CN105217601A - A kind of preparation method with the porous hollow carbon ball of high-specific surface area - Google Patents
A kind of preparation method with the porous hollow carbon ball of high-specific surface area Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 64
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000005406 washing Methods 0.000 claims abstract description 29
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 25
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 20
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 19
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 19
- 239000005011 phenolic resin Substances 0.000 claims abstract description 19
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- 229910000077 silane Inorganic materials 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 10
- 239000008098 formaldehyde solution Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 7
- 229920003987 resole Polymers 0.000 claims abstract description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 6
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 4
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 4
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 230000006872 improvement Effects 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 229920000428 triblock copolymer Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- -1 sensor Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Abstract
The invention discloses a kind of preparation method with the porous hollow carbon ball of high-specific surface area, by SiO
2ball is distributed in the mixing solutions of dehydrated alcohol and deionized water, adds cetyl trimethylammonium bromide and fully dissolves; Add Resorcinol, silane, formaldehyde solution and ammonia soln, through centrifugal, washing, dry acquisition phenolic resin balls after reaction; The charing of resol ball warp, silica removal, filtration, washing, the dry porous hollow carbon ball obtaining high-specific surface area.With SiO
2ball is template, and silane is pore-forming material, with formaldehyde and Resorcinol for carbon source, by coating technology, and through operating process such as charing silica removals, obtains hollow carbon sphere.This preparation method's technique is simple, and raw material is easy to get, easy and simple to handle, the obtained hollow carbon sphere being rich in micropore, and it has the features such as the large specific volume of high-ratio surface sum, particle diameter and wall thickness be controlled.
Description
Technical field
The present invention relates to field of inorganic materials, particularly relate to a kind of preparation method with the porous hollow carbon ball of high-specific surface area.
Background technology
In recent years, along with deepening continuously of carbon material research, the synthetic technology of spherical carbon material progressively improves.Wherein, porous hollow carbon ball is because having high specific surface area, large pore volume, the excellent advantage such as conductivity, good thermostability and by extensive concern, it is widely used in fields such as useful for drug delivery, catalysis, electrode materials, sensor, sorbent material, fuel cells.
The method of current synthesizing porous hollow carbon sphere is of common occurrence, wherein common with template, but mostly exists following not enough in building-up process: one, cost is high, complex steps; Two, cannot accomplish to carry out simple and effective regulation and control to spherome surface parameter.
As (J.Mater.Chem. such as Chen Zeqiang, 2011,21 (24): 8880-8886) with the silicon oxide particle of nucleocapsid structure for hard template, prepare the hollow ball-type carbon material with mesoporous lamella, its add-on by cetyl trimethylammonium bromide regulates meso-hole structure, described method and literature method difference are, regulate microvoid structure by changing tetraethoxy amount; (the Chem.Mater. such as Zhao Dongyuan, 2007,19 (13): 3271-3277) utilize silicon oxide colloid for macropore template, triblock copolymer F127 is mesoporous template, prepare the foramen magnum-mesoporous combined multi-stage hole carbon material of regular macropore arrangement, patent CN103072970A take spherical calcium carbonate as template, triblock copolymer is structure directing agent, by triblock copolymer adjustment hole structure, and then obtained meso-porous hollow carbon sphere,, there is high in cost of production problem in both raw materials used costliness.Patent CN102295281A with hollow mesoporous silicon sphere for template, the method utilizing nanometer to build obtains graded porous carbon, by changing silicon spherolite footpath, wall thickness and regulating the regulation and control of resol consumption realization to hollow carbon sphere pore structure, this method is length consuming time not only, and pore structure not easily accurately controls.Patent CN104058401A take hollow polymer microsphere as template, obtains porous carbon microsphere by carbon dioxide activation, and the method requirement for experiment condition is relatively harsh.Patent CN101993057A take nano silicon spheres as template, chemical Vapor deposition process is utilized to obtain carbon hollow nanospheres, the specific surface area of hollow ball is controlled by the deposit thickness changing layer of charcoal, although this method is simple, the obtained relatively low (200-600m of hollow carbon sphere specific surface area
2/ g).Based on As-Is, search out a kind of cost is low, raw material is simple and easy to get, easy and simple to handle preparation method has hierarchical porous structure hollow carbon sphere with synthesis, particularly important to the performance of its performance advantage.
Summary of the invention
For the weak point existed in the problems referred to above, the invention provides a kind of preparation method with the porous hollow carbon ball of high-specific surface area.
For achieving the above object, the invention provides a kind of preparation method with the porous hollow carbon ball of high-specific surface area, the method comprises:
Step one, by SiO
2ball is distributed in the mixing solutions of dehydrated alcohol and deionized water, adds cetyl trimethylammonium bromide and fully dissolves;
Step 2, add Resorcinol, silane, formaldehyde solution and ammonia soln, after reaction through centrifugal, washing, dryly obtain phenolic resin balls;
Step 3, the charing of resol ball warp, silica removal, filtration, washing, the dry porous hollow carbon ball obtaining high-specific surface area.
As a further improvement on the present invention, described step one specifically comprises:
Be the SiO of 50nm ~ 1000nm by diameter
2ball is placed in beaker, and add dehydrated alcohol, deionized water successively, ultrasonic vibration makes SiO
2ball is fully distributed in the mixing solutions of dehydrated alcohol and deionized water, adds cetyl trimethylammonium bromide, makes it fully dissolve.
As a further improvement on the present invention, described SiO
2the mass ratio of ball and dehydrated alcohol is 0.05:9.875, and the volume ratio of described dehydrated alcohol and deionized water is (12.5 ~ 15): (30 ~ 40).
As a further improvement on the present invention, the massfraction of described cetyl trimethylammonium bromide in reaction system is (0.04 ~ 0.18) %.
As a further improvement on the present invention, described step 2 specifically comprises:
Under continuous stirring, add Resorcinol, silane, formaldehyde solution and ammonia soln successively, after continuing to stir 24h, the centrifugal product of centrifugal acquisition;
Absolute ethanol washing 3 times, 70 DEG C of dry 12h, obtained phenolic resin balls.
As a further improvement on the present invention, the massfraction of described Resorcinol in reaction system is (0.04 ~ 0.40) %, and the massfraction of described formaldehyde solution is 37%, and the massfraction of described ammonia soln is 25%; In reaction system, the mol ratio of Resorcinol and formaldehyde is 1:5.6.
As a further improvement on the present invention, the one in tetraethoxy, methyl silicate, methyltrimethoxy silane, Union carbide A-162, propyl trimethoxy silicane, propyl-triethoxysilicane, mercaptopropyl trimethoxysilane or mercaptopropyltriethoxysilane selected by described silane, and described silane is (0 ~ 0.39) % as the massfraction of pore-forming material in reaction system.
As a further improvement on the present invention, described step 3 specifically comprises:
Phenolic resin balls carbonizes in a nitrogen atmosphere, and carbonization process is:
At room temperature with the ramp to 350 DEG C of 1 DEG C/min, insulation 2h, then with the ramp to 600 DEG C of 1 DEG C/min, insulation 4h;
Silica removal: be the hydrofluoric acid wash 24h of 10% with massfraction;
Filter, with deionized water wash to neutral, 70 DEG C of dry 12h, obtain the porous hollow carbon ball of high-specific surface area.
Compared with prior art, beneficial effect of the present invention is:
A kind of preparation method with the porous hollow carbon ball of high-specific surface area disclosed by the invention, with SiO
2ball is template, and silane is pore-forming material, and formaldehyde and Resorcinol are carbon source, by coating technology, and through operating process such as charing silica removals, obtains the porous hollow carbon ball of high-specific surface area.This preparation method's technique is simple, and raw material is easy to get, easy and simple to handle, the obtained hollow carbon sphere being rich in micropore, and it has the features such as the large specific volume of high-ratio surface sum, particle diameter and wall thickness be controlled;
Add silane in this preparation method as hollow carbon sphere sphere pore-forming material, regulate the micropore glass beads of hollow carbon sphere by changing its add-on, its specific surface area can up to about 1400m
2/ g;
Using Resorcinol and formaldehyde as carbon source presoma in this preparation method, can obtain by changing its consumption the hollow carbon sphere that wall thickness is 5 ~ 80nm.
Accompanying drawing explanation
Fig. 1 has the schema of the preparation method of the porous hollow carbon ball of high-specific surface area disclosed in an embodiment of the present invention;
Fig. 2 is the transmission electron microscope photo of the hollow carbon sphere of synthesis in embodiment 2;
Fig. 3 is the stereoscan photograph of the hollow carbon sphere of synthesis in embodiment 3;
Fig. 4 is nitrogen adsorption desorption curve and the pore size distribution schematic diagram of the hollow carbon sphere of synthesis in embodiment 7.
Embodiment
For making the object of the embodiment of the present invention, technical scheme and advantage clearly, below in conjunction with the accompanying drawing in the embodiment of the present invention, technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is a part of embodiment of the present invention, instead of whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under the prerequisite not making creative work, all belongs to the scope of protection of the invention.
As shown in Figure 1, the invention discloses and provide a kind of preparation method with the porous hollow carbon ball of high-specific surface area, the method comprises:
S101, by SiO
2ball is distributed in the mixing solutions of dehydrated alcohol and deionized water, adds cetyl trimethylammonium bromide and fully dissolves; Concrete steps are:
Be the SiO of 50nm ~ 1000nm by diameter
2ball is placed in beaker, adds dehydrated alcohol, deionized water successively, SiO
2the mass ratio of ball and dehydrated alcohol is 0.05:9.875, and the volume ratio of dehydrated alcohol and deionized water is (12.5 ~ 15): (30 ~ 40), ultrasonic vibration 15min makes SiO
2ball is fully distributed in the mixing solutions of dehydrated alcohol and deionized water, adds cetyl trimethylammonium bromide, and the massfraction of cetyl trimethylammonium bromide in reaction system is (0.04 ~ 0.18) %, makes it fully dissolve;
S102, add Resorcinol, silane, formaldehyde solution and ammonia soln, after reaction through centrifugal, washing, dryly obtain phenolic resin balls; Concrete steps are:
Under continuous stirring, add Resorcinol, silane, formaldehyde solution and ammonia soln successively, the massfraction of Resorcinol in reaction system is (0.04 ~ 0.40) %, and the massfraction of formaldehyde solution is 37%, and the massfraction of ammonia soln is 25%; In reaction system, the mol ratio of Resorcinol and formaldehyde is 1:5.6; The one in tetraethoxy, methyl silicate, methyltrimethoxy silane, Union carbide A-162, propyl trimethoxy silicane, propyl-triethoxysilicane, mercaptopropyl trimethoxysilane or mercaptopropyltriethoxysilane selected by silane, and silane is (0 ~ 0.39) % as the massfraction of pore-forming material in reaction system; After continuing to stir 24h, the centrifugal product of centrifugal acquisition;
Absolute ethanol washing 3 times, 70 DEG C of dry 12h, obtained phenolic resin balls.
S103, the charing of resol ball warp, silica removal, filtration, washing, the dry porous hollow carbon ball obtaining high-specific surface area; Concrete steps are:
Phenolic resin balls carbonizes in a nitrogen atmosphere, at room temperature with the ramp to 350 DEG C of 1 DEG C/min, and insulation 2h, then with the ramp to 600 DEG C of 1 DEG C/min, insulation 4h;
Silica removal: be the hydrofluoric acid wash 24h of 10% with massfraction;
Filter: with deionized water wash to neutral, 70 DEG C of dry 12h, obtain the porous hollow carbon ball of high-specific surface area.
Below in conjunction with accompanying drawing, the present invention is described in further detail:
Embodiment 1: a kind of preparation method with the porous hollow carbon ball of high-specific surface area described in the embodiment of the present invention, preparation process is: cut-off footpath is about the silica spheres 0.0500g of 180nm in small beaker, and add dehydrated alcohol 12.5mL, the ultrasonic 15min of deionized water 30mL, solution is poured in flask, and 0.0750g cetyl trimethylammonium bromide is added in flask, after it fully dissolves, add 0.0160g Resorcinol, tetraethoxy 17 μ L, after stirring 10min, add formaldehyde 61 μ L, ammoniacal liquor 230 μ L, stirring at room temperature 24h, products therefrom is centrifugal, absolute ethanol washing 3 times, 70 DEG C of dry 12h, obtained phenolic resin balls, carbonize under gained powder nitrogen atmosphere, with the ramp to 350 DEG C of 1 DEG C/min, keep 2h, then with the ramp to 600 DEG C of 1 DEG C/min, keep 4h, products therefrom is stirred 24h in 10% (massfraction) hydrofluoric acid solution, and filtration washing is drying to obtain hollow carbon sphere, and gained hollow carbon sphere particle diameter is about 190nm, and wall thickness is about 7nm.
Embodiment 2: a kind of preparation method with the porous hollow carbon ball of high-specific surface area described in the embodiment of the present invention, preparation process is: cut-off footpath is about the silica spheres 0.0500g of 180nm in small beaker, and add dehydrated alcohol 12.5mL, the ultrasonic 15min of deionized water 30mL, solution is poured in flask, and 0.0750g cetyl trimethylammonium bromide is added in flask, after it fully dissolves, add 0.0480g Resorcinol, methyl silicate 17 μ L, after stirring 10min, add formaldehyde 183 μ L, ammoniacal liquor 230 μ L, stirring at room temperature 24h, products therefrom is centrifugal, absolute ethanol washing 3 times, 70 DEG C of dry 12h, obtained phenolic resin balls, carbonize under gained powder nitrogen atmosphere, with the ramp to 350 DEG C of 1 DEG C/min, keep 2h, then with the ramp to 600 DEG C of 1 DEG C/min, keep 4h, products therefrom is stirred 24h in 10% (massfraction) hydrofluoric acid solution, and filtration washing is drying to obtain hollow carbon sphere, and gained hollow carbon sphere particle diameter is about 220nm, and wall thickness is about 20nm, and specific surface area is 514.1476m
2/ g, the transmission electron microscope photo of hollow carbon sphere as shown in Figure 2.
As seen from Figure 2, obtained hollow carbon sphere spherical morphology is intact, and hollow ball half particle diameter is more homogeneous.
Embodiment 3: a kind of preparation method with the porous hollow carbon ball of high-specific surface area described in the embodiment of the present invention, preparation process is: cut-off footpath is about the silica spheres 0.0500g of 180nm in small beaker, and add dehydrated alcohol 12.5mL, the ultrasonic 15min of deionized water 30mL, solution is poured in flask, and 0.0750g cetyl trimethylammonium bromide is added in flask, after it fully dissolves, add 0.160g Resorcinol, methyltrimethoxy silane 17 μ L, after stirring 10min, add formaldehyde 610 μ L, ammoniacal liquor 230 μ L, stirring at room temperature 24h, products therefrom is centrifugal, absolute ethanol washing 3 times, 70 DEG C of dry 12h, obtained phenolic resin balls, carbonize under gained powder nitrogen atmosphere, with the ramp to 350 DEG C of 1 DEG C/min, keep 2h, then with the ramp to 600 DEG C of 1 DEG C/min, keep 4h, products therefrom is stirred 24h in 10% (massfraction) hydrofluoric acid solution, and filtration washing is drying to obtain hollow carbon sphere, and gained hollow carbon sphere particle diameter is about 320nm, and wall thickness is about 80nm, the stereoscan photograph of hollow carbon sphere as shown in Figure 3.
As seen from Figure 3, increase Resorcinol and formaldehyde consumption, on obtained hollow carbon sphere spherical morphology without any impact, and hollow ball particle diameter obviously increases, and wall thickness also obviously increases.
Embodiment 4: a kind of preparation method with the porous hollow carbon ball of high-specific surface area described in the embodiment of the present invention, preparation process is: cut-off footpath is about the silica spheres 0.0500g of 180nm in small beaker, and add dehydrated alcohol 12.5mL, the ultrasonic 15min of deionized water 30mL, solution is poured in flask, and 0.0750g cetyl trimethylammonium bromide is added in flask, after it fully dissolves, add 0.0480g Resorcinol, Union carbide A-162 0 μ L, after stirring 10min, add formaldehyde 183 μ L, ammoniacal liquor 230 μ L, stirring at room temperature 24h, products therefrom is centrifugal, absolute ethanol washing 3 times, 70 DEG C of dry 12h, obtained phenolic resin balls, carbonize under gained powder nitrogen atmosphere, with the ramp to 350 DEG C of 1 DEG C/min, keep 2h, then with the ramp to 600 DEG C of 1 DEG C/min, keep 4h, products therefrom is stirred 24h in 10% (massfraction) hydrofluoric acid solution, and filtration washing is drying to obtain hollow carbon sphere, and gained hollow carbon sphere particle diameter is about 250nm, and wall thickness is about 26nm.
Embodiment 5: a kind of preparation method with the porous hollow carbon ball of high-specific surface area described in the embodiment of the present invention, preparation process is: cut-off footpath is about the silica spheres 0.0500g of 180nm in small beaker, and add dehydrated alcohol 12.5mL, the ultrasonic 15min of deionized water 30mL, solution is poured in flask, and 0.0750g cetyl trimethylammonium bromide is added in flask, after it fully dissolves, add 0.0480g Resorcinol, propyl trimethoxy silicane 0 μ L, after stirring 10min, add formaldehyde 183 μ L, ammoniacal liquor 690 μ L, stirring at room temperature 24h, products therefrom is centrifugal, absolute ethanol washing 3 times, 70 DEG C of dry 12h, obtained phenolic resin balls, carbonize under gained powder nitrogen atmosphere, with the ramp to 350 DEG C of 1 DEG C/min, keep 2h, then with the ramp to 600 DEG C of 1 DEG C/min, keep 4h, products therefrom is stirred 24h in 10% (massfraction) hydrofluoric acid solution, and filtration washing is drying to obtain hollow carbon sphere, and gained hollow carbon sphere particle diameter is about 280nm, and wall thickness is about 55nm.
Embodiment 6: a kind of preparation method with the porous hollow carbon ball of high-specific surface area described in the embodiment of the present invention, preparation process is: cut-off footpath is about the silica spheres 0.0500g of 180nm in small beaker, and add dehydrated alcohol 12.5mL, the ultrasonic 15min of deionized water 30mL, solution is poured in flask, and 0.0750g cetyl trimethylammonium bromide is added in flask, after it fully dissolves, add 0.0480g Resorcinol, mercaptopropyl trimethoxysilane 34 μ L, after stirring 10min, add formaldehyde 183 μ L, ammoniacal liquor 230 μ L, stirring at room temperature 24h, products therefrom is centrifugal, absolute ethanol washing 3 times, 70 DEG C of dry 12h, obtained phenolic resin balls, carbonize under gained powder nitrogen atmosphere, with the ramp to 350 DEG C of 1 DEG C/min, keep 2h, then with the ramp to 600 DEG C of 1 DEG C/min, keep 4h, products therefrom is stirred 24h in 10% (massfraction) hydrofluoric acid solution, and filtration washing is drying to obtain hollow carbon sphere, and gained hollow carbon sphere particle diameter is about 225nm, and wall thickness is about 24nm, and specific surface area is 706.1582m
2/ g.
Embodiment 7: a kind of preparation method with the porous hollow carbon ball of high-specific surface area described in the embodiment of the present invention, preparation process is: cut-off footpath is about the silica spheres 0.0500g of 180nm in small beaker, and add dehydrated alcohol 12.5mL, the ultrasonic 15min of deionized water 30mL, solution is poured in flask, and 0.0750g cetyl trimethylammonium bromide is added in flask, after it fully dissolves, add 0.0480g Resorcinol, mercaptopropyltriethoxysilane 102 μ L, after stirring 10min, add formaldehyde 183 μ L, ammoniacal liquor 230 μ L, stirring at room temperature 24h, products therefrom is centrifugal, absolute ethanol washing 3 times, 70 DEG C of dry 12h, obtained phenolic resin balls, carbonize under gained powder nitrogen atmosphere, with the ramp to 350 DEG C of 1 DEG C/min, keep 2h, then with the ramp to 600 DEG C of 1 DEG C/min, keep 4h, products therefrom is stirred 24h in 10% (massfraction) hydrofluoric acid solution, and filtration washing is drying to obtain hollow carbon sphere, and gained hollow carbon sphere particle diameter is about 218nm, and wall thickness is about 17nm, and specific surface area is 1368.6150m
2/ g.By its adsorption desorption curve, the nitrogen adsorption desorption curve of hollow carbon sphere as shown in Figure 4 and pore size distribution schematic diagram, can find out that it is obvious micro-porous adsorption, as can be seen from graph of pore diameter distribution, its pore size is about 0.7nm.
Embodiment 8: a kind of preparation method with the porous hollow carbon ball of high-specific surface area described in the embodiment of the present invention, preparation process is: cut-off footpath is about the silica spheres 0.0500g of 84nm in small beaker, and add dehydrated alcohol 12.5mL, the ultrasonic 15min of deionized water 30mL, solution is poured in flask, and 0.0750g cetyl trimethylammonium bromide is added in flask, after it fully dissolves, add 0.0480g Resorcinol, tetraethoxy 102 μ L, after stirring 10min, add formaldehyde 183 μ L, ammoniacal liquor 230 μ L, stirring at room temperature 24h, products therefrom is centrifugal, absolute ethanol washing 3 times, 70 DEG C of dry 12h, obtained phenolic resin balls, carbonize under gained powder nitrogen atmosphere, with the ramp to 350 DEG C of 1 DEG C/min, keep 2h, then with the ramp to 600 DEG C of 1 DEG C/min, keep 4h, products therefrom is stirred 24h in 10% (massfraction) hydrofluoric acid solution, and filtration washing is drying to obtain hollow carbon sphere, and gained hollow carbon sphere particle diameter is about 152nm.
Embodiment 9: a kind of preparation method with the porous hollow carbon ball of high-specific surface area described in the embodiment of the present invention, preparation process is: cut-off footpath is about the silica spheres 0.0500g of 285nm in small beaker, and add dehydrated alcohol 12.5mL, the ultrasonic 15min of deionized water 30mL, solution is poured in flask, and 0.0750g cetyl trimethylammonium bromide is added in flask, after it fully dissolves, add 0.0480g Resorcinol, tetraethoxy 102 μ L, after stirring 10min, add formaldehyde 183 μ L, ammoniacal liquor 230 μ L, stirring at room temperature 24h, products therefrom is centrifugal, absolute ethanol washing 3 times, 70 DEG C of dry 12h, obtained phenolic resin balls, carbonize under gained powder nitrogen atmosphere, with the ramp to 350 DEG C of 1 DEG C/min, keep 2h, then with the ramp to 600 DEG C of 1 DEG C/min, keep 4h, products therefrom is stirred 24h in 10% (massfraction) hydrofluoric acid solution, and filtration washing is drying to obtain hollow carbon sphere, and gained hollow carbon sphere particle diameter is about 317nm.
A kind of preparation method with the porous hollow carbon ball of high-specific surface area disclosed by the invention, with SiO
2ball is template, and silane is pore-forming material, and formaldehyde and Resorcinol are carbon source, by coating technology, and through operating process such as charing silica removals, obtains the porous hollow carbon ball of high-specific surface area.This preparation method's technique is simple, and raw material is easy to get, easy and simple to handle, the obtained hollow carbon sphere being rich in micropore, and it has the features such as the large specific volume of high-ratio surface sum, particle diameter and wall thickness be controlled; Add silane in this preparation method as hollow carbon sphere sphere pore-forming material, regulate the micropore glass beads of hollow carbon sphere by changing its add-on, its specific surface area can up to about 1400m
2/ g; Using Resorcinol and formaldehyde as carbon source presoma in this preparation method, can obtain by changing its consumption the hollow carbon sphere that wall thickness is 5 ~ 80nm.
These are only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. have a preparation method for the porous hollow carbon ball of high-specific surface area, it is characterized in that, the method comprises:
Step one, by SiO
2ball is distributed in the mixing solutions of dehydrated alcohol and deionized water, adds cetyl trimethylammonium bromide and fully dissolves;
Step 2, add Resorcinol, silane, formaldehyde solution and ammonia soln, after reaction through centrifugal, washing, dryly obtain phenolic resin balls;
Step 3, the charing of resol ball warp, silica removal, filtration, washing, the dry porous hollow carbon ball obtaining high-specific surface area.
2. have the preparation method of the porous hollow carbon ball of high-specific surface area as claimed in claim 1, it is characterized in that, described step one specifically comprises:
Be the SiO of 50nm ~ 1000nm by diameter
2ball is placed in beaker, and add dehydrated alcohol, deionized water successively, ultrasonic vibration makes SiO
2ball is fully distributed in the mixing solutions of dehydrated alcohol and deionized water, adds cetyl trimethylammonium bromide, makes it fully dissolve.
3. there is the preparation method of the porous hollow carbon ball of high-specific surface area as claimed in claim 2, it is characterized in that, described SiO
2the mass ratio of ball and dehydrated alcohol is 0.05:9.875, and the volume ratio of described dehydrated alcohol and deionized water is (12.5 ~ 15): (30 ~ 40).
4. have the preparation method of the porous hollow carbon ball of high-specific surface area as claimed in claim 2, it is characterized in that, the massfraction of described cetyl trimethylammonium bromide in reaction system is (0.04 ~ 0.18) %.
5. have the preparation method of the porous hollow carbon ball of high-specific surface area as claimed in claim 1, it is characterized in that, described step 2 specifically comprises:
Under continuous stirring, add Resorcinol, silane, formaldehyde solution and ammonia soln successively, after continuing to stir 24h, the centrifugal product of centrifugal acquisition;
Absolute ethanol washing 3 times, 70 DEG C of dry 12h, obtained phenolic resin balls.
6. there is the preparation method of the porous hollow carbon ball of high-specific surface area as claimed in claim 5, it is characterized in that, the massfraction of described Resorcinol in reaction system is (0.04 ~ 0.40) %, the massfraction of described formaldehyde solution is 37%, and the massfraction of described ammonia soln is 25%; In reaction system, the mol ratio of Resorcinol and formaldehyde is 1:5.6.
7. there is the preparation method of the porous hollow carbon ball of high-specific surface area as claimed in claim 5, it is characterized in that, the one in tetraethoxy, methyl silicate, methyltrimethoxy silane, Union carbide A-162, propyl trimethoxy silicane, propyl-triethoxysilicane, mercaptopropyl trimethoxysilane or mercaptopropyltriethoxysilane selected by described silane, and described silane is (0 ~ 0.39) % as the massfraction of pore-forming material in reaction system.
8. have the preparation method of the porous hollow carbon ball of high-specific surface area as claimed in claim 1, it is characterized in that, described step 3 specifically comprises:
Phenolic resin balls carbonizes in a nitrogen atmosphere, and carbonization process is:
At room temperature with the ramp to 350 DEG C of 1 DEG C/min, insulation 2h, then with the ramp to 600 DEG C of 1 DEG C/min, insulation 4h;
Silica removal: be the hydrofluoric acid wash 24h of 10% with massfraction;
Filter: with deionized water wash to neutral, 70 DEG C of dry 12h, obtain the porous hollow carbon ball of high-specific surface area.
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