CN102757034A - Method for preparing nitrogen-rich porous carbon material - Google Patents
Method for preparing nitrogen-rich porous carbon material Download PDFInfo
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- CN102757034A CN102757034A CN201210278030XA CN201210278030A CN102757034A CN 102757034 A CN102757034 A CN 102757034A CN 201210278030X A CN201210278030X A CN 201210278030XA CN 201210278030 A CN201210278030 A CN 201210278030A CN 102757034 A CN102757034 A CN 102757034A
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Abstract
The invention discloses a method for preparing a nitrogen-rich porous carbon material and belongs to the technical field of carbon materials. According to the method, edentate is used as a raw material and subjected to high temperature pyrolysis under the protection of an inert atmosphere and then to pickling and rinsing to obtain the simply prepared nitrogen-rich porous carbon material. The method for preparing the nitrogen-rich porous carbon material is simple and easy to operate. The carbon material is provided with a high nitrogen content and a developed porous structure, the nitrogen content can reach 1.6-15.5%, the specific surface area is 600-2000m<2>/g, the pore volume is 0.3-1.8 cm<3>/g, and the carbon material can be used in fields of electrochemistry energy storage, catalyst carriers, absorption, gas storage and the like.
Description
Technical field
The present invention relates to a kind of preparation method of rich nitrogen porous carbon material, belong to inorganic non-metallic carbon materials technical field.
Background technology
Porous carbon material; Also claim gac; Have high specific surface area and flourishing pore texture; Be a kind of sorbing material of excellent performance, be widely used in fields such as purification of water quality, waste gas pollution control and treatment, monosodium glutamate decolouring, solvent recuperation, chemical protection, also can be used for gas storage, support of the catalyst and electrochemical energy storage etc.The preparation of porous carbon material is a raw material with coal, resin and wood materials generally; Traditional preparation method is earlier with its Pintsch process charing in inert atmosphere, and then carries out physically activated (is acvator with water vapour, air or carbonic acid gas etc.) or chemical activation (with H
3PO
4, ZnCl
2, KOH, NaOH etc. be acvator).Charing has just formed preliminary hole, and general specific surface area is at 100m
2In/the g.The specific surface area of gac that adopts physically activated preparation is generally at 500-1000m
2/ g adopts the specific surface area of the gac of chemical activation preparation can reach 1000-3000m
2/ g.
Rich nitrogen porous carbon material is because a certain amount of nitrogen-atoms that in the structure of porous charcoal, mixed has improved its electroconductibility, electronation performance, alkalescence etc.; Thereby make it have many special performances; As: the electrode materials that is used for ultracapacitor not only can improve the wellability of electrode and electrolytic solution, also can produce pseudo-capacitance the ratio electric capacity of porous charcoal is improved greatly; As support of the catalyst catalytic activity is improved greatly, even can directly be used as catalyzer; Storage power to carbonic acid gas also significantly is superior to common gac.
The preparation method of rich nitrogen porous charcoal mainly contains two kinds.A kind of is post treatment method, with porous carbon material in nitrogenous gas (like ammonia etc.) thermal treatment or with itrogenous organic substance (like urea, amine, pyrimidine, Melamine etc.) heat altogether.Another kind is to be raw material with nitrogenous high molecular polymer, makes porous charcoal in the preparation process, can keep the part nitrogen-atoms in the raw material mix.Nitrogen containing polymer polymkeric substance commonly used mainly contain terpolycyantoamino-formaldehyde resin (Chem.Mater., 2005,17:1241), polyaniline (Carbon; 2009,47:2984), polyacrylonitrile (Electrochimi.Acta, 2010; 55:7021), polypyrrole (Energy Environ.Sci., 2011,4:717) and gelatin (Energy Environ.Sci.; 2012,5:7950) etc., corresponding preparation method mainly comprises charing-activation method, template, sol-gel method, polymer blending method etc.
Adopting nitrogenous organic acid salt is raw material, and the method that direct Pintsch process prepares rich nitrogen porous carbon material is not seen patent and bibliographical information.
Summary of the invention
The present invention proposes the method for the rich nitrogen porous carbon material of a kind of easy preparation; Its thinking is: with nitrogenous organic acid salt is precursor, and it is carried out Pintsch process under inert atmosphere protection, obtains the mixture of charcoal coated metal oxide; Remove MOX with acid again, obtain the raw material of wood-charcoal material.Owing to contain the nitrogen element in the organic acid as carbon source, therefore also residual part nitrogen element in the network structure of high-temperature split product charcoal; Discharge CO in the organic acid cracking
2, thereby water vapor and some small molecules contain the charing compound and produce a large amount of micropores; In fact MOX in the pyrolysis product has played the effect of template simultaneously; Can stay a certain amount of mesopore after adopting acid elution, so gained raw material of wood-charcoal material has flourishing vesicular structure again.Selection through presoma and change the regulation and control that pyrolytic process can realize nitrogen content and vesicular structure.
The concrete preparation method of this invention is following:
With the edetate is precursor, with its under the protection of rare gas element in 400-1200 ℃ of constant temperature pyrolysis 0.5-12h, MOX is removed in pickling, washing obtains nitrogen content 1.6～15.5%, specific surface area 600-2000m to neutral again
2/ g, pore volume 0.3～1.8cm
3The rich nitrogen porous carbon material of/g.
Said edetate is tetra-na salt, disodium salt, sodium magnesium salts, molysite, calcium salt or the manganese salt of YD 30.
The used acid of pickling of the present invention is more than one materials in hydrochloric acid, sulfuric acid, nitric acid, the phosphoric acid.
The used rare gas element of the present invention is nitrogen, argon gas or both mixed gass.
The present invention compared with prior art has following advantage:
(1) prepared raw material of wood-charcoal material has high nitrogen content and flourishing vesicular structure concurrently.Nitrogen content can reach 1.6-15.5%, specific surface area 600-2000m
2/ g, pore volume 0.3～1.8cm
3/ g.
(2) method is simple.Only needing charing, need not activation, is a kind of activatory preparation method that exempts from.
Description of drawings
Fig. 1 is the electron scanning micrograph of embodiment 1 gained raw material of wood-charcoal material.
Fig. 2 is the nitrogen adsorption isothermal line of embodiment 1 gained raw material of wood-charcoal material.
Fig. 3 is that the x-ray photoelectron of embodiment 1 gained raw material of wood-charcoal material can spectrogram.
Fig. 4 is embodiment 1 gained raw material of wood-charcoal material charging and discharging curve under the 50mA/g current density in 6mol/L KOH electrolytic solution.
Fig. 5 is the cycle performance curve of embodiment 1 gained raw material of wood-charcoal material in 6mol/L KOH electrolytic solution.
Embodiment
Through specific embodiment and accompanying drawing the present invention is further described below, but does not influence protection scope of the present invention.
Embodiment 1
Tetrasodium salt of EDTA is placed tube type resistance furnace central authorities, feed the high-purity argon gas protection, be heated to 700 ℃, constant temperature 5h treats to take out after furnace temperature is cooled to room temperature.Add excessive Hydrogen chloride, remove MOX.Extremely neutral with deionized water wash again, obtain rich nitrogen porous carbon material.
Fig. 1 is the electron scanning micrograph of gained raw material of wood-charcoal material.Calculating its BET specific surface area by the nitrogen adsorption isothermal line of gained raw material of wood-charcoal material shown in Figure 2 is 708m
2/ g, pore volume 0.366cm
3/ g.Obtaining its nitrogen content by the x-ray photoelectron power spectrum of gained raw material of wood-charcoal material shown in Figure 3 is 7.74%.This material is used for ultracapacitor, and calculating it by the charging and discharging curve under the 50mA/g current density of Fig. 4 gained raw material of wood-charcoal material in 6mol/L KOH electrolytic solution is 245F/g than electric capacity.Fig. 5 is gained raw material of wood-charcoal material 10000 round-robin performance curves in 6mol/L KOH electrolytic solution, and capacity does not have obvious decay.
Embodiment 2
Ethylenediamine tetraacetic acid disodium magnesium salt is placed the retort furnace of high pure nitrogen protection, be heated to 800 ℃, constant temperature 2h treats to take out after furnace temperature is cooled to room temperature.Add excessive dilute sulphuric acid, remove MOX.Extremely neutral with deionized water wash again, obtain rich nitrogen porous carbon material.The BET specific surface area of this raw material of wood-charcoal material is 1811m
2/ g, pore volume 1.02cm
3/ g, nitrogen content are 3.81%.
Embodiment 3
Ca-EDTA is placed tube type resistance furnace, feed the high pure nitrogen protection, be heated to 900 ℃, constant temperature 1h treats to take out after furnace temperature is cooled to room temperature.Add excessive Hydrogen chloride acid, remove MOX.Extremely neutral with deionized water wash again, obtain rich nitrogen porous carbon material.The BET specific surface area of this raw material of wood-charcoal material is 1350m
2/ g, pore volume 1.61cm
3/ g, nitrogen content are 2.32%.
Embodiment 4:
YD 30 manganese is placed tube type resistance furnace, feed the high pure nitrogen protection, be heated to 600 ℃, constant temperature 5h treats to take out after furnace temperature is cooled to room temperature.Add excessive rare salt nitric acid, remove MOX.Extremely neutral with deionized water wash again, obtain rich nitrogen porous carbon material.The BET specific surface area of this raw material of wood-charcoal material is 609m
2/ g, pore volume 0.55cm
3/ g, nitrogen content are 13.2%.
Claims (4)
1. the preparation method of a rich nitrogen porous carbon material; It is characterized in that: be precursor with the edetate; With its under the protection of rare gas element in 400-1200 ℃ of constant temperature pyrolysis 0.5-12h; MOX is removed in pickling, and washing obtains nitrogen content 1.6～15.5%, specific surface area 600-2000m to neutral again
2/ g, pore volume 0.3～1.8cm
3The rich nitrogen porous carbon material of/g.
2. the preparation method of a kind of rich nitrogen porous carbon material as claimed in claim 1 is characterized in that: described edetate is tetra-na salt, disodium salt, sodium magnesium salts, molysite, calcium salt or the manganese salt of YD 30.
3. the preparation method of a kind of rich nitrogen porous carbon material as claimed in claim 1 is characterized in that: the used acid of pickling is more than one materials in hydrochloric acid, sulfuric acid, nitric acid, the phosphoric acid.
4. the preparation method of a kind of rich nitrogen porous carbon material as claimed in claim 1 is characterized in that: described rare gas element is nitrogen, argon gas or both mixed gass.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103272559A (en) * | 2013-05-21 | 2013-09-04 | 北京化工大学 | Application of porous carbon electrode material in electrosorb technology |
| CN103288084A (en) * | 2013-06-07 | 2013-09-11 | 上海交通大学 | Method for preparing modified activated carbon at normal pressure |
| CN103964412A (en) * | 2013-01-30 | 2014-08-06 | 北京化工大学 | Preparation method of nitrogen-doped porous-structure carbon material |
| CN104332596A (en) * | 2014-10-22 | 2015-02-04 | 国家纳米科学中心 | Nitrogen-enriched porous material/carbon nano structure composite material as well as preparation method and application thereof |
| CN105439143A (en) * | 2014-08-21 | 2016-03-30 | 中国科学院大连化学物理研究所 | Hierarchical porous activated carbon used for a super capacitor and preparation method thereof |
| CN106276882A (en) * | 2016-08-25 | 2017-01-04 | 北京化工大学 | The preparation method of the graphitization porous carbon that a kind of transition metal recycles |
| CN106276851A (en) * | 2016-08-10 | 2017-01-04 | 石河子大学 | Nitrogen-doped carbon material and preparation method thereof |
| CN106564868B (en) * | 2016-10-09 | 2018-07-20 | 上海应用技术大学 | A kind of preparation method of nitrogen-doped porous carbon material |
| CN108584944A (en) * | 2018-06-26 | 2018-09-28 | 北京化工大学 | A kind of preparation method of the ultracapacitor rich nitrogen grading porous carbon electrode material of high-specific surface area |
| CN109467180A (en) * | 2018-09-25 | 2019-03-15 | 江苏天雨环保集团有限公司 | A kind of low concentration chemical industry wastewater through organic matter trap catalyst oxidation degradation method |
| CN109524248A (en) * | 2018-12-06 | 2019-03-26 | 中国科学院兰州化学物理研究所 | A kind of construction method of zinc ion mixed capacitor |
| CN110137518A (en) * | 2019-06-04 | 2019-08-16 | 北方民族大学 | A kind of self-supported Fe-N-C oxygen reduction catalyst and preparation method thereof |
| CN110182800A (en) * | 2019-07-15 | 2019-08-30 | 天津工业大学 | A kind of method for preparation of active carbon based on ethylene diamine tetraacetic acid sylvite |
| CN111634900A (en) * | 2020-05-08 | 2020-09-08 | 东风汽车集团有限公司 | Preparation method of nitrogen-doped porous carbon material |
| CN114334475A (en) * | 2021-10-01 | 2022-04-12 | 中国科学院宁波材料技术与工程研究所 | One-step synthesized high-specific-surface-area hierarchical pore carbon electrode material and preparation method and application thereof |
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| US7094276B2 (en) * | 2001-09-28 | 2006-08-22 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Hydrogen storage material and hydrogen storage apparatus |
| CN101740231A (en) * | 2010-01-12 | 2010-06-16 | 山东理工大学 | Preparation method of mesoporous carbon electrode material for supercapacitor |
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2012
- 2012-08-07 CN CN201210278030XA patent/CN102757034A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US7094276B2 (en) * | 2001-09-28 | 2006-08-22 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Hydrogen storage material and hydrogen storage apparatus |
| CN101740231A (en) * | 2010-01-12 | 2010-06-16 | 山东理工大学 | Preparation method of mesoporous carbon electrode material for supercapacitor |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103964412A (en) * | 2013-01-30 | 2014-08-06 | 北京化工大学 | Preparation method of nitrogen-doped porous-structure carbon material |
| CN103272559A (en) * | 2013-05-21 | 2013-09-04 | 北京化工大学 | Application of porous carbon electrode material in electrosorb technology |
| CN103288084A (en) * | 2013-06-07 | 2013-09-11 | 上海交通大学 | Method for preparing modified activated carbon at normal pressure |
| CN105439143A (en) * | 2014-08-21 | 2016-03-30 | 中国科学院大连化学物理研究所 | Hierarchical porous activated carbon used for a super capacitor and preparation method thereof |
| CN105439143B (en) * | 2014-08-21 | 2018-01-23 | 中国科学院大连化学物理研究所 | A kind of classifying porous activated carbon and preparation method for ultracapacitor |
| CN104332596A (en) * | 2014-10-22 | 2015-02-04 | 国家纳米科学中心 | Nitrogen-enriched porous material/carbon nano structure composite material as well as preparation method and application thereof |
| CN106276851A (en) * | 2016-08-10 | 2017-01-04 | 石河子大学 | Nitrogen-doped carbon material and preparation method thereof |
| CN106276882B (en) * | 2016-08-25 | 2020-10-02 | 北京化工大学 | Preparation method of graphitized porous carbon with cyclic utilization of transition metal elements |
| CN106276882A (en) * | 2016-08-25 | 2017-01-04 | 北京化工大学 | The preparation method of the graphitization porous carbon that a kind of transition metal recycles |
| CN106564868B (en) * | 2016-10-09 | 2018-07-20 | 上海应用技术大学 | A kind of preparation method of nitrogen-doped porous carbon material |
| CN108584944A (en) * | 2018-06-26 | 2018-09-28 | 北京化工大学 | A kind of preparation method of the ultracapacitor rich nitrogen grading porous carbon electrode material of high-specific surface area |
| CN109467180A (en) * | 2018-09-25 | 2019-03-15 | 江苏天雨环保集团有限公司 | A kind of low concentration chemical industry wastewater through organic matter trap catalyst oxidation degradation method |
| CN109524248A (en) * | 2018-12-06 | 2019-03-26 | 中国科学院兰州化学物理研究所 | A kind of construction method of zinc ion mixed capacitor |
| CN110137518A (en) * | 2019-06-04 | 2019-08-16 | 北方民族大学 | A kind of self-supported Fe-N-C oxygen reduction catalyst and preparation method thereof |
| CN110137518B (en) * | 2019-06-04 | 2022-05-17 | 北方民族大学 | Self-loading Fe-N-C oxygen reduction catalyst and preparation method thereof |
| CN110182800A (en) * | 2019-07-15 | 2019-08-30 | 天津工业大学 | A kind of method for preparation of active carbon based on ethylene diamine tetraacetic acid sylvite |
| CN111634900A (en) * | 2020-05-08 | 2020-09-08 | 东风汽车集团有限公司 | Preparation method of nitrogen-doped porous carbon material |
| CN114334475A (en) * | 2021-10-01 | 2022-04-12 | 中国科学院宁波材料技术与工程研究所 | One-step synthesized high-specific-surface-area hierarchical pore carbon electrode material and preparation method and application thereof |
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Application publication date: 20121031 |