CN103072972B - Preparation method of nitrogen and sulfur co-doping ordered mesoporous carbon materials - Google Patents
Preparation method of nitrogen and sulfur co-doping ordered mesoporous carbon materials Download PDFInfo
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- CN103072972B CN103072972B CN201310066557.0A CN201310066557A CN103072972B CN 103072972 B CN103072972 B CN 103072972B CN 201310066557 A CN201310066557 A CN 201310066557A CN 103072972 B CN103072972 B CN 103072972B
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Abstract
The invention relates to a preparation method of nitrogen and sulfur co-doping ordered mesoporous carbon materials. According to the method, pyrrole is used as carbon sources and nitrogen sources, sulfuric acid is used as acid catalysts and sulfur sources, pyrrole oligomers are used as precursors, mesoporous silica molecular sieves SBA-15 (space group P6mm) and KIT-6 (space group Ia3d) are used as templates, a primary wet impregnation method is combined with the high-temperature themolysis technology for preparing the nitrogen and sulfur co-doping ordered mesoporous carbon materials in two-dimensional orthohexagonal and three-dimensional cubic ordered mesostructures.
Description
Technical field
The present invention relates to the preparation method of a kind of nitrogen and sulphur codoped ordered mesoporous carbon material.
Background technology
Ordered mesoporous carbon (OMC) is a kind of new carbon of rising the nineties in last century, has the mesopore orbit of aperture homogeneous in its structure.Compared with traditional porous carbon materials, ordered mesopore carbon has the advantages such as pore size distribution is narrow, porosity is high, pore size is controlled, is with a wide range of applications at aspects such as support of the catalyst, hydrogen storage material, fractionation by adsorption and electrode materialss.The structure of its high-sequential can also be used to synthesising mesoporous zeolite molecular sieve and mesoporous transition metal oxide.Therefore, the preparation of ordered mesoporous carbon material and applied research have become forward position and the focus of current hole carbon material research.
Recent research shows, ordered mesoporous carbon material carried out to the element that Heteroatom doping (as boron, sulphur, phosphorus and nitrogen doping) can significantly change meso-porous carbon material and form, and manipulation surfactivity is improved its chemical property simultaneously.At present, the preparation to nitrogen doping and sulfur doping ordered mesopore carbon and performance study have patent and bibliographical information both at home and abroad.But there is no relevant report for nitrogen and sulphur codoped ordered mesoporous carbon material.
Summary of the invention
the object of this invention is to provide onethe preparation method of nitrogen and sulphur codoped ordered mesoporous carbon material.
The present invention is the preparation method of nitrogen and sulphur codoped ordered mesoporous carbon material, the steps include:
(1) get 1.0 mL pyrroles, 1:0.6 ~ 1:0.1 ratio adds dehydrated alcohol and the vitriol oil by volume, obtains pyrroles's oligopolymer, as precursor;
(2) precursor in above-mentioned (1) is filled in 1.0 g mesoporous silica molecular sieve ducts by just wet pickling process, vacuum-drying at 80 ℃, pre-carbonization 4 ~ 8 hours at 160 ~ 180 ℃ then, obtains sulfuric acid/presoma/meso-porous titanium dioxide silicon compound;
(3) mixture medium temperature roast under inert atmosphere protection in above-mentioned (2), 350 ~ 400 ℃ of maturing temperatures, roasting time 2 hours, 1 ~ 2 ℃/min of temperature rise rate, high temperature pyrolysis then, 650 ~ 950 ℃ of pyrolysis temperatures, pyrolysis time 2 hours, 2 ~ 5 ℃/min of temperature rise rate, is cooled to room temperature, obtains nitrogen and sulphur codoped ordered mesopore carbon/meso-porous titanium dioxide silicon compound;
(4) in above-mentioned (3), mixture soaks 6 ~ 24 hours in 30 mL 5% ~ 20% HF acid, use distilled water repetitive scrubbing, until drip after 2 mol/L ferric thiocyanide solution blood red colour-fast in washing water, vacuum-drying at 80 ℃ of temperature, obtains described nitrogen and sulphur codoped ordered mesoporous carbon material.
Tool of the present invention has the following advantages:
1, take pyrroles as Carbon and nitrogen sources, sulfuric acid is acid catalyst and sulphur source, and the oligopolymer that pyrroles forms under sulfuric acid catalysis is presoma.After presoma is packed into silica-based template duct, sulfuric acid cannot volatilize, and through low-temperature bake and high temperature pyrolysis, nitrogen and sulphur codoped are in carbon molecular network, thus acquisition nitrogen and sulphur codoped ordered mesoporous carbon material.Prepared nitrogen and sulphur codoped ordered mesoporous carbon material have excellent physics and chemistry activity, have preparation method simple simultaneously, and doping is high, and specific surface area is large, mesoporous rate advantages of higher.
2, prepared nitrogen and sulphur codoped ordered mesopore carbon doping are high, and by adjusting pyrolysis temperature, can regulate and control its nitrogen and sulfur doping amount within the specific limits.
Accompanying drawing explanation
Fig. 1 is the small angle X ray scattering collection of illustrative plates of the nitrogen doping ordered mesoporous carbon material that obtains of the embodiment of the present invention 1, is shown as two-dimentional six sides' order mesoporous structure;
Fig. 2 is the N of the nitrogen doping ordered mesoporous carbon material that obtains of the embodiment of the present invention 1
2adsorption and desorption isotherms, is shown as meso-hole structure, BET specific surface area 1021 m
2/ g;
Fig. 3 is the pore structure distribution plan of the nitrogen doping ordered mesoporous carbon material that obtains of the embodiment of the present invention 1, is shown as the meso-hole structure of homogeneous, and aperture center concentrates on 3.48 nm;
Fig. 4 is the small angle X ray scattering collection of illustrative plates of the nitrogen doping ordered mesoporous carbon material that obtains of the embodiment of the present invention 4, is shown as the order mesoporous structure of three-dimensional cubic;
Fig. 5 is the N of the nitrogen doping ordered mesoporous carbon material that obtains of the embodiment of the present invention 4
2adsorption and desorption isotherms, is shown as meso-hole structure, BET specific surface area 880 m
2/ g;
Fig. 6 is the pore structure distribution plan of the nitrogen doping ordered mesoporous carbon material that obtains of the embodiment of the present invention 4, is shown as the meso-hole structure of homogeneous, and aperture center concentrates on 4.02.
Embodiment
Embodiment 1:
Get 1.0 mL pyrroles, add 0.6 mL dehydrated alcohol and the 0.1 mL vitriol oil, obtain shallow yellow transparent solution and be pyrroles's oligopolymer.Above-mentioned oligomer solution is dropwise added drop-wise to 1.0 g SBA-15 mesopore molecular sieve surfaces; vacuum-drying 6 hours at 80 ℃, pre-carbonization 8 hours at 160 ℃ then, is placed in atmosphere tube type stove by acquisition dark-brown or black powder; under argon shield; be warming up to 350 ℃ with 1 ℃/min speed, roasting 2 hours, is then warming up to 950 ℃ with 5 ℃/min speed; pyrolysis 2 hours; under argon atmospher protection, be cooled to room temperature, by 20% HF acid soak 6 hours, wash to can't check F
-ion, dry, obtain nitrogen doping ordered mesoporous carbon material.
Nitrogen that the present embodiment obtains doping ordered mesoporous carbon material nitrogen doping is 4.82%, and sulfur doping amount is that 0.92%, BET specific surface area reaches 1021 m
2/ g, mesoporous pore volume 1.04 cm
3/ g, mesoporous pore volume accounts for 92.0% of total pore volume, mean pore size 3.48 nm.
Embodiment 2:
Get 1.0 mL pyrroles, add 0.8 mL dehydrated alcohol and the 0.1 mL vitriol oil, obtain shallow yellow transparent solution and be pyrroles's oligopolymer.Above-mentioned oligomer solution is dropwise added drop-wise to 1.0 g SBA-15 mesopore molecular sieve surfaces; vacuum-drying 6 hours at 80 ℃, pre-carbonization 4 hours at 180 ℃ then, is placed in atmosphere tube type stove by acquisition dark-brown or black powder; under argon shield; be warming up to 375 ℃ with 2 ℃/min speed, roasting 2 hours, is then warming up to 800 ℃ with 2 ℃/min speed; pyrolysis 2 hours; under argon atmospher protection, be cooled to room temperature, by 10% HF acid soak 15 hours, wash to can't check F
-ion, dry, obtain nitrogen doping ordered mesoporous carbon material.
Nitrogen that the present embodiment obtains doping ordered mesoporous carbon material nitrogen doping is 7.4%, and sulfur doping amount is that 0.81%, BET specific surface area reaches 983 m
2/ g, mesoporous pore volume 0.98 cm
3/ g, mesoporous pore volume accounts for 89.1% of total pore volume, mean pore size 3.42 nm.
Embodiment 3:
Get 1.0 mL pyrroles, add 1.0 mL dehydrated alcohols and the 0.1 mL vitriol oil, obtain shallow yellow transparent solution and be pyrroles's oligopolymer.Above-mentioned oligomer solution is dropwise added drop-wise to 1.0 g SBA-15 mesopore molecular sieve surfaces; vacuum-drying 6 hours at 80 ℃, pre-carbonization 6 hours at 170 ℃ then, is placed in atmosphere tube type stove by acquisition dark-brown or black powder; under argon shield; be warming up to 400 ℃ with 1.5 ℃/min speed, roasting 2 hours, is then warming up to 650 ℃ with 3.5 ℃/min speed; pyrolysis 2 hours; under argon atmospher protection, be cooled to room temperature, by 5% HF acid soak 24 hours, wash to can't check F
-ion, dry, obtain nitrogen doping ordered mesoporous carbon material.
Nitrogen that the present embodiment obtains doping ordered mesoporous carbon material nitrogen doping is 10.0%, and sulfur doping amount is that 0.69%, BET specific surface area reaches 978 m
2/ g, mesoporous pore volume 1.11 cm
3/ g, mesoporous pore volume accounts for 92.5% of total pore volume, mean pore size 3.54 nm.
Embodiment 4:
Get 1.0 mL pyrroles, add 1.0 mL dehydrated alcohols and the 0.1 mL vitriol oil, obtain shallow yellow transparent solution and be pyrroles's oligopolymer.Above-mentioned oligomer solution is dropwise added drop-wise to 1.0 g KIT-6 mesopore molecular sieve surfaces; vacuum-drying 6 hours at 80 ℃, pre-carbonization 4 hours at 180 ℃ then, is placed in atmosphere tube type stove by acquisition dark-brown or black powder; under argon shield; be warming up to 400 ℃ with 2 ℃/min speed, roasting 2 hours, is then warming up to 950 ℃ with 2 ℃/min speed; pyrolysis 2 hours; under argon atmospher protection, be cooled to room temperature, by 5% HF acid soak 24 hours, wash to can't check F
-ion, dry, obtain nitrogen doping ordered mesoporous carbon material.
Nitrogen that the present embodiment obtains doping ordered mesoporous carbon material nitrogen doping is 4.61%, and sulfur doping amount is 0.94%, BET specific surface area, 880 m
2/ g, mesoporous pore volume 1.05 cm
3/ g, mesoporous pore volume accounts for 92.9% of total pore volume, mean pore size 4.02 nm.
Embodiment 5:
Get 1.0 mL pyrroles, add 0.8 mL dehydrated alcohol and the 0.1 mL vitriol oil, obtain shallow yellow transparent solution and be pyrroles's oligopolymer.Above-mentioned oligomer solution is dropwise added drop-wise to 1.0 g KIT-6 mesopore molecular sieve surfaces; vacuum-drying 6 hours at 80 ℃, pre-carbonization 6 hours at 170 ℃ then, is placed in atmosphere tube type stove by acquisition dark-brown or black powder; under argon shield; be warming up to 350 ℃ with 1.0 ℃/min speed, roasting 2 hours, is then warming up to 800 ℃ with 5 ℃/min speed; pyrolysis 2 hours; under argon atmospher protection, be cooled to room temperature, by 10% HF acid soak 15 hours, wash to can't check F
-ion, dry, obtain nitrogen doping ordered mesoporous carbon material.
Nitrogen that the present embodiment obtains doping ordered mesoporous carbon material nitrogen doping is 9.08%, and sulfur doping amount is 0.88%, BET specific surface area, 693 m
2/ g, mesoporous pore volume 0.69 cm
3/ g, mesoporous pore volume accounts for 92.0% of total pore volume, mean pore size 3.13 nm.
Embodiment 6:
Get 1.0 mL pyrroles, add 0.6 mL dehydrated alcohol and the 0.1 mL vitriol oil, obtain shallow yellow transparent solution and be pyrroles's oligopolymer.Above-mentioned oligomer solution is dropwise added drop-wise to 1.0 g KIT-6 mesopore molecular sieve surfaces; vacuum-drying 6 hours at 80 ℃, pre-carbonization 8 hours at 160 ℃ then, is placed in atmosphere tube type stove by acquisition dark-brown or black powder; under argon shield; be warming up to 375 ℃ with 1.05 ℃/min speed, roasting 2 hours, is then warming up to 650 ℃ with 3.5 ℃/min speed; pyrolysis 2 hours; under argon atmospher protection, be cooled to room temperature, by 20% HF acid soak 6 hours, wash to can't check F
-ion, dry, obtain nitrogen doping ordered mesoporous carbon material.
Nitrogen that the present embodiment obtains doping ordered mesoporous carbon material nitrogen doping is 10.7%, and sulfur doping amount is that 0.75%, BET specific surface area reaches 1064 m
2/ g, mesoporous pore volume 1.68 cm
3/ g, mesoporous pore volume accounts for 94.3% of total pore volume, and pore size distribution presents double hole channel structure, and mesoporous aperture concentrates on respectively 2.80 nm and 12.95 nm, mean pore size 6.21 nm.
Claims (4)
1. the preparation method of nitrogen and sulphur codoped ordered mesoporous carbon material, the steps include:
(1) get 1.0 mL pyrroles, 1:0.6 ~ 1:0.1 ratio adds dehydrated alcohol and the vitriol oil by volume, obtains pyrroles's oligopolymer, as precursor;
(2) precursor in above-mentioned (1) is filled in 1.0 g mesoporous silica molecular sieve ducts by just wet pickling process, vacuum-drying at 80 ℃, pre-carbonization 4 ~ 8 hours at 160 ~ 180 ℃ then, obtains sulfuric acid/presoma/meso-porous titanium dioxide silicon compound;
(3) mixture medium temperature roast under inert atmosphere protection in above-mentioned (2), 350 ~ 400 ℃ of maturing temperatures, roasting time 2 hours, 1 ~ 2 ℃/min of temperature rise rate, high temperature pyrolysis then, 650 ~ 950 ℃ of pyrolysis temperatures, pyrolysis time 2 hours, 2 ~ 5 ℃/min of temperature rise rate, is cooled to room temperature, obtains nitrogen and sulphur codoped ordered mesopore carbon/meso-porous titanium dioxide silicon compound;
(4) in above-mentioned (3), mixture soaks 6 ~ 24 hours in 30 mL 5% ~ 20% HF acid, use distilled water repetitive scrubbing, until drip after 2 mol/L ferric thiocyanide solution blood red colour-fast in washing water, vacuum-drying at 80 ℃ of temperature, obtains described nitrogen and sulphur codoped ordered mesoporous carbon material.
2. the preparation method of nitrogen according to claim 1 and sulphur codoped ordered mesoporous carbon material, is characterized in that, take pyrroles as Carbon and nitrogen sources, sulfuric acid is acid catalyst and sulphur source.
3. the preparation method of nitrogen according to claim 1 and sulphur codoped ordered mesoporous carbon material, it is characterized in that, with HF acid soak nitrogen and sulphur codoped ordered mesopore carbon/meso-porous titanium dioxide silicon compound to remove silica-based template, HF acid concentration is 5% ~ 20%, soak time 6 ~ 24 hours, HF acid volume is 30 mL.
4. the preparation method of nitrogen according to claim 1 and sulphur codoped ordered mesoporous carbon material, is characterized in that, removes remaining F in nitrogen and sulphur codoped meso-porous carbon material by repetitive scrubbing
-ion, F in washing water
-ion is by dripping 2 mol/L ferric thiocyanide solution checks, until washing water are blood red colour-fast after dripping ferric thiocyanide solution.
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| CN104108698B (en) * | 2014-07-30 | 2015-11-18 | 兰州理工大学 | The preparation method of highly doped amount nitrogen sulphur codoped ordered mesopore carbon |
| CN104528685A (en) * | 2014-12-24 | 2015-04-22 | 中国石油大学(北京) | Sulfur-carbon-doped material and preparation method thereof |
| CN105752960A (en) * | 2016-03-08 | 2016-07-13 | 兰州理工大学 | Sulfur and phosphorus co-doped mesoporous carbon material and preparation method thereof |
| CN107188152A (en) * | 2016-03-13 | 2017-09-22 | 顾文珺 | A kind of method that use non-combustion method produces charcoal |
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| CN106517136B (en) * | 2016-10-26 | 2017-09-05 | 青岛科技大学 | A kind of preparation method of iron/nitrogen co-doped ordered mesoporous carbon material |
| CN107311139A (en) * | 2017-05-04 | 2017-11-03 | 东莞理工学院 | The meso-porous carbon material prepared by carbon source of glucose and its application |
| CN108288547B (en) * | 2018-01-14 | 2021-07-09 | 齐齐哈尔大学 | Preparation method of nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon material |
| CN109728246B (en) * | 2018-12-13 | 2021-08-06 | 太原理工大学 | Nitrogen-phosphorus co-doped ordered mesoporous carbon material and preparation method and application thereof |
| CN110028049A (en) * | 2019-04-17 | 2019-07-19 | 河北民族师范学院 | A kind of preparation method, electrode slice and the application of nitrogen sulphur codope ordered mesoporous carbon material |
| CN110759327B (en) * | 2019-10-12 | 2022-12-02 | 宁波海秀丰科技有限公司 | Preparation method of metal carbon crystal |
| CN113171785A (en) * | 2021-04-26 | 2021-07-27 | 嘉兴学院 | Nitrogen-sulfur co-doped ordered mesoporous carbon material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101435792A (en) * | 2008-12-17 | 2009-05-20 | 中国科学院上海硅酸盐研究所 | Mesoporous carbon immobilized enzyme biological sensing material doped with nitrogen and preparing method thereof |
| CN102826538A (en) * | 2012-09-17 | 2012-12-19 | 辽宁科技大学 | Method for preparing nitrogen-doped carbonaceous material by modifying polymer |
| CN102923688A (en) * | 2012-11-01 | 2013-02-13 | 中国科学院长春应用化学研究所 | Preparation method and application of nitrogen-doped carbon material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101435792A (en) * | 2008-12-17 | 2009-05-20 | 中国科学院上海硅酸盐研究所 | Mesoporous carbon immobilized enzyme biological sensing material doped with nitrogen and preparing method thereof |
| CN102826538A (en) * | 2012-09-17 | 2012-12-19 | 辽宁科技大学 | Method for preparing nitrogen-doped carbonaceous material by modifying polymer |
| CN102923688A (en) * | 2012-11-01 | 2013-02-13 | 中国科学院长春应用化学研究所 | Preparation method and application of nitrogen-doped carbon material |
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