CN109158106B - Self-supporting metal oxide nano fiber catalytic purification material and preparation method thereof - Google Patents
Self-supporting metal oxide nano fiber catalytic purification material and preparation method thereof Download PDFInfo
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- CN109158106B CN109158106B CN201811157760.8A CN201811157760A CN109158106B CN 109158106 B CN109158106 B CN 109158106B CN 201811157760 A CN201811157760 A CN 201811157760A CN 109158106 B CN109158106 B CN 109158106B
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- salt
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- chloride
- catalytic purification
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 91
- 239000000463 material Substances 0.000 title claims abstract description 84
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 55
- 238000000746 purification Methods 0.000 title claims abstract description 49
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 33
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 82
- 238000000034 method Methods 0.000 claims abstract description 42
- 150000003839 salts Chemical class 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 13
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 13
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 7
- 238000001523 electrospinning Methods 0.000 claims abstract description 4
- 229920000592 inorganic polymer Polymers 0.000 claims abstract 4
- 239000000084 colloidal system Substances 0.000 claims abstract 2
- 229920002521 macromolecule Polymers 0.000 claims abstract 2
- 238000001354 calcination Methods 0.000 claims description 41
- 238000009987 spinning Methods 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 30
- 230000007062 hydrolysis Effects 0.000 claims description 14
- 238000006460 hydrolysis reaction Methods 0.000 claims description 14
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 13
- 230000010412 perfusion Effects 0.000 claims description 13
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 9
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical group Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- WYOIGGSUICKDNZ-UHFFFAOYSA-N 2,3,5,6,7,8-hexahydropyrrolizin-1-one Chemical compound C1CCC2C(=O)CCN21 WYOIGGSUICKDNZ-UHFFFAOYSA-N 0.000 claims description 4
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 4
- 150000000703 Cerium Chemical class 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 150000001206 Neodymium Chemical class 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- 150000001213 Praseodymium Chemical class 0.000 claims description 4
- QDAYJHVWIRGGJM-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QDAYJHVWIRGGJM-UHFFFAOYSA-B 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 229960001759 cerium oxalate Drugs 0.000 claims description 4
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 claims description 4
- 150000001844 chromium Chemical class 0.000 claims description 4
- 150000002603 lanthanum Chemical class 0.000 claims description 4
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical group [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 150000002751 molybdenum Chemical class 0.000 claims description 4
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 claims description 4
- TXCOQXKFOPSCPZ-UHFFFAOYSA-J molybdenum(4+);tetraacetate Chemical compound [Mo+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O TXCOQXKFOPSCPZ-UHFFFAOYSA-J 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical group O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 4
- 229920005591 polysilicon Polymers 0.000 claims description 4
- 150000003608 titanium Chemical class 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 150000003657 tungsten Chemical class 0.000 claims description 4
- 150000003681 vanadium Chemical class 0.000 claims description 4
- 150000003746 yttrium Chemical class 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 3
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 claims description 2
- BYDYILQCRDXHLB-UHFFFAOYSA-N 3,5-dimethylpyridine-2-carbaldehyde Chemical compound CC1=CN=C(C=O)C(C)=C1 BYDYILQCRDXHLB-UHFFFAOYSA-N 0.000 claims description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 2
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical group [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- MQLVWQSVRZVNIP-UHFFFAOYSA-L ferrous ammonium sulfate hexahydrate Chemical compound [NH4+].[NH4+].O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MQLVWQSVRZVNIP-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- NFSAPTWLWWYADB-UHFFFAOYSA-N n,n-dimethyl-1-phenylethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=CC=C1 NFSAPTWLWWYADB-UHFFFAOYSA-N 0.000 claims description 2
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical group [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 2
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 claims description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 2
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 claims description 2
- HWZAHTVZMSRSJE-UHFFFAOYSA-H praseodymium(iii) sulfate Chemical compound [Pr+3].[Pr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HWZAHTVZMSRSJE-UHFFFAOYSA-H 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- 125000005287 vanadyl group Chemical group 0.000 claims description 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 2
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 2
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 2
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims 1
- VZLNSPSVSKXECI-UHFFFAOYSA-N ethanol;iron Chemical compound [Fe].CCO.CCO VZLNSPSVSKXECI-UHFFFAOYSA-N 0.000 claims 1
- 239000008394 flocculating agent Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 150000002505 iron Chemical class 0.000 claims 1
- 159000000014 iron salts Chemical class 0.000 claims 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 claims 1
- OYYAGAJDVFTKCK-UHFFFAOYSA-K sulfuric acid trichloroalumane Chemical compound Cl[Al](Cl)Cl.OS(O)(=O)=O OYYAGAJDVFTKCK-UHFFFAOYSA-K 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 29
- 239000003344 environmental pollutant Substances 0.000 abstract description 18
- 231100000719 pollutant Toxicity 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 5
- 238000000465 moulding Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 70
- 239000000835 fiber Substances 0.000 description 29
- 238000010041 electrostatic spinning Methods 0.000 description 25
- 238000001914 filtration Methods 0.000 description 25
- 239000012528 membrane Substances 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 15
- 238000002156 mixing Methods 0.000 description 12
- 239000002131 composite material Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 9
- 239000002657 fibrous material Substances 0.000 description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- POZJWRRDBOEZOO-UHFFFAOYSA-N [Mo]=O.[W]=O Chemical compound [Mo]=O.[W]=O POZJWRRDBOEZOO-UHFFFAOYSA-N 0.000 description 4
- GPVMZPSVDXBOGL-UHFFFAOYSA-N [O-2].[Ce+3].[Mo+2]=O.[O-2].[V+5] Chemical compound [O-2].[Ce+3].[Mo+2]=O.[O-2].[V+5] GPVMZPSVDXBOGL-UHFFFAOYSA-N 0.000 description 4
- SWFUVJZCUYQMRR-UHFFFAOYSA-N [O-2].[La+3].[O-2].[Pr+3] Chemical compound [O-2].[La+3].[O-2].[Pr+3] SWFUVJZCUYQMRR-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- TZIBOXWEBBRIBM-UHFFFAOYSA-N cerium(3+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Ce+3] TZIBOXWEBBRIBM-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- LNMNAFPIKQANTA-UHFFFAOYSA-N [Mo+2]=O.[O-2].[Ce+3] Chemical compound [Mo+2]=O.[O-2].[Ce+3] LNMNAFPIKQANTA-UHFFFAOYSA-N 0.000 description 3
- ODQDFZCDELEHRD-UHFFFAOYSA-N [O-2].[Mn+2].[O-2].[Ce+3].[O-2].[Zn+2] Chemical compound [O-2].[Mn+2].[O-2].[Ce+3].[O-2].[Zn+2] ODQDFZCDELEHRD-UHFFFAOYSA-N 0.000 description 3
- GQXDFHIXANOKHE-UHFFFAOYSA-N [O-2].[Y+3].[Ni]=O.[O-2].[O-2].[Y+3] Chemical compound [O-2].[Y+3].[Ni]=O.[O-2].[O-2].[Y+3] GQXDFHIXANOKHE-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004887 air purification Methods 0.000 description 3
- 238000003421 catalytic decomposition reaction Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- DCRSYTGOGMAXIA-UHFFFAOYSA-N zinc;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[Zn+2] DCRSYTGOGMAXIA-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 150000003297 rubidium Chemical class 0.000 description 2
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- FZUJWWOKDIGOKH-UHFFFAOYSA-N sulfuric acid hydrochloride Chemical compound Cl.OS(O)(=O)=O FZUJWWOKDIGOKH-UHFFFAOYSA-N 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical group CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BYMMIQCVDHHYGG-UHFFFAOYSA-N Cl.OP(O)(O)=O Chemical compound Cl.OP(O)(O)=O BYMMIQCVDHHYGG-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229940102127 rubidium chloride Drugs 0.000 description 1
- -1 rubidium nitrate hexahydrate Chemical group 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Abstract
本发明公开了一种自支撑金属氧化物纳米纤维催化净化材料，由金属盐和无机高分子絮凝剂按照摩尔比为1：0.001‑0.05制备而成。本发明还公开了一种自支撑金属氧化物纳米纤维催化净化材料的制备方法，步骤包括：1)将一种或多种金属盐水解形成金属氢氧化物纳米胶粒，随后加入无机高分子絮凝剂搅拌，得到前驱体溶液；2)将前驱体溶液通过静电纺丝成型工艺制成前驱体纳米纤维；3)将前驱体纳米纤维在空气下煅烧，得到自支撑金属氧化物纳米纤维催化净化材料。本发明的纳米纤维催化净化材料，在催化分解有害气体的同时可有效过滤颗粒污染物；本发明制备方法成本低、效果好。
The invention discloses a self-supporting metal oxide nanofiber catalytic purification material, which is prepared from a metal salt and an inorganic polymer flocculant in a molar ratio of 1:0.001-0.05. The invention also discloses a preparation method of a self-supporting metal oxide nanofiber catalytic purification material. The steps include: 1) hydrolyzing one or more metal salts to form metal hydroxide nano-colloids, and then adding inorganic macromolecules to flocculate 2) The precursor solution is made into precursor nanofibers by electrospinning molding process; 3) The precursor nanofibers are calcined in air to obtain self-supporting metal oxide nanofiber catalytic purification materials . The nanofiber catalytic purification material of the invention can effectively filter particulate pollutants while catalytically decomposing harmful gases; the preparation method of the invention has low cost and good effect.
Description
Technical Field
The invention belongs to the technical field of new material preparation, relates to a self-supporting metal oxide nanofiber catalytic purification material, and further relates to a preparation method of the self-supporting metal oxide nanofiber catalytic purification material.
Background
With the rapid development of industry and economy, the living standard of people is obviously improved, and meanwhile, the pollution problems of different degrees are brought to the atmospheric environment, such as various toxic and harmful gases and particle pollutants generated in industrial production and mass automobile use. Wherein the harmful gas is mainly CxHy、CO、NOx、H2S、SO2Common particulate pollutants are mainly PM10, PM5, PM2.5, PM1.0 and PM0.3, and the pollutants greatly affect the health and life quality of people. At present, air purification is mainly carried out by means of filtration, adsorption, absorption, catalytic decomposition and the like, the filtration means mainly aims at the purification of tiny particles, and the adsorption, absorption and catalytic decomposition are mainly used for treating harmful gases. The catalytic material can effectively reduce the energy required by chemical reaction and accelerate the chemical reaction rate, and compared with harmful gas purification means such as adsorption and absorption, the catalytic material can rapidly decompose harmful gas into harmless substances by using a catalyst, so that two air purification means of filtering and catalytic decomposition are combined, particle pollutants and harmful gas in the air can be effectively removed, and the aim of completely purifying the air is achieved.
Currently used air purification catalysts include rare earth catalysts, noble metal catalysts and metal oxide catalysts. Chinese patent CN101954286B discloses a rare earth catalyst for eliminating carbon monoxide at normal temperature and a preparation method thereof, and the rare earth catalyst prepared by the method has a powder structure and has the defects of difficult separation and difficult reutilization. The preparation method of the noble metal catalyst mainly comprises the steps of repeatedly soaking an alumina honeycomb ceramic carrier in noble metal immersion liquid, and preparing the noble metal catalyst with a multi-coating structure on the carrier, but the method has higher cost and relatively complex process, and is difficult to realize batch production [ Wangfubao, Sunpeng, mountain ] research on honeycomb catalysts for automobile exhaust purification [ J ] material engineering, 2003 (2): 41-42.]. Chinese patent CN102652903A discloses a preparation method of a high-temperature-resistant silica nanofiber filtering membrane, the nanofiber prepared by the method has good filtering performance and high-temperature resistance, but the fiber membrane has single function and does not have the capability of catalyzing and decomposing harmful gases. Chinese patent CN103806990B discloses a method for preparing an automobile exhaust gas processor with a ceramic fiber catalyst carrier, which comprises the steps of soaking alumina fibers in a sol solution containing a catalyst to make the catalyst adhere to the surface of the alumina fibers, and then calcining at high temperature to obtain the alumina fibers loaded with the catalyst, wherein the catalyst on the surface of the fibers is unevenly distributed and less in amount under the loading method, so that the catalytic efficiency of the fibers is relatively low.
Disclosure of Invention
The invention aims to provide a self-supporting metal oxide nanofiber catalytic purification material, which solves the problems of relatively low fiber catalytic efficiency and high production cost caused by unreasonable component arrangement and incomplete preparation method in the prior art.
The invention also aims to provide a preparation method of the self-supporting metal oxide nanofiber catalytic purification material.
The invention adopts the technical scheme that a self-supporting metal oxide nanofiber catalytic purification material is prepared from metal salt and an inorganic polymeric flocculant according to a molar ratio of 1: 0.001-0.05.
The invention adopts another technical scheme that the preparation method of the self-supporting metal oxide nanofiber catalytic purification material is implemented according to the following steps:
step 1: hydrolyzing one or more metal salts to form metal hydroxide nano colloidal particles, and then adding an inorganic polymeric flocculant and stirring for 5-100min to obtain a precursor solution;
the molar ratio of the metal salt to the inorganic polymeric flocculant is 1: 0.001-0.05;
step 2: preparing precursor nano-fibers from the precursor solution through an electrostatic spinning forming process;
and step 3: and calcining the precursor nanofiber in the air to obtain the self-supporting metal oxide nanofiber catalytic purification material.
The preparation method has the beneficial effects that the uniform and stable precursor solution is prepared by mixing the metal hydroxide nano colloidal particles formed by hydrolyzing the metal salt and the inorganic polymeric flocculant, and the precursor solution has a molecular chain of a stable three-dimensional interlocking net-shaped structure formed by the metal hydroxide nano colloidal particles and the long chain of the inorganic polymeric flocculant. According to the invention, no organic high molecular polymer is added in the precursor solution forming process, and the yield of the metal oxide fiber is obviously improved, so that the finally prepared self-supporting metal oxide nanofiber catalytic purification material has good flexibility and tensile strength, can effectively filter particulate pollutants while catalytically decomposing harmful gases, has a removal rate of the harmful gases of more than 95%, has a filtration efficiency of more than 99.99% on particulates with the particle size of 0.02-10 mu m, and has a resistance pressure drop of less than 200 Pa.
Drawings
FIG. 1 is a micrograph of a self-supporting metallic titanium oxide nanofiber catalytic purification material prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The self-supporting metal oxide nanofiber catalytic purification material provided by the invention is prepared from metal salt and an inorganic polymeric flocculant according to a molar ratio of 1: 0.001-0.05.
The metal salt is one or more of cobalt salt, nickel salt, titanium salt, manganese salt, cerium salt, chromium salt, ferric salt, lanthanum salt, rubidium salt, cupric salt, zinc salt, tungsten salt, cobalt salt, vanadium salt, molybdenum salt, yttrium salt, praseodymium salt and neodymium salt;
wherein, cobalt salt is selected from cobalt nitrate hexahydrate, cobalt oxalate or cobalt acetylacetonate;
the nickel salt is selected from nickel chloride, nickel acetylacetonate or nickel nitrate;
the titanium salt is selected from isopropyl titanate, tetrabutyl titanate or tetraethyl titanate;
manganese salt is selected from manganese chloride, manganese nitrate or manganese acetylacetonate;
cerium salt is selected from cerium chloride or cerium oxalate;
chromium salt is selected from chromium acetate or chromium nitrate nonahydrate;
ferric salt is selected from ferric acetylacetonate, ferric ethoxy, ferric trichloride or ferrous ammonium sulfate hexahydrate;
lanthanum salt is lanthanum acetate or lanthanum nitrate;
rubidium salt is rubidium nitrate hexahydrate or rubidium chloride;
the copper salt is selected from copper acetate, copper chloride or copper sulfate pentahydrate;
the zinc salt is selected from zinc chloride, zinc sulfate heptahydrate or zinc acetate;
the tungsten salt is selected from phosphotungstic acid, ammonium metatungstate or sodium tungstate;
cobalt salt is cobalt acetylacetonate, cobalt nitrate hexahydrate, cobalt oxalate or cobalt chloride hexahydrate;
the vanadium salt is selected from ammonium metavanadate, vanadyl sulfate or vanadyl trichloride;
molybdenum salt is selected from molybdenum pentachloride, molybdenum acetate or molybdenum phosphate;
yttrium salt is yttrium acetate, yttrium chloride or yttrium nitrate;
the praseodymium salt is selected from praseodymium nitrate, praseodymium acetate or praseodymium sulfate;
the neodymium salt is neodymium nitrate, neodymium chloride or neodymium acetate.
The inorganic polymeric flocculant is one of polyaluminium chloride, polyaluminium sulfate, polyferric chloride, polyferric sulfate, polyaluminium silicate, polyaluminum phosphonitrichloride, polyaluminum silicate chloride, polyaluminum sulfate chloride, polyaluminum silicate sulfate, polyaluminum silicate chloride or polyaluminum silicate zinc.
The physicochemical properties of the self-supporting metal oxide nano-fiber catalytic purification material are that the average diameter of the fiber is 10nm-1 μm, and the specific surface area is 10m2/g-200m2(ii)/g; stretchingThe strength is 5MPa-500 MPa.
The preparation method of the self-supporting metal oxide nanofiber catalytic purification material is implemented according to the following steps:
step 1: hydrolyzing one or more metal salts to form metal hydroxide nano colloidal particles, and then adding an inorganic polymeric flocculant and stirring for 5-100min to obtain a precursor solution; a large amount of hydroxyl on the surface of the metal hydroxide nano colloidal particle absorbs the inorganic polymeric flocculant through the hydrogen bond effect in the stirring process to form a molecular chain with a stable three-dimensional interlocking mesh structure, and the molecular chain exists in the solution in a large amount, so that the solution has certain viscosity and can be used as a precursor solution for spinning.
The metal salt hydrolysis means that strong base and weak acid salt are stirred for 5-200min to hydrolyze under the condition that the pH value is 3-5, or strong acid and weak base salt are stirred for 5-200min to hydrolyze under the condition that the pH value is 10-12, so that metal hydroxide nano colloidal particles are formed, and the size of the colloidal particles is 0.1-50 nm.
The mol ratio of the total amount of the metal salts to the inorganic polymeric flocculant is 1: 0.001-0.05, and the dynamic viscosity of the precursor solution is 0.01-5 Pa.s.
Step 2: preparing the precursor solution into precursor nano-fibers by an electrostatic spinning forming process,
when the repulsion force of the electric charges of the liquid drops at the tip of the spinning nozzle exceeds the surface tension force of the spinning nozzle, the jet flow jetted from the surface of the liquid drops is subjected to high-speed stretching of the electric field force and solvent volatilization, and finally is solidified and deposited on a receiving device to obtain precursor nanofiber, wherein the precursor nanofiber has the advantages of uniform fiber diameter and good continuity.
The electrostatic spinning process parameters are as follows: the temperature of the spinning environment is 10-28 ℃, the relative humidity of the spinning environment is 30-70%, the perfusion speed is 0.1-10 mL/h, the distance between the receiving device and the spinning nozzle is 10-30 cm, and the voltage applied by the spinning nozzle is 10-50 kV.
And step 3: calcining the precursor nano-fiber in the air, gradually increasing the calcining temperature from room temperature to 500-1300 ℃, increasing the temperature at a speed of 1-10 ℃/min, and keeping the temperature at the highest calcining temperature for 30-150 min to obtain the self-supporting metal oxide nano-fiber catalytic purification material (self-supporting metal oxide nano-fiber material for short).
The inorganic polymeric flocculant is mainly used in the field of industrial water treatment at present, and the purpose of purifying water quality is finally achieved by the adhesion, bridging and crosslinking actions of hydroxyl on the surface of the inorganic polymeric flocculant and larger-sized impurity particles (including colloidal particles, dyes, larger blocky particles and the like) in water, but in the preparation method of the invention, only hydrogen bonding action is carried out between the inorganic polymeric flocculant and metal hydroxide nano colloidal particles to form a stable three-dimensional interlocking reticular molecular chain, because the size of the metal hydroxide nano colloidal particles in the precursor solution is in nano-order of magnitude and is less than 100nm, and meanwhile, the quantity of the nano colloidal particles is huge to reach hundreds of millions, after a very small quantity of the inorganic polymeric flocculant is added, hydrogen bonding adsorption action is carried out between the metal hydroxide nano colloidal particles and the hydroxyl on the surface of the inorganic polymeric flocculant, the nano colloidal particle can completely wrap the inorganic polymeric flocculant to form, other hydroxyl groups on the surface of the nano colloidal particle can also adsorb other inorganic polymeric flocculant molecules to finally form a stable three-dimensional interlocking mesh-structure molecular chain, and in the process, due to the fact that a large amount of nano colloidal particles exist, the inorganic polymeric flocculant cannot generate a coagulating sedimentation effect, so that a spinnable precursor solution which is uniform and has certain viscosity can be obtained, and precursor nano fibers are uniform and good in continuity.
Organic high molecular polymer is not required to be added into the precursor solution, and the yield of the metal oxide fiber is remarkably improved, so that the finally prepared self-supporting metal oxide nanofiber material shows better flexibility and tensile strength, the average diameter of the fiber is 10nm-1 mu m, and the specific surface area is 10m2/g-200m2(ii)/g; the tensile strength is 5MPa-500 MPa; the self-supporting metal oxide nanofiber material can effectively filter particulate pollutants while catalytically decomposing harmful gases, the removal rate of the harmful gases is over 95 percent, the filtering efficiency of the self-supporting metal oxide nanofiber material on particles with the particle size of 0.02-10 mu m is over 99.99 percent, and the resistance pressure drop is less than 200 Pa.
Example 1
Preparing the self-supporting titanium oxide nano-fiber catalytic purification material.
Step 1: stirring isopropyl titanate for 50min under the condition that the pH value is 4 for hydrolysis to form titanium hydroxide nano colloidal particles with the colloidal particle size of 25nm, then adding an inorganic polymeric flocculant polymeric ferric sulfate, and continuously stirring for 40 min; wherein the molar ratio of the isopropyl titanate to the polymeric ferric sulfate is 1: 0.01; uniformly mixing to prepare a uniform and stable precursor solution with the dynamic viscosity of 0.3 Pa.s, wherein the molecular chain in the precursor solution has a stable three-dimensional interlocking network structure formed by titanium hydroxide nano colloidal particles and polymeric ferric sulfate long chains, and the structural formula is as follows:
stable three-dimensional interlocking network structure of example 1
Step 2: preparing precursor nano-fibers from the precursor solution through an electrostatic spinning forming process;
the electrostatic spinning process parameters are as follows: the spinning temperature is 20 ℃, the relative humidity is 45%, the perfusion speed is 6.5mL/h, the receiving distance is 28cm, and the spinning voltage is 35 kV;
and step 3: and calcining the precursor nano-fiber in the air, gradually increasing the calcining temperature from room temperature to 1100 ℃, increasing the temperature at the speed of 2 ℃/min, and keeping the temperature for 80min at the highest calcining temperature to obtain the self-supporting titanium oxide nano-fiber catalytic purification material.
Referring to fig. 1, a micrograph of the self-supporting metal oxide nanofiber catalytic purification material prepared in example 1 is shown. The average fiber diameter of the self-supporting titanium oxide nano fiber catalytic purification material is 200nm, and the specific surface area is 100m2The filter material has the advantages that the filter material has the tensile strength of 300MPa, is used for effectively filtering particle pollutants while catalytically decomposing harmful gases, has the removal rate of 96% for 1.2 wt% of hydrogen sulfide gas, has the filtering efficiency of 99.994% for particles with the particle size of 0.03-7 mu m, and has the resistance pressure drop of 132 Pa.
Example 2
Preparing the self-supporting lanthanum oxide nano-fiber catalytic purification material.
Step 1: stirring lanthanum nitrate under the condition that the pH value is 11 for 60min, hydrolyzing to form lanthanum hydroxide nano colloidal particles with the colloidal particle size of 18nm, then adding an inorganic polymeric flocculant polyaluminum silicate chloride, and continuously stirring for 45 min; wherein the molar ratio of lanthanum nitrate to poly-silicon aluminum chloride is 1: 0.05; uniformly mixing to prepare a uniform and stable precursor solution with the dynamic viscosity of 4.3 Pa.s, wherein the molecular chain in the precursor solution has a stable three-dimensional interlocking reticular structure formed by lanthanum hydroxide nano colloidal particles and poly-silicon aluminum chloride long chains, and the structural formula is as follows:
example 2 Stable three-dimensional interlocking mesh Structure
Step 2: preparing precursor nano-fibers from the precursor solution through an electrostatic spinning forming process;
the electrostatic spinning process parameters are as follows: the spinning temperature is 24 ℃, the relative humidity is 38%, the perfusion speed is 7.0mL/h, the receiving distance is 23cm, and the spinning voltage is 32 kV;
and step 3: and calcining the precursor nanofiber in air, gradually increasing the calcining temperature from room temperature to 850 ℃, increasing the temperature at a speed of 4 ℃/min, and keeping the temperature for 50min at the highest calcining temperature to obtain the self-supporting lanthanum oxide nanofiber catalytic purification material.
The average fiber diameter of the self-supporting lanthanum oxide nano fiber catalytic purification material is 430nm, and the specific surface area is 105m2The filter material has the advantages that the filter material is/g, the tensile strength is 360MPa, the filter material is used for effectively filtering particle pollutants while catalytically decomposing harmful gases, the removal rate of 0.5 wt% of sulfur dioxide gas is 98.3%, the filter efficiency of particles with the particle sizes of 0.03-8 mu m is 99.992%, and the resistance pressure drop is 102 Pa.
Example 3
Preparing the self-supporting titanium oxide-cerium oxide nano-fiber catalytic purification material.
Step 1: stirring tetraethyl titanate and cerium chloride for 10min under the condition that the pH value is 12 for hydrolysis to form composite hydroxide nano colloidal particles with the colloidal particle size of 10nm, then adding an inorganic polymeric flocculant polyaluminum phosphate chloride, and continuously stirring for 30min, wherein the molar ratio of the tetraethyl titanate to the cerium chloride is 50: 50, the molar ratio of the metal salt to the poly-phosphorus aluminum chloride is 1: 0.02; uniformly mixing to prepare a uniform and stable precursor solution with the dynamic viscosity of 3.2 Pa.s, wherein the molecular chain in the precursor solution has a stable three-dimensional interlocking reticular structure formed by composite hydroxide nano colloidal particles and long chains of poly-phosphorus aluminum chloride, and the structural formula is as follows:
stable three-dimensional interlocking network structure of example 3
Step 2: preparing precursor nano-fibers from the precursor solution through an electrostatic spinning forming process; the electrostatic spinning process parameters are as follows: the spinning temperature is 22 ℃, the relative humidity is 50%, the perfusion speed is 1.5mL/h, the receiving distance is 20cm, and the spinning voltage is 25 kV;
and step 3: calcining the precursor fiber material in an air atmosphere, gradually increasing the calcining temperature from room temperature to 800 ℃, increasing the temperature at a speed of 4 ℃/min, and keeping the highest calcining temperature for 60min to obtain the self-supporting titanium oxide-cerium oxide nano-fiber membrane material.
The self-supporting titanium oxide-cerium oxide fiber has an average diameter of 50nm and a specific surface area of 200m2The tensile strength of the fiber membrane material is 5MPa, the self-supporting titanium oxide-cerium oxide nano-fiber membrane material is used for effectively filtering particulate pollutants while catalytically reducing NOx, the removal rate of 0.4 wt% of NOx gas is 97%, the filtering efficiency of particulate matters with the particle size of 0.02-8 mu m is more than 99.99%, and the resistance pressure drop is 165 Pa.
Example 4
The self-supporting tungsten oxide-molybdenum oxide nano fiber catalytic purification material.
Step 1: and (2) stirring phosphotungstic acid and molybdenum pentachloride for 60min under the condition that the pH value is 11, hydrolyzing to form composite hydroxide nano colloidal particles with the colloidal particle size of 20nm, then adding an inorganic polymeric flocculant polymeric ferric chloride, and continuously stirring for 45min, wherein the molar ratio of the phosphotungstic acid to the molybdenum pentachloride is 45: 55, the molar ratio of the metal salt to the polymeric ferric chloride is 1: 0.001; uniformly mixing to prepare a uniform and stable precursor solution with the dynamic viscosity of 4.1 Pa.s, wherein the molecular chains in the precursor solution have a stable three-dimensional interlocking mesh structure similar to that in the embodiment 1;
step 2: preparing precursor nano-fibers from the precursor solution through an electrostatic spinning forming process; the electrostatic spinning process parameters are as follows: the spinning temperature is 22 ℃, the relative humidity is 70%, the perfusion speed is 0.5mL/h, the receiving distance is 15cm, and the spinning voltage is 15 kV;
and step 3: calcining the precursor fiber material in an air atmosphere, gradually increasing the calcining temperature from room temperature to 1000 ℃, increasing the temperature at the speed of 2 ℃/min, and keeping the highest calcining temperature for 45min to obtain the self-supporting tungsten oxide-molybdenum oxide nano-fiber membrane material.
The self-supporting tungsten oxide-molybdenum oxide fiber has the average diameter of 300nm, the specific surface area of 110m2/g and the tensile strength of a fiber membrane material of 340MPa, wherein the self-supporting tungsten oxide-molybdenum oxide nano fiber membrane material is used for effectively filtering particulate pollutants while catalytically reducing NOx, the removal rate of 0.8 wt% of NOx gas is 97%, the filtering efficiency of particulate matters with the particle size of 0.03-8 mu m is more than 99.99%, and the resistance pressure drop is 178 Pa.
Example 5
Preparing the self-supporting vanadium oxide-molybdenum oxide-cerium oxide nano-fiber catalytic purification material.
Step 1: stirring vanadium oxychloride, molybdenum phosphate and cerium chloride for 90min under the condition that the pH value is 12 for hydrolysis to form composite hydroxide nano colloidal particles with the colloidal particle size of 32nm, then adding an inorganic polymeric flocculant polyaluminium sulfate, and continuously stirring for 100min, wherein the molar ratio of the vanadium oxychloride to the molybdenum phosphate to the cerium chloride is 35: 25: 40, the molar ratio of the metal salt to the polyaluminium sulfate is 1: 0.04; uniformly mixing to prepare a uniform and stable precursor solution with the dynamic viscosity of 2.1 Pa.s, wherein the molecular chains in the precursor solution have a stable three-dimensional interlocking mesh structure similar to that in the embodiment 1;
step 2: preparing precursor nano-fibers from the precursor solution through an electrostatic spinning forming process; the electrostatic spinning process parameters are as follows: the spinning temperature is 16 ℃, the relative humidity is 45%, the perfusion speed is 5mL/h, the receiving distance is 30cm, and the spinning voltage is 50 kV;
and step 3: calcining the precursor fiber material in an air atmosphere, gradually increasing the calcining temperature from room temperature to 1100 ℃, increasing the temperature at a speed of 5 ℃/min, and keeping the highest calcining temperature for 90min to obtain the self-supporting vanadium oxide-molybdenum oxide-cerium oxide nano-fiber membrane material.
The self-supporting vanadium oxide-molybdenum oxide-cerium oxide fiber has the average diameter of 400nm, the specific surface area of 90m2/g and the tensile strength of a fiber membrane material of 380MPa, wherein the self-supporting vanadium oxide-molybdenum oxide-cerium oxide nano fiber membrane material is used for effectively filtering particulate pollutants while catalytically reducing NOx, the removal rate of 0.5 wt% of NOx gas is 97%, the filtering efficiency of particulate matters with the particle size of 0.02-7 mu m is more than 99.99%, and the resistance pressure drop is 98 Pa.
Example 6
Preparing the self-supporting molybdenum oxide-cerium oxide nano-fiber catalytic purification material.
Step 1: stirring molybdenum acetate and cerium oxalate for 30min under the condition that the pH value is 3 for hydrolysis to form composite hydroxide nano colloidal particles with the colloidal particle size of 50nm, then adding an inorganic polymeric flocculant poly-silicon ferric chloride, and continuously stirring for 30min, wherein the molar ratio of the molybdenum acetate to the cerium oxalate is 60: 40, the molar ratio of the metal salt to the polysilicon ferric chloride is 1: 0.012; uniformly mixing to prepare a uniform and stable precursor solution with the dynamic viscosity of 0.5 Pa.s, wherein the molecular chain in the precursor solution has a stable three-dimensional interlocking mesh structure similar to that in the embodiment 2;
step 2: preparing precursor nano-fibers from the precursor solution through an electrostatic spinning forming process; the electrostatic spinning process parameters are as follows: the spinning temperature is 12 ℃, the relative humidity is 30%, the perfusion speed is 3.5mL/h, the receiving distance is 28cm, and the spinning voltage is 40 kV;
and step 3: calcining the precursor fiber material in an air atmosphere, gradually increasing the calcining temperature from room temperature to 1000 ℃, increasing the temperature at a speed of 8 ℃/min, and keeping the highest calcining temperature for 60min to obtain the self-supporting molybdenum oxide-oxidized nano fiber membrane material.
The self-supporting molybdenum oxide-cerium oxide nanofiber has the average diameter of 800nm, the specific surface area of 20m2/g and the tensile strength of a fiber membrane material of 500MPa, wherein the self-supporting molybdenum oxide-cerium oxide nanofiber membrane material is used for effectively filtering particulate pollutants while catalytically reducing NOx, the removal rate of 0.7 wt% of NOx gas is 97%, the filtering efficiency of particulate matters with the particle size of 0.05-8 mu m is more than 99.99%, and the resistance pressure drop is 83 Pa.
Example 7
Preparing the self-supporting nickel oxide-yttrium oxide nano-fiber catalytic purification material.
Step 1: stirring nickel chloride and yttrium chloride for 30min under the condition that the pH value is 10 for hydrolysis to form composite hydroxide nano colloidal particles with the colloidal particle size of 0.5nm, then adding an inorganic polymeric flocculant polyaluminium sulfate chloride, and continuously stirring for 30min, wherein the molar ratio of the nickel chloride to the yttrium chloride is 30: 35: 35, the molar ratio of the metal salt to the polyaluminum sulfatochloride is 1: 0.014; uniformly mixing to prepare a uniform and stable precursor solution with the dynamic viscosity of 0.1 Pa.s, wherein the molecular chain in the precursor solution has a stable three-dimensional interlocking mesh structure similar to that in the embodiment 1;
step 2: preparing precursor nano-fibers from the precursor solution through an electrostatic spinning forming process; the electrostatic spinning process parameters are as follows: the spinning temperature is 15 ℃, the relative humidity is 30%, the perfusion speed is 0.5mL/h, the receiving distance is 15cm, and the spinning voltage is 40 kV;
and step 3: calcining the precursor fiber material in an air atmosphere, gradually increasing the calcining temperature from room temperature to 900 ℃, increasing the temperature at a speed of 3 ℃/min, and keeping the highest calcining temperature for 90min to obtain the self-supporting nickel oxide-yttrium oxide nano-fiber membrane material.
The self-supporting nickel oxide-yttrium oxide fiber has the average diameter of 10nm, the specific surface area of 200m2/g and the tensile strength of a fiber membrane material of 10MPa, is used for effectively filtering particulate pollutants while catalytically converting NOx, CO and HC in automobile exhaust, has the removal rate of 98% of mixed gas of 0.3 wt% of NOx, CO and HC, has the filtering efficiency of more than 99.99% of particulate matters with the particle size of 0.04-6 mu m, and has the resistance pressure drop of 192 Pa.
Example 8
Preparing the self-supporting praseodymium oxide-lanthanum oxide nano-fiber catalytic purification material.
Step 1: stirring praseodymium acetate and lanthanum acetate for 90min under the condition that the pH value is 3 for hydrolysis to form composite hydroxide nano colloidal particles with the colloidal particle size of 35nm, then adding an inorganic polymeric flocculant polyaluminium chloride, and continuously stirring for 90min, wherein the molar ratio of the praseodymium acetate to the lanthanum acetate is 40: 60, the molar ratio of the metal salt to the polyaluminium chloride is 1: 0.038; uniformly mixing to prepare a uniform and stable precursor solution with the dynamic viscosity of 3.5 Pa.s, wherein the molecular chain in the precursor solution has a stable three-dimensional interlocking mesh structure similar to that in the embodiment 1;
step 2: preparing precursor nano-fibers from the precursor solution through an electrostatic spinning forming process; the electrostatic spinning process parameters are as follows: the spinning temperature is 21 ℃, the relative humidity is 35%, the perfusion speed is 5mL/h, the receiving distance is 25cm, and the spinning voltage is 40 kV;
and step 3: calcining the precursor fiber material in an air atmosphere, gradually increasing the calcining temperature from room temperature to 800 ℃, increasing the temperature at a speed of 1 ℃/min, and keeping the highest calcining temperature for 60min to obtain the self-supporting praseodymium oxide-lanthanum oxide nano-fiber membrane material.
The self-supporting praseodymium oxide-lanthanum oxide fiber has the average diameter of 370nm and the specific surface area of 95m2The tensile strength of the fiber membrane material is 254MPa, the self-supporting praseodymium oxide-lanthanum oxide nano fiber membrane material is used for effectively filtering particulate pollutants while catalytically converting NOx, CO and HC in automobile exhaust, the removal rate of 0.8 wt% of mixed gas of NOx, CO and HC is 98%, the filtering efficiency of particulate matters with the particle size of 0.05-7 mu m is more than 99.99%, and the resistance pressure drop is 195 Pa.
Example 9
Preparing the self-supporting zinc oxide-cerium oxide-manganese oxide nano-fiber catalytic purification material.
Step 1: stirring zinc chloride, cerium chloride and manganese chloride for 90min under the condition that the pH value is 5 for hydrolysis to form composite hydroxide nano colloidal particles with the colloidal particle size of 20nm, then adding an inorganic polymeric flocculant polyaluminum silicate sulfate, and continuously stirring for 95 min; wherein the molar ratio of zinc chloride, cerium chloride and manganese chloride is 20: 40: 40, the molar ratio of the metal salt to the polyaluminum silicate sulfate is 1: 0.001; uniformly mixing to prepare a uniform and stable precursor solution with the dynamic viscosity of 2.8 Pa.s, wherein the molecular chain in the precursor solution has a stable three-dimensional interlocking mesh structure similar to that in the embodiment 2;
step 2: preparing precursor nano-fibers from the precursor solution through an electrostatic spinning forming process;
the electrostatic spinning process parameters are as follows: the spinning temperature is 17 ℃, the relative humidity is 45%, the perfusion speed is 5.5mL/h, the receiving distance is 27cm, and the spinning voltage is 40 kV;
and step 3: and calcining the precursor nanofiber in air, gradually increasing the calcining temperature from room temperature to 600 ℃, increasing the temperature at the speed of 2 ℃/min, and keeping the temperature for 55min at the highest calcining temperature to obtain the self-supporting zinc oxide-cerium oxide-manganese oxide nanofiber catalytic purification material.
The self-supporting zinc oxide-cerium oxide-manganese oxide fiber has an average diameter of 520nm and a specific surface area of 15m2The filter material has the advantages that the filter material is/g, the tensile strength is 490MPa, the filter material is used for effectively filtering particle pollutants while catalytically decomposing harmful gases, the removal rate of 0.9 wt% of sulfur dioxide gas is 99.8%, the filter efficiency of particles with the particle size of 0.05-8 mu m is 99.996%, and the resistance pressure drop is 38 Pa.
Example 10
Preparing the self-supporting nickel oxide nano-fiber catalytic purification material.
Step 1: stirring nickel nitrate under the condition that the pH value is 10 for 100min for hydrolysis to form nickel hydroxide nano colloidal particles with the colloidal particle size of 1nm, then adding an inorganic polymeric flocculant polyferric chloride, and continuously stirring for 75 min; wherein the molar ratio of the nickel nitrate to the polyferric chloride is 1: 0.004; uniformly mixing to prepare a uniform and stable precursor solution with the dynamic viscosity of 2 Pa.s, wherein the molecular chains in the precursor solution have a stable three-dimensional interlocking mesh structure similar to that in the embodiment 1;
step 2: preparing precursor nano-fibers from the precursor solution through an electrostatic spinning forming process;
the electrostatic spinning process parameters are as follows: the spinning temperature is 25 ℃, the relative humidity is 65%, the perfusion speed is 2.0mL/h, the receiving distance is 15cm, and the spinning voltage is 23 kV;
and step 3: and calcining the precursor nanofiber in air, gradually increasing the calcining temperature from room temperature to 1200 ℃, increasing the temperature at the speed of 6 ℃/min, and keeping the temperature for 70min at the highest calcining temperature to obtain the self-supporting nickel oxide nanofiber catalytic purification material.
The self-supporting nickel oxide fiber has an average diameter of 100nm and a specific surface area of 60m2The filter material has the advantages that the filter material is/g, the tensile strength is 450MPa, the filter material is used for effectively filtering particle pollutants while catalytically decomposing harmful gases, the removal rate of 0.1 wt% of sulfur dioxide gas is 99%, the filter efficiency of particles with the particle size of 0.05-9 mu m is 99.995%, and the resistance pressure drop is 68 Pa.
Example 11
Preparing the self-supporting zinc oxide-titanium oxide nano-fiber catalytic purification material.
Step 1: stirring zinc acetate and tetraethyl titanate for 175min under the condition that the pH value is 5 for hydrolysis to form composite hydroxide nano colloidal particles with the colloidal particle size of 22nm, then adding an inorganic polymeric flocculant to polymerize ferric silicate, and continuously stirring for 75 min; wherein the molar ratio of the zinc acetate to the tetraethyl titanate is 70: 30, the molar ratio of the metal salt to the polymeric ferric silicate is 1: 0.021; uniformly mixing to prepare a uniform and stable precursor solution with the dynamic viscosity of 1.6 Pa.s, wherein the molecular chains in the precursor solution have a stable three-dimensional interlocking mesh structure similar to that in the embodiment 1;
step 2: preparing precursor nano-fibers from the precursor solution through an electrostatic spinning forming process;
the electrostatic spinning process parameters are as follows: the spinning temperature is 27 ℃, the relative humidity is 58%, the perfusion speed is 6.5mL/h, the receiving distance is 21cm, and the spinning voltage is 33 kV;
and step 3: and calcining the precursor nano-fiber in the air, gradually increasing the calcining temperature from room temperature to 1200 ℃, increasing the temperature at the speed of 3 ℃/min, and keeping the highest calcining temperature for 85min to obtain the self-supporting zinc oxide-titanium oxide nano-fiber catalytic purification material.
The self-supporting zinc oxide-titanium oxide fiber has an average diameter of 535nm and a specific surface area of 165m2The filter material has the advantages that the filter material is/g, the tensile strength is 385MPa, the filter material is used for effectively filtering particle pollutants while catalytically decomposing harmful gases, the removal rate of 0.5 wt% of sulfur dioxide gas is 99.5%, the filter efficiency of particles with the particle size of 0.03-6 mu m is 99.998%, and the resistance pressure drop is 172 Pa.
The following preparation procedures of examples 12-31 are similar to example 1, with reference to tables 1-5 for precursor solution formulation parameters, electrospinning parameters, self-supporting metal oxide nanofiber membrane performance, and catalytic purification effect parameters, respectively. The stirring time 1 in tables 1 to 5 means that the stirring time for the metal salt hydrolysis to form metal hydroxide nano colloidal particles is 5 to 100 min; the stirring time 2 is 5-200min after the inorganic polymeric flocculant is added.
Table 1, comparison of Process parameter settings, Performance and catalytic cleaning effectiveness of examples 12 to 15
Table 2 comparison of Process parameter settings, Performance and catalytic cleaning effectiveness of examples 16 to 19
Table 3 comparison of the process parameter settings, performances and catalytic cleaning effects of examples 20 to 23
Table 4 comparison of Process parameter settings, Performance and catalytic cleaning effectiveness of examples 24 to 27
Table 5 comparison of Process parameter settings, Performance and catalytic cleaning effectiveness of examples 28 to 31
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