CN108339544A - Photochemical catalyst/super-hydrophobic film composite material of fullerene carboxy derivatives modification - Google Patents
Photochemical catalyst/super-hydrophobic film composite material of fullerene carboxy derivatives modification Download PDFInfo
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- CN108339544A CN108339544A CN201810168646.9A CN201810168646A CN108339544A CN 108339544 A CN108339544 A CN 108339544A CN 201810168646 A CN201810168646 A CN 201810168646A CN 108339544 A CN108339544 A CN 108339544A
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- Prior art keywords
- fullerene
- cooh
- modification
- super
- carboxy derivatives
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Links
- 238000012986 modification Methods 0.000 title claims abstract description 163
- 229910003472 fullerene Inorganic materials 0.000 title claims abstract description 93
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 74
- 230000004048 modification Effects 0.000 title claims abstract description 68
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 claims abstract description 45
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 229910001868 water Inorganic materials 0.000 claims description 43
- 229910052797 bismuth Inorganic materials 0.000 claims description 41
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 31
- 230000015556 catabolic process Effects 0.000 claims description 30
- 238000006731 degradation reaction Methods 0.000 claims description 30
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 24
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 24
- 239000011521 glass Substances 0.000 claims description 23
- 229940043267 rhodamine b Drugs 0.000 claims description 23
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 21
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 19
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 17
- 229940012189 methyl orange Drugs 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- -1 polytetrafluoroethylene Polymers 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 13
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 12
- YCIHPQHVWDULOY-FMZCEJRJSA-N (4s,4as,5as,6s,12ar)-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide;hydrochloride Chemical compound Cl.C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O YCIHPQHVWDULOY-FMZCEJRJSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005034 decoration Methods 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052789 astatine Inorganic materials 0.000 claims description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims 1
- 238000005215 recombination Methods 0.000 abstract description 5
- 230000006798 recombination Effects 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 description 31
- 239000000243 solution Substances 0.000 description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000012071 phase Substances 0.000 description 20
- 229910052760 oxygen Inorganic materials 0.000 description 18
- 239000001301 oxygen Substances 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000006555 catalytic reaction Methods 0.000 description 15
- 230000001699 photocatalysis Effects 0.000 description 15
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 14
- 238000005286 illumination Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 238000007146 photocatalysis Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000001362 electron spin resonance spectrum Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000004435 EPR spectroscopy Methods 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000001548 drop coating Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- VSQYNPJPULBZKU-UHFFFAOYSA-N mercury xenon Chemical compound [Xe].[Hg] VSQYNPJPULBZKU-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- WPZFLQRLSGVIAA-UHFFFAOYSA-N sodium tungstate dihydrate Chemical compound O.O.[Na+].[Na+].[O-][W]([O-])(=O)=O WPZFLQRLSGVIAA-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001976 improved effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 description 1
- 229910002703 Al K Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- 244000000626 Daucus carota Species 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WUTHJWCAESRVMV-UHFFFAOYSA-N [W].[Bi] Chemical compound [W].[Bi] WUTHJWCAESRVMV-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000005770 birds nest Nutrition 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 230000008439 repair process Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 235000005765 wild carrot Nutrition 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The present embodiments relate to a kind of photochemical catalyst/super-hydrophobic film composite materials of fullerene carboxy derivatives modification.Photochemical catalyst/super-hydrophobic film composite material of fullerene carboxy derivatives modification includes super-hydrophobic film, it is covered with to the surface portion of the super-hydrophobic film photochemical catalyst of fullerene carboxy derivatives modification, the photochemical catalyst of the fullerene carboxy derivatives modification is prepared by the raw material including following material：(1) at least one of photochemical catalyst and photochemical catalyst precursor；(2) fullerene carboxy derivatives.The composite structure is novel, has excellent performance, as photochemical catalyst in use, electron-hole recombinations probability is low.
Description
Technical field
The present invention relates to photocatalysis field, the photochemical catalysts modified further to fullerene carboxy derivatives/super-hydrophobic
Film composite material and its application.
Background technology
Photocatalitic Technique of Semiconductor is due to thorough with low energy consumption, low cost, non-secondary pollution, low temperature deep reaction, purification
Bottom and can directly using solar energy as light source come characteristics such as drive responses, and become a kind of environmental pollution improvement's skill of green
Art.
In recent years, the compound very big concern for causing scientists of catalysis material and Carbon materials.Existing light is urged
Change the composite material that material is formed with Carbon materials and improve the rate of light-catalyzed reaction to a certain extent, but is asked there are still following
Topic：Photo-generate electron-hole is inside semiconductor and surface is easy to compound, and the effective mobility of photogenerated charge is caused to decline, from
And photocatalytic activity is made to substantially reduce.In order to make photo-generate electron-hole can with longer-term, efficiently separate and be finally utilized,
A kind of feasible mode is that electronics is captured and utilized by using suitable and sufficient receptor, and oxygen is exactly a kind of main day
Right electron acceptor.However traditional light-catalyzed reaction carries out in aqueous phase system mostly, the solubility of oxygen in water is not
Height, diffusion coefficient is relatively low, significantly limits its utilization to light induced electron.
Bismuth tungstate material has relatively narrow optical band gap as a kind of typical perovskite stratiform structure oxide
(2.7eV) can be a kind of novel photocatalysis material with preferable photocatalytic activity, by ultraviolet light and excited by visible light
Utilization rate for helping to improve solar spectrum is studied it in the concern for causing more and more researchers, and itself has light
Photoetch phenomenon is not present in stability, all has application value in terms of new energy development and the depollution of environment.But tungsten bismuth tungstate material
For material as a kind of with visible light-responded novel photocatalysis material, the service life in light induced electron and hole is very short.Therefore it is carrying
In terms of the electron hole separative efficiency and photocatalytic activity of high bismuth tungstate oxide, also it is worth our further in-depth studies.
Fullerene is applied to multiple fields as a kind of carbon material with good optical characteristics and Quantum Properties and works as
In, physicochemical properties are extremely abundant, and type is various, and the point group symmetry of carbon cage is also numerous and disorderly changeable.
Being disclosed in the information of the background technology part, it is only intended to increase understanding of the overall background of the invention, without answering
It has been the prior art well known to persons skilled in the art when being considered as recognizing or imply that the information is constituted in any form.
Invention content
Goal of the invention
It is compound fast to solve existing catalysis material electron-hole, light induced electron receptor is used as during light-catalyzed reaction
Amount of oxygen is few and the slow problem of diffusion, the purpose of the present invention is to provide a kind of photocatalysis of fullerene carboxy derivatives modification
Agent/super-hydrophobic film composite material and its application, the composite structure is novel, has excellent performance, in use, can as photochemical catalyst
To accelerate oxygen diffusion and increase amount of oxygen so that have sufficient oxygen that can capture in light-catalyzed reaction system and utilize light
Raw electronics, to reduce electron-hole recombination probability.
Solution
Purpose to realize the present invention, an embodiment of the present invention provides a kind of photocatalysis of fullerene carboxy derivatives modification
Agent/super-hydrophobic film composite material, the composite material include super-hydrophobic film, are covered with fowler to the surface portion of the super-hydrophobic film
The photochemical catalyst of alkene carboxy derivatives modification, the photochemical catalyst of the fullerene carboxy derivatives modification is by including following material
Raw material be prepared：(1) at least one of photochemical catalyst and photochemical catalyst precursor；(2) fullerene carboxy derivatives.
In one possible implementation, the super-hydrophobic film includes super-hydrophobic carbon film to above-mentioned composite material, super-hydrophobic
At least one of silicon dioxide film, super-hydrophobic metal oxide film；It is optionally super-hydrophobic carbon film.
In one possible implementation, the super-hydrophobic carbon film is that surface is covered with super-hydrophobic material to above-mentioned composite material
The electro-conductive glass of material, wherein the super hydrophobic material includes octadecyl trichlorosilane alkane or polytetrafluoroethylene (PTFE), the electro-conductive glass
Including FTO electro-conductive glass or ITO electro-conductive glass.FTO electro-conductive glass is the SnO for adulterating fluorine2Electro-conductive glass, ITO electro-conductive glass are
For indium tin oxide-coated glass.
In one possible implementation, the preparation of the super-hydrophobic carbon film includes the following steps above-mentioned composite material：
Electro-conductive glass is put on candle and is calcined, after on cigarette ash uniform deposition to conductive glass surface, heating cools down again；It will surpass
After hydrophobic material is scattered to the uniform paving of the miscible fluid that solvent is formed on electro-conductive glass after cooling, continue to heat；It is wherein described to lead
Electric glass includes FTO electro-conductive glass or ITO electro-conductive glass, and the super hydrophobic material includes octadecyl trichlorosilane alkane or polytetrafluoro
Ethylene, the solvent include toluene, ethyl alcohol or DMF.
In one possible implementation, the photochemical catalyst includes bismuth tungstate, titanium dioxide, vanadium to above-mentioned composite material
At least one of sour bismuth, zinc oxide, tin oxide；The photochemical catalyst precursor includes in wolframic acid bismuth precursor, vanadic acid bismuth precursor
It is at least one.
In one possible implementation, the wolframic acid bismuth precursor includes bismuth nitrate, bismuth citrate to above-mentioned composite material
At least one of ammonium, bismuth oxide, the wolframic acid bismuth precursor further include sodium tungstate, wolframic acid, 5 (NH4)2O·12WO3·
5H2At least one of O.
In one possible implementation, the fullerene carboxy derivatives include empty fullerene to above-mentioned composite material
Carboxy derivatives or metal fullerene carboxy derivatives, wherein：The empty fullerene carboxy derivatives include C60(C
(COOH)2)n、C70(C(COOH)2)n、C76(C(COOH)2)n、C78(C(COOH)2)n、C84(C(COOH)2)nAt least one of,
The metal fullerene carboxy derivatives include for A2C2@C2m(C(COOH)2)nOr it is B3N@C2m(C(COOH)2)n, wherein A=
At least one of Sc, La, Y；Wherein at least one of B=Sc, La, Y, Ho, Lu, Dy, Er；M=39~44, n=1~4；
Optionally, fullerene carboxy derivatives are C60(C(COOH)2)3。
Above-mentioned composite material in one possible implementation, the photochemical catalyst of fullerene carboxy derivatives modification
Including C60(C(COOH)2)3The bismuth tungstate of modification includes optionally C60(C(COOH)2)3The Bi of modification2WO6。
Above-mentioned composite material in one possible implementation, the photochemical catalyst of fullerene carboxy derivatives modification
It is prepared by the raw material including following material：(1) as the bismuth nitrate and sodium tungstate of wolframic acid bismuth precursor；(2) C60(C
(COOH)2)3.If using the bismuth tungstate and C that prepare60(C(COOH)2)3It is reacted, binding force is weaker, uses wolframic acid
Bismuth precursor and C60(C(COOH)2)3The combination effect reacted is more preferable.
Above-mentioned composite material in one possible implementation, the photochemical catalyst of fullerene carboxy derivatives modification
For C60(C(COOH)2)3The graininess bismuth tungstate of modification is made by method comprising the following steps：By C60(C(COOH)2)3
It is uniformly mixed in ethylene glycol with sodium tungstate with the bismuth nitrate as wolframic acid bismuth precursor, solvent under conditions of 120 DEG C~200 DEG C
Thermal response 12h~for 24 hours；Optionally, solvent thermal reaction 15h is obtained under conditions of 160 DEG C.
Above-mentioned composite material in one possible implementation, C60(C(COOH)2)3The graininess bismuth tungstate of modification
In preparation method, C60(C(COOH)2)3Molar ratio with bismuth nitrate is 1：20~400, it is optionally 1：50~200,1：100~
200 or 1：200；The molar ratio of bismuth nitrate and sodium tungstate is 1.5~2.5：1, it is optionally 2：1；The content of ethylene glycol can fit
Amount selection.
Above-mentioned composite material in one possible implementation, the photochemical catalyst of fullerene carboxy derivatives modification
For C60(C(COOH)2)3The sheet bismuth tungstate of modification is made by method comprising the following steps：By C60(C(COOH)2)3、
Cetyl trimethylammonium bromide (CTAB) and bismuth nitrate as wolframic acid bismuth precursor are uniformly mixed in water with sodium tungstate,
20~26h of hydro-thermal reaction under conditions of 120 DEG C, it is optional for for 24 hours.
Above-mentioned composite material in one possible implementation, C60(C(COOH)2)3The system of the sheet bismuth tungstate of modification
In Preparation Method, C60(C(COOH)2)3Molar ratio with bismuth nitrate is 1：20~400, it is optionally 1：50~200,1：100~
200 or 1：200；The molar ratio of bismuth nitrate and sodium tungstate is 1.5~2.5：1, it is optionally 2：1；Water and cetyl trimethyl
Ammonium bromide can select in right amount.
By the selection of reaction system, such as：The selection of solvent, the selection for whether adding CTAB, heating temperature in reaction system
The selection of degree and heating time, can control C60(C(COOH)2)3The pattern of the bismuth tungstate of modification.Such as：Made using water merely
When for solvent without adding CTAB, the C of acquisition60(C(COOH)2)3The bismuth tungstate of modification is bulk sheet；And use water and
When adding CTAB, the C of acquisition60(C(COOH)2)3The bismuth tungstate of modification is uniform square pieces shape；If using water, use
PVP replaces CTAB, the C of acquisition60(C(COOH)2)3The bismuth tungstate of modification is the Bird's Nest structure of small pieces aggregation.
Above-mentioned composite material in one possible implementation, the photochemical catalyst portion that fullerene carboxy derivatives are modified
Point be covered in super-hydrophobic film surface method be：The photochemical catalyst that fullerene carboxy derivatives are modified is with binder in solvent
In be uniformly mixed, drop coating to super-hydrophobic film surface, removing solvent.
In one possible implementation, the binder includes octadecyl trichlorosilane alkane, gathers above-mentioned composite material
At least one of tetrafluoroethene, Kynoar；It is optionally octadecyl trichlorosilane alkane.
A kind of photochemical catalyst/super-hydrophobic film composite material using the modification of above-mentioned fullerene carboxy derivatives is to organic contamination
The method that object carries out photocatalytic degradation, includes the following steps：
It will be covered with fullerene carboxylic in photochemical catalyst/super-hydrophobic film composite material of above-mentioned fullerene carboxy derivatives modification
Being partially disposed in the water sample containing organic pollution for the photochemical catalyst of radical derivative modification, does not cover fullerene carboxy derivatives
The part of the photochemical catalyst of modification is exposed in air, later use the light containing visible light to the water sample containing organic pollution into
Row irradiation.During laboratory research, the step of being adsorbed under dark condition can be used, is in order to which accurate detection light is urged
Change degradation rate and degradation rate after reaction starts, when practical application in industry is degraded, without being inhaled under dark condition
It is attached, it can further increase degradation rate to degrade in absorption.
The method of above-mentioned photocatalytic degradation in one possible implementation, the organic pollution include rhodamine B,
At least one of methyl orange, methylene blue, quadracycline or acid red.
The method of above-mentioned photocatalytic degradation in one possible implementation, in the water sample containing organic pollution
The content of organic pollution in water is 5~50mg/L.
In one possible implementation, degradation 5~50mg/L organic pollutions need the method for above-mentioned photocatalytic degradation
2~the 10mg/L of photochemical catalyst for wanting fullerene carboxy derivatives to modify, is optionally 3mg/L.
The method of above-mentioned photocatalytic degradation in one possible implementation, the wave band of the visible light be 420nm~
800nm。
In one possible implementation, the illumination containing visible light is mapped to the energy of sample to the method for above-mentioned photocatalytic degradation
Amount can be 5~25mw；Irradiation time containing visible light can be 0.5~3h, be optionally 2h.
Advantageous effect
(1) inventor passes through the photochemical catalyst of the immobilized fullerene carboxy derivatives modification on super-hydrophobic film, structure gas (sky
Gas) Gu-(composite material of photochemical catalyst/super-hydrophobic film of fullerene carboxy derivatives modification)-liquid (contains organic pollution
Water sample) phase reaction catalyst system and catalyzing, water sample, which soaks the fullerene carboxy derivatives that porous super hydrophobic film surface covers, to be modified
Photochemical catalyst so that oxygen is passed through by gas phase without being immersed in inside porous super hydrophobic film and expand inside porous super hydrophobic film
It is scattered to solid-liquid reaction interface, high 4 orders of magnitude of catalyst surface is diffused into from water phase than oxygen, improves the conveying of oxygen
Efficiency, the light induced electron that sufficient oxygen is efficiently captured and generated using photochemical catalyst reduce light induced electron and hole
Recombination probability extends photo-generate electron-hole disengaging time, improves light-catalyzed reaction rate, increases the light of composite material
Absorption region.
(2) sufficient oxygen capture light induced electron can be quickly provided in catalytic reaction process and generate superoxide radical, utilized
The superoxide radical efficient degradation organic contamination of generation, can efficient photocatalytic degradation Some Organic Pollutants at room temperature,
Easy to operate, reaction condition is mild, and method is simply controllable, highly practical, good cycling stability, and catalyst recycling is convenient, weight
After recycling 3 times again, the rate of catalytic degradation organic dyestuff is not substantially reduced.
(3) bismuth tungstate materials band gap is relatively narrow, has characteristic absorption, photoresponse wider range, quantum in visible region
Efficiency is higher, and various structures, controllability is strong, and yield is high, and photochemical stability is good.
(4) fullerene carboxyl derivative structure is stablized, and has characteristic absorption in visible region, photoresponse range is wide, level structure
It is high with bismuth tungstate matching degree, by that in bismuth tungstate surface modification fullerene carboxy derivatives, easy, efficient can realize photoproduction electricity
The separation in son-hole pair, strong operability.
(5) the bismuth tungstate structure of fullerene carboxy derivatives modification produced by the present invention is adjustable, simple production process, condition
Mildly, required equipment investment is few, of low cost, and yield is high, easily operated, is conducive to industrialization large-scale production and popularization.
Description of the drawings
One or more embodiments are illustrated by the picture in corresponding attached drawing, these exemplary theorys
The bright restriction not constituted to embodiment.Dedicated word " exemplary " means " being used as example, embodiment or illustrative " herein.
Any embodiment here as illustrated by " exemplary " should not necessarily be construed as preferred or advantageous over other embodiments.
Figure 1A is C in the embodiment of the present invention 260(C(COOH)2)3The graininess Bi of modification2WO6The composite wood of/super-hydrophobic film
The degradation curve of the different materials photocatalytic degradation rhodamine Bs such as material, wherein：It is dark absorption phase before dotted line, in Figure 1A
C0For the concentration (i.e. 8mg/L) of the rhodamine B aqueous solution of initial formulation, CtIt includes dark absorption phase and light source illumination stage to be
Whole experiment process in the water sample sometime put in rhodamine B concentration；Figure 1B is C in the embodiment of the present invention 260(C
(COOH)2)3The graininess Bi of modification2WO6The different materials photocatalytic degradation rhodamine B such as composite material of/super-hydrophobic film moves
Force diagram, the C in Figure 1B0 lightLuo Dan when to have carried out dark absorption phase, will having started light source illumination stage in water sample
The concentration of bright B, CT lightRhodamine B concentration in the water sample sometime put after starting for light source illumination stage.
Fig. 2A is C in the embodiment of the present invention 260(C(COOH)2)3The graininess Bi of modification2WO6The composite wood of/super-hydrophobic film
The degradation curve of the different materials photo-catalytic degradation of methyl-orange such as material, wherein：It is dark absorption phase before dotted line, the C in Fig. 2A0
For the concentration (i.e. 10mg/L) of the methyl orange aqueous solution of initial formulation, CtIt includes dark absorption phase and light source illumination stage to be
Methyl orange concentration in the water sample sometime put in whole experiment process；Fig. 2 B are C in the embodiment of the present invention 260(C
(COOH)2)3The graininess Bi of modification2WO6The power of the different materials photo-catalytic degradation of methyl-orange such as composite material of/super-hydrophobic film
Learn curve, the C in Fig. 2 B0 lightMethyl orange when to have carried out dark absorption phase, will having started light source illumination stage in water sample
Concentration, CT lightMethyl orange concentration in the water sample sometime put after starting for light source illumination stage.
Fig. 3 A are C in the embodiment of the present invention 260(C(COOH)2)3The sheet Bi of modification2WO6The composite material of/super-hydrophobic film
The degradation curve of equal different materials photocatalytic degradation rhodamine B, wherein：It is dark absorption phase before dotted line, the C in Fig. 3 A0
For the concentration (i.e. 8mg/L) of the rhodamine B aqueous solution of initial formulation, CtIt includes dark absorption phase and light source illumination stage to be
Rhodamine B concentration in the water sample sometime put in whole experiment process；Fig. 3 B are C in the embodiment of the present invention 260(C
(COOH)2)3The sheet Bi of modification2WO6The power of the different materials photocatalytic degradation rhodamine B such as composite material of/super-hydrophobic film
Learn curve, the C in Fig. 3 B0 lightFor the rhodamine B for having carried out when dark absorption phase will start light source illumination stage in water sample
Concentration, CT lightRhodamine B concentration in the water sample sometime put after starting for light source illumination stage.
Fig. 4 A are C prepared by the embodiment of the present invention 160(C(COOH)2)3The graininess Bi of modification2WO6Transmission electron microscope
(TEM) figure；Fig. 4 B are surface Scanning Electron microscope (SEM) figure of super-hydrophobic carbon film prepared by the embodiment of the present invention 1；Fig. 4 C are
C prepared by the embodiment of the present invention 160(C(COOH)2)3The graininess Bi of modification2WO6The surface of the composite material of/super-hydrophobic carbon film
Scanning electron microscope (SEM) figure.
Fig. 5 is the graininess Bi prepared in the embodiment of the present invention 12WO6And C60(C(COOH)2)3The graininess Bi of modification2WO6
X-ray diffractogram (XRD).
Fig. 6 A are the graininess Bi prepared in the embodiment of the present invention 12WO6And C60(C(COOH)2)3The graininess of modification
Bi2WO6The full spectrogram of X-ray photoelectron spectroscopic analysis (the full spectrograms of XPS), Fig. 6 B be graininess Bi2WO6And C60(C(COOH)2)3
The graininess Bi of modification2WO6X-ray photoelectron spectroscopy the fine spectrograms of W4f, Fig. 6 C be C60(C(COOH)2)3Of modification
Granular Bi2WO6X-ray photoelectron spectroscopy the fine spectrograms of C1s.
Fig. 7 is the graininess Bi prepared in the embodiment of the present invention 12WO6、C60And C60(C(COOH)2)3The graininess of modification
Bi2WO6UV-Vis DRS light figure.
Fig. 8 is C prepared by the embodiment of the present invention 160(C(COOH)2)3The sheet Bi of modification2WO6Transmission electron microscope (TEM)
Figure.
Fig. 9 is the sheet Bi prepared in the embodiment of the present invention 12WO6And C60(C(COOH)2)3The sheet Bi of modification2WO6X
X ray diffration pattern x (XRD).
Figure 10 is the sheet Bi prepared in the embodiment of the present invention 12WO6And C60(C(COOH)2)3The sheet Bi of modification2WO6's
The fine spectrograms of O1s of x-ray photoelectron spectroscopy.
Figure 11 is the sheet Bi prepared in the embodiment of the present invention 12WO6、C60(C(COOH)2)3The sheet Bi of modification2WO6Purple
Outside-visible the figure that diffuses.
Figure 12 is graininess Bi in the embodiment of the present invention 12WO6And C60(C(COOH)2)3The graininess Bi of modification2WO6Light
Electric current spectrogram.
Figure 13 is graininess Bi in the embodiment of the present invention 12WO6And C60(C(COOH)2)3The graininess Bi of modification2WO6Electricity
Sub- paramagnetic resonance spectrum figure.
Specific implementation mode
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art
The every other embodiment obtained without creative efforts, shall fall within the protection scope of the present invention.Unless
Separately have it is other explicitly indicate that, otherwise in entire disclosure and claims, term " comprising " or its transformation such as "comprising" or
" including " etc. will be understood to comprise stated element or component, and not exclude other elements or other compositions
Part.
In addition, in order to better illustrate the present invention, numerous details is given in specific implementation mode below.
It will be appreciated by those skilled in the art that without certain details, the present invention can equally be implemented.In some instances, for
Method well known to those skilled in the art, means, element are not described in detail, in order to highlight the purport of the present invention.
The property that fullerene has electron deficient olefins similar, C=C double bonds are easy, by addition, to repair on the carbon cage of fullerene
Some functional moleculars are adornd, the novel substance for having both fullerene and functional molecular characteristic can be obtained, to the dissolving energy of regulatory molecule
Power, level structure, photoelectric properties and biochemical function, such as：Electronic transmission performance between molecule, the electronics occurred in reaction interface
Transfer process etc..Furthermore it is also possible to regulate and control excitation state dynamics by changing Fullerene Carbon cage symmetry and derivatization mode
Property.Compound and crystal the growth with conductor photocatalysis material is may advantageously facilitate, the stabilization chemical bond of formation is conducive to carry
The cyclicity and stability of its high material light catalysis property.Therefore, fullerene is a kind of ideal carrier of photocatalyst.
By the bismuth tungstate of the immobilized fullerene carboxy derivatives modification on super-hydrophobic film, gas-solid-liquid phase reaction is built
Catalyst system and catalyzing makes quickly provide sufficient oxygen capture light induced electron in catalytic reaction process and generates superoxide radical, profit
With the superoxide radical efficient degradation organic contamination of generation, meanwhile, oxygen constantly consumes light induced electron, is conducive to keep photoproduction electric
The compound minimum in son-hole, further increases light-catalyzed reaction rate, has for the practical application of catalysis material important
Meaning.
Fullerene carboxy derivatives C in following embodiment60(C(COOH)2)3Preparation according to Zhu et al. method (reference
Cheng,F.；Yang,X.；Zhu,H.；Sun,J.；Liu,Y.,Synthesis of oligoadducts of malonic
acid C60and their scavenging effects on hydroxyl radical.Journal of Physics
And Chemistry of Solids, 2000,61, (7), 1145-1148.), by 7 μ l DBU (1,8- diazabicylos 11
Carbon -7- alkene) it is dissolved in 2ml toluene, solution A is formed, 7.5 μ l bromo diethyl malonates are dissolved in 2ml toluene, form solution B, it will
10mg C60It is dissolved into 20ml toluene, forms solution C and solution A and B are added dropwise in solution C under stiring, formed mixed
Liquid is closed, mixed liquor room temperature is stirred into 5h at Ar, obtained product carries out isolated C using silicagel column60Three addition carboxylic acids
Ester (C60(C(COOEt)2)3), and 20h is dried in 60 DEG C of vacuum drying chambers after rotating immediately, solid D is obtained, 50mg is then taken
Solid D and 180mg NaH are dissolved in 30ml toluene, and 80 DEG C of mixed liquor stirs 10h at Ar and decomposed, then by 1ml methanol
Be added drop-wise in mixed liquor, add 20ml HCl and be acidified, the precipitation of acquisition is filtered, and successively use toluene, 2M HCl,
H2O, benzene are washed, and finally obtained solid is dissolved into methanol, centrifugation removal solid, then by solution revolving and 50 DEG C
Vacuum drying for 24 hours, obtains fullerene carboxy derivatives C60(C(COOH)2)3。
Embodiment 1C60(C(COOH)2)3The graininess Bi of modification2WO6/ super-hydrophobic carbon film composite material and C60(C
(COOH)2)3The sheet Bi of modification2WO6The preparation of/super-hydrophobic carbon film composite material
(1)C60(C(COOH)2)3The graininess Bi of modification2WO6And C60(C(COOH)2)3The sheet Bi of modification2WO6System
It is standby：
C60(C(COOH)2)3The graininess Bi of modification2WO6Preparation：By five nitric hydrate bismuths of 0.8mmol and 0.4mmol
Disodium tungstate (Na2WO4) dihydrate is added in 20ml ethylene glycol, forms uniform mixed liquor A, by the C of 0.004mmol60(C(COOH)2)3It is added
Into 20ml ethylene glycol, ultrasonic dissolution forms solution B, then solution B is added in above-mentioned mixed liquor A, forms mixed liquor C,
After stirring 1h, mixed liquor C is put into 160 DEG C of heat preservation 15h in 100ml reaction kettles, cools down after reaction and obtains containing C60(C
(COOH)2)3The graininess Bi of modification2WO6Solution, solution centrifugal filtration is first washed with deionized 3 times, then with anhydrous second
Alcohol washs 3 times, and C is obtained after being dried overnight in 80 DEG C of baking ovens60(C(COOH)2)3The graininess Bi of modification2WO6。
C in reaction process60(C(COOH)2)3- COOH group on ethylene glycol-OH groups formed ester bond be connected, second
The Bi that-OH the groups and five nitric hydrate bismuths not being combined on glycol ionize out3+The WO ionized out with Disodium tungstate (Na2WO4) dihydrate4 2-Phase
In conjunction with.
C60(C(COOH)2)3The sheet Bi of modification2WO6Preparation：By two water of 1mmol five nitric hydrate bismuths and 0.5mmol
It closes sodium tungstate to be added in 80ml water, forms uniform mixed liquor, 0.025gCTAB is then added, finally by the C of 0.005mmol60
(C(COOH)2)3It is added in mixed liquor, ultrasonic dissolution, after stirring 1h, mixed liquor is put into 120 DEG C of guarantors in 100ml reaction kettles
Temperature cools down for 24 hours, after reaction to be obtained containing C60(C(COOH)2)3The sheet Bi of modification2WO6Solution, solution centrifugal filtration first uses
Deionized water is washed 3 times, then is washed 3 times with absolute ethyl alcohol, and C is obtained after being dried overnight in 80 DEG C of baking ovens60(C(COOH)2)3It repaiies
The sheet Bi of decorations2WO6。
By the selection of reaction system, such as：The selection of solvent, the selection for whether adding CTAB, heating temperature in reaction system
The selection of degree and heating time, can control C60(C(COOH)2)3The Bi of modification2WO6Pattern.Such as：Use water conduct merely
When solvent is without adding CTAB, the C of acquisition60(C(COOH)2)3The Bi of modification2WO6It is bulk sheet；And using water and add
When adding CTAB, the C of acquisition60(C(COOH)2)3The Bi of modification2WO6It is uniform square pieces shape.
(2) preparation of super-hydrophobic carbon film：
In order by FTO electro-conductive glass water, ethyl alcohol, acetone, isopropanol is cleaned by ultrasonic 30min respectively, to be cleaned clean
Afterwards, FTO electro-conductive glass is put on candle and is calcined, after on cigarette ash uniform deposition to the surfaces FTO, by FTO electro-conductive glass
It is put on 200 DEG C of electric boiling plates and heats a period of time.By miscible (the 1% finger octadecane of 1% octadecyl trichlorosilane alkane and toluene
Base trichlorosilane volume accounts for the 1% of volume of toluene) solution A is formed, taking 60 μ l solution As, uniformly paving is scattered to entire FTO after cooling
On electro-conductive glass (wide 0.9cm* long 4cm), then electro-conductive glass is put on 150 DEG C of electric boiling plates and heats 5h, removed for use.
(3) the immobilized C on super-hydrophobic carbon film60(C(COOH)2)3The graininess Bi of modification2WO6Or C60(C(COOH)2)3It repaiies
The sheet Bi of decorations2WO6：
The immobilized C on super-hydrophobic carbon film60(C(COOH)2)3The graininess Bi of modification2WO6：Take the octadecyl three of 2.8 μ l
Chlorosilane is dissolved into 5ml ethyl alcohol, solution A is formed, then by 10mg C60(C(COOH)2)3The graininess Bi of modification2WO6It is added
Into the ethyl alcohol of 100 μ l, the solution A of 100 μ l is added after ultrasonic disperse is uniform, is formed mixture solution B, is then taken 60 μ l's
Mixture solution B (includes 3mg C60(C(COOH)2)3The graininess Bi of modification2WO6, the 10mg/200 μ μ of l × 60 l=3mg) uniformly
On the 0.9cm*2cm areas (i.e. drop coating area) of super-hydrophobic carbon film obtained by drop coating to step (2), after the solvent is volatilized,
The sample being cured is put into incubated overnight in 110 DEG C of baking oven, obtains C60(C(COOH)2)3The graininess Bi of modification2WO6/ super
The composite material of hydrophobic membrane.
The immobilized C on super-hydrophobic carbon film60(C(COOH)2)3The sheet Bi of modification2WO6：Only use the C of phase homogenous quantities60(C
(COOH)2)3The sheet Bi of modification2WO6Instead of C in the preceding paragraph preparation method60(C(COOH)2)3The graininess Bi of modification2WO6.
In addition, being not added with C60(C(COOH)2)3Under conditions of, Bi is also used in the embodiment2WO6Precursor bismuth nitrate and tungsten
Sour sodium is prepared for graininess Bi2WO6With sheet Bi2WO6, used for follow-up study.The specific method is as follows：
The Disodium tungstate (Na2WO4) dihydrate of five nitric hydrate bismuths of 0.8mmol and 0.4mmol is added in 40ml ethylene glycol, is formed equal
Mixed liquor after stirring 1h, is put into 160 DEG C of heat preservation 15h in 100ml reaction kettles, cools down after reaction and contained by one mixed liquor
Bi2WO6Solution, solution centrifugal filtration is first washed with deionized 3 times, then is washed 3 times with absolute ethyl alcohol, in 80 DEG C of baking ovens
0.4mmol graininess Bi is obtained after being dried overnight2WO6Solid powder.
During the Disodium tungstate (Na2WO4) dihydrate of five nitric hydrate bismuths of 1mmol and 0.5mmol is added in 80ml water, formed uniform mixed
Liquid is closed, 0.025gCTAB is then added, after stirring 1h, mixed liquor is put into 120 DEG C of heat preservations in 100ml reaction kettles and for 24 hours, is reacted
Cooling is obtained containing Bi afterwards2WO6The solution of nanometer sheet, solution centrifugal filtration are first washed with deionized 3 times, then use absolute ethyl alcohol
Washing 3 times, obtains 0.5mmol sheets Bi after being dried overnight in 80 DEG C of baking ovens2WO6。
Embodiment 2C60(C(COOH)2)3The graininess Bi of modification2WO6/ super-hydrophobic carbon film composite material and C60(C
(COOH)2)3The sheet Bi of modification2WO6/ super-hydrophobic carbon film composite material is used as photochemical catalyst
The 2 kinds of composite materials prepared in embodiment 1 are to rhodamine B, methyl orange and quadracycline and other are a variety of organic
There is excellent photocatalysis performance can reach 90% or more degradation in 2h for the degradation of pollutant.Below in conjunction with the accompanying drawings, with
C is shown for photocatalytic degradation rhodamine B, methyl orange and quadracycline60(C(COOH)2)3The graininess Bi of modification2WO6/ super
Hydrophobic carbon film composite material and C60(C(COOH)2)3The sheet Bi of modification2WO6/ super-hydrophobic carbon film composite degradation organic contamination
The effect of object.
Experimental procedure is as follows：It takes water samples of the 2.5ml containing organic pollution to be put into cuvette, will be made in embodiment 1
Good C60(C(COOH)2)3The graininess Bi of modification2WO61, the composite material or C of/super-hydrophobic carbon film60(C(COOH)2)3It repaiies
The sheet Bi of decorations2WO61, the composite material of/super-hydrophobic carbon film is inserted into the cuvette for filling above-mentioned water sample, will be immobilized
Photochemical catalyst (photochemical catalyst, that is, C here60(C(COOH)2)3The graininess Bi of modification2WO6Or C60(C(COOH)2)3Modification
Sheet Bi2WO6) part immerse water sample in, by the super-hydrophobic carbon film of not immobilized photochemical catalyst be partially disposed in water sample liquid level with
On.Then cuvette is put and stands 1h (be directed to graininess) or 0.5h (being directed to sheet) in the dark to adsorb organic pollution,
(it is directed to graininess) per 20min or 10min (being directed to sheet) sampling is examined using Shimadzu UV-2550 ultraviolet-visible spectrophotometers
(Detection wavelength of the absorbance adjusts the absorbance of survey water sample with the difference of the organic pollution of detection.Such as：Detect Luo Dan
When bright B, with the maximum absorption wavelength of rhodamine B；The maximum absorption wavelength of methyl orange is then used when detecting methyl orange), suction to be achieved
After attached balance, with (300W, λ>420nm) xenon-mercury lamp irradiates 2h as visible light source, and (graininess is directed to) or 10min per 20min
The absorbance of sample detection water sample in (being directed to sheet).
Photocatalytic degradation efficiency E is calculated by formula (1).
E=(C0-Ct)/C0× 100% (1)
In formula：C0For the initial absorbance before the water sample degradation containing organic pollution；CtFor the water sample containing organic pollution
Absorbance after product degradation.
It is right respectively using the above method：The rhodamine B aqueous solution of 8mg/L, the methyl orange aqueous solution or 50mg/L of 10mg/L
Quadracycline aqueous solution carried out degradation experiment, it is as a result as follows.
The graininess Bi prepared in embodiment 1 is calculated according to ultraviolet-visible spectrophotometer result2WO6、C60(C
(COOH)2)3The graininess Bi of modification2WO6And C60(C(COOH)2)3The graininess Bi of modification2WO6/ super-hydrophobic carbon film composite wood
Expect the degradation capability of photocatalysis rhodamine B, degradation curve and kinetic curve result are as shown in FIG. 1A and 1B, in visible light
Under irradiation, prepared graininess Bi2WO6Material has certain catalytic activity to photocatalytic degradation rhodamine B, is dropped in 2h
Solution is up to 50% or more；C60(C(COOH)2)3The graininess Bi of modification2WO6The activity of photocatalytic degradation rhodamine B increases,
It is degraded in 2h up to 80% or more, after introducing super-hydrophobic carbon film structure solid-liquid-gas three-phase system, the catalytic activity of material
It is further improved, 90% or more can reach to the degradation of rhodamine B in 2h, with pure graininess Bi2WO6Two-phase system is compared,
Kinetics rate has 3 times or so of raising.
Meanwhile the graininess Bi prepared in embodiment 1 is calculated according to ultraviolet-visible spectrophotometer result2WO6、C60(C
(COOH)2)3The graininess Bi of modification2WO6And C60(C(COOH)2)3The graininess Bi of modification2WO6/ super-hydrophobic carbon film composite wood
Expect the degradation capability of photocatalysis methyl orange, result is as shown in Figure 2 A and 2 B, under visible light illumination, prepared graininess
Bi2WO6It is not high to photo-catalytic degradation of methyl-orange catalytic activity, degrade only up to 30% or so in 2h；C60(C(COOH)2)3Modification
Graininess Bi2WO6The activity of photo-catalytic degradation of methyl-orange increases, and degrades up to 70% or more in 2h, is further drawing
After the hydrophobic carbon film of the excess of imports, 90% or so can reach to the degradation of methyl orange in 2h, with pure Bi2WO6Two-phase system is compared, reaction
Kinetic rate improves 4 times.
C60(C(COOH)2)3The graininess Bi of modification2WO6/ super-hydrophobic carbon film composite material photocatalysis 50mg/L hydrochloric acid Fourth Ring
When the degradation of plain solution, it can also reach the level of 90% or more degradation in 2h.
The sheet Bi prepared in embodiment 1 is calculated according to ultraviolet-visible spectrophotometer result2WO6、C60(C(COOH)2)3
The sheet Bi of modification2WO6And C60(C(COOH)2)3The sheet Bi of modification2WO6/ super-hydrophobic carbon film composite material photocatalysis Luo Dan
The degradation capability of bright B, degradation curve and kinetic curve result are as shown in Figure 3A and Figure 3B, under visible light illumination, made
Standby sheet Bi2WO6There is certain catalytic activity to photocatalytic degradation rhodamine B, degrade up to 60% or more, C in 1h60
(C(COOH)2)3The sheet Bi of modification2WO6The activity of photocatalytic degradation rhodamine B increases, and degrades up to 80% in 1h
More than, after introducing super-hydrophobic film structure solid-liquid-gas three-phase system, the catalytic activity of material is further improved, right in 1h
The degradation of rhodamine B can reach 90% or more, with pure Bi2WO6Two-phase system is compared, and kinetics rate is with 3 times or so
It improves.
Likewise, the quadracycline aqueous solution of the methyl orange aqueous solution or 50mg/L for 10mg/L, C60(C
(COOH)2)3The sheet Bi of modification2WO6/ super-hydrophobic carbon film composite material needs 2h that can degrade methyl orange or quadracycline
90%, and C under the same conditions60(C(COOH)2)3The graininess Bi of modification2WO6/ super-hydrophobic carbon film composite material only needs
50min can reach.
By the degradation curve and kinetic curve of embodiment 2, can significantly it find out, with C60(C(COOH)2)3Modification
Graininess Bi2WO6The composite material of/super-hydrophobic carbon film is compared, C60(C(COOH)2)3The sheet Bi of modification2WO6/ super-hydrophobic carbon
The composite material of film has better catalytic activity, and rhodamine B degradation is up to 90% or more in 50min under visible light, and C60
(C(COOH)2)3The graininess Bi of modification2WO6/ super-hydrophobic carbon film rhodamine B in 50min is only degraded 70%, and rate
It improves.It is relatively thin that this is mainly due to laminated structures, after being optically excited, the light induced electron of the generation institute from internal migration to surface
The distance of process is shorter, reduces the probability with hole-recombination, meanwhile, the sheet Bi of preparation2WO6Material has not coordination completely
Bi ions, during the reaction can directly and C60(C(COOH)2)3In conjunction with, and the C prepared60(C(COOH)2)3The particle of modification
Shape Bi2WO6It is connected by ethylene glycol when material, therefore C60(C(COOH)2)3The sheet Bi of modification2WO6Material more has
It is quickly transferred to C conducive to electronics60On, to achieve the purpose that electron-hole detaches, thus it is more advantageous in effect.
From the above, it can be seen that the introducing of fullerene carboxy derivatives is to Bi2WO6Light-catalyzed reaction have facilitation.
And the Bi for modifying fullerene carboxy derivatives2WO6Gas-solid-liquid phase reaction the light built on super-hydrophobic carbon film is immobilized on to urge
Change system can further improve the rate of light-catalyzed reaction, and oxygen constantly supplements, it is made still may be used under the irradiation of high density light
So that the recombination rate of photo-generate electron-hole is kept minimum for a long time, is of great significance to the practical application of catalysis material.
Embodiment 3
C prepared by 1 step of the embodiment of the present invention (1)60(C(COOH)2)3The graininess Bi of modification2WO6Transmission electron microscope
(tEM) figure is as shown in Figure 4 A, using Flied emission transmission electron microscope JEOL JEM-2100F come the microstructure of test sample,
Operating voltage 160kV, it can be seen that C60(C(COOH)2)3The graininess Bi of modification2WO6Assembled by many little particles, nothing
Fixed pattern.
Surface Scanning Electron microscope (SEM) figure such as Fig. 4 B of super-hydrophobic carbon film prepared by 1 step of the embodiment of the present invention (2)
It is shown, observation analysis is carried out to its pattern under 10kV high pressures using Japanese HITACHI S-4800 scanning electron microscope.It can
To find out, super-hydrophobic carbon film is that have multistage pore passage structure made of the little particle accumulation by many 20nm or so.
C prepared by 1 step of the embodiment of the present invention (3)60(C(COOH)2)3The graininess Bi of modification2WO6/ super-hydrophobic carbon film
Surface Scanning Electron microscope (SEM) figure is as shown in Figure 4 C, it can be seen that is being spotted with C60(C(COOH)2)3The graininess of modification
Bi2WO6Afterwards, the multi-stage artery structure on super-hydrophobic carbon film surface is uniformly covered, and is shown equal on the surface of super-hydrophobic carbon film
One layer of C in even fixation60(C(COOH)2)3The graininess Bi of modification2WO6。
The graininess Bi prepared in the embodiment of the present invention 12WO6And C60(C(COOH)2)3The graininess Bi of modification2WO6XRD
For figure as shown in figure 5, carrying out the test of Sample crystals structure using X-ray diffractometer, the wavelength of X-ray is λ=0.154nm, behaviour
It is 40kV to make voltage, and operation electric current 20mA, sweep speed is 10 °/min, and step width is 0.02 °, and 2 θ scanning ranges are 5-80 °.
From fig. 5, it can be seen that graininess Bi prepared in embodiment 12WO6It is 28.3 ° in 2 θ for orthorhombic crystalline structure, 32.8 °,
Diffraction maximum at 47.2 °, 55.8 °, 58.6 °, 68.8 °, 76.0 °, 78.4 ° and standard card Bi2WO6In (JCPDS 73-2020)
The indices of crystallographic plane are (113), and the diffraction maximum of (200), (220), (313), (226), (400), (139), (420) is corresponding.Simultaneously
As seen from Figure 5, C60(C(COOH)2)3The graininess Bi of modification2WO6Sample diffraction peak position does not change, but peak intensity
It dies down, shows that the introducing of fullerene carboxy derivatives does not destroy original crystal structure, but bearing due to fullerene carboxy derivatives
Carrying capacity is smaller, therefore does not show apparent fullerene characteristic diffraction peak in the composite.
The graininess Bi prepared in the embodiment of the present invention 12WO6And C60(C(COOH)2)3The graininess Bi of modification2WO6Sample
X-ray photoelectron spectroscopy as shown in Fig. 6 A- Fig. 6 C, using ESCALab250Xi multifunctional light electronics energy spectrometer analysis.Excitation
Source is the Al K α X-rays of monochromatization, power about 200W.It is 500 μm to analyze area.Base vacuum when analysis is 3 × 10- 9mbar.As can be seen from Figure 6A, C prepared in embodiment 160(C(COOH)2)3The graininess Bi of modification2WO6Mainly by Bi,
W, O and C element are constituted.Fig. 6 B show, prepared C in embodiment 160(C(COOH)2)3The graininess Bi of modification2WO6Middle W 4f
The combination energy peak of 5/2 and W 4f 7/2 is located at 35.1eV and 37.2eV, it means that W is with the state of+6 valences in crystal knot
Present in structure.With graininess Bi2WO6It compares, due to fullerene carboxy derivatives and Bi2WO6Between interaction, C60(C
(COOH)2)3The graininess Bi of modification2WO6In the peaks W 4f show slight change.Using the signal that deconvolutes after Gauss curve fitting
The C1s for obtaining Fig. 6 C is finely composed, the results showed that, C60(C(COOH)2)3The graininess Bi of modification2WO6XPS figures in C1S combination
284.8,286.0 and 288.8eV can be located at.Wherein the major peaks of C1s are located at 284.8eV, correspond to C60(C
(COOH)2)3On sp2Hydridization carbon, the spike positioned at 286.0eV corresponds to C-O keys, in addition, there is a phase in 288.8eV
To weaker peak, this peak is corresponding with O-C=O keys.Therefore, it is possible to judge that C60(C(COOH)2)3On surface-COOH group
Be combined to form C-O-C=O keys with the-OH groups on ethylene glycol, then, on ethylene glycol be not associated with-OH groups can with it is molten
The Bi ionized out in liquid3+And WO4 2-It is combined, the Bi that ethylene glycol surface combines under heating conditions3+And WO4 2-It generates
Bi2WO6。
The graininess Bi prepared in the embodiment of the present invention 12WO6And C60(C(COOH)2)3The graininess Bi of modification2WO6Purple
Outside-visible the spectrogram that diffuses is as shown in fig. 7, using Shimadzu UV-2550 ultraviolet specrophotometers to the light absorpting ability of sample
It is tested, measurement carries out at room temperature, with BaSO4For reference, measurement wave-length coverage is 220-800nm.It can from Fig. 7
Go out, prepared graininess Bi in embodiment 12WO6There is very high absorption value in the ultraviolet region of 300-400nm, due to
Bi2WO6The band gap of itself is narrow (2.7eV), and valence-band electrons visible light absorbing transits to conduction band, therefore in visible light region
Still there is certain absorption, but absorption intensity is weaker within the scope of 400-800nm.Fullerene C60There is characteristic absorption in visible light region,
There are two more apparent absorption peaks at 450nm and 625nm.We using fullerene visible region characteristic of field absorption,
In Bi2WO6Fullerene is modified in nano material, is conducive to absorption of the reinforcing material in visible light region, improves photo-quantum efficiency.
The results are shown in Figure 7, the graininess Bi of fullerene carboxy derivatives modification2WO6Light absorption spectrogram Uv and visible light area ring
Ying Junyou significantly enhances, and with fullerene carboxy derivatives it is compound after, composite material is expanded in the response of visible region
At 700nm, to showing that the introducing of carboxylated fullerene derivative not only contributes to the separation of photo-generate electron-hole pair, and
And the light abstraction width of composite material can be effectively widened, to improve photo-quantum efficiency.
Embodiment 4
C prepared by 1 step of the embodiment of the present invention (1)60(C(COOH)2)3The sheet Bi of modification2WO6Transmission electron microscope (TEM)
Figure is as shown in figure 8, using Flied emission transmission electron microscope JEOL JEM-2100F come the microstructure of test sample, work electricity
Press 160kV, it can be seen that C60(C(COOH)2)3It modifies in Bi2WO6It is laminated structure after upper.
The sheet Bi prepared in the embodiment of the present invention 12WO6And C60(C(COOH)2)3The sheet Bi of modification2WO6XRD diagram such as
Shown in Fig. 9, the test of Sample crystals structure is carried out using X-ray diffractometer, the wavelength of X-ray is λ=0.154nm, operation electricity
Pressure is 40kV, and operation electric current 20mA, sweep speed is 10 °/min, and step width is 0.02 °, and 2 θ scanning ranges are 10-70 °.From figure
9 can be seen that sheet Bi prepared in embodiment 12WO6It is 28.3 ° in 2 θ for orthorhombic crystalline structure, 32.8 °, 47.2 °,
Diffraction maximum at 55.8 °, 58.6 ° and standard card Bi2WO6(JCPDS73-2020) in the indices of crystallographic plane be (113), (200),
(220), the diffraction maximum of (313), (226) is corresponding.As seen from Figure 9, C has been modified60(C(COOH)2)3Sheet Bi2WO6
Diffraction maximum position does not change, and shows that the introducing of fullerene carboxy derivatives does not destroy original crystal structure, but due to richness
The load capacity for strangling alkene carboxy derivatives is smaller, therefore does not show apparent fullerene characteristic diffraction peak in the composite.
With C60(C(COOH)2)3The sheet Bi of modification2WO6It compares, C60(C(COOH)2)3The sheet Bi of modification2WO6XRD peak types more
It is sharp, it can be shown that prepared C60(C(COOH)2)3The sheet Bi of modification2WO6Crystallinity higher.
The sheet B prepared in the embodiment of the present invention 1i2WO6WithC60(C(COOH)2)3The sheet B of modificationi2WO6X-ray light
Electron spectrum is as shown in Figure 10, using ESCALab250Xi multifunctional light electronics energy spectrometer analysis.Excitaton source is the Al of monochromatization
K α X-rays, power about 200W.It is 500 μm to analyze area.Base vacuum when analysis is 3 × 10-9mbar.It can from Figure 10
Go out, prepared sheet B in embodiment 1i2WO6WithC60(C(COOH)2)3The sheet B of modificationi2WO6Distinguish at the combination energy peak of middle O1s
Positioned at 533.3eV, 531.9eV and 529.9eV, the wherein peak value of O1s is located at 533.3eV, corresponds to the peak of absorption water, is located at
The spike of 531.9eV corresponds to bridging peak hydroxy, in addition, at the peak that 529.9eV occurs, corresponds to the peak of Lattice Oxygen.From
Can significantly find out in Figure 10, with fullerene carboxy derivatives it is compound after,C60(C(COOH)2)3The sheet B of modificationi2WO6's
Peak content at 529.9eV is substantially reduced, this shows that C60 has been doped to sheet Bi2WO6In nanometer sheet, the change of lattice is caused
Change.
The sheet Bi prepared in the embodiment of the present invention 12WO6And C60(C(COOH)2)3The sheet Bi of modification2WO6It is ultraviolet-can
See that the spectrogram that diffuses is as shown in figure 11, the light absorpting ability of sample is carried out using Shimadzu UV-2550 ultraviolet specrophotometers
Test, measurement carries out at room temperature, with BaSO4For reference, measurement wave-length coverage is 220-800nm.It can be seen from figure 11 that real
Apply sheet Bi prepared in example 12WO6There is very high absorption value in the ultraviolet region of 300-400nm, due to Bi2WO6This
The band gap of body is narrow, and valence-band electrons visible light absorbing transits to conduction band, therefore within the scope of the 400-800nm of visible light region
Still there is certain absorption, but absorption intensity is weaker.In sheet Bi2WO6Upper modification fullerene carboxy derivatives, are conducive to strengthening material
Expect the absorption in visible light region, improves photo-quantum efficiency.As a result as shown in figure 11, the sheet of fullerene carboxy derivatives modification
Bi2WO6Light absorption spectrogram have an apparent enhancing in visible region response, and with fullerene carboxy derivatives it is compound after, it is compound
Material expands in the response of visible region, to show that the introducing of carboxylated fullerene derivative not only contributes to light induced electron-
The separation in hole pair, and the light abstraction width of composite material can be effectively widened, to improve photo-quantum efficiency.
Embodiment 5
C60(C(COOH)2)3The graininess Bi of modification2WO6Photoelectric current property research
Photoelectric current is tested using three-electrode system, and using Pt pieces as to electrode, calomel is as reference electrode, the sample of preparation
For product electrode as working electrode, electrolyte is the Na of 0.5mol/L2SO4Solution, (300W, λ>420nm) xenon-mercury lamp is as visible light
Light source, the bias of additional 0.4V.
Graininess Bi prepared by the embodiment of the present invention 12WO6And C60(C(COOH)2)3The graininess Bi of modification2WO6Light
Map of current is as shown in figure 12, uses (300W, λ>420nm) xenon-mercury lamp irradiates, and Electron absorption energy is excited in material valence band
Conduction band generates photo-generate electron-hole pair, and outside plus under the bias effect of 0.4V, light induced electron is transferred to Pt pieces from working electrode
Electrode generates current signal, and the current signal of the more voluminous life of light induced electron is stronger；When closing light source, electron-hole is compound,
Current signal disappears.It can be clearly seen that by Figure 12, under excited by visible light, C60(C(COOH)2)3The graininess of modification
Bi2WO6The photo-signal of generation is when electric current is stablized up to 100nA/cm2, with pure graininess Bi2WO6(50nA/cm2) compare,
With stronger photo-signal, show the introducing of fullerene carboxy derivatives, promotes point of electron-hole in composite material
From, to produce more light induced electrons, meanwhile, by Figure 12 it is observed that under the excitation of light repeatedly, fullerene carboxyl spreads out
The graininess Bi of bio-modification2WO6Photoresponse current signal may remain in 90nA/cm2More than, show that composite material has
Good photochemical stability.
Embodiment 6
C60(C(COOH)2)3The graininess Bi of modification2WO6Electronic transfer process research (ESR), steps are as follows：
The graininess Bi for taking 10mg embodiments 1 to prepare2WO6Sample and 10mg C60(C(COOH)2)3The graininess of modification
Bi2WO6Sample is dissolved in respectively in 0.5ml methanol, forms mixed liquor A and B, then takes DMPO and the 0.5ml methanol of 12.5ul mixed again
It is molten, it forms solution C and takes 50ulA or 50ulB to be mixed with 50ulC when test sample superoxide radical generates, form mixed liquor, it will
Mixed liquor is placed in capillary, it is seen that light (λ>It 420nm) irradiates, electron paramagnetic resonance spectrum (EPR) (ESR) property of test sample.This
Graininess Bi prepared by inventive embodiments 12WO6And C60(C(COOH)2)3The graininess Bi of modification2WO6Electron paramagnetic resonance
Wave spectrum (ESR) as shown in figure 13, in (λ>420nm) under radiation of visible light, specimen material generates photo-generate electron-hole pair, electronics
Superoxide radical can be generated with the oxygen interaction in methanol.The characteristic of oxygen radical can be captured using DMPO, DMPO can
Capture O2 -Form DMPO-O2 -, electron paramagnetic resonance can be detected, to obtain electron paramagnetic resonance spectrum (EPR) and to sample
Product electronic transfer process is studied, as a result as shown in figure 13.As shown in Figure 13, with graininess Bi2WO6It compares, C60(C
(COOH)2)3The graininess Bi of modification2WO6Electron paramagnetic resonance is stronger, therefore shows to produce more superoxide radicals, by
This can be seen that with fullerene carboxy derivatives it is compound after, material will generate more electronics under visible light illumination, therefore, can
To determine that the introducing of fullerene carboxy derivatives affects the electronic transmission performance between molecule, make electronics that electronics occur at interface
Transfer process changes the band structure of composite material, promotes the separation of photo-generate electron-hole, for promoting photocatalytic
There can be positive effect.
Embodiment 7
To C in embodiment 160(C(COOH)2)3The graininess Bi of modification2WO6Or C60(C(COOH)2)3The sheet of modification
Bi2WO6Upper C60(C(COOH)2)3Load capacity be optimized, i.e., bismuth nitrate and C are selected in preparation process60(C
(COOH)2)3Molar ratio control C60(C(COOH)2)3Load capacity, respectively in C60(C(COOH)2)3With mole of bismuth nitrate
Than being 1：400,1:200,1:133,1:100,1:50 (corresponding with load capacity 0.5%, 1%, 1.5%, 2% and 4% respectively)
Under conditions of reacted, other steps and condition are same as Example 1.It is unrestrained according to UV, visible light in embodiment 3 and embodiment 4
The method of reflection spectrum detection is detected, it can be seen that C from UV-vis DRS spectrum60(C(COOH)2)3Load
Amount is higher, and the absorption in visible light region is bigger.But be detected according to the detection method of photoelectric current in embodiment 5, it finds
In C60(C(COOH)2)3Molar ratio with bismuth nitrate is 1：Under conditions of 200, i.e., load capacity 1% when, C60(C(COOH)2)3Modification
Graininess Bi2WO6Or C60(C(COOH)2)3The sheet Bi of modification2WO6Upper C60(C(COOH)2)3Electron-hole separation effect
Fruit is best, and the promotion of photoelectric current is most apparent, when load is fewer or more, photocurrent variations all unobvious.
It is detected according to the method for carrying out ESR spectrum in embodiment 6, in C60(C(COOH)2)3Molar ratio with bismuth nitrate is 1：200
Under conditions of, i.e., load capacity 1% when, the rising of corresponding superoxide radical is most apparent.When load capacity is not up to 1%, drop
Solution rate increases with load capacity and is increased, and when load capacity is more than 1%, degradation rate increases with load capacity and reduced, so C60
(C(COOH)2)3The graininess Bi of modification2WO6Or C60(C(COOH)2)3The sheet Bi of modification2WO6Upper C60(C(COOH)2)3It is negative
Carrying capacity 1% is optimal.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, it will be understood by those of ordinary skill in the art that：It still may be used
With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features；
And these modifications or replacements, various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (14)
1. a kind of photochemical catalyst/super-hydrophobic film composite material of fullerene carboxy derivatives modification, including super-hydrophobic film, described super
It is covered with to the surface portion of hydrophobic membrane the photochemical catalyst of fullerene carboxy derivatives modification, the fullerene carboxy derivatives are repaiied
The photochemical catalyst of decorations is prepared by the raw material including following material：(1) in photochemical catalyst and photochemical catalyst precursor at least
It is a kind of；(2) fullerene carboxy derivatives.
2. photochemical catalyst/super-hydrophobic film composite material of fullerene carboxy derivatives modification according to claim 1, feature
It is, the super-hydrophobic film includes at least one in super-hydrophobic carbon film, super-hydrophobic silica film, super-hydrophobic metal oxide film
Kind；It is optionally super-hydrophobic carbon film.
3. photochemical catalyst/super-hydrophobic film composite material of fullerene carboxy derivatives modification according to claim 1, feature
It is, the super-hydrophobic carbon film is the electro-conductive glass that surface is covered with super hydrophobic material, wherein the super hydrophobic material includes ten
Eight alkyltrichlorosilanes or polytetrafluoroethylene (PTFE), the electro-conductive glass include FTO electro-conductive glass or ITO electro-conductive glass.
4. photochemical catalyst/super-hydrophobic film composite material of fullerene carboxy derivatives modification according to claim 1, feature
It is, the photochemical catalyst includes at least one of bismuth tungstate, titanium dioxide, pucherite, zinc oxide, tin oxide；The light
Catalyst precarsor includes at least one of wolframic acid bismuth precursor, vanadic acid bismuth precursor.
5. photochemical catalyst/super-hydrophobic film composite material of fullerene carboxy derivatives modification according to claim 1, feature
It is, the wolframic acid bismuth precursor includes at least one of bismuth nitrate, bismuth and ammonium citrate, bismuth oxide, before the bismuth tungstate
Body further includes sodium tungstate, wolframic acid, 5 (NH4)2O·12WO3·5H2At least one of O.
6. photochemical catalyst/super-hydrophobic film composite material of fullerene carboxy derivatives modification according to claim 1, feature
It is, the fullerene carboxy derivatives include empty fullerene carboxy derivatives or metal fullerene carboxy derivatives, wherein：
The empty fullerene carboxy derivatives include C60(C(COOH)2)n、C70(C(COOH)2)n、C76(C(COOH)2)n、C78(C
(COOH)2)n、C84(C(COOH)2)nAt least one of, the metal fullerene carboxy derivatives include for A2C2@C2m(C
(COOH)2)nOr it is B3N@C2m(C(COOH)2)n, wherein at least one of A=Sc, La, Y；Wherein B=Sc, La, Y, Ho,
At least one of Lu, Dy, Er；M=39~44, n=1~4；Optionally, fullerene carboxy derivatives are C60(C
(COOH)2)3。
7. photochemical catalyst/super-hydrophobic film composite material of fullerene carboxy derivatives modification according to claim 1, feature
It is, the photochemical catalyst of the fullerene carboxy derivatives modification includes C60(C(COOH)2)3The bismuth tungstate of modification, it is optional to wrap
Include C60(C(COOH)2)3The Bi of modification2WO6。
8. photochemical catalyst/super-hydrophobic film composite material of fullerene carboxy derivatives modification according to claim 1, feature
It is, the photochemical catalyst of the fullerene carboxy derivatives modification is prepared by the raw material including following material：(1) conduct
The bismuth nitrate and sodium tungstate of wolframic acid bismuth precursor；(2) C60(C(COOH)2)3。
9. photochemical catalyst/super-hydrophobic film composite material of fullerene carboxy derivatives modification according to claim 1, feature
It is, the photochemical catalyst of the fullerene carboxy derivatives modification is C60(C(COOH)2)3The graininess bismuth tungstate of modification leads to
Method comprising the following steps are crossed to be made：By C60(C(COOH)2)3With the bismuth nitrate as wolframic acid bismuth precursor with sodium tungstate in second
It is uniformly mixed in glycol, the solvent thermal reaction 12h~for 24 hours under conditions of 120 DEG C~200 DEG C；Optionally, in 160 DEG C of condition
Lower solvent thermal reaction 15h is obtained.
10. photochemical catalyst/super-hydrophobic film composite material of fullerene carboxy derivatives modification according to claim 1, special
Sign is that the photochemical catalyst of the fullerene carboxy derivatives modification is C60(C(COOH)2)3The sheet bismuth tungstate of modification leads to
Method comprising the following steps are crossed to be made：By C60(C(COOH)2)3, cetyl trimethylammonium bromide (CTAB) and as wolframic acid
The bismuth nitrate of bismuth precursor is uniformly mixed in water with sodium tungstate, and 20~26h of hydro-thermal reaction under conditions of 120 DEG C is optionally
24h。
11. according to photochemical catalyst/super-hydrophobic film composite material of the fullerene carboxy derivatives modification of claim 9 or 10,
It is characterized in that, C60(C(COOH)2)3The graininess bismuth tungstate and C of modification60(C(COOH)2)3The system of the sheet bismuth tungstate of modification
In Preparation Method, C60(C(COOH)2)3Molar ratio with bismuth nitrate is 1：20~400, it is optionally 1：50~200,1：100~
200 or 1：200；The molar ratio of bismuth nitrate and sodium tungstate is 1.5~2.5：1, it is optionally 2：1.
12. a kind of photochemical catalyst/super-hydrophobic film using one of the claim 1-11 fullerene carboxy derivatives modifications is multiple
The method that condensation material carries out photocatalytic degradation to organic pollution, includes the following steps：By one of the claim 1-11 richnesses
Strangle the light that the modification of fullerene carboxy derivatives is covered in photochemical catalyst/super-hydrophobic film composite material of alkene carboxy derivatives modification
Catalyst is partially disposed in the water sample containing organic pollution, does not cover the photochemical catalyst of fullerene carboxy derivatives modification
Part is exposed in air, is irradiated later to the water sample containing organic pollution using the light containing visible light.
13. according to the method for photocatalytic degradation described in claim 12, which is characterized in that the organic pollution includes rhodamine
B, at least one of methyl orange, methylene blue, quadracycline or acid red.
14. according to the method for photocatalytic degradation described in claim 12, which is characterized in that the water sample containing organic pollution
The content of middle organic pollution in water is 5~50mg/L；Degradation 5~50mg/L organic pollutions need fullerene carboxyl to derive
2~10mg/L of photochemical catalyst of object modification, is optionally 3mg/L.
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