CN103349963B - Mesoporous carbon material high in specific surface area and rich in oxygen surface functional groups, and preparation method thereof - Google Patents
Mesoporous carbon material high in specific surface area and rich in oxygen surface functional groups, and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a mesoporous carbon material high in specific surface area and rich in oxygen surface functional groups. The mesoporous carbon material has a specific surface area of 940-1365 m<2>/g, an average pore diameter of 3.1-3.8 nm, and a pore volume of 0.9-1.2 cc/g, and two or three of -COOH, -C-OH and -C=O are modified on the mesoporous carbon material. A preparation method of the mesoporous carbon material disclosed by the invention comprises the following steps of: heating a polysiloxane precursor and then enabling the polysiloxane precursor to perform a cross-linking reaction, then performing crushing, pyrolysis and ball-milling to obtain a porous carbon precursor; then performing chlorination etching on the porous carbon precursor by a method of deriving carbon from carbides, so as to obtain a mesoporous carbon material with Cl; finally performing aftertreatment by ammonia gas or hydrogen, so as to obtain a mesoporous carbon material without Cl. The mesoporous carbon material disclosed by the invention has the advantages of being low in raw material cost, simple and convenient in process steps, low in preparation temperature, good in product performance, and the like.
Description
Technical field
The present invention relates to a kind of material with carbon element and preparation thereof, particularly relate to a kind of micro-meso-porous carbon material and preparation method thereof.
Background technology
Porous carbon materials had both had carbonaceous material low-density, high strength, the feature that good biocompatibility, chemical stability (non-oxidizing atmosphere), excellent electric conductivity and machinability are strong, also has the porosity characteristics such as specific area is high, pore volume is large, pore passage structure is abundant.Wherein, a main application scenario of micro-meso-porous carbon material is absorption, and absorption not only needs high-specific surface area to strengthen physics absorption property, needs some surface functional groups to improve chemical adsorption capacity toward contact.
Method at present for the preparation of porous carbon mainly contains activation method (comprising Physical and chemical activation method), template (comprising hard template method and soft template method), catalytic activation method, mixed with polymers carbonizatin method, organic gel carbonization method and carbide-derived carbon method.But because carbon matrix precursor thermal cracking or the reaction of carbonisation generation hydroxyl condensation cause O, H to run off, or because adopting the raw material containing less (or not containing) O, H as carbon matrix precursor, this makes final obtained porous carbon materials be difficult to obtain high-ratio surface sum simultaneously and is rich in the surface functional groups such as COOH, C-OH, C=O, now needs to carry out follow-up activation process (as physics CO to porous carbon materials toward contact
2activation, chemical KOH activate), surface modification treatment (as low temperature air oxidation, pickling etc.), with acquisition while realizing high-specific surface area and being rich in oxygen surface functional group.But the difficulty of technological operation increases, flow process extends, cost increases by causing for follow-up activation process operation or surface modification treatment operation, and this is unfavorable for application and the popularization of porous carbon materials.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, there is provided that a kind of surface functional group enriches, cost is low, the micro-meso-porous carbon material of the high-ratio surface being rich in oxygen surface functional group of good product performance, also correspondingly provide that a kind of cost of material is low, processing step is simple and easy to do, preparation temperature is lower, properties of product are better, preparation method to low this micro-meso-porous carbon material of process equipment requirement.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of micro-meso-porous carbon material of high-ratio surface being rich in oxygen surface functional group, and the specific area of described micro-meso-porous carbon material is 940m
2/ g ~ 1365m
2/ g, average pore size is 3.1nm ~ 3.8nm, and pore capacities is 0.9cc/g ~ 1.2cc/g, and described micro-meso-porous carbon material is modified with two or three in-COOH ,-C-OH ,-C=O.
The molar fraction of C, O, H tri-kinds of elements contained in above-mentioned micro-meso-porous carbon material is preferably respectively:
C：81.4～90.5mol.%
O：5.9～11.6mol.%
H：3.6～7.0mol.%。
As a total technical conceive, the present invention also provides a kind of preparation method of above-mentioned micro-meso-porous carbon material, comprises the following steps:
(1) preparation of porous carbon presoma: make it that cross-linking reaction occur after polysiloxanes precursor being heated, cross-linking products is carried out fragmentation, then the cross-linking products particle after fragmentation is placed in pyrolysis furnace and carries out low temperature pyrolyzer, omnidistance nitrogen (N
2) or argon gas (Ar) carry out atmosphere protection, the product cool to room temperature after cracking, after ball milling, obtain the porous carbon presoma that particle diameter is less than 100 μm;
(2) chlorination etching: use carbide-derived carbon method principle to carry out chlorination etching to the porous carbon presoma that above-mentioned steps (1) obtains, obtain containing the micro-meso-porous carbon material of Cl;
(3) post processing: adopt NH
3or H
2what obtain above-mentioned steps (2) carries out post processing containing the micro-meso-porous carbon material of Cl, until removed by Cl element, obtains not containing micro-meso-porous carbon material of Cl.
The preparation method of above-mentioned micro-meso-porous carbon material, in described step (1), described polysiloxanes precursor is preferably the silicones containing Si-OH group.Polysiloxanes in the present invention mainly with-Si-O-Si-be main chain, with R for the high polymer that side chain is formed; Its molecular formula can be expressed as:
Wherein, R group can be saturated group (as: CH
3, C
2h
5, C
3h
7deng); Also can be unsaturated group (as: C
2h
3, C
6h
5deng); Also can be OH group etc.In the preparation process of precursor, can by controlling the chain length of R group, the character of group and the quantity of group regulate carbon content wherein.
The preparation method of above-mentioned micro-meso-porous carbon material, in described step (1), the temperature of described cross-linking reaction is preferably 150 DEG C ~ 300 DEG C, and the time of cross-linking reaction is preferably 2h ~ 6h; The particle size range distribution of the cross-linking products particle after fragmentation preferably controls at 150 μm ~ 250 μm.
The preparation method of above-mentioned micro-meso-porous carbon material, in described step (1), cracking temperature during described cracking preferably controls at 500 DEG C ~ 800 DEG C; Programming rate during cracking is preferably 5 DEG C/min ~ 20 DEG C/min.
The preparation method of above-mentioned micro-meso-porous carbon material, in described step (1), the time of described cracking preferably controls as 1h ~ 6h, and the time of described ball milling preferably controls as 5h ~ 40h.
The preparation method of above-mentioned micro-meso-porous carbon material, in described step (1), containing Si, C, O and H tetra-kinds of elements in described porous carbon presoma, its performance parameter as intermediate product preferably control be: the specific area of described porous carbon presoma is 34m
2/ g ~ 590m
2/ g, average pore size are 2.5nm ~ 8.9nm, pore capacities is 0.07cc/g ~ 0.40cc/g, and wherein, micropore hole content is 0.006cc/g ~ 0.237cc/g, and mesoporous hole content is 0.015cc/g ~ 0.071cc/g.
The preparation method of above-mentioned micro-meso-porous carbon material, in described step (2), the etching temperature of chlorination etching is 525 DEG C ~ 650 DEG C, programming rate is 5 DEG C/min ~ 20 DEG C/min, reaction atmosphere is Cl
2, logical N in whole chlorination etching process
2or Ar is as carrier gas, the time of chlorination etching is 3h ~ 10h.
The preparation method of above-mentioned micro-meso-porous carbon material, in described step (3), the treatment temperature of post processing is preferably 400 DEG C ~ 800 DEG C; The processing time of described post processing is preferably 0.5h ~ 4h.
Compared with prior art, the invention has the advantages that: the present invention adopts polysiloxanes as raw material, transformed by low temperature pyrolyzer and can obtain the porous carbon presoma being rich in H, O, then obtained high specific surface area by low temperature chlorination etching, be rich in micro-meso-porous carbon material of the functional groups such as COOH, C-OH, C=O, gained micro-meso-porous carbon material pore-size distribution is narrow, specific area is high.
The present invention realizes containing the fine setting of oxygen surface functional group concentration and pore structure by changing the technological parameters such as polysiloxanes kind, cracking atmosphere, temperature, etching temperature, post processing atmosphere, and then regulates, accurately controls the microstructure such as specific surface, aperture of micro-meso-porous carbon material on a large scale.
In addition, preparation temperature of the present invention is low, cost of material is cheap, and cost advantage is obvious.Of the present invention is carry out atmosphere cracking at low temperatures containing Si-OH polysiloxanes, obtains specific surface higher and be rich in the micro-meso-porous carbon material of oxygen surface functional group compared with low temperature chlorination etching; The present invention is by introducing polysiloxanes conversion method, and not only low raw-material cost, molecule can design, and processing step is simple and easy to do, and preparation temperature is lower, mouldability is better, require lower to process equipment; Can obtain by adopting method of the present invention that specific area is higher, pore-size distribution is narrow and be in micro-meso-porous carbon material of micro-macropore range.
Accompanying drawing explanation
Fig. 1 is the adsorption/desorption curve of micro-meso-porous carbon material obtained in the embodiment of the present invention 1.
Fig. 2 is the adsorption/desorption curve of micro-meso-porous carbon material obtained in the embodiment of the present invention 2.
Fig. 3 is the adsorption/desorption curve of micro-meso-porous carbon material obtained in the embodiment of the present invention 3.
Fig. 4 is the adsorption/desorption curve of micro-meso-porous carbon material obtained in the embodiment of the present invention 4.
Fig. 5 is the adsorption/desorption curve of micro-meso-porous carbon material obtained in the embodiment of the present invention 5.
Detailed description of the invention
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but protection domain not thereby limiting the invention.
Embodiment 1:
The micro-meso-porous carbon material of high-ratio surface being rich in oxygen surface functional group of the present invention, the specific area of this micro-meso-porous carbon material is 1364m
2/ g, average pore size is 3.2nm, and pore capacities is 1.089cc/g, this micro-meso-porous carbon material is modified with and comprises the multiple group such as-COOH ,-C-OH ,-C=O.The molar fraction of C, O, H tri-kinds of elements contained in micro-meso-porous carbon material of the present embodiment is respectively:
C：83.3mol.%
O：10.9mol.%
H：5.8mol.%。
Micro-meso-porous carbon material of above-mentioned the present embodiment prepares mainly through following steps:
(1) preparation of porous carbon presoma: cross-linking products after crosslinked 4h, is crushed to 150 μm ~ 250 μm by polysiloxanes precursor (polysiloxanes adopted in each embodiment is all the silicones containing Si-OH group) at 250 DEG C; Cross-linking products particle after fragmentation is placed in pyrolysis furnace and carries out cracking (whole process nitrogen or argon gas carry out atmosphere protection); cracking temperature is 500 DEG C; pyrolysis time 2h; programming rate is 5 DEG C/min; after stove cool to room temperature, then ball milling 10h, obtain the porous carbon presoma that particle size range is 0.1 μm ~ 50 μm; this porous carbon presoma contains Si, C, O, H tetra-kinds of elements, and its specific area is 35m
2/ g, average pore size is 8.9nm, and pore capacities is 0.077cc/g, and wherein, micropore hole content is 0.043cc/g, and mesoporous hole content is 0.015cc/g.
(2) chlorination etching: use carbide-derived carbon method principle that the porous carbon presoma that above-mentioned steps (1) obtains is placed in atmosphere tube type stove and carry out chlorination etching, etching temperature is 600 DEG C, and etch period is 3h, and programming rate is 5 DEG C/min; Reaction atmosphere is Cl
2, and N is led in whole process
2as carrier gas; Last with stove cool to room temperature, obtain the micro-meso-porous carbon material containing Cl element.
(3) post processing: adopt NH
3what obtain above-mentioned steps (2) carries out post processing containing the micro-meso-porous carbon material of Cl, and treatment temperature is 600 DEG C, time 2h, after being removed by Cl element, obtains not containing micro-meso-porous carbon material of Cl element.
The micro-meso-porous carbon material obtained to said method adopts gas absorption (BET) method and elemental microanalysis method and x-ray photoelectron power spectrum (XPS) to analyze it.BET method obtains adsorption/desorption curve as shown in Figure 1, known after testing, and micro-meso-porous carbon material specific area of the present embodiment is 1364m
2/ g, average pore size is 3.2nm, and pore capacities is 1.089cc/g, and wherein micropore hole content is 0.652cc/g, and mesoporous content is 0.313cc/g.XPS spectrum fitting result is as shown in table 1 below, from table 1, the micro-meso-porous carbon material surface of the present embodiment is except containing except graphitized carbon C-C (C-H) group (accounting for total 68.84%), also containing hydroxyl C-OH or ethers C-O-C group (accounting for sum 9.97%), carbonyl (C=O) group (accounting for sum 4.94%), carboxyl (COOH) or lactone group (COO) group (accounting for sum 3.48%), and basic group π → π * (accounting for sum 7.29%) exists.The molar fraction recording C element by elemental analysis method is the molar fraction of 83.3mol.%, O element is 10.9mol.%, and the molar fraction of H element is 5.8mol.%.
Table 1: the XPS spectrum fitting result of embodiment 1 product
| Peak position (ev) | Ratio (%) | Radical species |
| 284.63 | 68.84 | C-C，C-H |
| 285.90 | 9.97 | C-OH，C-O-C |
| 287.00 | 4.94 | C=O |
| 288.30 | 3.48 | COO |
| 290.18 | 7.29 | π→π* |
Embodiment 2:
The micro-meso-porous carbon material of high-ratio surface being rich in oxygen surface functional group of the present invention, the specific area of this micro-meso-porous carbon material is 1152m
2/ g, average pore size is 3.8nm, and pore capacities is 1.098cc/g, this micro-meso-porous carbon material is modified with and comprises the multiple group such as-COOH ,-C-OH ,-C=O.The molar fraction of C, O, H tri-kinds of elements contained in micro-meso-porous carbon material of the present embodiment is respectively:
C：81.4mol.%
O：11.6mol.%
H：7.0mol.%。
Micro-meso-porous carbon material of above-mentioned the present embodiment prepares mainly through following steps:
(1) preparation of porous carbon presoma: cross-linking products after crosslinked 4h, is crushed to 150 μm ~ 250 μm by polysiloxanes precursor at 250 DEG C; Cross-linking products particle after fragmentation is placed in pyrolysis furnace and carries out cracking (whole process nitrogen or argon gas carry out atmosphere protection); cracking temperature is 600 DEG C; pyrolysis time 2h; programming rate is 5 DEG C/min; after stove cool to room temperature, then ball milling 5h, obtain the porous carbon presoma that particle size range is 1 μm ~ 100 μm; this porous carbon presoma contains Si, C, O, H tetra-kinds of elements, and its specific area is 588m
2/ g, average pore size is 2.6nm, and pore capacities is 0.384cc/g, and wherein, micropore hole content is 0.237cc/g, and mesoporous hole content is 0.071cc/g.
(2) chlorination etching: use carbide-derived carbon method principle that the porous carbon presoma that above-mentioned steps (1) obtains is placed in atmosphere tube type stove and carry out chlorination etching, etching temperature is 600 DEG C, and etch period is 3h, and programming rate is 5 DEG C/min; Reaction atmosphere is Cl
2, and N is led in whole process
2as carrier gas; Last with stove cool to room temperature, obtain the micro-meso-porous carbon material containing Cl element.
(3) post processing: adopt NH
3what obtain above-mentioned steps (2) carries out post processing containing the micro-meso-porous carbon material of Cl, and treatment temperature is 600 DEG C, time 2h, after being removed by Cl element, obtains not containing micro-meso-porous carbon material of Cl element.
The micro-meso-porous carbon material obtained to said method adopts gas absorption (BET) method and elemental microanalysis method (EA) and x-ray photoelectron power spectrum (XPS) to analyze it.BET method obtains adsorption/desorption curve as shown in Figure 2, known after testing, and micro-meso-porous carbon material specific area of the present embodiment is 1152m
2/ g, average pore size is 3.8nm, and pore capacities is 1.098cc/g, and wherein micropore hole content is 0.543cc/g, and mesoporous content is 0.350cc/g.XPS spectrum fitting result is as shown in table 2 below, from table 2, the micro-meso-porous carbon material surface of the present embodiment is except containing except graphitized carbon C-C (C-H) group (accounting for total 63.50%), also containing hydroxyl C-OH or ethers C-O-C group (accounting for sum 9.73%), carbonyl (C=O) group (accounting for sum 4.01%), carboxyl (COOH) or lactone group (COO) group (accounting for sum 2.53%), and basic group π → π * (accounting for sum 4.46%).The molar fraction recording C element by elemental analysis method is the molar fraction of 81.4mol.%, O element is 11.6mol.%, and the molar fraction of H element is 7.0mol.%.
Table 2: the XPS spectrum fitting result of embodiment 2 product
| Peak position (ev) | Ratio (%) | Radical species |
| 284.64 | 63.50 | C-C，C-H |
| 285.95 | 9.73 | C-OH，C-O-C |
| 287.16 | 4.01 | C=O |
| 288.35 | 2.53 | COO |
| 289.97 | 4.46 | π→π* |
Embodiment 3:
The micro-meso-porous carbon material of high-ratio surface being rich in oxygen surface functional group of the present invention, the specific area of this micro-meso-porous carbon material is 1269m
3/ g, average pore size is 3.7nm, and pore capacities is 1.183cc/g, this micro-meso-porous carbon material is modified with and comprises the multiple group such as-COOH ,-C-OH ,-C=O.The molar fraction of C, O, H tri-kinds of elements contained in micro-meso-porous carbon material of the present embodiment is respectively:
C：83.7mol.%
O：11.5mol.%
H：4.8mol.%。
Micro-meso-porous carbon material of above-mentioned the present embodiment prepares mainly through following steps:
(1) preparation of porous carbon presoma: cross-linking products after crosslinked 4h, is crushed to 150 μm ~ 250 μm by polysiloxanes precursor at 250 DEG C; Cross-linking products particle after fragmentation is placed in pyrolysis furnace and carries out cracking (whole process nitrogen or argon gas carry out atmosphere protection); cracking temperature is 700 DEG C; pyrolysis time 2h; programming rate is 5 DEG C/min; after stove cool to room temperature, then ball milling 10h, obtain the porous carbon presoma that particle size range is 0.1 μm ~ 50 μm; this porous carbon presoma contains Si, C, O, H tetra-kinds of elements, and its specific area is 450m
2/ g, average pore size is 2.5nm, and pore capacities is 0.282cc/g, and wherein, micropore hole content is 0.168cc/g, and mesoporous hole content is 0.046cc/g.
(2) chlorination etching: use carbide-derived carbon method principle that the porous carbon presoma that above-mentioned steps (1) obtains is placed in atmosphere tube type stove and carry out chlorination etching, etching temperature is 600 DEG C, and etch period is 3h, and programming rate is 5 DEG C/min; Reaction atmosphere is Cl
2, and N is led in whole process
2as carrier gas; Last with stove cool to room temperature, obtain the micro-meso-porous carbon material containing Cl element.
(3) post processing: adopt NH
3what obtain above-mentioned steps (2) carries out post processing containing the micro-meso-porous carbon material of Cl, and treatment temperature is 600 DEG C, time 2h, after being removed by Cl element, obtains not containing micro-meso-porous carbon material of Cl element.
The micro-meso-porous carbon material obtained to said method adopts gas absorption (BET) method and elemental microanalysis method (EA) and x-ray photoelectron power spectrum (XPS) to analyze it.BET method obtains adsorption/desorption curve as shown in Figure 3, known after testing, and micro-meso-porous carbon material specific area of the present embodiment is 1269m
2/ g, average pore size is 3.7nm, and pore capacities is 1.183cc/g, and wherein micropore hole content is 0.531cc/g, and mesoporous content is 0.352cc/g.XPS spectrum fitting result is as shown in table 3 below, from table 3, the micro-meso-porous carbon material surface of the present embodiment is except containing except graphitized carbon C-C (C-H) group (accounting for total 59.61%), also containing hydroxyl C-OH or ethers C-O-C group (accounting for sum 10.57%), carbonyl (C=O) group (accounting for sum 5.06%), carboxyl (COOH) or lactone group (COO) group (accounting for sum 2.67%), and basic group π → π * (accounting for sum 5.10%).The molar fraction recording C element by elemental analysis method is the molar fraction of 83.7mol.%, O element is 11.5mol.%, and the molar fraction of H element is 4.8mol.%.
Table 3: the XPS spectrum fitting result of embodiment 3 product
| Peak position (ev) | Ratio (%) | Radical species |
| 284.62 | 59.61 | C-C，C-H |
| 285.92 | 10.57 | C-OH，C-O-C |
| 287.19 | 5.06 | C=O |
| 288.55 | 2.67 | COO |
| 290.35 | 5.10 | π→π* |
Embodiment 4:
The micro-meso-porous carbon material of high-ratio surface being rich in oxygen surface functional group of the present invention, the specific area of this micro-meso-porous carbon material is 1067m
3/ g, average pore size is 3.8nm, and pore capacities is 1.014cc/g, this micro-meso-porous carbon material is modified with and comprises the multiple group such as-COOH ,-C-OH ,-C=O.The molar fraction of C, O, H tri-kinds of elements contained in micro-meso-porous carbon material of the present embodiment is respectively:
C：83.9mol.%
O：11.3mol.%
H：4.8mol.%。
Micro-meso-porous carbon material of above-mentioned the present embodiment prepares mainly through following steps:
(1) preparation of porous carbon presoma: cross-linking products after crosslinked 4h, is crushed to 150 μm ~ 250 μm by polysiloxanes precursor at 250 DEG C; Cross-linking products particle after fragmentation is placed in pyrolysis furnace and carries out cracking (whole process nitrogen or argon gas carry out atmosphere protection); cracking temperature is 800 DEG C; pyrolysis time 2h; programming rate is 15 DEG C/min; after stove cool to room temperature, then ball milling 10h, obtain the porous carbon presoma that particle size range is 0.1 μm ~ 50 μm; this porous carbon presoma contains Si, C, O, H tetra-kinds of elements, and its specific area is 90m
2/ g, average pore size is 4.7nm, and pore capacities is 0.105cc/g, and wherein, micropore hole content is 0.006cc/g, and mesoporous hole content is 0.070cc/g.
(2) chlorination etching: use carbide-derived carbon method principle that the porous carbon presoma that above-mentioned steps (1) obtains is placed in atmosphere tube type stove and carry out chlorination etching, etching temperature is 600 DEG C, and etch period is 3h, and programming rate is 5 DEG C/min; Reaction atmosphere is Cl
2, and N is led in whole process
2as carrier gas; Last with stove cool to room temperature, obtain the micro-meso-porous carbon material containing Cl element.
(3) post processing: adopt NH
3what obtain above-mentioned steps (2) carries out post processing containing the micro-meso-porous carbon material of Cl, and treatment temperature is 600 DEG C, time 2h, after being removed by Cl element, obtains not containing micro-meso-porous carbon material of Cl element.
The micro-meso-porous carbon material obtained to said method adopts gas absorption (BET) method and elemental microanalysis method (EA) and x-ray photoelectron power spectrum (XPS) to analyze it.BET method obtains adsorption/desorption curve as shown in Figure 4, known after testing, and micro-meso-porous carbon material specific area of the present embodiment is 1067m
2/ g, average pore size is 3.8nm, and pore capacities is 1.014cc/g, and wherein micropore hole content is 0.491cc/g, and mesoporous content is 0.310cc/g.XPS spectrum fitting result is as shown in table 4 below, from table 4, the micro-meso-porous carbon material surface of the present embodiment is except containing except graphitized carbon C-C (C-H) group (accounting for total 60.27%), also containing hydroxyl C-OH or ethers C-O-C group (accounting for sum 11.06%), carbonyl (C=O) group (accounting for sum 4.83%), carboxyl (COOH) or lactone group (COO) group (accounting for sum 2.79%), and basic group π → π * (accounting for sum 5.62%).The mass fraction recording C element by elemental analysis method is the mass fraction of 83.9mol.%, O element is 11.3mol.%, and the mass fraction of H element is 4.8mol.%.
Table 4: the XPS spectrum fitting result of embodiment 4 product
| Peak position (ev) | Ratio (%) | Radical species |
| 284.61 | 60.27 | C-C，C-H |
| 285.89 | 11.06 | C-OH，C-O-C |
| 287.12 | 4.83 | C=O |
| 288.50 | 2.79 | COO |
| 290.42 | 5.62 | π→π* |
Embodiment 5:
The micro-meso-porous carbon material of high-ratio surface being rich in oxygen surface functional group of the present invention, the specific area of this micro-meso-porous carbon material is 940m
2/ g, average pore size is 3.1nm, and pore capacities is 0.984cc/g, this micro-meso-porous carbon material is modified with and comprises the multiple group such as-COOH ,-C-OH ,-C=O.The molar fraction of C, O, H tri-kinds of elements contained in micro-meso-porous carbon material of the present embodiment is respectively:
C：82.2mol.%
O：10.8mol.%
H：7.0mol.%。
Micro-meso-porous carbon material of above-mentioned the present embodiment prepares mainly through following steps:
(1) preparation of porous carbon presoma: cross-linking products after crosslinked 4h, is crushed to 150 μm ~ 250 μm by polysiloxanes precursor at 250 DEG C; Cross-linking products particle after fragmentation is placed in pyrolysis furnace and carries out cracking (whole process nitrogen or argon gas carry out atmosphere protection); cracking temperature is 600 DEG C; pyrolysis time 2h; programming rate is 5 DEG C/min; after stove cool to room temperature, then ball milling 10h, obtain the porous carbon presoma that particle size range is 0.1 μm ~ 50 μm; this porous carbon presoma contains Si, C, O, H tetra-kinds of elements, and its specific area is 588m
2/ g, average pore size is 2.6nm, and pore capacities is 0.384cc/g, and wherein, micropore hole content is 0.237cc/g, and mesoporous hole content is 0.071cc/g.
(2) chlorination etching: use carbide-derived carbon method principle that the porous carbon presoma that above-mentioned steps (1) obtains is placed in atmosphere tube type stove and carry out chlorination etching, etching temperature is 525 DEG C, and etch period is 6h, and programming rate is 5 DEG C/min; Reaction atmosphere is Cl
2, and N is led in whole process
2as carrier gas; Last with stove cool to room temperature, obtain the micro-meso-porous carbon material containing Cl element.
(3) post processing: adopt H
2what obtain above-mentioned steps (2) carries out post processing containing the micro-meso-porous carbon material of Cl, and treatment temperature is 600 DEG C, time 2h, after being removed by Cl element, obtains not containing micro-meso-porous carbon material of Cl element.
The micro-meso-porous carbon material obtained to said method adopts gas absorption (BET) method and elemental microanalysis method (EA) and x-ray photoelectron power spectrum (XPS) to analyze it.BET method obtains adsorption/desorption curve as shown in Figure 5, known after testing, and micro-meso-porous carbon material specific area of the present embodiment is 940m
2/ g, average pore size is 3.1nm, and pore capacities is 0.984cc/g, and wherein micropore hole content is 0.410cc/g, and mesoporous content is 0.189cc/g.XPS spectrum fitting result is as shown in table 5 below, from table 5, the micro-meso-porous carbon material surface of the present embodiment is except containing except graphitized carbon C-C (C-H) group (accounting for total 59.27%), also containing hydroxyl C-OH or ethers C-O-C group (accounting for sum 11.01%), carbonyl (C=O) group (accounting for sum 5.81%), carboxyl (COOH) or lactone group (COO) group (accounting for sum 2.48%), and basic group π → π * (accounting for sum 5.66%) exists.The mass fraction recording C element by elemental analysis method is the mass fraction of 82.2mol.%, O element is 10.8mol.%, and the mass fraction of H element is 7.0mol.%.
Table 5: the XPS spectrum fitting result of embodiment 5 product
| Peak position (ev) | Ratio (%) | Radical species |
| 284.62 | 59.27 | C-C，C-H |
| 285.88 | 11.01 | C-OH，C-O-C |
| 286.95 | 5.81 | C=O |
| 288.50 | 2.48 | COO |
| 290.52 | 5.66 | π→π* |
Above embodiment is the preferred embodiments of the present invention, but protection domain not thereby limiting the invention.
Claims (7)
1. be rich in the micro-meso-porous carbon material of high-ratio surface of oxygen surface functional group, it is characterized in that: the specific area of described micro-meso-porous carbon material is 940m
2/ g ~ 1365m
2/ g, average pore size is 3.1nm ~ 3.8nm, and pore capacities is 0.9cc/g ~ 1.2cc/g, and described micro-meso-porous carbon material is modified with two or three in-COOH ,-C-OH ,-C=O.
2. micro-meso-porous carbon material according to claim 1, is characterized in that, the molar fraction of C, O, H tri-kinds of elements contained in described micro-meso-porous carbon material is respectively:
C：81.4～90.5?mol.%
O：5.9～11.6?mol.%
H：3.6～7.0?mol.%。
3. a preparation method for micro-meso-porous carbon material as claimed in claim 1 or 2, comprises the following steps:
(1) preparation of porous carbon presoma: be make it that cross-linking reaction occur after the heating of polysiloxanes precursor by the silicones containing Si-OH group, cross-linking products is carried out fragmentation, then the cross-linking products particle after fragmentation is placed in pyrolysis furnace and carries out low temperature pyrolyzer, the temperature of cracking controls at 500 DEG C ~ 800 DEG C, programming rate during cracking is 5 DEG C/min ~ 20 DEG C/min, whole process nitrogen or argon gas carry out atmosphere protection, product cool to room temperature after cracking, obtains the porous carbon presoma that particle diameter is less than 100 μm after ball milling;
(2) chlorination etching: use carbide-derived carbon method principle to carry out chlorination etching to the porous carbon presoma that above-mentioned steps (1) obtains, obtain containing the micro-meso-porous carbon material of Cl, etching temperature is 525 DEG C ~ 650 DEG C, programming rate is 5 DEG C/min ~ 20 DEG C/min;
(3) post processing: adopt NH
3or H
2what obtain above-mentioned steps (2) carries out post processing containing the micro-meso-porous carbon material of Cl, until removed by Cl element, obtain not containing micro-meso-porous carbon material of Cl, the treatment temperature of post processing is 400 DEG C ~ 800 DEG C, and the processing time of described post processing is 0.5h ~ 4h.
4. preparation method according to claim 3, is characterized in that: in described step (1), and the temperature of described cross-linking reaction is 150 DEG C ~ 300 DEG C, and the time of cross-linking reaction is 2h ~ 6h; The particle size range distributed controll of the cross-linking products particle after fragmentation is at 150 μm ~ 250 μm.
5. preparation method according to claim 4, is characterized in that: in described step (1), and the time controling of described cracking is 1h ~ 6h, and the time controling of described ball milling is 5h ~ 40h.
6. preparation method according to claim 5, is characterized in that: containing Si, C, O and H tetra-kinds of elements in described porous carbon presoma, the specific area of described porous carbon presoma is 34m
2/ g ~ 590m
2/ g, average pore size are 2.5nm ~ 8.9nm, pore capacities is 0.07cc/g ~ 0.40cc/g, and wherein, micropore hole content is 0.006 cc/g ~ 0.237cc/g, and mesoporous hole content is 0.015cc/g ~ 0.071cc/g.
7. the preparation method according to any one of claim 3 ~ 6, is characterized in that: in described step (2), and reaction atmosphere is Cl
2, logical N in whole chlorination etching process
2or Ar is as carrier gas, the time of chlorination etching is 3h ~ 10h.
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