CN102258992A - Surface iron modified titanium dioxide photocatalyst as well as preparation method and application thereof - Google Patents
Surface iron modified titanium dioxide photocatalyst as well as preparation method and application thereof Download PDFInfo
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- CN102258992A CN102258992A CN 201110170381 CN201110170381A CN102258992A CN 102258992 A CN102258992 A CN 102258992A CN 201110170381 CN201110170381 CN 201110170381 CN 201110170381 A CN201110170381 A CN 201110170381A CN 102258992 A CN102258992 A CN 102258992A
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- iron
- titanium dioxide
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- photocatalyst
- catalyst
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 220
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 118
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- -1 iron modified titanium dioxide Chemical class 0.000 title abstract description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 181
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 64
- 239000002131 composite material Substances 0.000 claims abstract description 37
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims description 31
- 238000004380 ashing Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 230000015556 catabolic process Effects 0.000 claims description 12
- 238000006731 degradation reaction Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 230000001699 photocatalysis Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 6
- 238000007146 photocatalysis Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000005416 organic matter Substances 0.000 claims description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 125000004494 ethyl ester group Chemical group 0.000 claims description 3
- 150000002898 organic sulfur compounds Chemical class 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 11
- 239000010936 titanium Substances 0.000 abstract description 11
- 229910052719 titanium Inorganic materials 0.000 abstract description 11
- 230000000593 degrading effect Effects 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 150000002989 phenols Chemical class 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 239000012046 mixed solvent Substances 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 125000001424 substituent group Chemical group 0.000 abstract description 2
- 230000007704 transition Effects 0.000 abstract description 2
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 abstract 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 238000010304 firing Methods 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 9
- 238000001354 calcination Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229960005191 ferric oxide Drugs 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- 238000005303 weighing Methods 0.000 description 6
- 238000004435 EPR spectroscopy Methods 0.000 description 5
- 238000001237 Raman spectrum Methods 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 238000001362 electron spin resonance spectrum Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 241000894007 species Species 0.000 description 3
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 2
- 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 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 241000720974 Protium Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 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 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
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- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
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Abstract
The invention provides a surface iron modified titanium dioxide photocatalyst comprising titanium dioxide powder and/or film, wherein a highly-dispersive iron oxygen compound is contained in the surface of the titanium dioxide powder and/or film. The invention also provides a preparation method of the photocatalyst, comprising the steps of: adsorbing the iron phthalocyanine in a solution to the surface of the titanium dioxide through taking pre-burnt titanium dioxide as a titanium source, taking macromolecule iron phthalocyanine with different substituent groups as an iron source and taking water-organic solvent as a mixed solvent, firing at a specific temperature so as to destroy a ring structure of phthalocyanine, removing carbon, nitrogen, oxygen and hydrogen elements except the iron element in iron phthalocyanine molecule and finally obtaining the composite photocatalyst. The invention also provides application of the photocatalyst and the photocatalyst can be used for degrading phenol and chlorinated phenol organics by utilizing ultraviolet light. The photocatalyst provided by the invention has the advantages that raw materials are easy to get, the preparation method is simple, compared with a blank titanium dioxide photocatalyst, the iron modified titanium dioxide photocatalyst has obviously increased activity and the stability of the photocatalyst is good to ensure that phenomenons of salvation and form transition of iron do not happen in reaction processes.
Description
Technical field
The invention belongs to the photocatalyst technology field, relate to a kind of titania surface method of modifying, provided a kind of surperficial iron more specifically and modified the preparation method of titania photocatalyst and the purposes of ultraviolet catalytic degradation of organic substances.
Background technology
Enter 21 century, the environment and the energy become the significant problem that the mankind face and need to be resolved hurrily, exhausted day by day at traditional energies such as oil, coals, today that living environment constantly worsens, light-catalyzed reaction relies on the reaction condition and the application fields of its huge energy potentiality, gentleness and the degree of depth more to be subjected to people's attention.Since the eighties in 20th century, obtained the development of advancing by leaps and bounds aspect the processing of photocatalysis multiple pollutant in to water and gas phase, photocatalysis technology is more and more in the application study of field of environment protection.
Semiconductor light-catalyst causes that with its high activity, low cost, good stability people pay attention to greatly and research interest, is a kind of new material that great potential is arranged.Go through nearly 40 years studies show that, TiO
2It is present only environment-friendly type photochemical catalyst.But limited to by the character of itself, the commercialization process is very slow at present, and it is quite big to apply difficulty on a large scale.Weak point mainly shows this several aspects: (1) TiO
2Energy gap is about 3.2eV, thus can only be by less than the ultraviolet excitation below the 380nm, and this part energy only accounts for and reaches about 5% of earth surface solar radiation; (2) quick compound between charge carrier makes that the quantum yield be used for organic matter degradation is very low, be not higher than 20% usually, so the practical efficiency of solar energy has only about 1%.
In order to improve the photocatalysis efficiency of titanium dioxide, people adopt multiple means that it is improved, and mainly concentrate on the preparation of ad hoc structure and the modification of composition.Utilizing ferro element to come modified titanic oxide is one of more common method, and main according to having: (1) iron resource is abundant and with low cost; (2) by the band edge coupling between the compound, titanium dioxide surface independent F e
x O
y Bunch can promote separation of charge; When (3) hydrogen peroxide exists, can regenerate by the Fenton reaction after ferric iron is reduced by conduction band electron, and this process is accompanied by the generation of the hydroxyl radical free radical of strong oxidizing property.The preparation of this class composite catalyst mainly contains two kinds of approach, a kind of is to utilize sol-gel or hydro-thermal method that iron compound is inserted in the titanium dioxide lattice, another kind is by surface impregnation or sedimentation the oxide of iron to be coated to titanium dioxide surface, yet all more or less there are some defectives in these methods.At first, people's multiselect usefulness inorganic molysite such as iron chloride, ferric nitrate, ferric sulfate etc. are as source of iron at present, in the doping iron ion, can not guarantee that the anion in the substrate can be removed fully, there is report to point out that some anion might have the cancellation effect to active specy such as hydroxyl radical free radical, thereby weakened the photocatalytic activity of titanium dioxide itself.Secondly, composite catalyst need carry out high temperature sintering usually and improve degree of crystallinity, but the optimum temperature during for the corresponding separately the highest photolytic activity of titanium dioxide and iron oxide is but different, and this just makes people produce contradiction when discussion temperature effect.In addition, at high temperature ferro element can separate with titanium dioxide and forms independently crystalline phase, as Fe
2O
3And Fe
2TiO
5, from the titanium oxide to Fe
2O
3Or Fe
2TiO
5Electric charge shift the photolytic activity may weaken titanium oxide itself.The 3rd, whether can improve or reduce the concentration of oxygen defect for the doping of iron ion in the oxide lattice, also there is dispute at present.In addition, iron can cause Fe usually in the excessive or unequal loading of titania surface
x O
y Bunch gathering, and the dissolving of iron in the aqueous solution also is inevitably in the light-catalyzed reaction process, these phenomenons all are unfavorable for the recycling of the transfer of electronics and sample.
?
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of surperficial iron modified titanic oxide photochemical catalyst of highlight catalytic active.
The present invention addresses the above problem the technical scheme of being taked: it comprises titania powder and/or film, and described titania powder and/or film surface contain the iron oxide of high degree of dispersion.
The present invention can also adopt following further technical scheme: described iron oxide is with Fe (III)
x O
y Grid configuration is distributed in titanium dioxide surface, and wherein iron is trivalent, and accounting for mass fraction in composite photo-catalyst is 0 ~ 10 %.
Described titanium dioxide is the mixing of one or both or three kinds in Detitanium-ore-type, rutile-type, the brookite type.
The source of iron presoma of described iron oxide is wherein any one or two or three mixing of carboxyl FePC, phosphate FePC, carboxylic acid, ethyl ester base FePC.
Another technical problem to be solved by this invention is to provide a kind of preparation method of above-mentioned surperficial iron modified titanic oxide photochemical catalyst.
The present invention addresses the above problem the technical scheme of being taked: described preparation method is an absorption-ashing two-step method, may further comprise the steps when using titania powder and/or film:
(1), under the room temperature, will be in advance 400 ~ 1200 ℃ down burnt titania powders and/or film drop in the deionized water, ultrasonic 5 minutes, obtain finely dispersed titanium dioxide suspension and/or film;
(2), the source of iron presoma with described iron oxide adds in the solvent, or solvent is joined in the source of iron presoma of described iron oxide, obtain source of iron solution, described solvent is acetone, pyridine, nitrobenzene, chloronaphthalene, the concentrated sulfuric acid, N, the mixing of one or both in dinethylformamide (DMF), the dimethyl sulfoxide (DMSO) (DMSO);
(3), guarantee the lucifuge environment, under the vigorous stirring, the source of iron solution that step (2) is obtained adds in step (1) obtained the titanium dioxide suspension and/or film, or titanium dioxide suspension and/or film that step (1) is obtained, join in the source of iron solution that step (2) obtains, continue to stir 12 hours;
(4), after step (3) reaches adsorption equilibrium, with suspension and/or film suction filtration and/or taking-up, deionized water washing filter residue to organic solvent-free exists, 30 ~ 120 ℃ of oven dry filter residues;
(5), collect powder and/or film sample that step (4) obtains, 300 ~ 900 ℃ of following ashing 5 minutes ~ 20 hours;
(6), collect powder sample and/or film that step (5) obtains, promptly get the titanium dioxide composite photocatalyst of surperficial iron modification.
A technical problem more to be solved by this invention is to provide a kind of purposes of above-mentioned surperficial iron modified titanic oxide photochemical catalyst, is used for ultraviolet degradation phenol and chlorinated phenol type organic.
The present invention addresses the above problem the technical scheme of being taked: described catalyst can photocatalysis to degrade organic matter, for example phenol, arene, organic sulfur compound etc. under ultraviolet light.
The present invention can also adopt following further technical scheme: in the light-catalyzed reaction process, behind the hydrogen peroxide that adding 0.5 ~ 20.0 mM is every liter, the degradation rate of organic matter under ultraviolet light is higher than aerial speed.
The present invention compares with existing method, have that raw material is easy to get, the preparation method is simple, can control advantage such as trace iron modification, compare with blank titanium dioxide, iron is modified the back photocatalyst activity and is significantly increased, and the dissolving and the form transition phenomenon of iron do not take place in having good stability of photochemical catalyst in the course of reaction.
Description of drawings
Fig. 1 is the structural representation of surperficial iron modified titanic oxide composite photo-catalyst.
Fig. 2 is the electron paramagnetic resonance spectrum figure of sample among the embodiment 1, and wherein (a)-(c) is the titanium dioxide sample of modifying through surperficial iron, and pretreatment temperature is respectively 400,600,800 ℃, (a ')-(c ') be corresponding blank titanium dioxide sample.
Fig. 3 is the Raman spectrum of sample among the embodiment 2, and wherein (a)-(c) is the titanium dioxide sample of modifying through surperficial iron, and the ashing temperature is respectively 300,500,700 ℃.
Fig. 4 is the electron paramagnetic resonance spectrum figure of sample among the embodiment 2, and wherein (a)-(c) is the titanium dioxide sample of modifying through surperficial iron, and the ashing temperature is respectively 300,500,700 ℃.
Fig. 5 is the Raman spectrum of sample among the embodiment 3, wherein in (a)-(c) iron content be respectively 0,0.071,0.34wt%.
Fig. 6 is the electron paramagnetic resonance spectrum figure of sample among the embodiment 3, wherein in (a)-(g) iron content be respectively 0,0.014,0.036,0.071,0.14,0.21,0.34wt%.
Fig. 7 is the embodiment 1 phenol degrading first order kinetics constant during for photochemical catalyst.
Fig. 8 is the embodiment 2 phenol degrading first order kinetics constant during for photochemical catalyst.
Fig. 9 is embodiment 3 phenol and the 4-chlorophenol degraded first order kinetics constant during for photochemical catalyst.
The iron content that Figure 10 obtains for embodiment 3 is the circulation experiment of 0.071wt% photochemical catalyst degradation of phenol under ultraviolet light.
The iron content that Figure 11 embodiment 3,4 obtains is 0.071wt% photochemical catalyst phenol concentration change curve in time under ultraviolet light.(a, a ') blank TiO
2, (b, b ') blank TiO
2+ 10mM H
2O
2, (c, c ') Fe/TiO
2, (d, d ') Fe/TiO
2+ 10mM H
2O
2Rutile TiO
2(solid, a-d) with commodity Detitanium-ore-type TiO
2(hollow, a '-d ').
The specific embodiment
The invention provides a kind of surperficial iron modified titanic oxide photochemical catalyst, it comprises titanium dioxide powder particle or film, and iron is in the titanium dioxide surface high degree of dispersion, with Fe (III)
x O
y Grid configuration exists.Concrete structure is with reference to accompanying drawing 1.Wherein 1 is the titanium dioxide powder particle, the 2nd, and the iron oxide of surface mesh trellis.
Compare with blank titanium dioxide, physical propertys such as the degree of crystallinity of this composite photo-catalyst, crystalline phase composition, average grain diameter, pore structure and specific area do not change, but the active of ultraviolet catalytic degradation of phenol and chlorophenol type organic obviously improves.Through after the long-time illumination, this composite photo-catalyst stable in properties, good reproducibility, and iron titania surface not recurring structure change or dissolution phenomena.In addition, when containing hydrogen peroxide in the system, light-catalyzed reaction speed further improves.
The present invention also provides a kind of preparation method of surperficial iron modified titanic oxide photochemical catalyst, i.e. absorption-ashing two-step method.Concrete measure is: with burnt titanium dioxide in advance is the titanium source, the big molecule FePC of different substituents is a source of iron, with water-organic solvent is mixed solvent, after FePC in the solution is adsorbed to titanium dioxide surface, calcination is to destroy the phthalocyanine ring structure under specified temp, remove the carbon except that ferro element, nitrogen, oxygen, protium in the FePC molecule, under the prerequisite that does not change physical propertys such as the degree of crystallinity of titanium dioxide own, crystalline phase composition, average grain diameter, pore structure and specific area, finally obtain this composite photo-catalyst.
Traditional method mainly contains sol-gel process, hydro-thermal method, surface impregnation or sedimentation, compares with these methods, and this method is easy and simple to handle, process is easy to control, and is repeatable high, and iron is in the titania surface high degree of dispersion, be difficult for reuniting, be specially adapted to the modification of trace iron.Specific embodiment is as follows:
With commodity anatase titanium dioxide (CAT) is the titanium source, and carboxyl FePC (FeTCPc) is a source of iron, adopts absorption-ashing method, the composite photo-catalyst that pretreated titanium dioxide is modified through surperficial iron under the preparation different temperatures.
The first step under the room temperature, takes by weighing 0.250g in advance at 3 hours CAT of certain temperature lower calcination, and temperature is specifically as follows 400,500,600,700,800,900 ℃, drops in the 225mL deionized water, makes it to be uniformly dispersed in ultrasonic 5 minutes;
Second step guaranteed the lucifuge environment, under the vigorous stirring, was that solvent strength is that the FeTCPc solution of 100ppm joins in the titanium oxide suspension that the first step obtains with DMF with 25mL, continued lucifuge and stirred 12 hours;
In the 3rd step, FeTCPc can be adsorbed onto the CAT surface fully, the suction filtration suspension, and spend deionised water to having the DMF existence, 70 ℃ of lucifuges oven dry;
The 4th step, collect the solid sample in the 3rd step, place Muffle furnace to carry out ashing at 400 ℃;
The 5th step, collect the solid sample in the 4th step, grind into powder obtains the composite photo-catalyst that pretreated titanium dioxide is modified through surperficial iron under the different temperatures, is designated as Fe400/CAT
X1(
X1Be the titanium dioxide pretreatment temperature).
The 6th step, copied for first to the 5th step, use not the blank solvent of ferric source that commodity CAT is carried out the processing of same procedure, obtain blank titanium dioxide, be designated as 400/CAT
X1(
X1Be the titanium dioxide pretreatment temperature).
The sample segment that obtains has been carried out electron paramagnetic resonance (EPR) characterized, the result is with reference to accompanying drawing 2.The narrow peak at g ~ 2.0 places is the outer Fe of skeleton normally
3+Produce, near the broad peak g ~ 2.0 then is Fe
x O
y (hydroxyl) oxide cluster characteristic peak of oligomer or iron illustrates that iron evenly distributes with ferric iron oxygen compound form on the CAT surface.Along with the CAT pretreatment temperature raises, the iron of equivalent changes in the dispersiveness on surface.
With commodity anatase titanium dioxide (CAT) is the titanium source, and carboxyl FePC (FeTCPc) is a source of iron, adopts absorption-ashing method, prepares the surperficial iron modified titanic oxide composite photo-catalyst of different ashing Temperature Treatment.
The first step under the room temperature, takes by weighing 0.250g in advance at 3 hours CAT of 600 ℃ of calcinings, drops in the 225mL deionized water, makes it to be uniformly dispersed in ultrasonic 5 minutes;
The second and the 3rd step is with embodiment 1;
The 4th step, collect the solid sample in the 3rd step, place Muffle furnace under certain temperature, to carry out ashing, temperature is specifically as follows 300,400,500,600,700 ℃;
The the 5th and the 6th step obtained the surperficial iron modified titanic oxide and the blank titanium dioxide sample of different ashing Temperature Treatment with embodiment 1, was designated as Fe respectively
X2/ CAT600 and
X2/ CAT600(
X2Be the ashing temperature).
The sample segment that obtains has been carried out Raman spectrum and electron paramagnetic resonance (EPR) sign, and the result is respectively with reference to accompanying drawing 3 and accompanying drawing 4.When the ashing temperature was 300 and 500 ℃, (hydroxyl) oxide of iron and/or the eigen vibration peak of ferrotitanium hydrochlorate did not appear in the Raman spectrum of sample, when rising to 700 ℃, and 227 and 294 cm
-1Two new vibration peak have appearred in the place, with α-Fe
2O
3Characteristic peak conform to.This presentation of results is that the iron high degree of dispersion assembles forming α-Fe in the CAT surface in the composite catalyst of source of iron preparation after the high temperature ashing with FeTCPc
2O
3Nano particle.Electron paramagnetic resonance is the result also illustrate, along with the rising of ashing temperature, iron increases the weight of in the gathering on CAT surface.
With commodity anatase titanium dioxide (CAT) is the titanium source, and carboxyl FePC (FeTCPc) is a source of iron, adopts absorption-ashing method, prepares the surperficial iron modified titanic oxide composite photo-catalyst of different iron contents.
The first step is with embodiment 1;
Second step guaranteed the lucifuge environment, under the vigorous stirring, was that the FeTCPc solution of solvent concentration joins in the titanium dioxide suspension that the first step obtains with the pyridine with 25mL, continued lucifuge and stirred 12 hours.FeTCPc (DMF) concentration can be specially 0,20,50,80,100,120,150,180,200,250,300,500ppm;
The the 3rd to the 5th step obtained the surperficial iron modified titanic oxide composite photo-catalyst of different iron contents with embodiment 1, was designated as Fe400/CAT600.Wherein the mass fraction of iron in solid be specially 0,0.014,0.036,0.057,0.071,0.085,0.11,0.12,0.14,0.17,0.21,0.34wt%.
The sample segment that obtains has been carried out Raman spectrum and electron paramagnetic resonance (EPR) sign, and the result is respectively with reference to accompanying drawing 5 and accompanying drawing 6.Along with the increase of iron content, anatase is at 517cm
-1Characteristic peak be split into 514 and 533cm
-1Two peaks are in addition at 776cm
-1New vibration peak has appearred, and the ferriferous oxide crystal or the ferrotitanium hydrochlorate of these emerging vibration peak and existing report and misfit, we fail to find the standard substance that conforms to.The characteristic signal of g in the EPR spectrogram ~ 2 place's iron species is not only strengthened along with the increase of iron content, also broadens thereupon, and this illustrates TiO
2The size of surface iron species is in continuous increase.
With self-control rutile titanium dioxide (SRT) is the titanium source, and carboxyl FePC (FeTCPc) is a source of iron, adopts absorption-ashing method, prepares the composite photo-catalyst that different crystalline phase titanium dioxide are modified through surperficial iron.
The first step under the room temperature, takes by weighing 0.250g in advance at 3 hours rutile titanium dioxide of 600 ℃ of calcinings, drops in the 225mL deionized water, makes it to be uniformly dispersed in ultrasonic 5 minutes;
Second to the 6th step obtained the composite photo-catalyst that rutile titanium dioxide is modified through surperficial iron with embodiment 1, was designated as Fe400/SRT600.
With the brookite type titanium dioxide is the titanium source, and carboxyl FePC (FeTCPc) is a source of iron, adopts absorption-ashing method, prepares the composite photo-catalyst that different crystalline phase titanium dioxide are modified through surperficial iron.
The first step under the room temperature, takes by weighing 0.250g in advance at 3 hours titanium dioxide of 600 ℃ of calcinings, drops in the 225mL deionized water, makes it to be uniformly dispersed in ultrasonic 5 minutes;
Second to the 6th step obtained the composite photo-catalyst that brookite type titanium dioxide is modified through surperficial iron with embodiment 1.
With commodity P25 type titanium dioxide (P25) is the titanium source, and carboxyl FePC (FeTCPc) is a source of iron, adopts absorption-ashing method, prepares the composite photo-catalyst that different crystalline phase titanium dioxide are modified through surperficial iron.
The first step under the room temperature, takes by weighing 0.250g in advance at 3 hours titanium dioxide of 600 ℃ of calcinings, drops in the 225mL acetone deionized water, makes it to be uniformly dispersed in ultrasonic 5 minutes;
Second to the 6th step obtained the composite photo-catalyst that P25 type titanium dioxide is modified through surperficial iron with embodiment 1, was designated as Fe400/P25 (600).
Embodiment 7
With the good anatase titanium dioxide film of prepared beforehand is the titanium source, and carboxyl FePC (FeTCPc) is a source of iron, adopts absorption-ashing method, the composite photo-catalyst that preparation film-type titanium dioxide is modified through surperficial iron.
The first step under the room temperature, takes by weighing 0.250g in advance at 3 hours anatase titanium dioxide film of 600 ℃ of calcinings, drops in the 225mL deionized water;
Second step to the 5th step is with embodiment 1, but notes after the ashing not ground sample, to guarantee the integrality of film, obtains the composite photo-catalyst that film-type titanium dioxide is modified through surperficial iron.
Embodiment 8
With commodity anatase titanium dioxide (CAT) is the titanium source, adopts absorption-ashing method, prepares the composite photo-catalyst of the surperficial iron modification of different sources of iron.
The first step is with embodiment 2;
Second step guaranteed the lucifuge environment, under the vigorous stirring, was that solvent strength is that the source of iron solution of 100ppm joins in the titanium oxide suspension that the first step obtains with nitrobenzene with 25mL, continued lucifuge and stirred 12 hours.Wherein the source of iron material can be specially phosphate FePC and carboxylic acid, ethyl ester base FePC;
The the 3rd to the 5th step obtained the surperficial iron modified titanic oxide composite photo-catalyst of different sources of iron with embodiment 1.
With commodity anatase titanium dioxide (CAT) is the titanium source, and carboxyl FePC (FeTCPc) is a source of iron, and dimethyl sulfoxide (DMSO) (DMSO) is the source of iron solvent, adopts absorption-ashing method, prepares the titanium dioxide composite photocatalyst that surperficial iron is modified.
The first step is with embodiment 2;
Second step guaranteed the lucifuge environment, under the vigorous stirring, was that solvent, concentration are that the FeTCPc solution of 100ppm joins in the titanium oxide suspension that the first step obtains with DMSO with 25mL, continued lucifuge and stirred 12 hours;
The the 3rd to the 5th step obtained the surperficial iron modified titanic oxide composite photo-catalyst of different source of iron solvents with embodiment 1.
The present invention also provides the purposes of above-mentioned surperficial iron modified titanic oxide photochemical catalyst, is used for ultraviolet degradation phenol and chlorinated phenol type organic.Promptly in air atmosphere or after adding hydrogen peroxide, with phenol, chloro phenols, arene, inorganic sulphide and organic sulfur compound etc. is the degraded substrate, the surface iron modified titanic oxide is a photochemical catalyst, high-pressure sodium lamp is a light source, with the UV-irradiation Pyrex glass reactor of wavelength greater than 320nm, sampling at regular intervals detects concentration of substrate, characterizes the photocatalytic activity of this composite photo-catalyst.
The surperficial iron modified titanic oxide photochemical catalyst that said method is obtained is used for different light-catalyzed reactions, the assessment photocatalyst activity.Test condition is: ultraviolet source is the 375W high-pressure sodium lamp, radiation dominant wavelength 365nm, and light source and Pyrex glass reactor all have the condensed water chuck.Add the substrate solution of 50mL 40ppm in the reactor, catalyst quality is 0.050g, carries out illumination after first lucifuge magnetic agitation 1h reached adsorption equilibrium after reactant mixed.After illumination begins, at regular intervals, pipette the 2mL suspension, filter membrane (aperture 0.22 μ m) filters, and filtrate carries out qualitative and quantitative analysis with high performance liquid chromatography (HPLC).Analysis condition is: Dionex P680 type HPLC, and UV-detector UVD 170U, Apollo C18 reversed-phase column, flowing is methyl alcohol: water=3:2 mutually, contains 1 ‰ acetate, flow velocity 1.0mL/min detects wavelength 280nm.
Concrete application result is as follows:
Application examples 1
Surperficial iron modified titanic oxide that obtains with embodiment 1 and corresponding blank titanium dioxide carry out the ultraviolet catalytic degraded of phenol in the air atmosphere as photochemical catalyst, investigate the effect of titanium dioxide calcining heat.The first order kinetics speed constant of phenol degrading all is 700 ℃ with reference to the optimum calcinating temperature of 7, two kinds of photochemical catalysts of accompanying drawing, but 600 ℃ the time sample photocatalytic activity after iron is modified to improve effect the most obvious.
Application examples 2
Surperficial iron modified titanic oxide that obtains with embodiment 2 and corresponding blank titanium dioxide carry out the ultraviolet catalytic degraded of phenol in the air atmosphere as photochemical catalyst, investigate the ashing Temperature Influence.The first order kinetics speed constant of phenol degrading is with reference to accompanying drawing 8, and this temperature value does not almost have influence to the photocatalytic activity of blank titanium dioxide, and the best ashing temperature of the titanium dioxide that iron is modified is 400 ℃.
Application examples 3
The surperficial iron modified titanic oxide that obtains with embodiment 3 is as photochemical catalyst, carries out the ultraviolet catalytic degraded of phenol and 4-chlorophenol in the air atmosphere, investigates the influence of iron content.The first order kinetics speed constant of two kinds of degradation of substrates is with reference to accompanying drawing 9, and along with the rising of iron content, speed constant rises earlier and afterwards descends, and best iron content is 0.071wt%.
Application examples 4
The iron content that obtains with embodiment 3 is the surperficial iron modified titanic oxide photochemical catalyst of 0.071wt%, carries out the circulation experiment of phenol degrading in the air atmosphere, with reference to accompanying drawing 10.Through four circulations, the degradation rate of phenol has only the slack-off of not half.This may be because sample analysis makes the minimizing of catalytic amount and the competitive reaction of intermediate product cause.Generally speaking, the photocatalysis property of this surperficial iron modified titanic oxide photochemical catalyst under long-time illumination is very stable.
Application examples 5
The surperficial iron modified titanic oxide that obtains with embodiment 3,4 is as photochemical catalyst, and iron content is 0.071wt% in the sample, contains in air atmosphere or in the system under the condition of hydrogen peroxide, carries out the degradation experiment of phenol.Hydrogen peroxide is after suspension lucifuge stirring and adsorbing balance, add before the illumination, and concentration is 10.0mM.The concentration changes with time curve of phenol under different photochemical catalyst effects is with reference to accompanying drawing 11.In the air atmosphere, compare with blank titanium dioxide sample, the degradation rate of anatase titanium dioxide phenol behind finishing iron is obviously accelerated, and rutile titanium dioxide activity after iron is modified slightly reduces on the contrary.After adding hydrogen peroxide, the phenol degrading speed under all samples effect is all significantly accelerated, and the raising of surperficial iron modified titanic oxide activity is then more obvious, and the effect of rutile even also better than anatase.
The above-mentioned specific embodiment is used for the present invention that explains; only be the preferred embodiments of the present invention; rather than limit the invention; in the protection domain of spirit of the present invention and claim; any modification that the present invention is made, be equal to replacement, improvement etc., all fall into protection scope of the present invention.
Claims (7)
1. titanium dioxide composite photocatalyst that surperficial iron is modified, it is characterized in that: it comprises titania powder and/or film, described titania powder and/or film surface contain the iron oxide of high degree of dispersion.
2. according to the described composite photo-catalyst of claim 1, it is characterized in that: described iron oxide is with Fe (III)
x O
y Grid configuration is distributed in titanium dioxide surface, and wherein iron is trivalent, and accounting for mass fraction in composite photo-catalyst is 0 ~ 10 %.
3. according to the composite photo-catalyst of claim 1, it is characterized in that: described titanium dioxide is the mixing of one or both or three kinds in Detitanium-ore-type, rutile-type, the brookite type.
4. according to the composite photo-catalyst of claim 1 or 2, it is characterized in that: the source of iron presoma of described iron oxide is wherein any one or two or three mixing of carboxyl FePC, phosphate FePC, carboxylic acid, ethyl ester base FePC.
5. the preparation method of the composite photo-catalyst of a claim 1, it is characterized in that: described preparation method is an absorption-ashing two-step method, may further comprise the steps when using titania powder and/or film:
(1), under the room temperature, will be in advance 400 ~ 1200 ℃ down burnt titania powders and/or film drop in the deionized water, ultrasonic 5 minutes, obtain finely dispersed titanium dioxide suspension and/or film;
(2), the source of iron presoma with described iron oxide adds in the solvent, or solvent is joined in the source of iron presoma of described iron oxide, obtain source of iron solution, described solvent is acetone, pyridine, nitrobenzene, chloronaphthalene, the concentrated sulfuric acid, N, the mixing of one or both in dinethylformamide (DMF), the dimethyl sulfoxide (DMSO) (DMSO);
(3), guarantee the lucifuge environment, under the vigorous stirring, the source of iron solution that step (2) is obtained adds in step (1) obtained the titanium dioxide suspension and/or film, or titanium dioxide suspension and/or film that step (1) is obtained, join in the source of iron solution that step (2) obtains, continue to stir 12 hours;
(4), after step (3) reaches adsorption equilibrium, with suspension and/or film suction filtration and/or taking-up, deionized water washing filter residue to organic solvent-free exists, 30 ~ 120 ℃ of oven dry filter residues;
(5), collect powder and/or film sample that step (4) obtains, 300 ~ 900 ℃ of following ashing 5 minutes ~ 20 hours;
(6), collect powder sample and/or film that step (5) obtains, promptly get the titanium dioxide composite photocatalyst of surperficial iron modification.
6. the purposes of the titanium dioxide composite photocatalyst of the surperficial iron modification of a claim 1 is characterized in that described catalyst can photocatalysis to degrade organic matter, for example phenol, arene, organic sulfur compound etc. under ultraviolet light.
7. according to the purposes of the described composite photo-catalyst of claim 6, it is characterized in that: in the light-catalyzed reaction process, behind the hydrogen peroxide that adding 0.5 ~ 20.0 mM is every liter, the degradation rate of organic matter under ultraviolet light is higher than aerial speed.
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