CN115573168A - MOF @ activated carbon fiber composite material and preparation method and application thereof - Google Patents
MOF @ activated carbon fiber composite material and preparation method and application thereof Download PDFInfo
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- CN115573168A CN115573168A CN202211220651.2A CN202211220651A CN115573168A CN 115573168 A CN115573168 A CN 115573168A CN 202211220651 A CN202211220651 A CN 202211220651A CN 115573168 A CN115573168 A CN 115573168A
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- activated carbon
- constant temperature
- sol
- metal cluster
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- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 55
- 239000002184 metal Substances 0.000 claims abstract description 55
- 238000005406 washing Methods 0.000 claims abstract description 55
- 239000003446 ligand Substances 0.000 claims abstract description 32
- 238000002791 soaking Methods 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 238000011282 treatment Methods 0.000 claims abstract description 13
- 238000000967 suction filtration Methods 0.000 claims abstract description 12
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 97
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 23
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 22
- 230000001590 oxidative effect Effects 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 18
- 239000007800 oxidant agent Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 12
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 8
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- -1 zirconium bis (diethylcitrate) dipropionate Chemical compound 0.000 claims description 3
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 2
- WFNRNCNCXRGUKN-UHFFFAOYSA-N 2,3,5,6-tetrafluoroterephthalic acid Chemical compound OC(=O)C1=C(F)C(F)=C(C(O)=O)C(F)=C1F WFNRNCNCXRGUKN-UHFFFAOYSA-N 0.000 claims description 2
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 2
- HJCNSOVRAZFJLK-UHFFFAOYSA-N C1=CC(C(=O)O)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 HJCNSOVRAZFJLK-UHFFFAOYSA-N 0.000 claims description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000005750 Copper hydroxide Substances 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000005416 organic matter Substances 0.000 claims 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 53
- 238000006731 degradation reaction Methods 0.000 abstract description 19
- 230000015556 catabolic process Effects 0.000 abstract description 16
- 238000011068 loading method Methods 0.000 abstract description 11
- 230000001681 protective effect Effects 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 7
- 239000002575 chemical warfare agent Substances 0.000 abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 22
- 239000012621 metal-organic framework Substances 0.000 description 21
- GBNVXYXIRHSYEG-UHFFFAOYSA-N 1-chloro-2-ethylsulfanylethane Chemical compound CCSCCCl GBNVXYXIRHSYEG-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 229920002239 polyacrylonitrile Polymers 0.000 description 13
- 239000000835 fiber Substances 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003517 fume Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910007926 ZrCl Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001784 detoxification Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910002703 Al K Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LDKDGDIWEUUXSH-UHFFFAOYSA-N Thymophthalein Chemical compound C1=C(O)C(C(C)C)=CC(C2(C3=CC=CC=C3C(=O)O2)C=2C(=CC(O)=C(C(C)C)C=2)C)=C1C LDKDGDIWEUUXSH-UHFFFAOYSA-N 0.000 description 1
- 239000013207 UiO-66 Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001147 anti-toxic effect Effects 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
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- 210000005036 nerve Anatomy 0.000 description 1
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- 150000002894 organic compounds Chemical class 0.000 description 1
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- 230000000149 penetrating effect Effects 0.000 description 1
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- 229920001568 phenolic resin Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 239000013096 zirconium-based metal-organic framework Substances 0.000 description 1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic System; Titanates; Zirconates; Stannates; Plumbates
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
- D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
- D06M11/65—Salts of oxyacids of nitrogen
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the technical field of composite material preparation, and discloses an MOF @ activated carbon fiber composite material as well as a preparation method and application thereof. The preparation method comprises the following steps: carrying out suction filtration on the activated carbon fiber subjected to oxidation treatment by using nano zirconium Sol to obtain Zr-Sol/ACF; soaking the metal cluster into a constant-temperature heated metal cluster solution for treatment, washing the metal cluster, soaking the metal cluster into a constant-temperature heated ligand solution for treatment, taking out the metal cluster for cleaning; repeating for 3-30 times, sequentially washing the obtained product with organic solvent and ethanol, and drying to obtain the MOF @ activated carbon fiber composite material. The composite material has high degradation performance on CEES, can prolong the protection time by utilizing the 'adsorption-degradation' synergistic effect of activated carbon fiber and MOF, can improve the broad spectrum of the composite material applicable to different chemical weapons by changing the types and the loading capacity of loaded metal ions, and can be applied to the preparation of chemical warfare agent protective articles.
Description
Technical Field
The invention belongs to the technical field of composite material preparation, and particularly relates to an MOF @ activated carbon fiber composite material as well as a preparation method and application thereof.
Background
Since world war, chemical warfare agents have the characteristics of strong toxicity, high action speed, wide killing range, lasting toxicity and the like, and are widely used as large-scale destructive weapons. Currently, nerve agents and blister agents are the subject of overseas military equipment, in which mustard gas, a typical blister agent, has been frequently used in chemical weapons war in recent years. Mustard gas can cause irreversible erosion of human skin and can diffuse to the whole body through a respiratory system, so that organs of the whole body fail in a short time, and any specific anti-toxic medicament is not found yet. Therefore, effective protection of chemical warfare agents such as mustard gas remains a key point and a difficulty in current individual protection research.
At present, the first type of common protective clothing is isolated protective clothing, which is generally made of elastic butyl rubber, and the protective clothing can effectively prevent Chemical warfares (CWAS for short) from penetrating through, but is heavy, comfortable and not beneficial to long-time operation; the other type is a breathable chemical protective garment, which mainly utilizes an adsorbent to adsorb outside toxic gas so as to achieve the protective effect. However, such protective clothing does not have the detoxification effect, can cause the failure of protection after reaching the adsorption saturation, and can be used for the second time only by being processed after being used, so that the secondary pollution is easily caused by improper treatment. For this reason, researchers have turned their focus to developing materials that can achieve rapid degradation of CWAs or materials that can achieve self-cleaning.
The new generation of detoxification materials mainly comprises enzymes, metal oxides, polyoxometallates, metal-Organic Frameworks (MOFs) and the like. Although the oxometallate and the metal oxide have good performance, the oxometallate and the metal oxide have unstable properties in the air and cannot be used as a protective material for a long time. Although the enzyme has better effect on degradation, the use condition is harsh, and the enzyme is not suitable for being loaded on textiles. The MOF is a crystalline porous material with a periodic network structure formed by self-assembly of transition metal ions and organic ligands, and has attracted extensive attention in this field because of its advantages of high specific surface area, abundant active sites, excellent degradation performance to CWAs, good stability, and the like. However, since MOFs are powdery materials, they are prone to agglomeration and difficult to recover during use.
Disclosure of Invention
In view of the above, the invention aims to provide an MOF @ Activated carbon fiber composite material and a preparation method and application thereof, the MOF @ Activated carbon fiber composite material prepared by the preparation method can form stronger complex force with mustard gas simulator 2-chloroethyl ethyl sulfide (CEES), so that the MOF @ Activated carbon fiber composite material has high degradation performance on the CEES, and the protection time can be prolonged by utilizing the 'adsorption-degradation' synergistic effect of Activated Carbon Fiber (ACF) and MOF.
The technical scheme adopted by the invention is as follows:
a preparation method of an MOF @ activated carbon fiber composite material comprises the following steps:
s1, dipping activated carbon fibers in an oxidant solution for oxidation treatment, filtering, cleaning and drying, then performing suction filtration by using nano zirconium Sol, and then drying to obtain Zr-Sol/ACF;
s2, soaking Zr-Sol/ACF into a metal cluster solution with the pH value of 3-7 and heated at a constant temperature for a period of time, taking out the metal cluster solution, washing the metal cluster solution with an organic solvent, soaking the metal cluster solution into a ligand solution heated at a constant temperature for a period of time, taking out the ligand solution, and washing the ligand solution with the organic solvent; the concentration of the metal cluster solution is 0.01-10mol/L; the temperature of the constant-temperature heated ligand solution is the same as that of the constant-temperature heated metal cluster solution;
s3, repeating the step S23-30 times, then sequentially washing the obtained product with an organic solvent and ethanol, and drying to obtain the MOF @ activated carbon fiber composite material.
Further, the oxidant solution is one of a nitric acid solution, a hydrogen peroxide solution, a potassium permanganate solution, an acetic acid solution, a sulfuric acid solution, a hydrochloric acid solution, a potassium dichromate solution and a periodic acid solution; the concentration of the oxidant solution is 0.5-10mol/L.
Furthermore, the specific surface area of the activated carbon fiber is 800-1500m 2 (iv)/g, microporosity greater than 90%.
Further, the activated carbon fiber is selected from one of pitch-based activated carbon fiber, phenolic resin-based activated carbon fiber and polymer-based activated carbon fiber.
Further, the oxidant solution is a nitric acid solution with the concentration of 1 mol/L.
Further, in step S1, the impregnation ratio of the impregnation is 20.
Furthermore, the nano zirconium sol is nano zirconium dioxide sol, the particle size is 5-20nm, and the concentration is 0.1-5wt%.
Further, the concentration of the nano zirconia sol is 1wt%.
Further, the suction filtration is specifically that the activated carbon fiber after oxidation treatment is immersed in the nano zirconium dioxide sol by an isometric immersion method, and the volume of the sol is determined by the volume of water required when the activated carbon fiber is completely immersed.
Further, in step S1, the drying specifically includes: drying at 80-100 deg.C for 360-720min.
Further, in the metal cluster solution, the solute is one or more of zirconium tetrachloride, zirconium N-propoxide, zirconium hydroxide, zirconium bis (diethylcitrate) dipropionate, copper hydroxide, ferric chloride and ferrous chloride, and the solvent is N, N-dimethylformamide; the concentration of the metal cluster solution is 0.01-10mol/L.
Further, the preparation method of the metal cluster solution with the pH value of 3-7 comprises the following steps: preparing a metal cluster solution, and then adding an acid solution with the concentration of 0.1-5mol/L to adjust the pH value.
Further, the acid solution is selected from one or two of hydrochloric acid solution, sulfuric acid solution and acetic acid solution, and the volume of the acid solution is 0.1-5% of that of the metal cluster solution.
Further, the pH of the metal cluster solution is 5 to 6.
Furthermore, the heating mode of the constant temperature heating is selected from one of a water bath kettle, an oil bath kettle, an oven and a reaction kettle.
Further, in the ligand solution, the solute is one of 2,3,5, 6-tetrafluoroterephthalic acid, tetra [4- (4 '-carboxyphenyl) phenyl ] ethylene, terephthalic acid, 2-amino-terephthalic acid, trimesic acid, 4-carboxyphenylporphyrin, 4' -terphthalic acid and pyromellitic formic acid, the solvent is N, N-dimethylformamide, and the concentration of the ligand solution is 0.1-10mol/L.
Further, step S2 specifically includes:
s21, zrCl is adopted 4 Preparing DMF and HCl to obtain a metal cluster solution, zrCl 4 The amounts of DMF and HCl were 1.25g 50ml;
s22, heating the metal cluster solution prepared in the step S21 to 120-130 ℃, keeping a constant temperature heating state, soaking Zr-Sol/ACF into the constant temperature heated metal cluster solution, continuing to heat at the constant temperature for 10-20 min, taking out, washing with an organic solvent, soaking into a ligand solution heated at the constant temperature of 120-130 ℃, keeping at the constant temperature for 10-20 min, taking out, and washing with the organic solvent; the solute of the ligand solution is terephthalic acid.
Further, step S2 specifically includes:
s21, adopting Zr (OPr) 4 Preparing PrOH solution, DMF and acetic acid to obtain metal cluster solution, zr (OPr) 4 The dosage of the/PrOH solution, DMF and acetic acid is 355 uL, 350mL;
s22, heating the metal cluster solution prepared in the step S21 to 120-130 ℃, keeping a constant temperature heating state, soaking Zr-Sol/ACF into the constant temperature heated metal cluster solution, continuing to heat at the constant temperature for 10-20 min, taking out, washing with an organic solvent, soaking into a ligand solution heated at the constant temperature of 120-130 ℃, keeping at the constant temperature for 10-20 min, taking out, and washing with the organic solvent; the solute of the ligand solution is 2-amino-1, 4 terephthalic acid.
Further, step S2 specifically includes:
s21, cu (NO) is adopted 3 ) 2 ·3H 2 Dissolving O in deionized water, stirring to dissolve completely to obtain metal cluster solution, cu (NO) 3 ) 2 ·3H 2 The mass ratio of O to deionized water is 3.56;
s22, heating the metal cluster solution prepared in the step S21 to 80-90 ℃, keeping a constant temperature heating state, soaking Zr-Sol/ACF into the constant temperature heated metal cluster solution, continuing to heat at the constant temperature for 10-20 min, taking out, washing with an organic solvent, soaking into a ligand solution heated at the constant temperature of 80-90 ℃, keeping at the constant temperature for 10-20 min, taking out, and washing with the organic solvent; the solute of the ligand solution is 2-amino-1, 4 terephthalic acid.
The invention also provides the MOF @ activated carbon fiber composite material prepared by the preparation method.
The invention also provides application of the MOF @ activated carbon fiber composite material in adsorption of thioether organic matters.
Furthermore, the MOF @ activated carbon fiber composite material can be applied to chemical warfare agent protective articles.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a method for firmly loading a large number of MOF particles on the surface of activated carbon fiber, which comprises the following steps: the activated carbon fiber has fewer oxygen-containing groups and active sites, and MOF loading is difficult, so that on one hand, the quantity of oxygen-containing functional groups on the surface of the activated carbon fiber is increased through oxidation treatment, and the MOF material can be more coordinated on the surface of the activated carbon fiber; on the other hand, by suction filtration of the zirconium sol, active sites on the surface of the activated carbon fiber can be remarkably increased, so that MOF particles which are originally poor in loading condition and low in loading fastness can be greatly and firmly loaded on the surface of the activated carbon fiber.
(2) The invention provides a controllable preparation technology of an MOF @ activated carbon fiber composite material, which comprises the following steps: the metal ions loaded on the surface of the composite material can form stronger complexing force on specific organic compounds, the composite material improves the degradation capability of the mustard gas simulation agent CEES, and in practical application, the chemical structure of the surface of the activated carbon fiber can be changed by changing the type and the loading amount of the loaded metal ions, so that the problem of non-selectivity of adsorption of the composite material is solved, and the broad spectrum of the composite material suitable for different chemical weapons is improved.
(3) The invention utilizes the synergistic action of adsorption and degradation to realize the rapid degradation and long-acting protection of chemical warfare agents: the MOF @ activated carbon fiber composite material prepared by the invention can form stronger complexing force with a mustard gas simulation agent CEES, so that the composite material has high degradation performance on the CEES, and can remove chemical warfare agents adsorbed on the surface of the activated carbon fiber by utilizing the adsorption-degradation synergistic effect of the activated carbon fiber and the MOF, thereby realizing self-cleaning of the activated carbon fiber and prolonging the protection time.
Drawings
FIG. 1 is a flow chart of the preparation process of MOF @ activated carbon fiber composite material;
FIG. 2 is an XRD spectrum of the MOF @ activated carbon fiber composite obtained in example 1;
FIG. 3 is an SEM photograph of materials obtained in comparative examples 1 to 3 and example 1;
fig. 4 is XPS pictures of example 1, comparative example 1 and comparative example 2.
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as detailed in the claims.
The invention provides a preparation method of an MOF @ activated carbon fiber composite material, which comprises the following steps as shown in figure 1:
s1, dipping activated carbon fibers in an oxidant solution for oxidation treatment, filtering, cleaning and drying, performing suction filtration by using a nano zirconium Sol, and drying to obtain Zr-Sol/ACF;
specifically, the method comprises the following steps:
s11, pretreating the activated carbon fiber to remove surface impurities, specifically, repeatedly washing the commercially available polyacrylonitrile-based activated carbon fiber with deionized water, washing soluble impurities on the surface of the polyacrylonitrile-based activated carbon fiber, filtering, and drying in an oven for later use;
in this step, the activated carbon fiber is preferably one of pitch-based activated carbon fiber, phenol resin-based activated carbon fiber, and polymer-based activated carbon fiber. More preferably, the specific surface area is 800-1500m 2 A polyacrylonitrile-based activated carbon fiber having a microporosity of greater than 90%.
S12, completely soaking the pretreated activated carbon fiber obtained in the step S11 in an oxidant solution for oxidation, then filtering to obtain the ACF, washing the ACF to be neutral by using deionized water, and drying in vacuum for later use.
In this step, the impregnation is preferably carried out using 20; the oxidizing agent solution is preferably one of a nitric acid solution having a concentration of 0.5 to 10mol/L, a hydrogen peroxide solution, a potassium permanganate solution, an acetic acid solution, a sulfuric acid solution, a hydrochloric acid solution, a potassium dichromate solution, and a periodic acid solution, and more preferably a nitric acid solution having a concentration of 1 mol/L. The oxidation process preferably employs: heating and oxidizing in a water bath at 70 deg.C for 240min, and standing in a fume hood at room temperature for 120min. The vacuum drying condition is preferably 80-100 deg.C for 360-720min, more preferably 75 deg.C for 720min.
S13, carrying out suction filtration on the ACF dried in the step S12 by using nano zirconium Sol to enable the surface of the ACF to be loaded with metal ions, washing the ACF by using deionized water once, filtering, and then drying to obtain Zr-Sol/ACF;
in the step, the nano zirconium sol preferably adopts nano zirconium dioxide sol with the concentration of 0.1-5wt% and the particle size of 5-20nm, and more preferably adopts nano zirconium dioxide sol with the concentration of 1wt%.
Preferably, the suction filtration is specifically to dip the oxidized Activated Carbon Fiber (ACF) in the nano zirconium dioxide sol by an isometric dipping method, wherein the volume of the sol is determined by the volume of water required when the activated carbon fiber is completely soaked.
The drying condition is preferably 80-100 deg.C for 360-720min, more preferably 80 deg.C for 720min under vacuum.
S2, soaking Zr-Sol/ACF into a constant-temperature heated metal cluster solution with the pH of 3-7 and the concentration of 0.01-10mol/L for a period of time, taking out the metal cluster solution, washing the metal cluster solution with an organic solvent, soaking the metal cluster solution into a constant-temperature heated ligand solution for a period of time, taking out the ligand solution, and washing the ligand solution with the organic solvent; the temperature of the ligand solution heated at the constant temperature is the same as that of the metal cluster solution heated at the constant temperature. The heating mode of constant temperature heating preferably adopts one of a water bath kettle, an oil bath kettle, an oven and a reaction kettle.
S3, repeating the step S23-30 times, preferably 18 times, then sequentially washing the obtained product with an organic solvent and ethanol, and drying to obtain the MOF @ activated carbon fiber composite material.
Example 1
Step 1, repeatedly washing commercially available polyacrylonitrile-based activated carbon fibers with deionized water, washing soluble impurities on the surfaces of the polyacrylonitrile-based activated carbon fibers, filtering, and drying in an oven for later use;
step 2, taking a nitric acid solution with the concentration of 1mol/L as an oxidant, completely soaking the pretreated activated carbon fiber in the oxidant for oxidation, performing the oxidation process in a water bath kettle, keeping the temperature at 70 ℃, heating and oxidizing for 240min, then placing the activated carbon fiber in a fume hood for standing at room temperature for 120min, then filtering to obtain the activated carbon fiber ACF, washing the activated carbon fiber ACF to be neutral by using deionized water, and performing vacuum drying at 75 ℃ for 720min for later use;
step 3, performing suction filtration on the activated carbon fiber ACF dried in the step 2 by using prepared 1wt% nano zirconium dioxide Sol to load metal ions on the surface of the ACF, washing the ACF once by using deionized water, filtering, and performing vacuum drying at 80 ℃ for 720min to obtain a sample, namely Zr-Sol/ACF;
step 4, add 1.25g ZrCl to vial 4 Taking 50mL of DMF and 1.2mL of HCl as metal cluster solutions, heating to 130 ℃, preserving heat for 15min, then soaking the Zr-Sol/ACF dried in the step 3 into the metal cluster solutions, preserving heat for 15min at 130 ℃, and washing with DMF for 3 times after heat preservation is finished;
and 6, repeating the steps 4 and 5 for 18 times in total, washing with DMF (dimethyl formamide), washing with ethanol for 3 times, and drying to obtain the final product MOF @ activated carbon fiber composite material.
The material obtained in example 1 was scanned with a Cu ka target (λ =0.15406 nm) at 40kV and 30mA using an X-ray diffractometer model DY5261/Xpert 3. The scanning speed is 5 DEG/min, the scanning range is 5-35 DEG, the XRD scanning image is shown as figure 2, figure 2 shows that the 'steamed bun peaks' appear at 2 theta =7.03 DEG and 25.78 DEG, and compared with the standard XRD pattern of UiO-66, the main peak value is basically consistent with the main peak value.
Example 2
Zr-Sol/ACF was obtained according to steps 1-3 of example 1;
step 4, 355. Mu.L of Zr (OPr) 4 the/PrOH solution was mixed with 35mL of DMF and 20mL of acetic acid in a 100mL round bottom flask and the mixture was heated at 130 ℃ for 2h as a metal cluster solution. Soaking the dried Zr-Sol/ACF in the step 3 into a metal cluster solution, preserving the heat for 15min at 130 ℃, and washing the solution for 3 times by using DMF after the heat preservation is finished;
in step 5, 408.9mg of 2-amino-1, 4 terephthalic acid was dissolved in 50mL of DMF and heated at 130 ℃ for 2h to serve as a ligand solution. Immersing the material washed in the step 4 in the solution, preserving the heat at 130 ℃ for 15min, and washing the material with DMF for three times after the heat preservation is finished;
and 6, repeating the steps 4 and 5 for 18 times in total, washing with DMF (dimethyl formamide), washing with ethanol for 3 times, and drying to obtain the final product MOF @ activated carbon fiber composite material.
Example 3
Zr-Sol/ACF was obtained according to the procedure from 1 to 3 in example 1;
in step 4, 3.56g of Cu (NO 3) 2.3H 2O is weighed and dissolved in 24.62g of deionized water, and the mixture is vigorously stirred for 30min to obtain a metal cluster solution. Sealing, heating to 90 ℃, preserving heat for 15min, soaking the Zr-Sol/ACF dried in the step 3 into a metal cluster solution, preserving heat for 15min at 130 ℃, and washing with DMF for three times after finishing preserving heat;
in the step 5, 1.03g of trimesic acid is weighed, dissolved in 23.03g of trimesic acid, stirred for 30min, then heated to 90 ℃, kept warm for 15min, the material washed in the step 4 is immersed in the solution, kept warm for 15min at 90 ℃, and washed three times by deionized water after the heat preservation is finished.
And 6, repeating the steps 4 and 5 for 18 times in total, washing with DMF (dimethyl formamide), washing with ethanol for 3 times, and drying to obtain the final product MOF @ activated carbon fiber composite material.
Comparative example 1 No filtration treatment with nano zirconia sol and no MOF loading
Step 1, repeatedly washing commercially available polyacrylonitrile-based activated carbon fibers with deionized water, washing soluble impurities on the surfaces of the polyacrylonitrile-based activated carbon fibers, filtering, and drying in an oven for later use;
and 2, completely soaking the pretreated activated carbon fiber in an oxidant by using a nitric acid solution with the concentration of 1mol/L as the oxidant for oxidation, performing the oxidation process in a water bath kettle, keeping the temperature at 70 ℃, heating and oxidizing for 240min, standing in a fume hood at room temperature for 120min, filtering to obtain the activated carbon fiber ACF, washing to be neutral by using deionized water, and performing vacuum drying at 75 ℃ for 720min.
Comparative example 2 unsupported MOF
Step 1, repeatedly washing commercially available polyacrylonitrile-based activated carbon fibers with deionized water, washing soluble impurities on the surfaces of the polyacrylonitrile-based activated carbon fibers, filtering, and drying in an oven for later use;
step 2, taking a nitric acid solution with the concentration of 1mol/L as an oxidant, completely soaking the pretreated activated carbon fiber in the oxidant for oxidation, performing the oxidation process in a water bath kettle, keeping the temperature at 70 ℃, heating and oxidizing for 240min, then placing the activated carbon fiber in a fume hood for standing at room temperature for 120min, then filtering to obtain an activated carbon fiber ACF, washing the activated carbon fiber ACF to be neutral by using deionized water, and performing vacuum drying for 720min at 75 ℃ for later use;
step 3, performing suction filtration on the activated carbon fiber ACF dried in the step 2 by using prepared 1wt% nano zirconium dioxide Sol to load metal ions on the surface of the ACF, washing the ACF once by using deionized water, filtering, and performing vacuum drying at 80 ℃ for 720min to obtain a sample, namely Zr-Sol/ACF;
comparative example 3
Step 1, repeatedly washing commercially available polyacrylonitrile-based activated carbon fibers with deionized water, washing off soluble impurities on the surfaces of the polyacrylonitrile-based activated carbon fibers, filtering, and drying in an oven for later use;
step 2, 1.25g ZrCl was added to the vial 4 Taking 50mL of DMF and 1.2mL of HCl as metal cluster solutions, heating to 130 ℃, preserving heat for 15min, immersing the polyacrylonitrile-based activated carbon fiber dried in the step 1 into the metal cluster solution, preserving heat for 15min at 130 ℃, and washing with DMF for 3 times after heat preservation is finished;
step 3, adding 50mL of DMF and 0.619g of terephthalic acid into another small bottle to serve as a ligand solution, heating to 130 ℃, preserving heat for 15min, immersing the material washed in the step 2 into the solution, preserving heat for 15min at 130 ℃, and washing for 3 times by using DMF after the heat preservation is finished;
and 4, repeating the step 2 and the step 3 for 18 times in total, washing with DMF (dimethyl formamide), washing with ethanol for 3 times, and drying.
The surface topography of comparative example 1, comparative example 2, comparative example 3 and example 1 was observed using a Hitachi S-3400N bench top Scanning Electron Microscope (SEM), and the SEM is shown in FIG. 3, where FIG. 3a is a SEM of the material obtained in comparative example 1, FIG. 3b is a SEM of the material obtained in comparative example 2, and FIG. 3d is a SEM of the material obtained in example 1.
As can be seen from fig. 3, fig. 3 (a) shows the activated carbon fiber obtained in comparative example 1 (nitric acid oxidation), the fiber surface is smooth and tidy, and the natural grooves on the surface of the polyacrylonitrile-based activated carbon fiber can be clearly seen. FIG. 3 (b) is an SEM image of the material obtained in comparative example 2, and as shown in FIG. 3 (b), after the filtration treatment of 1wt% nano zirconia sol, a sol layer similar to a film appears on the fiber surface, and tiny nano zirconia particles are uniformly loaded on the sol layer. FIG. 3 (c) is an SEM image of the material obtained in comparative example 3, and according to FIG. 3 (c), it can be seen that the fibers without nano zirconia sol treatment have a smaller amount of MOF-supporting particles after the preparation is finished, and the fiber surfaces show clearly visible grooves; FIG. 3 (d) is an SEM image of the material obtained in example 1, and it can be seen from FIG. 3 (d) that a large number of MOF "scale layers" are uniformly supported on the fiber surface after pretreatment of the nano zirconia sol. The active carbon fiber has smooth surface, less oxygen-containing groups and less active sites, MOF is difficult to be uniformly attached to the fiber surface, and after the fiber is treated by the nano zirconium dioxide sol, the nano zirconium dioxide particles deposited on the fiber surface effectively increase the surface active sites, so that the loading capacity of the MOF is remarkably improved.
XPS pictures of the materials prepared in example 1, comparative example 1 and comparative example 2 were obtained by measuring the electron binding energy of each element using Al K α as an emission light source and a vacuum degree of 1 × 10-7 (power) Pa and carbon C1s =284.6eV as an internal standard, as shown in fig. 4. From the whole spectrum of fig. 4 (a), it can be seen that the activated carbon fiber treated by the oxidant mainly has two characteristic peaks, which represent C1s and O1s respectively. After the filtration treatment of the zirconium sol, a new peak appears, and the height of O1s is increased to some extent, which may be caused by zirconium oxide particles in the zirconium sol. After MOF loading, the intensity of the characteristic peak of C1s is obviously reduced, and Zr 3d and Zr 3p are increased. As can be seen from the peak-splitting spectrum of C1s in FIG. 4 (b), the surface of the acidified activated carbon fiber has more oxygen-containing groups but mainly contains C-O. After the zirconium sol is subjected to suction filtration, more zirconium elements appear, but the spectrogram of the C1s element is hardly changed, which indicates that the zirconium sol suction filtration does not influence the chemical structure of the activated carbon fiber, and the characteristic peak shifts to the direction of a low energy spectrum, which probably results in that the surface electron density is changed because the zirconium sol is uniformly covered on the surface of the fiber. After 18 cycles, the peak height and the peak width of the characteristic peak corresponding to the C = O bond are improved, and the content of the C = O bond is increased, which indicates that the coordination between the metal cluster and the ligand is possible to form a complex by C = O. In addition, the characteristic peak also shifts to the direction of low binding energy, indicating that the resulting particles are adsorbed on the surface of the activated carbon fiber, resulting in an increase in the electron density thereof. As can be seen from the peak spectrum of O1s in fig. 4 (c), O1s of the three samples respectively consist of three kinds of oxygen, including lattice Oxygen (OL), surface oxygen (Ov), and other weakly bound oxygen (Oe), where Oe includes carbonate, adsorbed molecular water, and hydroxyl. With the MOF loading, the intensity and the width of the characteristic peak corresponding to the OL are increased, which indicates that the proportion of the OL is gradually increased, thereby indirectly confirming the occurrence of the coordination reaction. From the peak separation spectrum of Zr 3d in FIG. 4 (d), it can be shown that the zirconium element participates in the coordination. From the results of XRD in fig. 4, it can be confirmed that the preparation method of example 1 of the present application successfully synthesizes a zirconium-based MOF on activated carbon fiber.
Test example 1
The specific surface area and pore structure of the composite materials prepared in example 1 and comparative examples 1 to 3 were measured at 77K using a specific surface area and pore structure analyzer model ASAP2020, micromeritics, USA, using nitrogen as the adsorption medium, wherein the specific surface area was calculated by the BET method from the nitrogen adsorption isotherm and the total pore volume was calculated as P/P 0 The adsorption result of =0.995 was calculated and the results are shown in table 1.
TABLE 1 specific surface area and pore structure parameters of the samples
The specific surface area and pore structure parameters for the four samples are given in table 1. With the loading of the nano zirconium dioxide, a thin film is formed on the surface of the fiber, so that the specific surface area and the total pore volume are reduced. As MOFs are synthesized on the fiber surface, the stacking of layers causes the pores outside the part of the material to be covered, resulting in a decrease in specific surface area, but the composite material still has a higher microporosity.
Test example 2
5 mu L of CEES is added into 1mL of n-hexane, and after uniform shaking, 200 mu L of CEES is taken out and added into 800 mu L of n-hexane, and the obtained mixture is uniformly shaken to be used as a CEES stock solution for later use. A blue reagent was prepared by dissolving 0.04g NaOH and 0.1g thymolphthalein in 1.25mL water and 8.75mL ethanol. Blue reagents with different concentrations are prepared, and standard curves of CEES absorbance with different concentrations are obtained through ultraviolet light splitting test for absorbance values at 445 nm. Accurately weighing 0.03g of the dried sample, transferring the sample into a 1.5mL centrifuge tube, adding 1mL of prepared normal hexane solution of CEES with a certain concentration, and sealing the centrifuge tube. After oscillating for 5min, standing at room temperature for 3, 6, 12 and 24 hours; after the time is reached, 0.5mL of n-hexane is added for extraction for 15min, 20 mu L of supernatant is taken by a micro-sampling needle, the absorbance at 445nm is measured by referring to the method for preparing the standard solution, the concentration of the solution is calculated according to a standard curve, and the degradation rate eta can be obtained, and the result is shown in Table 2.
TABLE 2 removal Performance (degradation. Eta.) of each sample on CEES
As can be seen from Table 2, the degradation rate of the MOF @ activated carbon fiber composite material prepared in example 1 to CEES after 24 hours can reach 84.23%, while the degradation rate of the activated carbon fiber not loaded with MOF is only 21.54%, and the removal effect is remarkably improved. The MOF @ activated carbon fiber composite material prepared in the embodiment 2 has a degradation rate of 93.69% to CEES after 24 hours, and has a good removal performance to CEES. Compared with example 1, in example 2, due to the modification of amino, the capacity of MOF material for complexing and degrading CEES is improved, so that the degradation rate is improved. Experimental results show that the structure and the performance of the MOF can be regulated and controlled by changing the types of the ligands. The MOF @ activated carbon fiber composite material prepared in the embodiment 3 has a degradation rate of 79.31% to CEES after 24 hours, and the result shows that after the central metal element is replaced, the composite material can also have a good removal performance to CEES.
Claims (10)
1. A preparation method of MOF @ activated carbon fiber composite material is characterized by comprising the following steps:
s1, dipping activated carbon fibers in an oxidant solution for oxidation treatment, filtering, cleaning and drying, performing suction filtration by using a nano zirconium Sol, and drying to obtain Zr-Sol/ACF;
s2, soaking Zr-Sol/ACF into a metal cluster solution with the pH value of 3-7 and heated at a constant temperature for a period of time, taking out the Zr-Sol/ACF, washing the Zr-Sol/ACF with an organic solvent, soaking the Zr-Sol/ACF into a ligand solution heated at a constant temperature for a period of time, taking out the Zr-Sol/ACF, and washing the Zr-Sol/ACF with the organic solvent; the concentration of the metal cluster solution is 0.01-10mol/L; the temperature of the ligand solution heated at constant temperature is the same as that of the metal cluster solution heated at constant temperature;
s3, repeating the step S23-30 times, then sequentially washing the obtained product with an organic solvent and ethanol, and drying to obtain the MOF @ activated carbon fiber composite material.
2. The production method according to claim 1, wherein the oxidizing agent solution is one of a nitric acid solution, a hydrogen peroxide solution, a potassium permanganate solution, an acetic acid solution, a sulfuric acid solution, a hydrochloric acid solution, a potassium dichromate solution, and a periodic acid solution; the concentration of the oxidant solution is 0.5-10mol/L.
3. The method according to claim 1, wherein the nano zirconium sol is a nano zirconium dioxide sol having a particle size of 5 to 20nm and a concentration of 0.1 to 5wt%.
4. The method according to claim 1, wherein the solute in the metal cluster solution is one or more of zirconium tetrachloride, zirconium N-propoxide, zirconium hydroxide, zirconium bis (diethylcitrate) dipropionate, copper hydroxide, ferric chloride, and ferrous chloride, and the solvent is N, N-dimethylformamide; the concentration of the metal cluster solution is 0.01-10mol/L.
5. The process according to claim 1, wherein the ligand solution contains one of 2,3,5, 6-tetrafluoroterephthalic acid, tetrakis [4- (4 '-carboxyphenyl) phenyl ] ethylene, terephthalic acid, 2-amino-terephthalic acid, trimesic acid, 4-carboxyphenylporphyrin, 4' -terphthalic acid and pyromellitic acid as a solute, and N, N-dimethylformamide as a solvent, and the concentration of the ligand solution is 0.1 to 10mol/L.
6. The method according to claim 1, wherein step S2 specifically comprises:
s21, zrCl is adopted 4 Preparing DMF and HCl to obtain a metal cluster solution, zrCl 4 Use of DMF and HClAmount 1.25g;
s22, heating the metal cluster solution prepared in the step S21 to 120-130 ℃, keeping a constant temperature heating state, soaking Zr-Sol/ACF into the constant temperature heated metal cluster solution, continuing to heat at the constant temperature for 10-20 min, taking out, washing with an organic solvent, soaking into a ligand solution heated at the constant temperature of 120-130 ℃, keeping at the constant temperature for 10-20 min, taking out, and washing with the organic solvent; the solute of the ligand solution is terephthalic acid.
7. The method according to claim 1, wherein step S2 specifically comprises:
s21, adopting Zr (OPr) 4 the/PrOH solution, DMF and acetic acid were prepared to obtain a metal cluster solution, zr (OPr) 4 The dosage of the/PrOH solution, DMF and acetic acid is 355 uL, 350mL;
s22, heating the metal cluster solution prepared in the step S21 to 120-130 ℃, keeping a constant temperature heating state, immersing Zr-Sol/ACF into the constant temperature heated metal cluster solution, continuing to heat at the constant temperature for 10-20 min, taking out, washing with an organic solvent, immersing into a 120-130 ℃ constant temperature heated ligand solution, keeping at the constant temperature for 10-20 min, taking out, and washing with the organic solvent; the solute of the ligand solution is 2-amino-1, 4 terephthalic acid.
8. The method according to claim 1, wherein step S2 specifically comprises:
s21, cu (NO) is adopted 3 ) 2 ·3H 2 Dissolving O in deionized water, stirring to dissolve completely to obtain metal cluster solution, cu (NO) 3 ) 2 ·3H 2 The mass ratio of O to deionized water is 3.56;
s22, heating the metal cluster solution prepared in the step S21 to 80-90 ℃, keeping a constant temperature heating state, soaking Zr-Sol/ACF into the constant temperature heated metal cluster solution, continuing to heat at the constant temperature for 10-20 min, taking out, washing with an organic solvent, soaking into a ligand solution heated at the constant temperature of 80-90 ℃, keeping at the constant temperature for 10-20 min, taking out, and washing with the organic solvent; the solute of the ligand solution is 2-amino-1, 4 terephthalic acid.
9. The MOF @ activated carbon fiber composite material prepared by the preparation method of any one of claims 1 to 8.
10. The use of the mof @ activated carbon fiber composite of claim 9 in the adsorption of thioether-like organic matter.
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