CN108455557B - Nitrogen sulphur codope ordered mesoporous carbon material and its preparation method and application - Google Patents
Nitrogen sulphur codope ordered mesoporous carbon material and its preparation method and application Download PDFInfo
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- CN108455557B CN108455557B CN201810195318.8A CN201810195318A CN108455557B CN 108455557 B CN108455557 B CN 108455557B CN 201810195318 A CN201810195318 A CN 201810195318A CN 108455557 B CN108455557 B CN 108455557B
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
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Abstract
The invention discloses a kind of nitrogen sulphur codope ordered mesoporous carbon materials and its preparation method and application, the ordered mesoporous carbon material is mainly using SBA-15 as mesopore molecular sieve template, dithizone is single carbon source, sulphur source and nitrogen source, it is polymerize using carbon tetrachloride as solvent, form nitrogen sulphur codope ordered mesopore carbon polymer, after resulting polymers high temperature pyrolysis, etched removal mesoporous molecular sieve SBA-15 obtains nitrogen sulphur codope ordered mesoporous carbon material.Preparation method includes Zeolite synthesis, polymer preparation and pyrolysis, template removal.Nitrogen sulphur codope ordered mesoporous carbon material of the invention has the advantages that high mechanical strength, uniform pore diameter, stability are strong, bio-compatibility is good, Electrochemical Detection superior performance, it is that one kind can be with the environmentally friendly ordered mesoporous carbon material of extensive utilization, preparation method has many advantages, such as that process flow is simple, reaction condition is mild, environmental protection, can be used for large scale preparation.
Description
Technical field
The invention belongs to the electrochemical sensing technical fields of functional form material, are related to a kind of element codope ordered mesopore carbon
Material and its preparation method and application, and in particular to a kind of nitrogen sulphur codope ordered mesoporous carbon material and preparation method thereof and electrification
Learn Application in Sensing.
Background technique
Porous carbon refers to the carbon material with certain cellular structure.According to determining for International Union of Pure and Applied Chemistry
Justice, porous carbon materials can be divided into following three classes according to pore size: porous carbon materials of the aperture less than 2nm are micropore carbon materials
Material, the porous carbon materials greater than 50nm are macropore carbon material, and the porous carbon materials between 2-50nm are meso-porous carbon material.Wherein,
Whether mesoporous carbon can orderly be divided into ordered mesoporous carbon material and unordered meso-porous carbon material according to mesoporous.
Ordered mesoporous carbon material is a kind of novel non-silicon-based mesoporous material, the hole with uniform aperture, high-sequential
Road distribution and huge specific surface area and Kong Rong, absorption, catalysis and in terms of be with a wide range of applications.
Wherein, ordered mesoporous carbon material has since it is with biggish specific surface area, relatively large aperture and regular cellular structure
Conducive to the enrichment and transmission of ion, and itself has high activity, is easy to surface modification or functionalization, so that order mesoporous carbon materials
Material, which rapidly develops, becomes a kind of emerging electrochemical material.
Numerous studies document shows that S, B, P, F, N are adulterated in ordered mesoporous carbon material not only can change urging for material
Change performance, while also oxygen-containing functional group can be introduced into material surface, to improve absorption and the redox ability of carbon material.
Relative to single ordered mesoporous carbon material, electric conductivity, wettability and the hydrophily of hybrid ordered mesoporous carbon material are all obtained
Biggish promotion.Currently, the doping of dual element can cause carbon material for the ordered mesopore carbon of single element doping
Certain change occurs for crystal structure, is conducive to the raising of chemical property, and still, the ordered mesopore carbon of dual element doping is often
Many kinds of substance is needed to provide corresponding element source, and preparation process is relative complex, and preparation cost also further increases, and is unfavorable for
Large scale preparation and application, limit its application and develop, and the ordered mesopore carbon of dual element doping is mainly used in raising
Electrocatalysis characteristic, application range are smaller.Therefore, the novel ordered mesopore carbon that can be applied to the other directions of electrochemical field is explored
Material has important practical significance and current demand.
Summary of the invention
The technical problem to be solved in the invention is to overcome the deficiencies of the prior art and provide a kind of high mechanical strength, aperture
Uniformly, stability is strong, bio-compatibility is good, Electrochemical Detection superior performance and environmental-friendly nitrogen sulphur codope are order mesoporous
Carbon material and its preparation method and application, the application refer in particular to the application in electrochemical sensing (also making Electrochemical Detection) field.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of nitrogen sulphur codope ordered mesoporous carbon material, the nitrogen sulphur codope ordered mesoporous carbon material is mainly with SBA-15
It is polymerize using carbon tetrachloride as solvent, shape for mesopore molecular sieve template with dithizone for single carbon source, sulphur source and nitrogen source
At nitrogen sulphur codope ordered mesopore carbon polymer, nitrogen sulphur codope ordered mesopore carbon polymer is carved after high temperature pyrolysis makes carbonization
Etching off removes mesoporous molecular sieve SBA-15, obtains nitrogen sulphur codope ordered mesoporous carbon material.
As a general technical idea, the present invention also provides a kind of preparation sides of nitrogen sulphur codope ordered mesoporous carbon material
Method, comprising the following steps:
The synthesis of S1, mesoporous molecular sieve SBA-15: by block copolymer P123 and tetraethyl orthosilicate in hydrochloric acid solution
It is uniformly mixed, then carries out crystallization and roasting, obtain mesoporous molecular sieve SBA-15；
The preparation of S2, nitrogen sulphur codope ordered mesopore carbon polymer: by gained mesoporous molecular sieve SBA-15, dithizone and four
The mixing of chlorination carbon and ultrasonic disperse, carry out heating polymerization for gained mixture, obtain nitrogen sulphur codope ordered mesopore carbon polymer；
S3, high temperature pyrolysis: by gained nitrogen sulphur codope ordered mesopore carbon polymer grinding after under inert gas protection into
Row high temperature pyrolysis, makes polymer carbonization, obtains thermal decomposition product；
The etching of S4, mesoporous molecular sieve SBA-15: gained thermal decomposition product being added in sodium hydroxide solution and is stirred, with
Etching removal mesoporous molecular sieve SBA-15 template, is washed out and dries, obtain nitrogen sulphur codope ordered mesoporous carbon material.
In the preparation method of above-mentioned nitrogen sulphur codope ordered mesoporous carbon material, it is preferred that described mesoporous in the step S2
The mass ratio of molecular sieve SBA-15 and dithizone is 1: 1~1.25, and the time of the ultrasonic disperse is 2h~4h, the ultrasound point
After dissipating gained mixture is first stirred into 10h~12h at normal temperature, then be warming up to 60 DEG C~100 DEG C and polymerize, polymerization time is
6h~12h.
In the preparation method of above-mentioned nitrogen sulphur codope ordered mesoporous carbon material, it is preferred that described embedding in the step S1
The mass ratio of section copolymer p 123 and tetraethyl orthosilicate is 1: 2~3, and described be uniformly mixed refers in 35 DEG C~40 DEG C water-bath items
Stir 20h~for 24 hours under part, the crystallization refer at 85 DEG C~135 DEG C heating water bath for 24 hours~48h makes to generate crystallization, the roasting
The temperature of burning is 550 DEG C~800 DEG C, and the time of the roasting is 5h~8h.
In the preparation method of above-mentioned nitrogen sulphur codope ordered mesoporous carbon material, it is preferred that described lazy in the step S3
Property gas be nitrogen, the high temperature pyrolysis uses procedural heating: being risen to first with 2 DEG C/min~5 DEG C/min heating rate
600 DEG C~900 DEG C, then keep 2h~4h.
In the preparation method of above-mentioned nitrogen sulphur codope ordered mesoporous carbon material, it is preferred that in the step S4, the hydrogen
The concentration of sodium hydroxide solution is 1mol/L~2mol/L, and the temperature of the sodium hydroxide solution stirring is 80 DEG C~100 DEG C, described
Dry temperature is 60 DEG C~100 DEG C.
In the preparation method of above-mentioned nitrogen sulphur codope ordered mesoporous carbon material, it is preferred that, first will be embedding in the step S1
Section copolymer p 123 is placed in dissolution in hydrochloric acid solution and obtains the hydrochloric acid solution of block copolymer P123, then by tetraethyl orthosilicate
It is added dropwise in the hydrochloric acid solution of block copolymer P123 and is mixed.
In the preparation method of above-mentioned nitrogen sulphur codope ordered mesoporous carbon material, it is preferred that in the step S4, the heat
Solution product filters after being placed in sodium hydroxide solution stirring 0.5h~1h, and the sodium hydroxide solution then more renewed repeats abovementioned steps
2~4 times, to realize etching process.
As a general technical idea, the present invention also provides a kind of above-mentioned nitrogen sulphur codope ordered mesoporous carbon material or
Nitrogen sulphur codope ordered mesoporous carbon material answering in electrochemical sensing (Electrochemical Detection) made from the above-mentioned preparation method of person
With.
In above-mentioned application, it is preferred that the application is the following steps are included: by nitrogen sulphur codope ordered mesoporous carbon material point
It is scattered in perfluorinated sulfonic acid Nafion and drop coating is in glassy carbon electrode surface, air-dry at room temperature, as in three electrode system
Working electrode, the reference electrode in three electrode system are saturated calomel electrode, are platinum electrode to electrode；The nitrogen sulphur is total
Adulterate ordered mesoporous carbon material additive amount be the nitrogenous sulphur codope ordered mesopore carbon 50mg of every 5mL~10mL perfluorinated sulfonic acid~
100mg。
In step S2 of the invention, heating polymerization can carry out in a vacuum drying oven, equal using vacuum or non-vacuum environment
Can, material has also obtained drying in polymerization process, makes the material for being put into the carbonization of tube furnace high temperature without containing moisture.
In step S2 of the invention, carbon tetrachloride is intended only as solvent, can vapor away in stirring and heating process, because
This is appropriate.
In step S3 of the invention, the procedural temperature program setting for referring to tube furnace that heats up is for two stages, and one
For the temperature rise period, one is temperature holding stage, by being artificially arranged, by the process control of tube furnace.
In application of the invention, by nitrogen sulphur codope ordered mesoporous carbon material drop coating in glassy carbon electrode surface, mainly answer
Pollutant is detected for electrochemical sensing, the materials conductive performance is good, and there is big specific surface area can load more
For detecting the probe of pollutant, can efficient application in electrochemical sensing detection field.
Main innovation point of the invention is:
1, in the prior art, ordered mesoporous carbon material be applied to mostly electro-catalysis field and adsorbing domain (with redox,
Absorption etc. is based on performances), and based on being adulterated with single element, even if there are multi-element dopings, it is also desirable to which many kinds of substance provides
Corresponding element source, preparation is complicated, at high cost.Applicant is on the basis of numerous studies, it was found that existing ordered mesopore carbon
A variety of limitations present in material propose and improve its technology of preparing, widen the technical goal of its application field, creatively
It is carved by the synthesis of mesoporous molecular sieve SBA-15, the preparation of nitrogen sulphur codope ordered mesopore carbon polymer, high temperature pyrolysis and template
Integrated artistic technology is lost to effectively improve chemical property (cyclic voltammetry and the friendship of nitrogen sulphur codope ordered mesoporous carbon material
After flow impedance method can intuitively illustrate that ordered mesoporous carbon material is connected to glassy carbon electrode surface, so that glass-carbon electrode electric conductivity improves,
To which the electrochemical sensing performance for symbolizing the material is good), it realizes ordered mesoporous carbon material and is led in electrochemical sensing (detection)
The efficient application in domain.
2, the present invention uses mesoporous molecular sieve SBA-15 during preparing nitrogen sulphur codope ordered mesoporous carbon material
Synthesis, nitrogen sulphur codope ordered mesopore carbon polymerization, high temperature pyrolysis and template etching technics, process flow is simple, reaction
Mild condition, environmental protection, and can be prepared on a large scale.Wherein, polymerization technique mainly polymerize SBA-15 with dithizone, so that
Nitrogen, element sulphur can be successfully doped into ordered mesoporous carbon material, in polymerization technique, also specially use ultrasonic disperse, mesh
Be that dithizone (nitrogen, element sulphur provide source) be provided can into the duct of SBA-15, improve material meso-hole structure at
The success rate of type.
3, element codope ordered mesoporous carbon material large specific surface area prepared by the present invention, uniform pore diameter, high mechanical strength,
And there is good electric conductivity, materials'use can be expanded as useful signal in Electrochemical Detection (electrochemical sensing), and
And the element codope can bring a large amount of active site, can connect more probes for being used for Electrochemical Detection, so that
The sensitivity of Electrochemical Detection greatly improves.Therefore, element codope ordered mesoporous carbon material prepared by the present invention is applied to electricity
It has broad application prospects in chemical sensitisation detection.
Compared with the prior art, the advantages of the present invention are as follows:
1. the present invention provides a kind of nitrogen sulphur codope ordered mesoporous carbon material, which replicates well
The orderly hexagon cellular structure of mesoporous molecular sieve SBA-15, have the advantages that it is similar with mesoporous molecular sieve SBA-15, including
With high-specific surface area, big Kong Rong, uniform sequential cellular structure etc.；And after high temperature cabonization, there is mechanical strength
It is high, stability is strong, bio-compatibility is good (fire successful carbon material all and be nontoxic, can bio-compatible), electric conductivity is excellent
More and advantages of environment protection.
2. the present invention provides a kind of preparation method of nitrogen sulphur codope ordered mesoporous carbon material, the ordered mesoporous carbon material
Mainly using SBA-15 as mesopore molecular sieve template, dithizone be single carbon source, sulphur source and nitrogen source, using carbon tetrachloride as solvent into
Row polymerization forms nitrogen sulphur codope ordered mesopore carbon polymer for the polymer high temperature cabonization and then etches mesopore molecular sieve
Nitrogen sulphur codope ordered mesoporous carbon material is prepared in SBA-15.The element codope ordered mesoporous carbon material is only with double sulphur
Hydrazone does not need additional substance as single carbon source, sulphur source and nitrogen source to provide corresponding element source, preparation cost is low；
And handled by ultrasonic disperse and polymerization so that the meso-hole structure of nitrogen sulphur codope ordered mesopore carbon is easier to form and nitrogen,
Element sulphur can Effective Doping into order mesoporous carbon structure；In addition, the present invention is using mesoporous molecular sieve SBA-15 as hard mold
Plate synthetic nitrogen sulphur codope ordered mesopore carbon, reaction condition is mild, preparation process is simple, requires relatively experimental instrument and equipment
Material that is low, preparing is environmentally friendly material, can be used for large scale preparation.
3. the present invention also provides a kind of application of nitrogen sulphur codope ordered mesoporous carbon material in electrochemical sensing, mesh
Before, nitrogen sulphur codope ordered mesoporous carbon material is mainly used in electro-catalysis field, and also there are certain applications in adsorbing domain, but
Never there is the precedent applied to electrochemical sensing detection field.Nitrogen sulphur codope ordered mesopore carbon itself has huge specific surface
Product, further, since the doping of nitrogen, element sulphur causes spin density and charge density in carbon material between adjacent atom to be reallocated,
So that the material significantly improves with a large amount of active site, catalytic performance and has higher electron transfer rate, very greatly
The material electrochemical performance is improved in degree, this makes the material have broad application prospects in electrochemical sensing field.
Detailed description of the invention
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, the technical scheme in the embodiment of the invention is clearly and completely described.
Fig. 1 is the scanning electron microscope (SEM) photograph of nitrogen sulphur codope ordered mesoporous carbon material in the embodiment of the present invention 1.
Fig. 2 is the transmission electron microscope picture of nitrogen sulphur codope ordered mesoporous carbon material in the embodiment of the present invention 1.
Fig. 3 is the energy spectrum diagram of nitrogen sulphur codope ordered mesoporous carbon material in the embodiment of the present invention 1.
Fig. 4 is that the electrochemical current signal of nitrogen sulphur codope ordered mesoporous carbon material in the embodiment of the present invention 2 detects figure.
Fig. 5 is the electrochemical impedance signal detection figure of nitrogen sulphur codope ordered mesoporous carbon material in the embodiment of the present invention 3.
Fig. 6 is the transmission electricity of the nitrogen sulphur codope ordered mesoporous carbon material without S2 step process in comparative example 1 of the present invention
Mirror figure.
Specific embodiment
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and
It limits the scope of the invention.
Material employed in following embodiment and instrument are commercially available.
Embodiment 1
A kind of nitrogen sulphur codope ordered mesoporous carbon material of the invention, the nitrogen sulphur codope ordered mesoporous carbon material mainly with
SBA-15 is mesopore molecular sieve template, and dithizone is single carbon source, sulphur source and nitrogen source, is gathered using carbon tetrachloride as solvent
It closes, forms nitrogen sulphur codope ordered mesopore carbon polymer, after resulting polymers high temperature pyrolysis is made polymer carbonization, then etch
Mesoporous molecular sieve SBA-15 is removed, nitrogen sulphur codope ordered mesoporous carbon material is obtained.
A kind of preparation method of the nitrogen sulphur codope ordered mesoporous carbon material of the present embodiment, comprising the following steps:
The synthesis of S1, mesoporous molecular sieve SBA-15: 2g block copolymer P123 is placed in hydrochloric acid solution and is dissolved, hydrochloric acid is molten
It is that 2mol/L hydrochloric acid is mixed to get with 15mL deionized water that liquid, which is by 60mL concentration, and the salt of block copolymer P123 is obtained after dissolution
Acid solution.Then 4.25g tetraethyl orthosilicate is added dropwise in block copolymer P123 solution, the stirring in water bath at 35 DEG C
For 24 hours, it transfers in the high-temperature high-pressure reaction kettle of polytetrafluoroethylsubstrate substrate, heating water bath carries out crystalline substance for 24 hours under the conditions of 100 DEG C
Change, obtains mixed liquor.Mixed liquor suction filtration is taken into precipitating again, is washed with deionized to neutrality, is dried, place into tube furnace with
The heating rate of 5 DEG C/min is warming up to 550 DEG C and keeps 5h, obtains mesoporous molecular sieve SBA-15.
The preparation of S2, nitrogen sulphur codope ordered mesopore carbon polymer: 1g mesoporous molecular sieve SBA-15 and 1g dithizone are added
Enter into 20mL carbon tetrachloride, after ultrasonic disperse 2h, then stir 10h at normal temperature, so that dithizone and mesopore molecular sieve SBA-
15 are uniformly mixed, and then gained mixture is placed in 60 DEG C of vacuum drying ovens and polymerize 12h, obtains nitrogen sulphur codope ordered mesopore carbon
Polymer.
S3, nitrogen sulphur codope ordered mesopore carbon polymer high temperature pyrolysis: gained nitrogen sulphur codope ordered mesopore carbon is polymerize
Object grinding, is subsequently placed in quartz boat, rises to 800 DEG C under nitrogen protection with the heating rate of 3 DEG C/min, then at 800 DEG C
Place keeps 3h, makes polymer carbonization, obtains thermal decomposition product.
The etching of S4, mesoporous molecular sieve SBA-15: gained thermal decomposition product is placed in the NaOH of 80mL, 2mol/L at 80 DEG C
It is filtered after being stirred one hour in solution, the NaOH solution then more renewed repeats abovementioned steps three times, with mesoporous point of etching removal
Son sieve SBA-15 template, then solution is washed to neutrality and dries 4h in 100 DEG C of baking ovens, it is order mesoporous to obtain nitrogen sulphur codope
Carbon material.
Fig. 1 is the scanning electron microscope (SEM) photograph of nitrogen sulphur codope ordered mesoporous carbon material in the present embodiment, from fig. 1, it can be seen that nitrogen sulphur is total
Doping ordered mesopore carbon is elongated, and the regular arrangement of orderly cellular structure, this illustrates that nitrogen sulphur codope ordered mesopore carbon is fine
Ground replicates the structure of mesoporous molecular sieve SBA-15.
Fig. 2 is the transmission electron microscope picture of nitrogen sulphur codope ordered mesoporous carbon material in the present embodiment, as can be seen from Figure 2, the material
Internal aperture is uniform sequential, and aperture diameter is about 8nm.
Fig. 3 is the energy spectrum diagram of nitrogen sulphur codope ordered mesoporous carbon material in the present embodiment, as can be seen from Figure 3, C, O, S, N element
It is uniformly dispersed in sample, this illustrates that S, N element are successfully doped into order mesoporous carbon structure.
Embodiment 2
A kind of electrochemical current signal detection of the nitrogen sulphur codope ordered mesoporous carbon material of embodiment 1, including following step
It is rapid:
(1) using glass-carbon electrode as working electrode, saturated calomel electrode is used as reference electrode, platinum electrode to electricity
Aforementioned three electrodes connect with electrochemical workstation, establish three-electrode system by pole；
(2) nitrogen sulphur codope ordered mesoporous carbon material is dispersed in Nafion and drop coating is in glassy carbon electrode surface, then
It to bare electrode and is spotted with the glass-carbon electrode of nitrogen sulphur codope ordered mesoporous carbon material respectively and follow the scanning of bad voltammetry.
Fig. 4 is that the electrochemical current signal of nitrogen sulphur codope ordered mesoporous carbon material in the present embodiment detects figure, can from Fig. 4
Know, the glass-carbon electrode current peak for being spotted with nitrogen sulphur codope ordered mesoporous carbon material significantly increases, this illustrates nitrogen sulphur codope
The electric conductivity of ordered mesoporous carbon material is good, has higher electron transfer rate, and can be used as in electrochemical sensing has
Imitate amplification of signal materials'use.
Embodiment 3
A kind of electrochemical impedance signal detection of the nitrogen sulphur codope ordered mesoporous carbon material of embodiment 1, including following step
It is rapid:
(1) using glass-carbon electrode as working electrode, saturated calomel electrode is used as reference electrode, platinum electrode to electricity
Aforementioned three electrodes connect with electrochemical workstation, establish three-electrode system by pole；
(2) nitrogen sulphur codope ordered mesopore carbon is dispersed in Nafion and drop coating is in glassy carbon electrode surface, then distinguished
Electrochemical impedance spectroscopy scanning is carried out to bare electrode and the glass-carbon electrode for being spotted with nitrogen sulphur codope ordered mesopore carbon.
Fig. 5 is the electrochemical impedance signal detection figure of nitrogen sulphur codope ordered mesoporous carbon material in the present embodiment, cross in figure
Coordinate represents impedance real part, and ordinate represents imaginary impedance.Electrochemical impedance spectroscopy is made of a circular arc and straight line, is
When arc-shaped, voltage change is in high band, corresponds to electrochemical system median surface electronics transfer limited situation, i.e. polarization electricity
Resistance；When it is linear, voltage change is in low-frequency range, corresponds to electrolyte solution diffusion limited process, ie in solution resistance.From
For Fig. 5 it is found that the glass-carbon electrode resistance value for being spotted with nitrogen sulphur codope ordered mesoporous carbon material is obviously reduced, this and above-mentioned electrochemistry are electric
It is consistent to flow signal detecting result, equally illustrates that the electric conductivity of nitrogen sulphur codope ordered mesoporous carbon material is superior, has higher
Electron transfer rate, can in electrochemical sensing as useful signal expand materials'use.
Comparative example 1
A kind of ordered mesoporous carbon material, essentially identical with the preparation process of embodiment 1, difference is only that: not using step
S2, but after mesoporous molecular sieve SBA-15, dithizone and carbon tetrachloride are mixed and are dried at normal temperature, it directly carries out high
Warm solution, obtains ordered mesoporous carbon material.Through detecting, as shown in fig. 6, total without the nitrogen sulphur of ultrasonic disperse and polymerization procedure
Doping ordered mesopore carbon part meso-hole structure collapses, and specific surface area also accordingly reduces, therefore can not expand as useful signal
Increase materials'use.
The above described is only a preferred embodiment of the present invention, being not intended to limit the present invention in any form.Though
So the present invention is disclosed as above with preferred embodiment, and however, it is not intended to limit the invention.It is any to be familiar with those skilled in the art
Member, in the case where not departing from Spirit Essence of the invention and technical solution, all using in the methods and techniques of the disclosure above
Appearance makes many possible changes and modifications or equivalent example modified to equivalent change to technical solution of the present invention.Therefore,
Anything that does not depart from the technical scheme of the invention are made to the above embodiment any simple according to the technical essence of the invention
Modification, equivalent replacement, equivalence changes and modification, all of which are still within the scope of protection of the technical scheme of the invention.
Claims (10)
1. a kind of nitrogen sulphur codope ordered mesoporous carbon material, which is characterized in that the nitrogen sulphur codope ordered mesoporous carbon material with
SBA-15 is mesopore molecular sieve template, with dithizone for single carbon source, sulphur source and nitrogen source, is mixed simultaneously using carbon tetrachloride as solvent
Ultrasonic disperse, then polymerize, form nitrogen sulphur codope ordered mesopore carbon polymer, nitrogen sulphur codope ordered mesopore carbon polymer
After high temperature pyrolysis makes carbonization, etching removal mesoporous molecular sieve SBA-15 obtains nitrogen sulphur codope ordered mesoporous carbon material；
The mass ratio of mesoporous molecular sieve SBA-15 and dithizone is 1: 1~1.25；
After the ultrasonic disperse gained mixture is first stirred into 10h~12h at normal temperature, then is warming up to 60 DEG C~100 DEG C progress
Polymerization, polymerization time are 6h~12h.
2. a kind of preparation method of nitrogen sulphur codope ordered mesoporous carbon material, comprising the following steps:
The synthesis of S1, mesoporous molecular sieve SBA-15: block copolymer P123 and tetraethyl orthosilicate are mixed in hydrochloric acid solution
Uniformly, crystallization and roasting are then carried out, mesoporous molecular sieve SBA-15 is obtained；
The preparation of S2, nitrogen sulphur codope ordered mesopore carbon polymer: by gained mesoporous molecular sieve SBA-15, dithizone and four chlorinations
Carbon mixing and ultrasonic disperse, carry out heating polymerization for gained mixture, obtain nitrogen sulphur codope ordered mesopore carbon polymer；
S3, high temperature pyrolysis: it will be carried out under inert gas protection after the grinding of gained nitrogen sulphur codope ordered mesopore carbon polymer high
Warm solution, makes polymer carbonization, obtains thermal decomposition product；
The etching of S4, mesoporous molecular sieve SBA-15: gained thermal decomposition product being added in sodium hydroxide solution and is stirred, with etching
Mesoporous molecular sieve SBA-15 template is removed, is washed out and dries, obtain nitrogen sulphur codope ordered mesoporous carbon material；
The mass ratio of the mesoporous molecular sieve SBA-15 and dithizone is 1: 1~1.25；
In the step S2, gained mixture is first stirred into 10h~12h at normal temperature after the ultrasonic disperse, then be warming up to 60
DEG C~100 DEG C polymerize, polymerization time be 6h~12h.
3. the preparation method of nitrogen sulphur codope ordered mesoporous carbon material according to claim 2, which is characterized in that the step
In rapid S2, the time of the ultrasonic disperse is 2h~4h.
4. the preparation method of nitrogen sulphur codope ordered mesoporous carbon material according to claim 2, which is characterized in that the step
In rapid S1, the mass ratio of the block copolymer P123 and tetraethyl orthosilicate is 1: 2~3, and described be uniformly mixed refers to 35
DEG C~40 DEG C of water bath conditions under stir 20h~for 24 hours, the crystallization refer at 85 DEG C~135 DEG C heating water bath for 24 hours~48h makes
Crystallization is generated, the temperature of the roasting is 550 DEG C~800 DEG C, and the time of the roasting is 5h~8h.
5. the preparation method of nitrogen sulphur codope ordered mesoporous carbon material according to claim 2, which is characterized in that the step
In rapid S3, the inert gas is nitrogen, and the high temperature pyrolysis uses procedural heating: first with 2 DEG C/min~5 DEG C/min
Heating rate rises to 600 DEG C~900 DEG C, then keeps 2h~4h.
6. the preparation method of nitrogen sulphur codope ordered mesoporous carbon material according to claim 2, which is characterized in that the step
In rapid S4, the concentration of the sodium hydroxide solution is 1mol/L~2mol/L, and the temperature of the sodium hydroxide solution stirring is 80
DEG C~100 DEG C, the temperature of the drying is 60 DEG C~100 DEG C.
7. the preparation method of nitrogen sulphur codope ordered mesoporous carbon material, feature according to any one of claim 2~6
It is, in the step S1, block copolymer P123 is first placed in dissolution in hydrochloric acid solution and obtains the salt of block copolymer P123
Then tetraethyl orthosilicate is added dropwise in the hydrochloric acid solution of block copolymer P123 and mixes by acid solution.
8. the preparation method of nitrogen sulphur codope ordered mesoporous carbon material, feature according to any one of claim 2~6
It is, in the step S4, the thermal decomposition product filters after being placed in sodium hydroxide solution stirring 0.5h~1h, then more renews
Sodium hydroxide solution repeats abovementioned steps 2~4 times, to realize etching process.
9. a kind of nitrogen sulphur codope ordered mesoporous carbon material as described in claim 1 or any one of such as claim 2~8
Application of the nitrogen sulphur codope ordered mesoporous carbon material in electrochemical sensing made from the preparation method.
10. application according to claim 9, which is characterized in that the application is the following steps are included: nitrogen sulphur is co-doped with
Sequence meso-porous carbon material is distributed in perfluorinated sulfonic acid Nafion and drop coating is in glassy carbon electrode surface, is air-dried at room temperature, as three electricity
Working electrode in the work system of pole, the reference electrode in three electrode system are saturated calomel electrode, are platinum filament to electrode
Electrode；The additive amount of the nitrogen sulphur codope ordered mesoporous carbon material is that every nitrogenous sulphur of 5mL~10mL perfluorinated sulfonic acid is co-doped with
Sequence mesoporous carbon 50mg~100mg.
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