission scanning electron microscopes (FE-
SEM its pattern and microstructure) are characterized.As a result as shown in Fig. 2 a-b：Show NDPC-0.25-800 in worm stratiform accumulation knot
Structure；Its porosity is characterized with JEOL-2100F projection electron microscopes, as a result as shown in Fig. 2 c-d：Show NDPC-0.25-800
With the nano grade pore being evenly distributed；Its surface area and pore-size distribution are tested with 3H-2000PM2 specific surfaces and micropore analyzer,
As a result such as Fig. 3：NDPC-0.25-800 specific surface areas 1211m is obtained according to BET equation calculations2/ g, total pore volume 0.96cm3/ g (figures
3a)；Analyzing its pore-size distribution according to non-localized density functional theory (NLDFT) shows NDPC-0.25-800 in micropore areaWith very narrow pore-size distribution, most of pore volume all contributes (Fig. 3 b) by micro-porous area；With AXIS UltaDLD
Type x-ray photoelectron spectroscopy (XPS) characterizes chemical state and the elemental composition analysis of aeroge, as shown in fig. 4 a：Show NDPC-
0.25-800 nitrogen contents reach 7.5wt%.Its CO is tested with 3H-2000PM2 specific surfaces and micropore analyzer2Adsorption capacity, such as
Shown in Fig. 4 b：Show the CO of NDPC-0.25-800 when 0 DEG C and 25 DEG C of normal pressure2Adsorption capacity respectively reach 6.8mmol/g and
4.3mmol/g。
Embodiment 2
(1) P4VP/ ethanol solutions are prepared：At room temperature, 1.05g P4VP are taken to be added in 250ml absolute ethyl alcohols, magnetic
Power stirring makes P4VP dissolve to obtain the P4VP/ ethanol solutions of a concentration of 0.04mol/L, for use.
(2) coordinating metal solution is prepared (with Fe3+For)：Take 2.7g FeCl3It is dissolved in 250ml absolute ethyl alcohols, magnetic force
Stirring makes FeCl3Dissolving obtains the FeCl of a concentration of 0.04mol/L3/ ethanol solution, for use.
(3) preparation of carbonization presoma：Under the conditions of room temperature magnetic agitation, 100ml FeCl are taken3/ ethanol solution is added
Into 100ml P4VP/ ethanol solutions, molar ratio (P4VP：Fe3+=1:1；Reaction for 24 hours, it is heavy to form stable complex
It forms sediment, then is evaporated under reduced pressure through 60 DEG C, 120 DEG C of vacuum drying 12h are carbonized presoma to obtain the final product.
(4) it is carbonized：Carbonization presoma is positioned in quartz boat, quartz boat is then put into tube type resistance furnace, nitrogen is protected
Shield is warming up to 1000 DEG C with 5 DEG C of heating rate, keeps the temperature 8h then natural coolings, obtains the nitrogen-doped carbon (Fe- containing metal
NDC-1-1000)。
(5) pickling：100mg Fe-NDC-1-1000 are taken to be fitted into the flask of 250ml, with a concentration of 1mol/L's of 100ml
HCl is washed 3 times, then is washed 3 times through deionization, filtering, and 80 DEG C of vacuum drying are for 24 hours up to nitrogen-doped porous carbon material (NDPC-1-
1000)。
The nitrogen-doped carbon material NDPC-1-1000 of above-mentioned gained.With S-4800 field emission scanning electron microscopes (FE-
SEM its pattern and microstructure) are characterized.As a result as shown in Fig. 5 a-b：Show that larger linked hole occur in the surfaces NDPC-1-1000
Structure, and be in worm stratiform packed structures；Its porosity is characterized with JEOL-2100F projection electron microscopes, as a result such as Fig. 5 c-d
It is shown：Show that NDPC-1-1000 has the nano grade pore being evenly distributed；It is tested with 3H-2000PM2 specific surfaces and micropore analyzer
Its surface area and pore-size distribution, as a result such as Fig. 6：NDPC-1-1000 specific surface areas 737m is obtained according to BET equation calculations2/ g, total hole
Volume 0.96cm3/ g (Fig. 6 a)；Its pore-size distribution, which is analyzed, according to non-localized density functional theory (NLDFT) shows NDPC-1-
1000 in micropore areaWith very narrow pore-size distribution, it can be seen that micro pore volume accounts for from accumulation pore volume curve
The ratio of total pore volume is decreased obviously (Fig. 6 b)；With AXIS UltaDLDType x-ray photoelectron spectroscopy (XPS) characterizes aeroge
Chemical state and elemental composition analysis, as shown in Figure 7a：Show that NDPC-1-1000 nitrogen contents reach 4.7wt%.With 3H-
2000PM2 specific surfaces and micropore analyzer test its CO2Adsorption capacity, as shown in Figure 7b：When showing 0 DEG C and 25 DEG C of normal pressure
The CO of NDPC-1-10002Adsorption capacity respectively reaches 4.2mmol/g and 3.1mmol/g.
Embodiment 3
(1) P4VP/ ethanol solutions are prepared：At room temperature, 1.05g P4VP are taken to be added in 250ml absolute ethyl alcohols, magnetic
Power stirring makes P4VP dissolve to obtain the P4VP/ ethanol solutions of a concentration of 0.04mol/L, for use.
(2) coordinating metal solution is prepared (with Fe3+For)：Take 2.7g FeCl3It is dissolved in 250ml absolute ethyl alcohols, magnetic force
Stirring makes FeCl3Dissolving obtains the FeCl of a concentration of 0.04mol/L3/ ethanol solution, for use.
(3) preparation of carbonization presoma：Under the conditions of room temperature magnetic agitation, 100ml FeCl are taken3/ ethanol solution is added
Into 25ml P4VP/ ethanol solutions, molar ratio (P4VP：Fe3+=1:4；Reaction for 24 hours, forms stable complex precipitation,
It is evaporated under reduced pressure again through 60 DEG C, 120 DEG C of vacuum drying 12h are carbonized presoma to obtain the final product.
(4) it is carbonized：Carbonization presoma is positioned in quartz boat, quartz boat is then put into tube type resistance furnace, nitrogen is protected
Shield is warming up to 1000 DEG C with 5 DEG C of heating rate, keeps the temperature 8h then natural coolings, obtains the nitrogen-doped carbon (Fe- containing metal
NDC-4-1000)。
(5) pickling：100mg Fe-NDC-1-1000 are taken to be fitted into the flask of 250ml, with a concentration of 1mol/L's of 100ml
HCl is washed 3 times, then is washed 3 times through deionization, filtering, and 80 DEG C of vacuum drying are for 24 hours up to nitrogen-doped porous carbon material (NDPC-4-
1000)。
The nitrogen-doped carbon material NDPC-4-1000 of above-mentioned gained.With S-4800 field emission scanning electron microscopes (FE-
SEM its pattern and microstructure) are characterized.As a result as shown in figure 8 a-b：Show that larger linked hole occur in the surfaces NDPC-1-800
Structure, and be in worm stratiform packed structures；Its porosity is characterized with JEOL-2100F projection electron microscopes, as a result such as Fig. 8 c-d
It is shown：Show that NDPC-4-1000 has the nano grade pore being evenly distributed；It is tested with 3H-2000PM2 specific surfaces and micropore analyzer
Its surface area and pore-size distribution, the results are shown in Figure 9：N2 adsorption/desorption curve types belong to IV type thermoisopleth and H2Type is stagnant
Ring illustrates that NDPC-4-1000 has mesoporous or macroporous structure caused by hole link afterwards, and NDPC- is obtained according to BET equation calculations
4-1000 specific surface areas 307m2/ g, total pore volume 0.76cm3/ g (Fig. 9 a)；According to non-localized density functional theory (NLDFT) point
Analysing its pore-size distribution shows NDPC-4-1000 in micropore areaIt is bent from accumulation pore volume with very narrow pore-size distribution
It can be seen that the pore passage structure of big pore size almost contributes to the half (Fig. 9 b) of total pore volume on line；With AXIS UltaDLDType
X-ray photoelectron spectroscopy (XPS) characterizes chemical state and the elemental composition analysis of aeroge, as shown in Figure 10 a：Show NDPC-
4-1000 nitrogen contents reach 2.7wt%.Its CO is tested with 3H-2000PM2 specific surfaces and micropore analyzer2Adsorption capacity is such as schemed
Shown in 10b：Show the CO of NDPC-4-1000 when 0 DEG C and 25 DEG C of normal pressure2Adsorption capacity respectively reach 1.3mmol/g and
0.8mmol/g。
The foregoing describe the basic principles, principal features and advantages of the present invention, and the present invention is not by above-described embodiment
Limitation, the above embodiments and description only illustrate the principle of the present invention, is not departing from spirit and scope of the invention
Under the premise of, the present invention also has changes and improvements, these changes and improvements are both fallen in claimed the scope of the present invention.
Claims (8)
1. a kind of preparation method of nitrogen-doped porous carbon material, which is characterized in that be as follows：
(1) P4VP/ ethanol solutions are prepared：Poly 4 vinyl pyridine P4VP and absolute ethyl alcohol are mixed, stirring, is obtained
P4VP/ ethanol solutions；
(2) coordinating metal solution is prepared：Molysite and absolute ethyl alcohol are mixed, stir to get coordinating metal solution；
(3) preparation of carbonization presoma：At room temperature, coordinating metal solution and P4VP/ ethanol solutions are mixed, forms cooperation
Object precipitates, then through being evaporated under reduced pressure, being dried in vacuo up to carbonization presoma；
(4) it is carbonized：Carbonization presoma is placed in tube furnace and is carbonized, is taken out after cooling, obtains the nitrogen-doped carbon containing Fe；
(5) pickling：It by the nitrogen-doped carbon acid elution containing Fe, is washed with water, filtering, to obtain N doping porous for vacuum drying
Carbon.
2. preparation method according to claim 1, which is characterized in that in step (1), P4VP/ ethanol solutions it is dense
Degree is 0.02~0.2mol/L.
3. preparation method according to claim 1, which is characterized in that in step (2), molysite is iron chloride or sulfuric acid
Iron；A concentration of 0.02~0.2mol/L of coordinating metal solution.
4. preparation method according to claim 1, which is characterized in that in step (3), the Fe in coordinating metal solution3+From
The molar ratio of son and P4VP are 1:4~4:1.
5. preparation method according to claim 1, which is characterized in that in step (4), when carbonization, heating schedule is：With 2
~5 DEG C of heating rate is warming up to 800~1200 DEG C, and heat preservation 8~for 24 hours.
6. preparation method according to claim 1, which is characterized in that in step (5), acid be 1~2mol/L hydrochloric acid or
Person's sulfuric acid.
7. a kind of preparation method according to one of claim 1-6, which is characterized in that obtained nitrogen-doped porous carbon material
Nitrogen content be 2.7~9.9wt%.
8. preparation method according to claim 7, which is characterized in that nitrogen content is 4.7~7.5wt%.
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| CN110395711A (en) * | 2019-09-04 | 2019-11-01 | 河北省科学院能源研究所 | The preparation method and applications of nitrogenous porous carbon materials based on polyaspartic acid salts |
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| CN112390246A (en) * | 2020-11-12 | 2021-02-23 | 同济大学 | Nitrogen-doped porous carbon synthesized by anion-induced selective growth of ultra-small copper template in carbon nanosheet, and method and application thereof |
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