CN115448310A - 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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- CN115448310A CN115448310A CN202211164428.0A CN202211164428A CN115448310A CN 115448310 A CN115448310 A CN 115448310A CN 202211164428 A CN202211164428 A CN 202211164428A CN 115448310 A CN115448310 A CN 115448310A
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- porous carbon
- containing porous
- alkali metal
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000013315 hypercross-linked polymer Substances 0.000 claims abstract description 61
- 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 29
- 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 19
- 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 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910017604 nitric acid Inorganic materials 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
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 10
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 229960000583 acetic acid Drugs 0.000 claims abstract description 8
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 8
- 238000004132 cross linking Methods 0.000 claims abstract description 7
- 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 4
- 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
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 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
- 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 22
- 238000010438 heat treatment Methods 0.000 abstract description 10
- 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 42
- 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 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 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
- 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
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 229920000642 polymer Polymers 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
- 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
- 125000000524 functional group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 238000011056 performance test Methods 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
- 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
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 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
- 230000002349 favourable effect 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
- 239000002861 polymer material Substances 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
- 238000006557 surface reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
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 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 cross-linked polymer; adding the nitrogen-containing hypercrosslinked polymer into a mixed solution of concentrated hydrochloric acid, concentrated sulfuric acid and concentrated nitric acid, carrying out primary reaction at-5-0 ℃, carrying out secondary reaction at 20-80 ℃, washing, filtering and drying to obtain the nitrogen-containing hypercrosslinked polymer; and then reacting the nitrogen-containing hypercrosslinked polymer with an alkali metal solution at 24-26 ℃, washing, filtering, drying, and then 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 is simple in process, the raw materials are cheap and easy to obtain, 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, pore channel structure easy to modify, good adsorption kinetics, high carbon dioxide adsorption capacity and the like. At present, the preparation method of the carbon material is various, and the most common method is a high-temperature pyrolysis preparation method. The precursor for preparing the carbon material by the pyrolysis method has wide sources, and comprises biomass, fossil fuel, polymer, metal organic framework material and the like, wherein the biomass and fossil fuel have more impurities, pore channels are not easy to regulate, the metal organic framework material has high cost, and the polymer has the relative advantages of adjustable pore channels, low cost and the like, so that the polymer is a good choice.
The hypercrosslinked polymer is an organic porous polymer material with a highly cross-linked rigid structure generated through hypercrosslinked reaction, and has the advantages of large specific surface area, rich micropores, high thermal stability, high chemical stability and the like, so that the hypercrosslinked 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 used for carbon dioxide adsorption is still lower at present, and the nitrogen-doped carbon material has more excellent carbon dioxide adsorption capacity compared with a pure carbon material. When nitrogen atoms are introduced into a carbon matrix, the carbon material doped with the nitrogen atoms shows better excellent physicochemical activity due to charge delocalization and change in electronic structure. In addition, due to the difference of the carbon atom and the heteroatom in atomic radius, bond length and coordination capacity, doping of the heteroatom into the carbon matrix can also cause new defects in the material, so that defect sites with rich charges are locally generated, which is also very effective for increasing the catalytic activity sites of the carbon material. However, in the prior art, nitrogen is introduced into the carbon material to obtain the nitrogen-doped carbon material, but the synthesis method is complex, and the prepared nitrogen-containing carbon material is not uniform in nitrogen doping, which is not favorable for the performance of the material. Therefore, the development of the nitrogen-containing porous carbon material with strong carbon dioxide adsorption capacity is of great significance.
Disclosure of Invention
The invention provides a preparation method of a nitrogen-containing porous carbon material, aiming at the problems of weak adsorption capacity of carbon dioxide adsorption of the existing porous carbon material and the like.
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 crosslinking agent in glacial acetic acid, and performing crosslinking 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 crosslinking agent is at least one of terephthalaldehyde or m-phthalaldehyde; b, adding the nitrogen-containing hypercrosslinked polymer into a mixed solution of concentrated hydrochloric acid, concentrated sulfuric acid and concentrated nitric acid, carrying out primary reaction at-5-0 ℃, then carrying out secondary reaction at 20-80 ℃, washing, filtering and drying to obtain the nitrogen-containing hypercrosslinked polymer; step c, adding the oxidized nitrogen-containing hypercrosslinked polymer into an alkali metal solution, reacting at 24-26 ℃, washing, filtering and drying to obtain an alkali metal modified oxidized hypercrosslinked polymer; and d, roasting the alkali metal modified oxidized hypercrosslinked polymer at the temperature of 600-900 ℃ for 2-8 h under 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, the nitrogen element content in the nitrogen-containing hypercrosslinked polymer is favorably improved, so that more targets are provided for the subsequent introduction of alkali metal ions, the specific aldehyde crosslinking agent can completely react with the nitrogen-containing compound to generate the nitrogen-containing hypercrosslinked polymer with a specific pore structure, and an excellent precursor is further provided for the subsequent improvement of the carbon dioxide adsorption performance; according to the invention, a specific monomer and a specific cross-linking agent are preferably selected to react in a solvent to generate a nitrogen-containing super cross-linked polymer with a specific pore structure, and the nitrogen-containing super cross-linked polymer is used for preparing the porous carbon material, so that more nitrogen elements in the porous carbon material can be maintained, and the adsorption effect of the porous carbon material on carbon dioxide is further improved; by adding a mixed solution of concentrated hydrochloric acid, concentrated sulfuric acid and concentrated nitric acid into the nitrogen-containing hypercrosslinked polymer, further, by carrying out a secondary reaction at 20-80 ℃ after carrying out a primary reaction at-5-0 ℃, the nitrogen-containing hypercrosslinked polymer can be subjected to strong acid oxidation, and various functional groups can be introduced into the surface of the nitrogen-containing compound to act together with nitrogen elements in the nitrogen-containing hypercrosslinked polymer while nitrogen atom sites in the nitrogen-containing hypercrosslinked polymer are not affected, so that the adsorption performance on carbon dioxide is improved; the nitrogen-containing oxide super-crosslinked polymer with the specific pore structure contains more target sites, metal elements are uniformly doped in the nitrogen-containing oxide super-crosslinked polymer by adding a specific alkali metal solution, and then the nitrogen-containing oxide super-crosslinked polymer is roasted at high temperature under the protection of inert atmosphere, so that the nitrogen element and the metal elements in the prepared nitrogen-containing porous carbon material can be prevented from being decomposed, the sites of the nitrogen element and the metal elements can be stabilized, the nitrogen element and the metal elements in the prepared nitrogen-containing porous carbon material can act synergistically, and the adsorption effect of the nitrogen-containing porous carbon material on carbon dioxide can be 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.
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 5000mL to 10000mL per mole of nitrogen-containing compound.
Preferably, in step a, the reaction is carried out under an inert gas atmosphere.
Further, the inert gas is nitrogen.
Further, after the reaction, the reaction product is subjected to post-treatment to obtain the nitrogen-containing hypercrosslinked polymer, wherein the post-treatment comprises washing and drying of a solid product generated by the reaction.
The purpose of the washing is to remove unreacted nitrogen-containing compounds, aldehyde crosslinking agents or glacial acetic acid.
Preferably, in the step b, the time of the primary reaction is 0.2-5 h; the time of the secondary reaction is 2-24 h.
The preferred crosslinking time can be controlled to introduce functional groups on the surface of the nitrogen-containing compound without affecting the sites of nitrogen atoms in the nitrogen-containing hypercrosslinked polymer.
Preferably, in the step b, the mass-to-volume ratio of the nitrogen-containing hypercrosslinked polymer to the mixed solution of concentrated hydrochloric acid, concentrated sulfuric acid and concentrated nitric acid is 1g (20-80) mL.
Preferably, in the step b, the volume ratio of the concentrated hydrochloric acid, the concentrated sulfuric acid and the concentrated nitric acid in the mixed solution of the concentrated hydrochloric acid, the concentrated sulfuric acid and the concentrated nitric acid is (0.01-0.7): (0.01-1.5): 1.
The preferred ratio of concentrated hydrochloric acid, concentrated sulfuric acid and concentrated nitric acid mixed solution can provide more additional functional groups.
Preferably, in step c, the concentration of the alkali metal solution is 0.8mol/L to 4mol/L.
Preferably, in 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 (0.01-0.5) to 1 (0.01-0.5).
The preferred ratio of alkali metal solution further enhances the adsorption of carbon dioxide.
Preferably, in the step b and the step c, the filtering is stopped under the condition that the pH value of the filtrate reaches 6-8; the drying temperature is 60-120 ℃, and the drying time is 4-24 h.
Further, the washing conditions are that the mass-to-volume ratio of the single-use deionized water to the oxidized nitrogen-containing hypercrosslinked polymer is (100-1000) mL:1g, wherein the filtering stopping condition is that the pH value of the filtrate reaches 6-8 when the filtration is carried out after the completion of single washing.
Preferably, in step c, the reaction time is 12-48 h.
Preferably, in step c, the mass-to-volume ratio of the oxidized nitrogen-containing hypercrosslinked polymer to the alkali metal solution is 1g (200-400) mL.
The preferable proportion of the nitrogen oxide-containing hypercrosslinked polymer and the alkali metal solution can ensure that metal elements are uniformly doped in the nitrogen oxide-containing hypercrosslinked polymer and can improve the adsorption capacity of carbon dioxide by the combined action of the metal elements and nitrogen elements.
It should be noted that, in the step d, the temperature rising rate is 2 ℃/min to 5 ℃/min.
The stable temperature rise rate can improve the stability of nitrogen elements and metal elements in the oxidized nitrogen-containing super-crosslinked polymer and improve the adsorption effect of the prepared nitrogen-containing porous carbon material on carbon dioxide.
Preferably, in step d, the inert atmosphere is at least one of nitrogen, helium or argon.
The reaction is carried out in an inert atmosphere, so that the decomposition of the nitrogen-containing oxide hypercrosslinked polymer can be avoided, 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 carbon dioxide adsorption.
The preparation method of the nitrogen-containing porous carbon material provided by the invention is simple in process, the raw materials are cheap and easy to obtain, 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 hypercrosslinked polymer in example 1;
FIG. 2 is an SEM photograph of a nitrogen-containing hypercrosslinked polymer in example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The embodiment provides a preparation method of a nitrogen-containing hypercrosslinked polymer, which comprises the following specific steps:
introducing nitrogen into a reaction vessel with a condensing reflux system at 25 ℃, purging for 30min, sequentially adding 50mL of glacial acetic acid, 0.80g of pyrimidine and 1.34g of m-phthalaldehyde, and reacting for 30min at normal temperature; and then adding 0.34g of aluminum trichloride, continuing to react for 4 hours at normal temperature, stopping introducing nitrogen, placing the reaction solution in a hydrothermal reaction kettle, and heating at 178 ℃ for reaction for 70 hours. The obtained solid product was washed sequentially 3 times with deionized water, methanol, and acetone, and then extracted with methanol in a soxhlet extractor for 24 hours. Drying the obtained product to obtain the nitrogen-containing hypercrosslinked polymer. The morphology of the nitrogen-containing hypercrosslinked polymer material is shown in FIG. 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; and then adding 0.34g of aluminum trichloride, continuing to react for 3 hours at normal temperature, stopping introducing nitrogen, placing the reaction solution in a hydrothermal reaction kettle, and heating at 180 ℃ for reaction for 72 hours. The obtained solid product was washed sequentially 3 times with deionized water, methanol, and acetone, and then extracted with methanol in a soxhlet extractor for 24 hours. Drying the obtained product to obtain the nitrogen-containing hypercrosslinked polymer. The morphology of the nitrogen-containing hypercrosslinked polymer material is shown in FIG. 2.
Example 3
In this embodiment, a method for preparing a nitrogen-containing porous carbon material using the nitrogen-containing hypercrosslinked polymer in embodiment 1 includes the following steps:
adding 1g of nitrogen-containing hypercrosslinked polymer into 20mL of a mixed solution of concentrated hydrochloric acid, concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 0.7 to 1.5, reacting for 5h at-5 ℃, then reacting for 24h at 20-80 ℃, washing and filtering a reaction product by using 1000mL of deionized water, repeating the operation, stopping filtering when the pH of the filtrate is 6-7, and drying for 24h at 60 ℃ to obtain the nitrogen-containing hypercrosslinked polymer oxide;
adding 200mL of alkali metal solution with the concentration of 0.8mol/L into the oxidized nitrogen-containing hypercrosslinked 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; reacting for 12h at 24 ℃, washing with 1000mL deionized water, filtering, repeating the operations until the pH of the filtrate is 7-8, stopping filtering, and drying at 120 ℃ for 4h to obtain the alkali metal modified oxidized hypercrosslinked polymer;
placing the alkali metal modified oxidized hypercrosslinked polymer in a tubular 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
In this embodiment, a method for preparing a nitrogen-containing porous carbon material using the nitrogen-containing hypercrosslinked polymer of embodiment 2 includes the following steps:
adding 1g of nitrogen-containing hypercrosslinked polymer into 80mL of a mixed solution of concentrated hydrochloric acid, concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 0.01 to 0.01, reacting for 0.2h at 0 ℃, then reacting for 2h at 80 ℃, washing and filtering a reaction product by using 100mL of deionized water, repeating the operation, stopping filtering when the pH of the filtrate is 6-7, and drying for 4h at 120 ℃ to obtain the nitrogen-containing hypercrosslinked polymer oxide;
adding 400mL of an alkali metal solution with the concentration of 4mol/L into the oxidized nitrogen-containing hypercrosslinked 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 being 0.01; reacting for 48 hours at 26 ℃, washing and filtering by using 100mL of deionized water, repeating the operations until the pH value of the filtrate is 7-8, stopping filtering, and drying for 24 hours at 60 ℃ to obtain the alkali metal modified oxidized hypercrosslinked polymer;
placing the alkali metal modified oxidized hypercrosslinked polymer in a tubular furnace under the protection of helium, heating to 900 ℃ at the speed of 5 ℃/min, and roasting for 2 hours to obtain the nitrogen-containing porous carbon material.
Example 5
In this embodiment, a method for preparing a nitrogen-containing porous carbon material using the nitrogen-containing hypercrosslinked polymer of embodiment 1 includes the following steps:
adding 1g of nitrogen-containing hypercrosslinked polymer into 60mL of a mixed solution of concentrated hydrochloric acid, concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 0.15 to 0.35, reacting at-2 ℃ for 3h, then reacting at 50 ℃ for 12h, washing and filtering a reaction product by using 500mL of deionized water, repeating the operation, stopping filtering when the pH of the filtrate is 6-7, and drying at 100 ℃ for 10h to obtain the nitrogen-containing hypercrosslinked polymer oxide;
adding 300mL of alkali metal solution with the concentration of 2.4mol/L into the oxidized nitrogen-containing hypercrosslinked 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; reacting for 20h at 25 ℃, washing with 300mL of deionized water, filtering, repeating the operations until the pH of the filtrate is 7-8, stopping filtering, and drying at 100 ℃ for 20h to obtain the alkali metal modified oxidized hypercrosslinked polymer;
placing the alkali metal modified oxidized hypercrosslinked polymer in a tubular furnace under the protection of helium, heating to 700 ℃ at the speed of 4 ℃/min, and roasting for 4h to obtain the nitrogen-containing porous carbon material.
Comparative example 1
This comparative example provides a method for producing 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 being 1;
the remaining procedure was 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 9.75g of anhydrous ferric chloride is added, stirring is continued for 20min, the introduction of nitrogen is stopped, and the reaction is continued for 2h; controlling the reaction temperature to 25 ℃, and reacting for 2h; heating to 40 ℃, and carrying out pre-crosslinking reaction for 4 hours; then slowly heating to 80 ℃ and reacting for 19h. The solid product obtained was washed 5 times with methanol and then extracted with methanol in a soxhlet extractor for 24h. And drying the obtained product to obtain the 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 nitrogen-containing hypercrosslinked polymer was replaced with the hypercrosslinked polymer prepared by the above procedure, and the rest of the procedure was exactly the same as in example 5.
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; and then adding 0.34g of aluminum trichloride, continuing to react for 3 hours at normal temperature, stopping introducing nitrogen, placing the reaction solution in a hydrothermal reaction kettle, and heating at 180 ℃ for reaction for 72 hours. The obtained solid product was washed sequentially 3 times with deionized water, methanol, and acetone, and then extracted with methanol in a soxhlet extractor for 24 hours. And drying the obtained product to obtain the hypercrosslinked polymer.
This comparative example also provides a method for producing a porous carbon material, which is different from example 5 in that: the nitrogen-containing hypercrosslinked polymer was replaced with the hypercrosslinked polymer prepared by the above procedure, and the rest of the procedure was exactly the same as in example 5.
And (3) determining the carbon dioxide adsorption performance of the sample by a mass method by adopting a thermogravimetric adsorption instrument. During testing, a small amount of sample is weighed and spread in a sample tray, firstly, the temperature is raised to 120 ℃ under the blowing of argon, the temperature is kept for 1 hour, then, the temperature is lowered to 40 ℃, and the temperature is kept constantAnd (5) heating for 30min, and introducing carbon dioxide gas for carrying out adsorption performance test. Wherein the gas feed was 0.15bar (15 Vol.% CO) 2 +85Vol.％N 2 ) The carbon dioxide adsorption performance of the different samples is as follows in table 1:
TABLE 1 Performance test results
The preparation method of the nitrogen-containing porous carbon material provided by the invention is simple in process, the raw materials are cheap and easy to obtain, and the prepared nitrogen-containing porous carbon material has better carbon dioxide adsorption performance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a nitrogen-containing porous carbon material is characterized by comprising the following steps: step a, dissolving a nitrogen-containing compound and an aldehyde crosslinking agent in glacial acetic acid, and performing crosslinking 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 crosslinking agent is at least one of terephthalaldehyde or m-phthalaldehyde; b, adding the nitrogen-containing hypercrosslinked polymer into a mixed solution of concentrated hydrochloric acid, concentrated sulfuric acid and concentrated nitric acid, carrying out primary reaction at-5-0 ℃, then carrying out secondary reaction at 20-80 ℃, washing, filtering and drying to obtain the nitrogen-containing hypercrosslinked polymer; c, adding the oxidized nitrogen-containing hypercrosslinked polymer into an alkali metal solution, reacting at 24-26 ℃, washing, filtering and drying to obtain an alkali metal modified oxidized hypercrosslinked polymer; and d, roasting the alkali metal modified oxidized hypercrosslinked polymer at the temperature of 600-900 ℃ for 2-8 h under inert atmosphere to obtain the nitrogen-containing porous carbon material.
2. The method for preparing 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 h.
4. The method for producing a nitrogen-containing porous carbon material according to claim 1, wherein the mass-to-volume ratio of the nitrogen-containing hypercrosslinked polymer to the mixed solution of concentrated hydrochloric acid, concentrated sulfuric acid and concentrated nitric acid in step b is 1g (20-80) mL.
5. The method for producing a nitrogen-containing porous carbon material according to claim 1, wherein in step c, the alkali metal solution is a mixed solution of sodium hydroxide, potassium hydroxide and lithium hydroxide;
in the step c, the concentration of the alkali metal solution is 0.8-4 mol/L.
6. The method for producing a nitrogen-containing porous carbon material according to claim 1, wherein in the step b, the volume ratio of the concentrated hydrochloric acid, the concentrated sulfuric acid and the concentrated nitric acid in the mixed solution of the concentrated hydrochloric acid, the concentrated sulfuric acid and the concentrated nitric acid is (0.01-0.7): 1 (0.01-1.5); and/or
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 (0.01-0.5) to 1 (0.01-0.5).
7. The method for producing a nitrogen-containing porous carbon material according to claim 1, wherein in step c, the reaction time is 12 to 48 hours.
8. The method for producing a nitrogen-containing porous carbon material according to claim 1, wherein in step c, the mass-to-volume ratio of the oxidized nitrogen-containing hypercrosslinked polymer to the alkali metal solution is 1g (200 to 400) mL.
9. A nitrogen-containing porous carbon material produced by the method for producing a nitrogen-containing porous carbon material according to any one of claims 1 to 8.
10. Use of the nitrogen-containing porous carbon material according to claim 9 for adsorbing carbon dioxide.
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