CN115448310B - Nitrogen-containing porous carbon material and preparation method and application thereof - Google Patents
Nitrogen-containing porous carbon material and preparation method and application thereof Download PDFInfo
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- CN115448310B CN115448310B CN202211164428.0A CN202211164428A CN115448310B CN 115448310 B CN115448310 B CN 115448310B CN 202211164428 A CN202211164428 A CN 202211164428A CN 115448310 B CN115448310 B CN 115448310B
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 72
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 31
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 25
- 238000001914 filtration Methods 0.000 claims abstract description 21
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 229960000583 acetic acid Drugs 0.000 claims abstract description 8
- 238000004132 cross linking Methods 0.000 claims abstract description 8
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 238000010517 secondary reaction Methods 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 150000001299 aldehydes Chemical class 0.000 claims description 8
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 5
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 4
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 3
- IZALUMVGBVKPJD-UHFFFAOYSA-N benzene-1,3-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=C1 IZALUMVGBVKPJD-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 2
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 20
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 239000011261 inert gas Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 23
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000010926 purge Methods 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/354—After-treatment
- C01B32/36—Reactivation or regeneration
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
The invention provides a preparation method of a nitrogen-containing porous carbon material, which specifically comprises the following preparation steps: dissolving a nitrogen-containing compound and a crosslinking agent in glacial acetic acid, and carrying out crosslinking reaction under the action of a catalyst to obtain a nitrogen-containing super-crosslinked polymer; adding the nitrogen-containing super-crosslinked polymer into a mixed solution of concentrated hydrochloric acid, concentrated sulfuric acid and concentrated nitric acid, performing primary reaction at the temperature of-5-0 ℃, performing secondary reaction at the temperature of 20-80 ℃, washing, filtering and drying to obtain the nitrogen-containing super-crosslinked polymer; and then reacting the nitrogen-containing super-crosslinked polymer with an alkali metal solution at 24-26 ℃, washing, filtering, drying, and heating and roasting under the protection of inert gas to obtain the nitrogen-containing porous carbon material. The preparation method of the nitrogen-containing porous carbon material provided by the invention has the advantages of simple process, low-cost and easily available raw materials, and the prepared nitrogen-containing porous carbon material has better carbon dioxide adsorption performance.
Description
Technical Field
The invention relates to the technical field of porous carbon materials, in particular to a nitrogen-containing porous carbon material, and a preparation method and application thereof.
Background
The carbon material has the advantages of high physical and chemical stability, low preparation cost, good regeneration performance, easy-to-modify pore channel structure, good adsorption kinetics, high carbon dioxide adsorption capacity and the like. At present, the preparation methods of carbon materials are various, and the most common method is a preparation method of high-temperature pyrolysis. The precursor sources for preparing the carbon material by the pyrolysis method are wide, and biomass, fossil fuel, polymer, metal organic frame materials and the like are available, wherein the biomass and fossil fuel have a plurality of impurities, the pore channels are not easy to regulate and control, the metal organic frame materials have high cost, and the polymer becomes a good choice due to the relative advantages of adjustable pore channels, low cost and the like.
The super-crosslinked polymer is an organic porous polymer material with a highly crosslinked rigid structure, which is produced by a super-crosslinking reaction, and has the advantages of large specific surface area, abundant micropores, high thermal stability, high chemical stability and the like, so that the super-crosslinked polymer is more and more concerned in the fields of gas storage, clean energy, environmental problems and the like, but the performance of the carbon material for carbon dioxide adsorption is still lower, and compared with the pure carbon material, the nitrogen-doped carbon material has more excellent carbon dioxide adsorption capacity. When nitrogen atoms are introduced into the carbon matrix, these nitrogen atom doped carbon materials exhibit better and superior physicochemical activity due to charge delocalization and changes in electronic structure. In addition, due to the difference in atomic radius, bond length and coordination ability between carbon atoms and heteroatoms, doping of heteroatoms into a carbon matrix also results in new defects in the material, which in turn locally create defect sites with abundant charges, which is also very effective in increasing the catalytically active sites of the carbon material. However, in the prior art, the nitrogen-doped carbon material is obtained by introducing nitrogen into the carbon material, but the synthesis method is complex, and the prepared nitrogen-doped carbon material is often uneven in nitrogen doping, so that the performance of the material is not facilitated. Therefore, the development of the nitrogen-containing porous carbon material with strong carbon dioxide adsorption capacity has important significance.
Disclosure of Invention
Aiming at the problems of weak carbon dioxide adsorption capacity and the like of the existing porous carbon material, the invention provides a preparation method of a nitrogen-containing porous carbon material.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of a nitrogen-containing porous carbon material comprises the following steps:
step a, dissolving a nitrogen-containing compound and an aldehyde cross-linking agent in glacial acetic acid, and carrying out a cross-linking reaction under the action of a catalyst to obtain a nitrogen-containing super-crosslinked polymer; the nitrogen-containing compound is at least one of imidazole, thiazole, carbazole, oxazole, pyrazole, pyridine, pyrimidine, pyridazine, piperazine or tetraphenylporphyrin; the aldehyde cross-linking agent is at least one of terephthalaldehyde or isophthalaldehyde; step b, adding the nitrogen-containing super-crosslinked polymer into a mixed solution of concentrated hydrochloric acid, concentrated sulfuric acid and concentrated nitric acid, performing primary reaction at the temperature of-5-0 ℃, performing secondary reaction at the temperature of 20-80 ℃, washing, filtering and drying to obtain an oxidized nitrogen-containing super-crosslinked polymer; step c, adding the oxidized nitrogen-containing super-crosslinked polymer into an alkali metal solution, reacting at 24-26 ℃, washing, filtering and drying to obtain an alkali metal modified oxidized super-crosslinked polymer; and d, roasting the alkali metal modified oxidized super-crosslinked polymer at 600-900 ℃ for 2-8 hours in an inert atmosphere to obtain the nitrogen-containing porous carbon material.
Compared with the prior art, the preparation method of the nitrogen-containing porous carbon material provided by the invention has the advantages that the specific nitrogen-containing compound has higher nitrogen content, so that the nitrogen element content in the nitrogen-containing super-crosslinked polymer is improved, more targets are provided for subsequent introduction of alkali metal ions, the specific aldehyde crosslinking agent can thoroughly react with the nitrogen-containing compound to generate the nitrogen-containing super-crosslinked polymer with a specific pore structure, and an excellent precursor is provided for subsequent improvement of carbon dioxide adsorption performance; the method is characterized in that a specific monomer and a specific cross-linking agent react under a solvent to generate the nitrogen-containing super-crosslinked polymer with a specific pore structure, and the nitrogen-containing super-crosslinked polymer is utilized to prepare the porous carbon material, so that more nitrogen elements in the porous carbon material can be kept, and the adsorption effect of the porous carbon material on carbon dioxide is further improved; the mixed solution of the concentrated hydrochloric acid, the concentrated sulfuric acid and the concentrated nitric acid is added into the nitrogen-containing super-crosslinked polymer, and further, the secondary reaction is carried out at 20-80 ℃ after the primary reaction is carried out at-5-0 ℃, so that the nitrogen-containing super-crosslinked polymer is subjected to strong acid oxidation, the site of nitrogen atoms in the nitrogen-containing super-crosslinked polymer is not influenced, and meanwhile, various functional groups can be introduced into the surface of the nitrogen-containing compound to act together with nitrogen elements in the nitrogen-containing super-crosslinked polymer, and the adsorption performance on carbon dioxide is improved; the oxidized nitrogen-containing super-crosslinked polymer with the specific pore structure contains more target sites, the metal elements are uniformly doped in the oxidized nitrogen-containing super-crosslinked polymer by adding the specific alkali metal solution, and then the oxidized nitrogen-containing super-crosslinked polymer is roasted at a high temperature under the protection of inert atmosphere, so that the oxidized nitrogen-containing super-crosslinked polymer can be prevented from being decomposed, the sites of the nitrogen elements and the metal elements can be stabilized, the nitrogen elements and the metal elements in the prepared nitrogen-containing porous carbon material act synergistically, and the adsorption effect of the nitrogen-containing porous carbon material on carbon dioxide is greatly improved.
Preferably, in the step a, the molar ratio of the nitrogen-containing compound to the aldehyde crosslinking agent is 0.8-1:1; the catalyst is at least one of magnesium chloride or aluminum trichloride.
Preferably, the molar ratio of the nitrogen-containing compound to the catalyst is 1:0.25-0.3.
Preferably, in the step a, the temperature of the crosslinking reaction is 178-180 ℃, and the reaction time is 48-72 h.
Preferably, in step a, the amount of glacial acetic acid used is from 5000mL to 10000mL per mole of nitrogen-containing compound.
Preferably, in step a, the reaction is carried out under inert gas.
Further, the inert gas is nitrogen.
Further, the nitrogen-containing super cross-linked polymer is obtained by post-treatment of the reaction product after the reaction, wherein the post-treatment comprises washing and drying the solid product produced by the reaction.
The purpose of the washing is to remove unreacted nitrogen-containing compounds, aldehyde crosslinkers or glacial acetic acid.
Preferably, in the step b, the time of the primary reaction is 0.2 to 5 hours; the time of the secondary reaction is 2-24 hours.
The preferred crosslinking time can be controlled so as not to affect the site of the nitrogen atom in the nitrogen-containing super-crosslinked polymer, and functional groups can be introduced into the surface of the nitrogen-containing compound.
Preferably, in the step b, the mass volume ratio of the nitrogen-containing super-crosslinked polymer to the mixed solution of the concentrated hydrochloric acid, the concentrated sulfuric acid and the concentrated nitric acid is 1g (20-80) mL.
Preferably, in the step b, the volume ratio of the concentrated hydrochloric acid to the concentrated sulfuric acid to the concentrated nitric acid in the mixed solution of the concentrated hydrochloric acid and the concentrated sulfuric acid is (0.01-0.7): 0.01-1.5): 1.
The preferred ratio of the mixed solution of concentrated hydrochloric acid, concentrated sulfuric acid and concentrated nitric acid provides still other functional groups.
Preferably, in the step c, the concentration of the alkali metal solution is 0.8mol/L to 4mol/L.
Preferably, in the step c, the alkali metal solution is a mixed solution of sodium hydroxide, potassium hydroxide and lithium hydroxide;
preferably, in the step c, the alkali metal solution is a mixed solution of sodium hydroxide, potassium hydroxide and lithium hydroxide with the molar mass ratio of alkali metal ions of (0.01-0.5) 1 (0.01-0.5).
The preferred proportion of alkali metal solution may further enhance the adsorption of carbon dioxide.
Preferably, in the step b and the step c, the stop condition of the filtration is that the pH of the filtrate reaches 6-8; the drying temperature is 60-120 ℃, and the drying time is 4-24 hours.
Further, the washing condition is that the mass volume ratio of the deionized water to the oxidized nitrogen-containing super cross-linked polymer is (100-1000) mL:1g, wherein the stop condition of the filtration is that the pH value of the filtrate reaches 6-8 when the filtration is carried out after the single washing is finished.
Preferably, in step c, the reaction time is 12 to 48 hours.
Preferably, in the step c, the mass volume ratio of the oxidized nitrogen-containing super-crosslinked polymer to the alkali metal solution is 1g (200-400) mL.
The ratio of the preferable oxidized nitrogen-containing super-crosslinked polymer to the alkali metal solution can enable the metal element to be uniformly doped in the oxidized nitrogen-containing super-crosslinked polymer, and the metal element and the nitrogen element act together to improve the carbon dioxide adsorption capacity.
It should be noted that in the step d, the heating rate is 2 ℃/min-5 ℃/min.
The stable temperature rising rate can improve the stability of nitrogen and metal elements in the oxidized nitrogen-containing super-crosslinked polymer and the adsorption effect of the prepared nitrogen-containing porous carbon material on carbon dioxide.
Preferably, in the step d, the inert atmosphere is at least one of nitrogen, helium or argon.
The reaction can be carried out in an inert atmosphere, so that the oxidative nitrogen-containing super-crosslinked polymer is prevented from being decomposed, and the yield of the final nitrogen-containing porous carbon material is improved.
The invention provides a nitrogen-containing porous carbon material, which is prepared by the preparation method of the nitrogen-containing porous carbon material.
Further, the invention also provides application of the nitrogen-containing porous carbon material in adsorbing carbon dioxide.
The preparation method of the nitrogen-containing porous carbon material provided by the invention has the advantages of simple process, low-cost and easily available raw materials, and the prepared nitrogen-containing porous carbon material has better carbon dioxide adsorption performance.
Drawings
FIG. 1 is an SEM photograph of a nitrogen-containing super cross-linked polymer of example 1;
FIG. 2 is an SEM photograph of a nitrogen-containing super cross-linked polymer of example 2.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The embodiment provides a preparation method of a nitrogen-containing super cross-linked polymer, which comprises the following specific steps:
introducing nitrogen into a reaction vessel with a condensation reflux system at 25 ℃, purging for 30min, sequentially adding 50mL of glacial acetic acid, 0.80g of pyrimidine and 1.34g of isophthalaldehyde, and reacting for 30min at normal temperature; then 0.34g of aluminum trichloride is added, the reaction is continued for 4 hours at normal temperature, the nitrogen is stopped being introduced, the reaction solution is placed in a hydrothermal reaction kettle, and the reaction is heated at 178 ℃ for 70 hours. The resulting solid product was washed 3 times with deionized water, methanol, and acetone in sequence, and then extracted with methanol in a soxhlet extractor for 24 hours. And drying the obtained product to obtain the nitrogen-containing super-crosslinked polymer. The morphology of the nitrogen-containing super cross-linked polymer material is shown in figure 1.
Example 2
Introducing nitrogen into a reaction vessel with a condensation reflux system at 25 ℃, purging for 30min, sequentially adding 50mL of glacial acetic acid, 0.791g of pyridine and 1.34g of terephthalaldehyde, and reacting for 20min at normal temperature; then 0.34g of aluminum trichloride is added, the reaction is continued for 3 hours at normal temperature, the nitrogen is stopped being introduced, the reaction solution is placed in a hydrothermal reaction kettle, and the reaction is heated for 72 hours at 180 ℃. The resulting solid product was washed 3 times with deionized water, methanol, and acetone in sequence, and then extracted with methanol in a soxhlet extractor for 24 hours. And drying the obtained product to obtain the nitrogen-containing super-crosslinked polymer. The morphology of the nitrogen-containing super cross-linked polymer material is shown in figure 2.
Example 3
The preparation method of the nitrogen-containing porous carbon material provided by the embodiment by using the nitrogen-containing super-crosslinked polymer of the embodiment 1 specifically comprises the following steps:
adding 1g of nitrogen-containing super-crosslinked polymer into 20mL of mixed solution of concentrated hydrochloric acid, concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 0.7:1.5:1, reacting for 5 hours at the temperature of minus 5 ℃, then reacting for 24 hours at the temperature of 20-80 ℃, washing and filtering the reaction product by 1000mL of deionized water, repeating the above operation, stopping filtering when the pH value of the filtrate is 6-7, and drying for 24 hours at the temperature of 60 ℃ to obtain the oxidized nitrogen-containing super-crosslinked polymer;
adding 200mL of alkali metal solution with the concentration of 0.8mol/L into the oxidized nitrogen-containing super-crosslinked polymer, wherein the alkali metal solution is a mixed solution of sodium hydroxide, potassium hydroxide and lithium hydroxide with the molar mass ratio of alkali metal ions of 0.5:1:0.01; reacting for 12 hours at 24 ℃, washing with 1000mL of deionized water, filtering, repeating the operation until the pH value of the filtrate is 7-8, stopping filtering, and drying for 4 hours at 120 ℃ to obtain the alkali metal modified oxidized super-crosslinked polymer;
and (3) placing the alkali metal modified oxidized super-crosslinked polymer in a tube furnace under the protection of helium, heating to 600 ℃ at the speed of 2 ℃/min, and roasting for 8 hours to obtain the nitrogen-containing porous carbon material.
Example 4
The preparation method of the nitrogen-containing porous carbon material provided by the embodiment by using the nitrogen-containing super-crosslinked polymer of the embodiment 2 specifically comprises the following steps:
adding 1g of nitrogen-containing super-crosslinked polymer into 80mL of mixed solution of concentrated hydrochloric acid, concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 0.01:0.01:1, reacting for 0.2h at 0 ℃, then reacting for 2h at 80 ℃, washing the reaction product with 100mL of deionized water, filtering, repeating the above operation, stopping filtering when the pH value of the filtrate is 6-7, and drying for 4h at 120 ℃ to obtain the oxidized nitrogen-containing super-crosslinked polymer;
adding 400mL of alkali metal solution with the concentration of 4mol/L into the oxidized nitrogen-containing super-crosslinked polymer, wherein the alkali metal solution is a mixed solution of sodium hydroxide, potassium hydroxide and lithium hydroxide with the molar mass ratio of alkali metal ions of 0.01:1:0.5; reacting at 26 ℃ for 48 hours, washing with 100mL of deionized water, filtering, repeating the operation until the pH value of the filtrate is 7-8, stopping filtering, and drying at 60 ℃ for 24 hours to obtain the alkali metal modified oxidized super-crosslinked polymer;
and (3) placing the alkali metal modified oxidized super-crosslinked polymer in a tube furnace under the protection of helium, heating to 900 ℃ at a speed of 5 ℃/min, and roasting for 2 hours to obtain the nitrogen-containing porous carbon material.
Example 5
The preparation method of the nitrogen-containing porous carbon material provided by the embodiment by using the nitrogen-containing super-crosslinked polymer of the embodiment 1 specifically comprises the following steps:
adding 1g of nitrogen-containing super-crosslinked polymer into 60mL of mixed solution of concentrated hydrochloric acid, concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 0.15:0.35:1, reacting for 3 hours at the temperature of minus 2 ℃, then reacting for 12 hours at the temperature of 50 ℃, washing and filtering the reaction product by 500mL of deionized water, repeating the above operation, stopping filtering when the pH value of the filtrate is 6-7, and drying for 10 hours at the temperature of 100 ℃ to obtain the oxidized nitrogen-containing super-crosslinked polymer;
adding 300mL of alkali metal solution with the concentration of 2.4mol/L into the oxidized nitrogen-containing super-crosslinked polymer, wherein the alkali metal solution is a mixed solution of sodium hydroxide, potassium hydroxide and lithium hydroxide with the molar mass ratio of alkali metal ions of 0.4:1:0.25; reacting at 25 ℃ for 20 hours, washing with 300mL of deionized water, filtering, repeating the operation until the pH value of the filtrate is 7-8, stopping filtering, and drying at 100 ℃ for 20 hours to obtain the alkali metal modified oxidized super-crosslinked polymer;
and (3) placing the alkali metal modified oxidized super-crosslinked polymer in a tube furnace under the protection of helium, heating to 700 ℃ at the speed of 4 ℃/min, and roasting for 4 hours to obtain the nitrogen-containing porous carbon material.
Comparative example 1
This comparative example provides a method for preparing a nitrogen-containing porous carbon material, which is different from example 5 in that: the alkali metal solution is a mixed solution of potassium hydroxide and lithium hydroxide with the molar mass ratio of alkali metal ions of 1:20;
the remaining steps are exactly the same as in example 5.
Comparative example 2
Introducing nitrogen into a reaction vessel with a condensation reflux system at 25 ℃, purging for 30min, sequentially adding 50mL of dichloroethane, 1.98g of cyclopentadiene and 5.3mL of dimethanol formal, and stirring for 20min; then adding 9.75g of anhydrous ferric trichloride, continuously stirring for 20min, stopping introducing nitrogen, and continuously reacting for 2h; controlling the reaction temperature to 25 ℃ and reacting for 2 hours; heating to 40 ℃, and pre-crosslinking for 4 hours; then the temperature was slowly raised to 80℃and the reaction was carried out for 19h. The resulting solid product was washed 5 times with methanol and then extracted with methanol in a soxhlet extractor for 24h. The resulting product was dried to obtain a super crosslinked polymer.
This comparative example also provides a method for producing a porous carbon material, which is different from example 5 in that: the procedure of example 5 was followed except that the nitrogen-containing super-crosslinked polymer was replaced with the super-crosslinked polymer prepared in the above-mentioned manner.
Comparative example 3
Introducing nitrogen into a reaction vessel with a condensation reflux system at 25 ℃, purging for 30min, sequentially adding 50mL of glacial acetic acid, 0.6709g of pyrrole and 1.34g of terephthalaldehyde, and reacting for 20min at normal temperature; then 0.34g of aluminum trichloride is added, the reaction is continued for 3 hours at normal temperature, the nitrogen is stopped being introduced, the reaction solution is placed in a hydrothermal reaction kettle, and the reaction is heated for 72 hours at 180 ℃. The resulting solid product was washed 3 times with deionized water, methanol, and acetone in sequence, and then extracted with methanol in a soxhlet extractor for 24 hours. The resulting product was dried to obtain a super crosslinked polymer.
This comparative example also provides a method for producing a porous carbon material, which is different from example 5 in that: the procedure of example 5 was followed except that the nitrogen-containing super-crosslinked polymer was replaced with the super-crosslinked polymer prepared in the above-mentioned manner.
And measuring the carbon dioxide adsorption performance of the sample by a mass method by adopting a thermal heavy adsorption instrument. During testing, a small amount of sample is weighed and paved in a sample tray, firstly, the temperature is raised to 120 ℃ under argon purging, the temperature is kept for 1h, then the temperature is lowered to 40 ℃, the temperature is kept for 30min, and carbon dioxide gas is introduced to perform adsorption performance testing. Wherein the gas feed was 0.15bar (15 Vol.% CO) 2 +85Vol.％N 2 ) The carbon dioxide adsorption properties of the different samples are shown in table 1 below:
TABLE 1 Performance test results
The preparation method of the nitrogen-containing porous carbon material provided by the invention has the advantages of simple process, low-cost and easily available raw materials, and the prepared nitrogen-containing porous carbon material has better carbon dioxide adsorption performance.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The preparation method of the nitrogen-containing porous carbon material is characterized by comprising the following steps of: step a, dissolving a nitrogen-containing compound and an aldehyde cross-linking agent in glacial acetic acid, and carrying out a cross-linking reaction under the action of a catalyst to obtain a nitrogen-containing super-crosslinked polymer; the nitrogen-containing compound is at least one of imidazole, thiazole, carbazole, oxazole, pyrazole, pyridine, pyrimidine, pyridazine, piperazine or tetraphenylporphyrin; the aldehyde cross-linking agent is at least one of terephthalaldehyde or isophthalaldehyde; step b, adding the nitrogen-containing super-crosslinked polymer into a mixed solution of concentrated hydrochloric acid, concentrated sulfuric acid and concentrated nitric acid, performing primary reaction at the temperature of-5-0 ℃, performing secondary reaction at the temperature of 20-80 ℃, washing, filtering and drying to obtain an oxidized nitrogen-containing super-crosslinked polymer; step c, adding the oxidized nitrogen-containing super-crosslinked polymer into an alkali metal solution, reacting at 24-26 ℃, washing, filtering and drying to obtain an alkali metal modified oxidized super-crosslinked polymer; step d, roasting the alkali metal modified oxidized super-crosslinked polymer at 600-900 ℃ for 2-8 hours in an inert atmosphere to obtain a nitrogen-containing porous carbon material;
in the step c, the alkali metal solution is a mixed solution of sodium hydroxide, potassium hydroxide and lithium hydroxide;
in the step b, the volume ratio of the concentrated hydrochloric acid to the concentrated sulfuric acid to the concentrated nitric acid in the mixed solution of the concentrated hydrochloric acid and the concentrated sulfuric acid is (0.01-0.7): 0.01-1.5): 1.
2. The method for producing a nitrogen-containing porous carbon material according to claim 1, wherein in the step a, the molar ratio of the nitrogen-containing compound to the aldehyde crosslinking agent is 0.8 to 1:1; and/or
In the step a, the catalyst is at least one of magnesium chloride or aluminum trichloride; and/or
In the step a, the temperature of the crosslinking reaction is 178-180 ℃, and the reaction time is 48-72 h.
3. The method for producing a nitrogen-containing porous carbon material according to claim 1, wherein in the step b, the time of the primary reaction is 0.2 to 5 hours; and/or
In the step b, the time of the secondary reaction is 2-24 hours.
4. The method for preparing a nitrogen-containing porous carbon material according to claim 1, wherein in the step b, the mass volume ratio of the nitrogen-containing super cross-linked polymer to the mixed solution of the concentrated hydrochloric acid, the concentrated sulfuric acid and the concentrated nitric acid is 1g (20-80 mL).
5. The method for producing a nitrogen-containing porous carbon material according to claim 1, wherein in the step c, the concentration of the alkali metal solution is 0.8mol/L to 4mol/L.
6. The method for producing a nitrogen-containing porous carbon material according to claim 1, wherein in the step c, the alkali metal solution is a mixed solution of sodium hydroxide, potassium hydroxide and lithium hydroxide in a molar mass ratio of alkali metal ions of (0.01 to 0.5): 1 (0.01 to 0.5).
7. The method for preparing a nitrogen-containing porous carbon material according to claim 1, wherein in the step c, the reaction time is 12 to 48 hours.
8. The method for preparing a nitrogen-containing porous carbon material according to claim 1, wherein in the step c, the mass-to-volume ratio of the oxidized nitrogen-containing super cross-linked polymer to the alkali metal solution is 1g (200-400) mL.
9. A nitrogen-containing porous carbon material, characterized by being prepared by the method for preparing a nitrogen-containing porous carbon material according to any one of claims 1 to 8.
10. Use of the nitrogen-containing porous carbon material of claim 9 for adsorbing carbon dioxide.
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