CN109174075A - A kind of rare-earth element modified titanium dioxide nano photocatalysis material and preparation method thereof for photocatalytic degradation VOCs - Google Patents
A kind of rare-earth element modified titanium dioxide nano photocatalysis material and preparation method thereof for photocatalytic degradation VOCs Download PDFInfo
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- CN109174075A CN109174075A CN201811026084.0A CN201811026084A CN109174075A CN 109174075 A CN109174075 A CN 109174075A CN 201811026084 A CN201811026084 A CN 201811026084A CN 109174075 A CN109174075 A CN 109174075A
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- titanium dioxide
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 295
- 239000000463 material Substances 0.000 title claims abstract description 165
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 113
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 31
- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 12
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract 16
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 226
- 239000012046 mixed solvent Substances 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000011259 mixed solution Substances 0.000 claims abstract description 44
- 238000001354 calcination Methods 0.000 claims abstract description 32
- 239000010936 titanium Substances 0.000 claims abstract description 28
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001868 water Inorganic materials 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 530
- 239000011248 coating agent Substances 0.000 claims description 153
- 238000000576 coating method Methods 0.000 claims description 153
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 123
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 84
- 230000015556 catabolic process Effects 0.000 claims description 79
- 238000006731 degradation reaction Methods 0.000 claims description 79
- 235000019441 ethanol Nutrition 0.000 claims description 68
- 238000003756 stirring Methods 0.000 claims description 53
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 46
- 229910052691 Erbium Inorganic materials 0.000 claims description 44
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000006555 catalytic reaction Methods 0.000 claims description 23
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000002086 nanomaterial Substances 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 8
- 230000002779 inactivation Effects 0.000 claims description 8
- 229910052775 Thulium Inorganic materials 0.000 claims description 5
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 5
- -1 rare-earth salt Chemical class 0.000 claims description 5
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 150000001345 alkine derivatives Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- 238000010422 painting Methods 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 235000010215 titanium dioxide Nutrition 0.000 description 210
- 239000004408 titanium dioxide Substances 0.000 description 203
- 239000007789 gas Substances 0.000 description 90
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 55
- 229960004756 ethanol Drugs 0.000 description 50
- 239000011941 photocatalyst Substances 0.000 description 50
- 239000012071 phase Substances 0.000 description 40
- 238000002474 experimental method Methods 0.000 description 37
- 230000003197 catalytic effect Effects 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 33
- 239000000843 powder Substances 0.000 description 33
- 229910052724 xenon Inorganic materials 0.000 description 31
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 31
- 238000005286 illumination Methods 0.000 description 29
- 239000011521 glass Substances 0.000 description 28
- 239000000758 substrate Substances 0.000 description 28
- 238000000498 ball milling Methods 0.000 description 26
- 238000001548 drop coating Methods 0.000 description 26
- 238000012360 testing method Methods 0.000 description 26
- 239000008367 deionised water Substances 0.000 description 25
- 229910021641 deionized water Inorganic materials 0.000 description 25
- 238000001291 vacuum drying Methods 0.000 description 24
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 description 20
- 238000000227 grinding Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 10
- 239000003344 environmental pollutant Substances 0.000 description 10
- 231100000719 pollutant Toxicity 0.000 description 10
- 239000000356 contaminant Substances 0.000 description 8
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- 238000005516 engineering process Methods 0.000 description 6
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- 239000002957 persistent organic pollutant Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 229910003087 TiOx Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
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- 238000006243 chemical reaction Methods 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000001782 photodegradation Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- 241000208340 Araliaceae Species 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 2
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 2
- 235000003140 Panax quinquefolius Nutrition 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
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- 241000282461 Canis lupus Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910003089 Ti–OH Inorganic materials 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical class [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
- 210000000133 brain stem Anatomy 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
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- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
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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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- 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
- B01J23/90—Regeneration or reactivation
- B01J23/92—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The rare-earth element modified titanium dioxide nano photocatalysis material and preparation method thereof that the present invention relates to a kind of for photocatalytic degradation VOCs, the preparation method include: (1) by the uniformly mixing of pure and mild acid, obtain mixed solvent；(2) gained in the mixed solvent is dispersed by titanium source and water is added dropwise, obtain mixed solution A；(3) rare earth source is added in gained mixed solution A again, obtains mixed solution B；(4) gained mixed solution B is stirred 0.5~5 hour at normal temperature, obtains colloidal sol；(5) by gained drying sol and calcining, then it is ground, obtain rare-earth element modified titanium dioxide nano photocatalysis material.
Description
Technical field
The present invention relates to a kind of rare-earth element modified titanium dioxide nano photocatalysis materials and preparation method thereof to drop with it
The application for solving volatile organic gaseous contamination object in air, belongs to gaseous environment photocatalysis technology field.
Background technique
Air pollution problems inherent is on the rise in recent years, threatens human health and Environmental security.Wherein, nitrogen oxides, sulphur
Oxide, volatility organic pollutant (VOCS) it is major pollutants.According to the definition of the mechanisms such as the World Health Organization, VOCs
Refer to boiling point at 50 DEG C -250 DEG C, saturated vapor pressure is more than 133.32Pa at room temperature, is present in sky in vapour form at normal temperature
A type organic in gas, volatile organic matter (VOCs) are done great harm to human body, and the certain density VOCs short time can hurt
The liver of victimization, kidney, brain and nervous system.Part VOCs such as benzene, toluene and formaldehyde have been cited as carcinogen.In addition,
VOCs becomes in the atmospheric environment of oxidisability and forms PM2.5Precursor.Therefore, low concentration in atmospheric environment how is realized
The degradation of VOCs to guarantee environment safety, human health and inhibit haze take place frequently with important research value (reference literature 1,
Document 2).
In existing VOCs degradation technique, thermocatalytic technology need hot conditions, ozonation technology it is toxic and unstable,
Adsorption technology cannot effectively degrade VOCs the deficiencies of place limit their applications in VOCs, and photocatalysis technology have it is anti-
Answer mild condition, can directly utilize solar energy, depth mineralising pollutant and it is substantially without secondary pollution the advantages that become and most answer
With one of the environmentally protective air purifying process of prospect.Titanium dioxide because have physicochemical properties stablize, low cost, safety with
And the advantages such as nontoxic, become the commercial photochemical catalyst being most widely used at present, and be successfully applied to water pollutant and consolidated
Determine the degradation (reference literature 3,4) of phase gas pollutant.Compared with water pollutant and stationary phase are degraded, practical indoor and outdoor surroundings
In volatile gaseous pollutant have the characteristics that flowing is fast, concentration is low, small with catalyst contact time section, area, therefore, how
Using optically catalytic TiO 2 performance, efficient degradation VOCs polluted gas, there is important application value.
Rare earth element is a kind of transition state element with special 4f electronic structure for modifying titanium dioxide, then can be with two
Electronics transfer is carried out between titanium oxide, promotes the separation of electron hole pair, to improve the photocatalysis performance of material, another party
Face, rare earth element have Upconversion luminescence, i.e., launch the light of higher energy under near-infrared or excited by visible light, therefore will
Rare earth is to TiO2It is modified, TiO can be widened2The efficiency of light energy utilization is improved in extinction area, further promotes photocatalytic activity (reference
Document 5,6).Therefore, how rare-earth element modified photocatalysis material of titanium dioxide is utilized, promotes its absorption to target contaminant
Ability is realized under visible light effectively degradation gas phase target contaminant, is had in terms of purifying air using photocatalysis technology
Important application value.
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nanostructures to what extent do metal nanoparticles improve the
photocatalytic activity of TiO2Films? The Journal of Physical Chemistry B
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Ag@TiO2core-shell composite clusters under UV-irradiation.Journal of the
American Chemical Society 2005,127,3928-3934.；
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lanthanide doped nanoparticles.Chemical Society Reviews 2015,44,4922-4952.；
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Summary of the invention
In view of the above-mentioned problems, the purpose of the present invention is to provide a kind of rare-earth element modified titanium dioxide nano photocatalysis materials
Material and preparation method thereof, another object of the present invention is to provide a kind of rare-earth element modified titanium dioxide nano photocatalysis materials
Application in low concentration pollution gas purification.
In a first aspect, the present invention provides a kind of preparation sides of rare-earth element modified titanium dioxide nano photocatalysis material
Method, comprising:
(1) by the uniformly mixing of pure and mild acid, mixed solvent is obtained；
(2) gained in the mixed solvent is dispersed by titanium source and water is added dropwise, obtain mixed solution A；
(3) rare earth source is added in gained mixed solution A again, obtains mixed solution B；
(4) gained mixed solution B is stirred 0.5~5 hour at normal temperature, obtains colloidal sol；
(5) by gained drying sol and calcining, then it is ground, obtain rare-earth element modified titanium dioxide nano photocatalysis material
Material.
In the present invention, the in the mixed solvent containing pure and mild acid is dispersed by titanium source and stir 10~20min, then with dropwise addition
A certain amount of water is added in form, obtains mixed solution A.(i.e. water is stirred secondly, rare earth source is added in mixed solution A again
Solution preocess).Water can provide oxygen donor and generate bridging oxygen key-O- in hydrolytie polycondensation in hydrolytic process, and alcohol plays dispersion in a solvent
Effect can be such that metal ion in rare earth source and titanium source disperses more uniform with alcohol, and crystal form is more intact, sour conduct in a solvent
Complexing agent, i.e., the H formed under acid condition again3O+(OR) can be replaced3Part alkoxy grp (OR) in Ti-OH is in-Ti-
Complex reaction occurs for OH, forms colloidal sol.Since acid also reacts to form gel with alcohol esterification, will have during gained drying sol
The effect of template, i.e. induced product form chain or highly cross-linked reticular structure.By gained gel again through calcination processing, most
The rare-earth element modified titanium dioxide with excellent properties such as high-specific surface area, particle size are small and particle diameter distribution is uniform is obtained eventually
Titanium nano-photocatalyst material.Wherein dominant mechanism (1) titanium source hydrolyzes to form colloidal sol: nTi (OR)4+4nH2O→nTi(OH)4+
4nHOR；(2) polycondensation reaction of Titanium alkoxides: nTi (OH)4→nTiO2+2n H2O。
Preferably, the alcohol is at least one of ethyl alcohol, methanol, isopropanol, ethylene glycol, n-butanol, n-hexyl alcohol；It is described
Acid is at least one of acetic acid, propionic acid, citric acid.
Preferably, the titanium source is the compound of hydrolyzable titaniferous, preferably isopropyl titanate, butyl titanate, titanium tetrachloride
At least one of.
Preferably, the volume ratio of the water, pure and mild acid is 1:(5~50): (1~20), preferably 1:(10~20): (2~
10), more preferably 1:(5~20): (1~8), most preferably 1:(10~15): (2~5).Water, alcohol are utilized in hydrolytic process
With the mixed solvent of acid, water provides oxygen donor and generates bridging oxygen key-O- in hydrolytie polycondensation, and alcohol plays dispersion in a solvent, uses
It is more uniform that alcohol can be such that metal ion disperses, and crystal form is more intact, and acid is used as complexing agent in a solvent, forms colloidal sol, simultaneously
Due to reacting to form gel with alcohol esterification in forming gel process, there is template.
Preferably, the addition rate of the water be 0.01~0.5ml/ seconds, preferably 0.05~0.5ml/ seconds, more preferably
0.05~0.1ml/ seconds.It is beneficial to that rear-earth-doped uniform and particle size distribution is prepared within the scope of above-mentioned drop rate
Uniform titanium dioxide granule.
Preferably, the rare earth source is the soluble nitrate containing at least one of Yb, Er, Tm, Pr, Ho element,
Preferably at least one of rare earth nitrades, rare earth nitrades hydrate.
Preferably, the titanium source and the molar ratio of water are 1:(3~50).
Preferably, the molar ratio of the rare earth source and titanium source is (0.001~0.10): 1, preferably (0.0025~
0.015):1。
Preferably, the temperature of the stirring is 20~30 DEG C, the time is 0.5~5 hour, is beneficial to obtain rear-earth-doped equal
Even titanium dioxide granule.
Preferably, the temperature of the drying is 40~120 DEG C, the time is 5~30 hours；The temperature of the calcining is 200
~800 DEG C, the time is 0.5~5.5 hour.
Second aspect, the present invention also provides a kind of rare-earth element modified nano titanias prepared according to the above method
Catalysis material, the molar ratio of rare earth element and titanium dioxide in the rare-earth element modified titanium dioxide nano photocatalysis material
For (0.001~0.10): 1, preferably (0.0015~0.015): 1.
Preferably, the partial size of the rare-earth element modified titanium dioxide nano photocatalysis material be 3~40nm, preferably 8
~15nm.
The third aspect, the present invention also provides one kind to be received by the rare-earth element modified titanium dioxide of claim 11 or 12
The catalysis material coating of rice material preparation, the thickness of the coating can be 0.1~100 μm, preferably 10~50 μm.
Fourth aspect, the present invention also provides a kind of rare-earth element modified titanium dioxide nano materials to wave in photocatalytic degradation
Application in hair property organic compound, the rare-earth element modified titanium dioxide nano photocatalysis material is in 320~1100nm wave
Long, the lower degradation and removal that can be achieved to volatile organic compounds VOCs of 50~1000W power light irradiation.
In light-catalyzed reaction, gas phase system and liquid-phase system have difference substantially, this is mainly derived from goal response
Contact difference, intermediate active substance difference etc. of the object with catalyst surface.In gaseous environment, catalyst is stationary phase, air
In goal response object be flowing gas phase, and the first step for being catalyzed reaction is adsorption reaction object, therefore photocatalyst applications are in gas
Phase contaminant degradation difficult point first is that realizing absorption to goal response object.The inventors discovered that by rare-earth element modified titanium dioxide
Titanium Application of micron can effectively improve the absorption to vapor phase contaminants in vapor phase contaminants degradation, because passing through rare earth member
Element makes it have biggish specific surface area to titania modified, may be implemented and promotes material to gaseous-phase organic pollutant molecule
Absorption.In addition, rare earth element (for example, Yb, Er, Tm, Pr, Ho etc.) has light induced electron because of its special 4f electronic structure
There is good transferance, therefore light induced electron and the compound of hole are inhibited, and make more light induced electrons by catalyst
The oxygen reduction on surface is at superoxide radical.Therefore rare-earth element modified titanium dioxide nano photocatalysis material is applied to gas phase
Contaminant degradation has good advantage.Wherein, the present invention is based on the photoproduction inspired in rare earth modified titanium deoxide catalyst
Electronics and hole, the quantity and the cost in practical application for generating light induced electron and hole pair.The wavelength of light first is shorter, energy
Amount is higher, more easy excitated light induced electron and hole active specy out, secondly the shorter light induced electron inspired of wavelength of light and sky
Cave quantity is more, power under the same conditions, the shorter degradation rate that can make volatile organic matter of wavelength increases, but wavelength is got over
It is short larger to the production cost of human injury and light, in conclusion the wavelength of event preferably light is in 320~1100nm；In addition,
The power of light is bigger under identical optical wavelength, and luminous flux is bigger, so that degradation rate increases, conversely, the power of light is smaller, and luminous flux
Reduce, so that degradation rate declines, but optical power is excessive, and the production cost increases, in conclusion therefore the power of preferably light 50~
1000W。
Preferably, the volatile organic compounds VOCs is formaldehyde, acetaldehyde, benzene, toluene, ortho-xylene, alkene, alkynes
At least one of hydrocarbon, aromatic hydrocarbon, concentration are 1~1000ppm.
5th aspect, the present invention also provides a kind of rare-earth element modified titanium dioxide nano materials and rare-earth element modified
Regeneration method after the catalysis material coating inactivation of titanium dioxide nano material preparation, the rare earth element after inactivation is changed
Property titanium dioxide nano photocatalysis material or rare-earth element modified titanium dioxide nano material preparation catalysis material apply stratification
It in air atmosphere, is irradiated 0.5~5 hour under the ultraviolet light of 50~1000W, so that rare-earth element modified two after inactivation
TiOx nano catalysis material can restore its photo-catalysis capability.
In the disclosure, it using sol-gal process, is arrived rare earth doped in titanium dioxide lattice, to obtain rare earth
Element modified titanium dioxide nano photocatalysis material, while by adjusting rare earth element and TiO2Different molar ratios is adjusted
The photocatalytic activity of the rare-earth element modified titanium dioxide nano photocatalysis material, to obtain the optimal institute of photocatalytic activity
State rare-earth element modified titanium dioxide nano photocatalysis material.And by it using photocatalytic degradation second under ultraviolet light and visible light
The volatile organic compounds such as aldehyde, ortho-xylene, it was demonstrated that such material can degrade low concentration VOCs effectively to purify air.
The present invention has a characteristic that
(1) rare earth element with special 4f electronic structure is modified photocatalysis material of titanium dioxide by the present invention, success
It is prepared for the rare-earth element modified titanium dioxide nano photocatalysis material for being bigger serface and high catalytic performance, rare earth
The special 4f electronic structure of element can effectively realize light induced electron water conservancy diversion, the light induced electron energy in titanium dioxide in the presence of one side
On effective mobility to the special 4f track of element, to inhibit the compound of photo-generate electron-hole pairs, it can promote under illumination condition
The material system generates more living radicals, improves photohole and electronics utilization rate；Another aspect bigger serface energy
Absorption of the material for organic pollutant is enough greatly promoted, so that the local concentration of organic pollutant is improved, to improve
The photocatalytic activity of photocatalysis material of titanium dioxide；
(2) present invention prepares rare earth Er modifying titanium dioxide nano-photocatalyst material by sol-gal process, quickly and easily makes
For with high catalytic activity, the rare earth Er modifying titanium dioxide nano-photocatalyst material that suction-operated is strong, visible light-responded.This
Present invention is simple and easy, lower to experiment condition requirement, and experimental raw is cheap and easy to get, and molecule is obtained in the very short time
Horizontal uniformity realizes the Uniform Doped on molecular level, and energy conservation and environmental protection, low in cost, and yield is high, it can be achieved that big rule
Mould production application；
(3) present invention prepared by rare-earth element modified titanium dioxide nano photocatalysis material can effectively degrade low concentration flowing
The volatile organic compounds such as phase acetaldehyde, ortho-xylene gas, the photocatalytic degradation with higher under ultraviolet light and visible light
Performance.In terms of removal haze precursor pollutant, industrial organic pollutant and indoor polluted gas with wide before
Scape；
(4) present invention prepared by rare-earth element modified titanium dioxide nano photocatalysis material chemical stability it is good, repeatedly into
Preferable photocatalytic activity is still able to maintain after row photocatalytic degradation vapor phase contaminants；And good biocompatibility, it is non-hazardous to environment.
Detailed description of the invention
Fig. 1 is the SEM figure of the pure titinium dioxide sample prepared in comparative example 1；
Fig. 2 is the SEM figure of the rare earth Er modifying titanium dioxide nano-photocatalyst material prepared in embodiment 1-5；
Fig. 3 is the TEM figure of the rare earth Er modifying titanium dioxide material prepared in embodiment 5；
Fig. 4 is the rare earth Er modifying titanium dioxide nano-photocatalyst material prepared in embodiment 1-5 and prepares in comparative example 1 pure
The XRD diagram of titanium oxide；
Fig. 5 is the rare earth Er modifying titanium dioxide nano-photocatalyst material prepared in embodiment 1-5 and prepares in comparative example 1 pure
The Raman of titanium oxide schemes；
Fig. 6 is the catalysis material of different rare earth Er modifying titanium dioxide material molar ratios in comparative example 1,5 and embodiment 1-5
The coating of preparation respectively under 20sccm gas flow rate, ultraviolet light conditions aldehydes gas degradation curve；
Fig. 7 is the photocatalysis material of different rare earth Er modifying titanium dioxide material molar ratios in comparative example 2,6 and embodiment 6-10
Expect the coating of preparation respectively in 20sccm gas flow rate, it is seen that the degradation curve of aldehydes gas under the conditions of light；
Fig. 8 is the catalysis material of different rare earth Er modifying titanium dioxide material molar ratios in comparative example 3 and embodiment 11-14
The coating of preparation respectively under 20sccm gas flow rate, ultraviolet light conditions ortho-xylene gas degradation curve；
Fig. 9 be in embodiment 20 the rare earth Er modifying titanium dioxide material for preparing under ultraviolet irradiation condition to mobile phase acetaldehyde
Recycle degradation curve；
Figure 10 is the coating of rare earth Er modifying titanium dioxide nano-photocatalyst material preparation in comparative example 4,7 and embodiment 15-19
Respectively under ultraviolet light for the degradation curve of lower adjacent aldehydes gas different in flow rate.
Specific embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
In the disclosure, rare-earth element modified titanium dioxide nano photocatalysis material includes: titanium dioxide and is scattered in
Rare earth element in titanium dioxide.Wherein the molar ratio of rare earth element and titanium dioxide nano photocatalysis material be (0.001~
0.10): 1, preferably (0.0015~0.015): 1.It is preferred that rare earth element ke is Yb, Er, Tm, Pr, at least one of Ho member
Element.Wherein, the partial size of rare-earth element modified titanium dioxide granule can be 3~40nm, preferably 8~15nm.
In an embodiment of the present invention, being selected as Er as example using rare earth element, further the present invention will be described.
Rare earth Er modifying titanium dioxide nano-photocatalyst material contains rare earth Er and titanium dioxide granule.Rare earth ion Er is modified titanium dioxide
The molar ratio of rare earth Er and titanium dioxide can be (0.001~0.1) in titanium nano-photocatalyst material: 1, preferably (0.0025~
0.015): 1.In the disclosure, the photocatalysis performance of rare earth Er modifying titanium dioxide nano material and rare earth Er and titanium dioxide
Mole specific gravity is related.When rare earth Er content is excessively rare earth Er and titanium dioxide mass ratio is higher than 0.015, on the one hand can cover
The firmly surface-active site of titanium dioxide hinders absorption of the titanium dioxide to light, furthermore excessive rare earth Er produces material surface
Raw complex centre, the ability for promoting photo-generated carrier compound cause the catalytic activity of material to decline, and on the other hand, work as rare earth Er
Content it is very few i.e. molar ratio be lower than 0.001 when, efficiently separating for photo-generate electron-hole pairs cannot be promoted, lead to the photocatalysis of material
Performance is lower, therefore the molar ratio of rare earth Er and titanium dioxide can be in the rare earth Er modifying titanium dioxide nano-photocatalyst material
(0.001~0.1): 1, preferably (0.0025~0.015): 1.
In alternative embodiments, the partial size of rare earth Er modifying titanium dioxide nano-photocatalyst material can be 3~40nm,
It is preferred that 8~15nm.Partial size is smaller to be conducive to shorten the time that photo-generate electron-hole moves to surface, and it is several to reduce Carrier recombination
Rate, while increasing specific surface area.Anatase can be presented in titanium dioxide granule titanium oxide.
Illustrate to following exemplary the preparation method of rare-earth element modified titanium dioxide nano photocatalysis material.
By the uniformly mixing of pure and mild acid, mixed solvent is obtained.In alternative embodiments, (dispersing agent makes metal ion to alcohol
Disperse more uniform) it can be at least one of ethyl alcohol, methanol, isopropanol, ethylene glycol, n-butanol, n-hexyl alcohol etc..Optional
In embodiment, sour (complexing agent) can be at least one of acetic acid, propionic acid, citric acid etc..
In the mixed solvent stirring certain time is dispersed by titanium source, is slow added into a certain amount of water (for example, deionization
Water), obtain mixed solution A.In alternative embodiments, titanium source be hydrolyzable titaniferous compound, preferably isopropyl titanate,
At least one of butyl titanate, titanium tetrachloride etc..In alternative embodiments, water, pure and mild acid volume ratio can be 1:
(5~50): (1~20), more preferably 1:(10~20): (2~10).Wherein, part water can be used for dissolving titanium source, this is used for molten
The volume ratio of the water, pure and mild acid that solve titanium source can be 1:(5~20): (1~8), preferably 1:(10~15): (2~5).In addition, water
It can be 0.01~0.5ml/ seconds that rate, which is added, preferably 0.05~0.5ml/ seconds, more preferably 0.05~0.1ml/ seconds, facilitate
Obtain the uniform titanium dioxide granule of particle size distribution.Titanium source and the molar ratio of water can be 1:(3~50).
Rare earth source is added in mixed solution A, mixed solution B is obtained.In alternative embodiments, rare earth in rare earth source
Element can be at least one of Yb, Er, Tm, Pr, Ho etc..Rare earth source can be the soluble compound containing above-mentioned element
At least one of (soluble salt), preferably rare earth nitrades, rare earth nitrades hydrate etc..Wherein, rare earth source with it is described
The molar ratio of titanium source is (0.001~0.10): 1, preferably (0.0025~0.015): 1.
Mixed solution B is stirred 0.5~5 hour at normal temperature, obtains colloidal sol.In alternative embodiments, stirring
Temperature is 20~30 DEG C, and the time is 0.5~5 hour, is beneficial to obtain rear-earth-doped uniform titanium dioxide granule.
Colloidal sol is 5~30 hours dry at 40~120 DEG C, xerogel is obtained, dominant mechanism: nTi (OH)4→nTiO2+
2n H2O。
Xerogel is calcined 0.5~5.5 hour at 200~800 DEG C, obtains rare-earth element modified nano titania light
Catalysis material.Also rare-earth element modified titanium dioxide nano photocatalysis material can be subjected to further milled processed.
With rare earth element er as an example, the preparation of rare earth Er modifying titanium dioxide nano-photocatalyst material is described in detail.
In this example, rare earth Er is prepared using sol-gal process3+Modifying titanium dioxide material.Pure and mild acid-mixed is dispersed by organic titanium source
Bonding solvent, obtains after mixed solution that sustained response for a period of time, is slowly added to one into gained mixed solution at a certain temperature
Quantitative water (preferably deionized water), then suitable soluble rare earth erbium source is added into mixed solution, one is stirred at normal temperature
It fixes time to obtain colloidal sol, colloidal sol is transferred in vacuum oven and dries certain time at a certain temperature and obtains gel, then will
Gel is transferred to calcine at a certain temperature in Muffle furnace and grind after a certain period of time, obtains rare earth Er modifying titanium dioxide nanometer light
Catalysis material.The organic titanium source can be at least one of isopropyl titanate, titanium tetrachloride, butyl titanate.The mixing is molten
Alcohol in agent can be at least one of ethyl alcohol, methanol, isopropanol, ethylene glycol, n-butanol, n-hexyl alcohol.The in the mixed solvent
Acid can be at least one of acetic acid, propionic acid, citric acid.The molar ratio in the organic titanium source and erbium source can for 1:(0.001~
0.1), preferably 1:(0.0025~0.015).The alcohol, acid and water volume ratio can be (5~50): (1~20): 1, preferably
1:(10~20): (2~10).Under this reaction ratio, titanium source hydrolysis rate is moderate, helps to obtain partial size 3~40nm's
Titan oxide particles.In one example, mixing time can be 0.5~5h, preferably 1~3h；Drying temperature can be 40~120 DEG C,
Preferably 60~100 DEG C；Drying time can be 5~30h, preferably 10~20h；Calcination temperature can be 200~800 DEG C, preferably
It is 400~500 DEG C；Calcination time can be 0.5~5.5h, preferably 2~3h.As a detailed example, 30 are measured first
~60ml ethyl alcohol and 4~10ml acetic acid are uniformly mixed to form mixed solvent, disperse above-mentioned mixing for 8~15ml butyl titanate
In solvent, 3~6ml deionized water is added dropwise after 8~20min of stir about and obtains mixed solution, then is added into solution
The erbium nitrate of 0.106g~1.060g stirs the drying 10 at 60~100 DEG C in a vacuum drying oven of 1~3h postposition at normal temperature
~20h obtains gel, gained gel is transferred in Muffle furnace after calcining 0.5~5.5h at 400~500 DEG C and is ground, obtained
Rare earth Er modifying titanium dioxide nano-photocatalyst material.
In the disclosure, the uniform rare-earth element modified nano titania light of pattern has been made using sol-gal process to urge
Change material.Referring to fig. 2 it is found that the rare earth Er modifying titanium dioxide nano-photocatalyst material prepared by the above method, pattern
Homogeneous texture is stablized, wherein the partial size of the titania-doped particle of Er in rare earth Er modifying titanium dioxide nano-photocatalyst material
It can be 3~40nm, preferably 8~15nm.
In the disclosure, a kind of rare-earth element modified titanium dioxide nano photocatalysis material is additionally provided in air cleaning
Application, specifically degradation light-concentration volatile gaseous organic compound (VOCs) in application.The volatility has
Machine compound can be formaldehyde, acetaldehyde, benzene, toluene, ortho-xylene, alkene, alkynes, aromatic hydrocarbon etc..With the modified titanium dioxide of rare earth Er
Titanium nano-photocatalyst material is as an example, coat shape on substrate for the rare earth Er modifying titanium dioxide nano-photocatalyst material
At coating, the coating can effectively degrade VOCs (gaseous pollutant) in the case where ultraviolet light and visible light shine, and especially effectively drop
Solve low concentration gaseous pollutant.Such as the concentration of gaseous pollutant can be 1~1000ppm.The power of ultraviolet light can for 50~
1000W.Rare earth Er modifying titanium dioxide nano-photocatalyst material of the invention to low concentration gaseous pollutant ultraviolet light with can
Degradation efficiency under the conditions of light-exposed can be 80.6%~99.2%, 17.4%~25.8%.The flow of gaseous pollutant can be 20
~80sccm.
It is low dense in low-power ultraviolet light and progress photocatalytic degradation under visible light to above-mentioned coating as a detailed example
Spend mobile phase ortho-xylene, aldehydes gas test.Wherein ortho-xylene is 25ppm, the concentration of aldehydes gas is 500ppm；It is ultraviolet
Light illumination condition can 500W xenon lamp, gas flow rate is 20sccm.The rare earth Er modifying titanium dioxide prepared by the present invention is received
Rice catalysis material can be 80.6%~99.2% to the ultraviolet degradation efficiency of aldehydes gas；To the visible light (λ of aldehydes gas
> 420nm) degradation efficiency can be 17.4%~25.8%；To the ultraviolet degradation efficiency of ortho-xylene gas can for 63.2%~
88.1%；Respectively referring to Fig. 6, Fig. 7 and Fig. 8 it is found that for utilizing rare earth Er modifying titanium dioxide nanometer light obtained by the above method
Catalysis material, for low concentration gaseous acetaldehyde in degradation under the conditions of 500W xenon lamp, 4 (Er of embodiment3+-TiO2Mol%=
1.5%) the sample photocatalytic activity highest in the relatively other several embodiments of photocatalytic activity imitates the degradation of aldehydes gas
Rate reaches 99.2%.1 (Er of embodiment3+-TiO2Mol%=0.25%), 2 (Er of embodiment3+-TiO2Mol%=0.5%), real
Apply 3 (Er of example3+-TiO2) and 5 (Er of embodiment mol%=1%3+-TiO2Mol%=2% photocatalytic activity) is above pair
Ratio 1 (comparative sample pure titinium dioxide coating) and comparative example 5 (commercial P25 coating).For low concentration gaseous acetaldehyde 500W can
In degradation under the conditions of light-exposed (λ > 420nm), 9 (Er of embodiment3+-TiO2Mol%=1.5% photocatalytic activity) is with respect to it
Sample photocatalytic activity highest in its several embodiment, reaches 25.8% to the degradation efficiency of aldehydes gas.6 (Er of embodiment3 +-TiO2Mol%=0.25%), 7 (Er of embodiment3+-TiO2Mol%=0.5%), 8 (Er of embodiment3+-TiO2Mol%=1%)
And 10 (Er of embodiment3+-TiO2Mol%=2% photocatalytic activity) is above comparative example 2, and (comparative sample pure titinium dioxide applies
Layer) and comparative example 6 (commercial P25 coating).Wherein in the degradation for low concentration gaseous ortho-xylene under the conditions of 500W xenon lamp,
14 (Er of embodiment3+-TiO2Mol%=1.5% photocatalytic activity highest), reaches the degradation efficiency of ortho-xylene gas
88.1%, 11 (Er of embodiment3+-TiO2Mol%=0.25%), 12 (Er of embodiment3+-TiO2Mol%=0.5%), embodiment
13(Er3+-TiO2) and 15 (Er of embodiment mol%=1%3+-TiO2Mol%=2% photocatalytic activity) is above comparison
Example 3 (comparative sample pure titinium dioxide coating).The rare earth Er modifying titanium dioxide nano-photocatalyst material coating to aldehydes gas,
The photodegradation rate of ortho-xylene gas compares unmodified pure titinium dioxide material and increases.Also, rare earth Er modified two
TiOx nano catalysis material still has 99% or more photodegradation rate (referring to figure to aldehydes gas after eight loop tests
9), the rare earth Er modifying titanium dioxide nano-photocatalyst material has excellent chemical stability.
In the disclosure, a kind of rare-earth element modified titanium dioxide nano photocatalysis material is additionally provided after inactivation again
Raw method.With rare earth Er modifying titanium dioxide nano-photocatalyst material as an example, by the rare earth Er modified two after inactivation
The catalysis material painting of TiOx nano catalysis material or the preparation of rare-earth element modified titanium dioxide nano material is placed on one
Determine to irradiate a period of time under light intensity ultraviolet light, material can restore its photo-catalysis capability after a period of time.Wherein, ultraviolet light can use 50
~1000W xenon lamp provides.Irradiation time can be 0.5~5 hour.
The disclosure has synthesized rare earth Er modifying titanium dioxide nano-photo catalytic material using simple and environmentally-friendly sol-gal process
Material.Rare earth Er modifying titanium dioxide nano-photocatalyst material prepared by the present invention ultraviolet light with it is with higher under visible light
Photocatalytic Degradation Property, the volatile organic compounds such as acetaldehyde, ortho-xylene gas under the low concentration current system that can effectively degrade
Object.The material has wide in removal atmosphere in terms of low concentration organic pollutant, industrial waste gas and indoor polluted gas
Application prospect.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Embodiment 1
It measures 48ml ethyl alcohol first and 6ml acetic acid is uniformly mixed to form mixed solvent, disperse 10.2ml butyl titanate in
State in the mixed solvent, (it is 0.1ml/ second that control, which instills rate) addition 3ml deionized water is mixed dropwise after stir about 15min
Solution, then into gained mixed solution be added 0.0265g erbium nitrate, at normal temperature stir 1.5h postposition in a vacuum drying oven
Dry 15h obtains gel at 80 DEG C, gained gel is transferred in Muffle furnace after calcining 2.5h at 500 DEG C grinding to get
To rare earth Er modifying titanium dioxide nano-photocatalyst material.The molar ratio of rare earth Er (is denoted as 0.25% for 0.25% in the material
Er3+-TiO2Mol%=0.25%).Referring to fig. 2, it is shown as gained rare earth Er modifying titanium dioxide nano-photocatalyst material powder
SEM figure, can be it is found that gained rare earth Er modifying titanium dioxide nano-photocatalyst material be graininess from figure, pattern is uniform.Ginseng
Fig. 4, Fig. 5 are seen it is found that wherein Anatase is presented in titanium oxide；
The above-mentioned rare earth Er modifying titanium dioxide powder of 0.2g is taken, 2g dehydrated alcohol is added, obtains rare earth Er modifying titanium dioxide second
Alcohol dispersant liquid drop, which is coated in the glass sheet substrate of 6cm*13cm, forms coating, is dried to obtain rare earth Er modifying titanium dioxide coating
(32 μm of thickness), by low concentration mobile phase aldehydes gas degradation experiment, to gained rare earth Er modifying titanium dioxide coating into
Catalytic activity test under row ultraviolet light, the rare earth Er modifying titanium dioxide coating quality are 0.1g, the starting of aldehydes gas
Concentration is 500ppm, and flow velocity 20sccm, it is 500W xenon lamp that illumination condition is tested in photocatalysis, the modified dioxy of rare earth Er in the present embodiment
Change titanium coating photocatalysis performance and see Fig. 6, wherein 0.25%Er3+-TiO2For sample described in embodiment 1, degradation efficiency 80.6%.
Embodiment 2
It measures 48ml ethyl alcohol first and 6ml acetic acid is uniformly mixed to form mixed solvent, disperse 10.2ml butyl titanate in
State in the mixed solvent, (it is 0.1ml/ second that control, which instills rate) addition 3ml deionized water is mixed dropwise after stir about 15min
Solution, then into gained mixed solution be added 0.0530g erbium nitrate, at normal temperature stir 1.5h postposition in a vacuum drying oven
Dry 15h obtains gel at 80 DEG C, gained gel is transferred in Muffle furnace after calcining 2.5h at 500 DEG C grinding to get
To rare earth Er modifying titanium dioxide nano-photocatalyst material.The molar ratio of rare earth Er (is denoted as 0.5%Er for 0.5% in the material3 +-TiO2Mol%=0.5%).Referring to fig. 2, it is shown as gained rare earth Er modifying titanium dioxide nano-photocatalyst material powder
SEM figure, can be it is found that gained rare earth Er modifying titanium dioxide nano-photocatalyst material be graininess, pattern stable homogeneous from figure.
Referring to fig. 4, Fig. 5 is it is found that wherein Anatase is presented in titanium oxide；
The above-mentioned rare earth Er modifying titanium dioxide powder of 0.2g is taken to be scattered in 2g ethyl alcohol, glass of the drop coating in 6cm*13cm after ball milling 8h
Coating is formed in piece substrate and is dried to obtain rare earth Er modifying titanium dioxide coating (32 μm of thickness), passes through low concentration mobile phase acetaldehyde
Gas degradation experiment carries out the catalytic activity under ultraviolet light to gained rare earth Er modifying titanium dioxide coating and tests, described dilute
Native Er modifying titanium dioxide coating quality is 0.1g, and the initial concentration of aldehydes gas is 500ppm, flow velocity 20sccm, photocatalysis reality
Testing illumination condition is 500W xenon lamp, and the photocatalysis performance of rare earth Er modifying titanium dioxide coating is shown in Fig. 6 in the present embodiment, wherein
0.5%Er3+-TiO2For sample described in embodiment 2, degradation efficiency 90.5%.
Embodiment 3
It measures 48ml ethyl alcohol first and 6ml acetic acid is uniformly mixed to form mixed solvent, disperse 10.2ml butyl titanate in
State in the mixed solvent, (it is 0.1ml/ second that control, which instills rate) addition 3ml deionized water is mixed dropwise after stir about 15min
Solution, then into gained mixed solution be added 0.1060g erbium nitrate, at normal temperature stir 1.5h postposition in a vacuum drying oven
Dry 15h obtains gel at 80 DEG C, gained gel is transferred in Muffle furnace after calcining 2.5h at 500 DEG C grinding to get
To rare earth Er modifying titanium dioxide nano-photocatalyst material.The molar ratio of rare earth Er (is denoted as 1%Er for 1% in the material3+-
TiO2Mol%=1%).Referring to fig. 2, it is shown as the SEM of gained rare earth Er modifying titanium dioxide nano-photocatalyst material powder
Figure, can be it is found that gained rare earth Er modifying titanium dioxide nano-photocatalyst material be graininess from figure, and pattern is uniform.Referring to figure
4, Fig. 5 is it is found that wherein Anatase is presented in titanium oxide；
The above-mentioned rare earth Er modifying titanium dioxide powder of 0.2g is taken to be scattered in 2g ethyl alcohol, glass of the drop coating in 6cm*13cm after ball milling 8h
Coating is formed in piece substrate, rare earth Er modifying titanium dioxide coating (32 μm of thickness) is dried to obtain, passes through low concentration mobile phase second
Aldehyde gas degradation experiment carries out the catalytic activity under ultraviolet light to gained rare earth Er modifying titanium dioxide coating and tests, described
Rare earth Er modifying titanium dioxide coating quality is 0.1g, and the initial concentration of aldehydes gas is 500ppm, flow velocity 20sccm, photocatalysis
Experiment illumination condition is 500W xenon lamp, and the photocatalysis performance of rare earth Er modifying titanium dioxide coating is shown in Fig. 6 in the present embodiment, wherein
1%Er3+-TiO2For sample described in embodiment 3, degradation efficiency 94.0%.
Embodiment 4
It measures 48ml ethyl alcohol first and 6ml acetic acid is uniformly mixed to form mixed solvent, disperse 10.2ml butyl titanate in
State in the mixed solvent, (it is 0.1ml/ second that control, which instills rate) addition 3ml deionized water is mixed dropwise after stir about 15min
Solution, then into gained mixed solution be added 0.1590g erbium nitrate, at normal temperature stir 1.5h postposition in a vacuum drying oven
Dry 15h obtains gel at 80 DEG C, gained gel is transferred in Muffle furnace after calcining 2.5h at 500 DEG C grinding to get
To rare earth Er modifying titanium dioxide nano-photocatalyst material.The molar ratio of rare earth Er (is denoted as 1.5%Er for 1.5% in the material3 +-TiO2Mol%=1.5%).Referring to fig. 2, it is shown as gained rare earth Er modifying titanium dioxide nano-photocatalyst material powder
SEM figure, as seen from the figure, gained rare earth Er modifying titanium dioxide nano-photocatalyst material is graininess, and pattern is uniform.Referring to fig. 4,
Fig. 5 is it is found that wherein Anatase is presented in titanium oxide；
The above-mentioned rare earth Er modifying titanium dioxide powder of 0.2g is taken to be scattered in 2g ethyl alcohol, glass of the drop coating in 6cm*13cm after ball milling 8h
Coating is formed in piece substrate, rare earth Er modifying titanium dioxide coating (32 μm of thickness) is dried to obtain, passes through low concentration mobile phase second
Aldehyde gas degradation experiment carries out the catalytic activity under ultraviolet light to gained rare earth Er modifying titanium dioxide coating and tests, described
Rare earth Er modifying titanium dioxide coating quality is 0.1g, and the initial concentration of aldehydes gas is 500ppm, flow velocity 20sccm, photocatalysis
Experiment illumination condition is 500W xenon lamp, and the photocatalysis performance of rare earth Er modifying titanium dioxide coating is shown in Fig. 6 in the present embodiment, wherein
1.5%Er3+-TiO2For sample described in embodiment 4, degradation efficiency 99.2%.
Embodiment 5
It measures 48ml ethyl alcohol first and 6ml acetic acid is uniformly mixed to form mixed solvent, disperse 10.2ml butyl titanate in
State in the mixed solvent, (it is 0.1ml/ second that control, which instills rate) addition 3ml deionized water is mixed dropwise after stir about 15min
Solution, then into gained mixed solution be added 0.2120g erbium nitrate, at normal temperature stir 1.5h postposition in a vacuum drying oven
Dry 15h obtains gel at 80 DEG C, gained gel is transferred in Muffle furnace after calcining 2.5h at 500 DEG C grinding to get
To rare earth Er modifying titanium dioxide nano-photocatalyst material.The molar ratio of rare earth Er (is denoted as 2%Er for 2% in the material3+-
TiO2Mol%=2%).Referring to fig. 2, it is shown as the SEM of gained rare earth Er modifying titanium dioxide nano-photocatalyst material powder
Figure, as seen from the figure, gained rare earth Er modifying titanium dioxide nano-photocatalyst material are graininess, and pattern is uniform.It is institute referring to Fig. 3
The TEM figure of rare earth Er modifying titanium dioxide powder is obtained, the crystallite dimension of gained rare earth Er modifying titanium dioxide is about 9.5nm.Ginseng
B, Fig. 4, Fig. 5 in Fig. 3 are seen it is found that Anatase is presented in titanium dioxide in gained rare earth Er modifying titanium dioxide；
The above-mentioned rare earth Er modifying titanium dioxide powder of 0.2g is taken to be scattered in 2g ethyl alcohol, glass of the drop coating in 6cm*13cm after ball milling 8h
Coating is formed in piece substrate, rare earth Er modifying titanium dioxide coating (32 μm of thickness) is dried to obtain, passes through low concentration mobile phase second
Aldehyde gas degradation experiment carries out the catalytic activity under ultraviolet light to gained rare earth Er modifying titanium dioxide coating and tests, described
Rare earth Er modifying titanium dioxide coating quality is 0.1g, and the initial concentration of aldehydes gas is 500ppm, flow velocity 20sccm, photocatalysis
Experiment illumination condition is 500W xenon lamp, and the photocatalysis performance of rare earth Er modifying titanium dioxide coating is shown in Fig. 6 in the present embodiment, wherein
2%Er3+-TiO2For sample described in embodiment 5, degradation efficiency 67.4%.
Embodiment 6
It measures 48ml ethyl alcohol first and 6ml acetic acid is uniformly mixed to form mixed solvent, disperse 10.2ml butyl titanate in
State in the mixed solvent, (it is 0.1ml/ second that control, which instills rate) addition 3ml deionized water is mixed dropwise after stir about 15min
Solution, then into gained mixed solution be added 0.0265g erbium nitrate, at normal temperature stir 1.5h postposition in a vacuum drying oven
Dry 15h obtains gel at 80 DEG C, gained gel is transferred in Muffle furnace after calcining 2.5h at 500 DEG C grinding to get
To rare earth Er modifying titanium dioxide material.The molar ratio of rare earth Er (is denoted as 0.25%Er for 0.25% in the material3+-
TiO2Mol%=0.25%)；
The above-mentioned rare earth Er modifying titanium dioxide powder of 0.2g is taken to be scattered in 2g ethyl alcohol, glass of the drop coating in 6cm*13cm after ball milling 8h
Coating is formed in piece substrate, rare earth Er modifying titanium dioxide coating (32 μm of thickness) is dried to obtain, passes through low concentration mobile phase second
Aldehyde gas degradation experiment carries out the catalytic activity under visible light (λ > 420nm) to gained rare earth Er modifying titanium dioxide coating
Test, the rare earth Er modifying titanium dioxide coating quality are 0.1g, and the initial concentration of aldehydes gas is 500ppm, flow velocity
20sccm, it is 500W xenon lamp that illumination condition is tested in photocatalysis, the photocatalysis of rare earth Er modifying titanium dioxide coating in the present embodiment
Performance is shown in Fig. 7, wherein 0.25%Er3+-TiO2For sample described in embodiment 6, degradation efficiency 18.1%.
Embodiment 7
It measures 48ml ethyl alcohol first and 6ml acetic acid is uniformly mixed to form mixed solvent, disperse 10.2ml butyl titanate in
State in the mixed solvent, (it is 0.1ml/ second that control, which instills rate) addition 3ml deionized water is mixed dropwise after stir about 15min
Solution, then into gained mixed solution be added 0.0530g erbium nitrate, at normal temperature stir 1.5h postposition in a vacuum drying oven
Dry 15h obtains gel at 80 DEG C, gained gel is transferred in Muffle furnace after calcining 2.5h at 500 DEG C grinding to get
To rare earth Er modifying titanium dioxide catalysis material.The molar ratio of rare earth Er (is denoted as 0.5%Er for 0.5% in the material3+-
TiO2Mol%=0.5%)；
The above-mentioned rare earth Er modifying titanium dioxide powder of 0.2g is taken to be scattered in 2g ethyl alcohol, glass of the drop coating in 6cm*13cm after ball milling 8h
Coating is formed in piece substrate, rare earth Er modifying titanium dioxide coating (32 μm of thickness) is dried to obtain, passes through low concentration mobile phase second
Aldehyde gas degradation experiment carries out the catalytic activity under visible light (λ > 420nm) to gained rare earth Er modifying titanium dioxide coating
Test, the rare earth Er modifying titanium dioxide coating quality are 0.1g, and the initial concentration of aldehydes gas is 500ppm, flow velocity
20sccm, it is 500W xenon lamp that illumination condition is tested in photocatalysis, the photocatalysis of rare earth Er modifying titanium dioxide coating in the present embodiment
Performance is shown in Fig. 7, wherein 0.5%Er3+-TiO2For sample described in embodiment 7, degradation efficiency 20.0%.
Embodiment 8
It measures 48ml ethyl alcohol first and 6ml acetic acid is uniformly mixed to form mixed solvent, disperse 10.2ml butyl titanate in
State in the mixed solvent, (it is 0.1ml/ second that control, which instills rate) addition 3ml deionized water is mixed dropwise after stir about 15min
Solution, then into gained mixed solution be added 0.1060g erbium nitrate, at normal temperature stir 1.5h postposition in a vacuum drying oven
Dry 15h obtains gel at 80 DEG C, gained gel is transferred in Muffle furnace after calcining 2.5h at 500 DEG C grinding to get
To rare earth Er modifying titanium dioxide nano-photocatalyst material.The molar ratio of rare earth Er (is denoted as 1%Er for 1% in the material3+-
TiO2Mol%=1%)；
The above-mentioned rare earth Er modifying titanium dioxide powder of 0.2g is taken to be scattered in 2g ethyl alcohol, glass of the drop coating in 6cm*13cm after ball milling 8h
Coating is formed in piece substrate, rare earth Er modifying titanium dioxide coating (32 μm of thickness) is dried to obtain, passes through low concentration mobile phase second
Aldehyde gas degradation experiment carries out the catalytic activity under visible light (λ > 420nm) to gained rare earth Er modifying titanium dioxide coating
Test, the rare earth Er modifying titanium dioxide coating quality are 0.1g, and the initial concentration of aldehydes gas is 500ppm, flow velocity
20sccm, it is 500W xenon lamp that illumination condition is tested in photocatalysis, the photocatalysis of rare earth Er modifying titanium dioxide coating in the present embodiment
Performance is shown in Fig. 7, wherein 1%Er3+-TiO2For sample described in embodiment 8, degradation efficiency 21.2%.
Embodiment 9
It measures 48ml ethyl alcohol first and 6ml acetic acid is uniformly mixed to form mixed solvent, disperse 10.2ml butyl titanate in
State in the mixed solvent, (it is 0.1ml/ second that control, which instills rate) addition 3ml deionized water is mixed dropwise after stir about 15min
Solution, then into gained mixed solution be added 0.1590g erbium nitrate, at normal temperature stir 1.5h postposition in a vacuum drying oven
Dry 15h obtains gel at 80 DEG C, gained gel is transferred in Muffle furnace after calcining 2.5h at 500 DEG C grinding to get
To rare earth Er modifying titanium dioxide material.The molar ratio of rare earth Er (is denoted as 1.5%Er for 1.5% in the material3+-TiO2Mol%
=1.5%)；
The above-mentioned rare earth Er modifying titanium dioxide powder of 0.2g is taken to be scattered in 2g ethyl alcohol, glass of the drop coating in 6cm*13cm after ball milling 8h
Coating is formed in piece substrate, is dried to obtain rare earth Er modifying titanium dioxide coating, is degraded by low concentration mobile phase aldehydes gas
Experiment carries out the catalytic activity under visible light (λ > 420nm) to gained rare earth Er modifying titanium dioxide coating and tests, described
Rare earth Er modifying titanium dioxide coating quality is 0.1g, and the initial concentration of aldehydes gas is 500ppm, flow velocity 20sccm, photocatalysis
Experiment illumination condition is 500W xenon lamp, and the photocatalysis performance of rare earth Er modifying titanium dioxide coating is shown in Fig. 7 in the present embodiment, wherein
1.5%Er3+-TiO2For sample described in embodiment 9, degradation efficiency 25.8%.
Embodiment 10
It measures 48ml ethyl alcohol first and 6ml acetic acid is uniformly mixed to form mixed solvent, disperse 10.2ml butyl titanate in
State in the mixed solvent, (it is 0.1ml/ second that control, which instills rate) addition 3ml deionized water is mixed dropwise after stir about 15min
Solution, then into gained mixed solution be added 0.2120g erbium nitrate, at normal temperature stir 1.5h postposition in a vacuum drying oven
Dry 15h obtains gel at 80 DEG C, gained gel is transferred in Muffle furnace after calcining 2.5h at 500 DEG C grinding to get
To rare earth Er modifying titanium dioxide nano-photocatalyst material.The molar ratio of rare earth Er (is denoted as 2%Er for 2% in the material3+-
TiO2Mol%=2%)；
The above-mentioned rare earth Er modifying titanium dioxide powder of 0.2g is taken to be scattered in 2g ethyl alcohol, glass of the drop coating in 6cm*13cm after ball milling 8h
Coating is formed in piece substrate, rare earth Er modifying titanium dioxide coating (32 μm of thickness) is dried to obtain, passes through low concentration mobile phase second
Aldehyde gas degradation experiment carries out the catalytic activity under visible light (λ > 420nm) to gained rare earth Er modifying titanium dioxide coating
Test, the rare earth Er modifying titanium dioxide coating quality are 0.1g, and the initial concentration of aldehydes gas is 500ppm, flow velocity
20sccm, it is 500W xenon lamp that illumination condition is tested in photocatalysis, the photocatalysis of rare earth Er modifying titanium dioxide coating in the present embodiment
Performance is shown in Fig. 7, wherein 2%Er3+-TiO2For sample described in embodiment 10, degradation efficiency 17.4%.
Embodiment 11
It measures 48ml ethyl alcohol first and 6ml acetic acid is uniformly mixed to form mixed solvent, disperse 10.2ml butyl titanate in
State in the mixed solvent, (it is 0.1ml/ second that control, which instills rate) addition 3ml deionized water is mixed dropwise after stir about 15min
Solution, then into gained mixed solution be added 0.0530g erbium nitrate, at normal temperature stir 1.5h postposition in a vacuum drying oven
Dry 15h obtains gel at 80 DEG C, gained gel is transferred in Muffle furnace after calcining 2.5h at 500 DEG C grinding to get
To rare earth Er modifying titanium dioxide material.The molar ratio of rare earth Er (is denoted as 0.5%Er for 0.5% in the material3+-TiO2Mol%
=0.5%)；
The above-mentioned rare earth Er modifying titanium dioxide powder of 0.2g is taken to be scattered in 2g ethyl alcohol, glass of the drop coating in 6cm*13cm after ball milling 8h
Coating is formed in piece substrate, rare earth Er modifying titanium dioxide coating (32 μm of thickness) is dried to obtain, passes through low concentration mobile phase phase
Ortho-xylene gas degradation experiment carries out the catalytic activity under ultraviolet light to gained rare earth Er modifying titanium dioxide coating and surveys
Examination, the rare earth Er modifying titanium dioxide coating quality are 0.1g, and the initial concentration of ortho-xylene gas is 25ppm, flow velocity
20sccm, it is 500W xenon lamp that illumination condition is tested in photocatalysis, the photocatalysis of rare earth Er modifying titanium dioxide coating in the present embodiment
Performance is shown in Fig. 8, wherein 0.5%Er3+-TiO2For sample described in embodiment 11, degradation efficiency 66.4%.
Embodiment 12
It measures 48ml ethyl alcohol first and 6ml acetic acid is uniformly mixed to form mixed solvent, disperse 10.2ml butyl titanate in
State in the mixed solvent, (it is 0.1ml/ second that control, which instills rate) addition 3ml deionized water is mixed dropwise after stir about 15min
Solution, then into gained mixed solution be added 0.1060g erbium nitrate, at normal temperature stir 1.5h postposition in a vacuum drying oven
Dry 15h obtains gel at 80 DEG C, gained gel is transferred in Muffle furnace after calcining 2.5h at 500 DEG C grinding to get
To rare earth Er modifying titanium dioxide nano-photocatalyst material.The molar ratio of rare earth Er (is denoted as 1%Er for 1% in the material3+-
TiO2Mol%=1%)；
The above-mentioned rare earth Er modifying titanium dioxide powder of 0.2g is taken to be scattered in 2g ethyl alcohol, glass of the drop coating in 6cm*13cm after ball milling 8h
Coating is formed in piece substrate, rare earth Er modifying titanium dioxide coating (32 μm of thickness) is dried to obtain, passes through low concentration mobile phase phase
Ortho-xylene gas degradation experiment carries out the catalytic activity under ultraviolet light to gained rare earth Er modifying titanium dioxide coating and surveys
Examination, the rare earth Er modifying titanium dioxide coating quality are 0.1g, and the initial concentration of ortho-xylene gas is 25ppm, flow velocity
20sccm, it is 500W xenon lamp that illumination condition is tested in photocatalysis, the photocatalysis of rare earth Er modifying titanium dioxide coating in the present embodiment
Performance is shown in Fig. 8, wherein 1%Er3+-TiO2For sample described in embodiment 12, degradation efficiency 72.6%.
Embodiment 13
It measures 48ml ethyl alcohol first and 6ml acetic acid is uniformly mixed to form mixed solvent, disperse 10.2ml butyl titanate in
State in the mixed solvent, (it is 0.1ml/ second that control, which instills rate) addition 3ml deionized water is mixed dropwise after stir about 15min
Solution, then into gained mixed solution be added 0.1590g erbium nitrate, at normal temperature stir 1.5h postposition in a vacuum drying oven
Dry 15h obtains gel at 80 DEG C, gained gel is transferred in Muffle furnace after calcining 2.5h at 500 DEG C grinding to get
To rare earth Er modifying titanium dioxide material.The molar ratio of rare earth Er (is denoted as 1.5%Er for 1.5% in the material3+-TiO2Mol%
=1.5%)；
The above-mentioned rare earth Er modifying titanium dioxide powder of 0.2g is taken to be scattered in 2g ethyl alcohol, glass of the drop coating in 6cm*13cm after ball milling 8h
Coating is formed in piece substrate, rare earth Er modifying titanium dioxide coating (32 μm of thickness) is dried to obtain, passes through low concentration mobile phase phase
Ortho-xylene gas degradation experiment, to gained rare earth Er modifying titanium dioxide coating carry out can the catalytic activity under ultraviolet light survey
Examination, the rare earth Er modifying titanium dioxide coating quality are 0.1g, and the initial concentration of ortho-xylene gas is 25ppm, flow velocity
20sccm, it is 500W xenon lamp that illumination condition is tested in photocatalysis, the photocatalysis of rare earth Er modifying titanium dioxide coating in the present embodiment
Performance is shown in Fig. 8, wherein 1.5%Er3+-TiO2For sample described in embodiment 13, degradation efficiency 88.1%.
Embodiment 14
It measures 48ml ethyl alcohol first and 6ml acetic acid is uniformly mixed to form mixed solvent, disperse 10.2ml butyl titanate in
State in the mixed solvent, (it is 0.1ml/ second that control, which instills rate) addition 3ml deionized water is mixed dropwise after stir about 15min
Solution, then into gained mixed solution be added 0.2120g erbium nitrate, at normal temperature stir 1.5h postposition in a vacuum drying oven
Dry 15h obtains gel at 80 DEG C, gained gel is transferred in Muffle furnace after calcining 2.5h at 500 DEG C grinding to get
To rare earth Er modifying titanium dioxide nano-photocatalyst material.The molar ratio of rare earth Er (is denoted as 2%Er for 2% in the material3+-
TiO2Mol%=2%)；
The above-mentioned rare earth Er modifying titanium dioxide powder of 0.2g is taken to be scattered in 2g ethyl alcohol, glass of the drop coating in 6cm*13cm after ball milling 8h
Coating is formed in piece substrate, rare earth Er modifying titanium dioxide coating (32 μm of thickness) is dried to obtain, passes through low concentration mobile phase phase
Ortho-xylene gas degradation experiment, to gained rare earth Er modifying titanium dioxide coating carry out can the catalytic activity under ultraviolet light survey
Examination, the rare earth Er modifying titanium dioxide coating quality are 0.1g, and the initial concentration of ortho-xylene gas is 25ppm, flow velocity
20sccm, it is 500W xenon lamp that illumination condition is tested in photocatalysis, the photocatalysis of rare earth Er modifying titanium dioxide coating in the present embodiment
Performance is shown in Fig. 8, wherein 2%Er3+-TiO2For sample described in embodiment 14, degradation efficiency 63.1%.
Embodiment 15
It measures 48ml ethyl alcohol first and 6ml acetic acid is uniformly mixed to form mixed solvent, disperse 10.2ml butyl titanate in
In the mixed solvent is stated, adds (it is 0.1ml/ seconds that control, which instills rate) to enter 3ml deionized water after stir about 15min dropwise and is mixed
Solution, then into gained mixed solution be added 0.0265g erbium nitrate, at normal temperature stir 1.5h postposition in a vacuum drying oven
Dry 15h obtains gel at 80 DEG C, gained gel is transferred in Muffle furnace after calcining 2.5h at 500 DEG C grinding to get
To rare earth Er modifying titanium dioxide material.The molar ratio of rare earth Er (is denoted as 0.25%Er for 0.25% in the material3+-
TiO2Mol%=0.25%)；
The above-mentioned rare earth Er modifying titanium dioxide powder of 0.2g is taken to be scattered in 2g ethyl alcohol, glass of the drop coating in 6cm*13cm after ball milling 8h
Coating is formed in piece substrate, rare earth Er modifying titanium dioxide coating (32 μm of thickness) is dried to obtain, passes through low concentration mobile phase second
Aldehyde gas degradation experiment carries out the catalytic activity under ultraviolet light to gained rare earth Er modifying titanium dioxide coating and tests, described
Rare earth Er modifying titanium dioxide coating quality is 0.1g, and the initial concentration of aldehydes gas is 500ppm, flow velocity 80sccm, photocatalysis
Experiment illumination condition is 500W xenon lamp, and the photocatalysis performance of rare earth Er modifying titanium dioxide coating is shown in Figure 10 in the present embodiment,
Middle 0.25%Er3+-TiO2For sample described in embodiment 15, degradation efficiency 49.1%.
Embodiment 16
It measures 48ml ethyl alcohol first and 6ml acetic acid is uniformly mixed to form mixed solvent, disperse 10.2ml butyl titanate in
In the mixed solvent is stated, adds (it is 0.1ml/ seconds that control, which instills rate) to enter 3ml deionized water after stir about 15min dropwise and is mixed
Solution, then into gained mixed solution be added 0.0530g erbium nitrate, at normal temperature stir 1.5h postposition in a vacuum drying oven
Dry 15h obtains gel at 80 DEG C, gained gel is transferred in Muffle furnace after calcining 2.5h at 500 DEG C grinding to get
To rare earth Er modifying titanium dioxide material.The molar ratio of rare earth Er (is denoted as 0.5%Er for 0.5% in the material3+-TiO2Mol%
=0.5%)；
The above-mentioned rare earth Er modifying titanium dioxide powder of 0.2g is taken to be scattered in 2g ethyl alcohol, glass of the drop coating in 6cm*13cm after ball milling 8h
Coating is formed in piece substrate, rare earth Er modifying titanium dioxide coating (32 μm of thickness) is dried to obtain, passes through low concentration mobile phase second
Aldehyde gas degradation experiment carries out the catalytic activity under ultraviolet light to gained rare earth Er modifying titanium dioxide coating and tests, described
Rare earth Er modifying titanium dioxide coating quality is 0.1g, and the initial concentration of aldehydes gas is 500ppm, flow velocity 80sccm, photocatalysis
Experiment illumination condition is 500W xenon lamp, and the photocatalysis performance of rare earth Er modifying titanium dioxide coating is shown in Figure 10 in the present embodiment,
Middle 0.5%Er3+-TiO2For sample described in embodiment 16, degradation efficiency 54.0%.
Embodiment 17
It measures 48ml ethyl alcohol first and 6ml acetic acid is uniformly mixed to form mixed solvent, disperse 10.2ml butyl titanate in
In the mixed solvent is stated, adds (it is 0.1ml/ seconds that control, which instills rate) to enter 3ml deionized water after stir about 15min dropwise and is mixed
Solution, then into gained mixed solution be added 0.1060g erbium nitrate, at normal temperature stir 1.5h postposition in a vacuum drying oven
Dry 15h obtains gel at 80 DEG C, gained gel is transferred in Muffle furnace after calcining 2.5h at 500 DEG C grinding to get
To rare earth Er modifying titanium dioxide nano-photocatalyst material.The molar ratio of rare earth Er (is denoted as 1%Er for 1% in the material3+-
TiO2Mol%=1%)；
The above-mentioned rare earth Er modifying titanium dioxide powder of 0.2g is taken to be scattered in 2g ethyl alcohol, glass of the drop coating in 6cm*13cm after ball milling 8h
Coating is formed in piece substrate, rare earth Er modifying titanium dioxide coating (32 μm of thickness) is dried to obtain, passes through low concentration mobile phase second
Aldehyde gas degradation experiment carries out the catalytic activity under ultraviolet light to gained rare earth Er modifying titanium dioxide coating and tests, described
Rare earth Er modifying titanium dioxide coating quality is 0.1g, and the initial concentration of aldehydes gas is 500ppm, flow velocity 80sccm, photocatalysis
Experiment illumination condition is 500W xenon lamp, and the photocatalysis performance of rare earth Er modifying titanium dioxide coating is shown in Figure 10 in the present embodiment,
Middle 1%Er3+-TiO2For sample described in embodiment 17, degradation efficiency 59.1%.
Embodiment 18
It measures 48ml ethyl alcohol first and 6ml acetic acid is uniformly mixed to form mixed solvent, disperse 10.2ml butyl titanate in
State in the mixed solvent, (it is 0.1ml/ second that control, which instills rate) addition 3ml deionized water is mixed dropwise after stir about 15min
Solution, then into gained mixed solution be added 0.1590g erbium nitrate, at normal temperature stir 1.5h postposition in a vacuum drying oven
Dry 15h obtains gel at 80 DEG C, gained gel is transferred in Muffle furnace after calcining 2.5h at 500 DEG C grinding to get
To rare earth Er modifying titanium dioxide material.The molar ratio of rare earth Er (is denoted as 1.5%Er for 1.5% in the material3+-TiO2Mol%
=1.5%)；
The above-mentioned rare earth Er modifying titanium dioxide powder of 0.2g is taken to be scattered in 2g ethyl alcohol, glass of the drop coating in 6cm*13cm after ball milling 8h
Coating is formed in piece substrate, rare earth Er modifying titanium dioxide coating (32 μm of thickness) is dried to obtain, passes through low concentration mobile phase second
Aldehyde gas degradation experiment, to gained rare earth Er modifying titanium dioxide coating carry out can the catalytic activity under ultraviolet light test, institute
Stating rare earth Er modifying titanium dioxide coating quality is 0.1g, and the initial concentration of aldehydes gas is 500ppm, flow velocity 80sccm, and light is urged
Changing experiment illumination condition is 500W xenon lamp, and the photocatalysis performance of rare earth Er modifying titanium dioxide coating is shown in Figure 10 in the present embodiment,
Wherein 1.5%Er3+-TiO2For sample described in embodiment 18, degradation efficiency 62.9%.
Embodiment 19
It measures 48ml ethyl alcohol first and 6ml acetic acid is uniformly mixed to form mixed solvent, disperse 10.2ml butyl titanate in
State in the mixed solvent, (it is 0.1ml/ second that control, which instills rate) addition 3ml deionized water is mixed dropwise after stir about 15min
Solution, then into gained mixed solution be added 0.2120g erbium nitrate, at normal temperature stir 1.5h postposition in a vacuum drying oven
Dry 15h obtains gel at 80 DEG C, gained gel is transferred in Muffle furnace after calcining 2.5h at 500 DEG C grinding to get
To rare earth Er modifying titanium dioxide nano-photocatalyst material.The molar ratio of rare earth Er (is denoted as 2%Er for 2% in the material3+-
TiO2Mol%=2%)；
The above-mentioned rare earth Er modifying titanium dioxide powder of 0.2g is taken to be scattered in 2g ethyl alcohol, glass of the drop coating in 6cm*13cm after ball milling 8h
Coating is formed in piece substrate, rare earth Er modifying titanium dioxide coating (32 μm of thickness) is dried to obtain, passes through low concentration mobile phase second
Aldehyde gas degradation experiment carries out the catalytic activity under ultraviolet light to gained rare earth Er modifying titanium dioxide coating and tests, described
Rare earth Er modifying titanium dioxide coating quality is 0.1g, and the initial concentration of aldehydes gas is 500ppm, flow velocity 80sccm, photocatalysis
Experiment illumination condition is 500W xenon lamp, and the photocatalysis performance of rare earth Er modifying titanium dioxide coating is shown in Figure 10 in the present embodiment,
Middle 2%Er3+-TiO2For sample described in embodiment 19, degradation efficiency 39%.
Embodiment 20
Prepared rare earth Er modifying titanium dioxide powder in 0.2g embodiment 4 is taken, 2g ethyl alcohol is added, ball milling 8h obtains rare earth Er
Modifying titanium dioxide alcohol dispersion liquid drop coating forms coating in the glass sheet substrate of 6cm*13cm, and it is modified to be dried to obtain rare earth Er
Coating of titanium dioxide, by the degradation mobile phase aldehydes gas experiment of above-mentioned coating cycle, to the modified titanium dioxide of gained rare earth Er
Titanium coating carry out can catalytic activity test under ultraviolet light, the rare earth Er modifying titanium dioxide coating quality is 0.1g, acetaldehyde
The initial concentration of gas is 500ppm, and flow velocity 20sccm, it is 500W xenon lamp that illumination condition is tested in photocatalysis.Rare earth in the present embodiment
Eight circulation photocatalytic degradation performances of Er modifying titanium dioxide coating are shown in Fig. 9, it is seen that the rare earth Er modifying titanium dioxide light is urged
99% or more photodegradation rate, the carbon rare earth Er modifying titanium dioxide are remained after material eight times circulations of change to aldehydes gas
Catalysis material has excellent chemical stability.
Comparative example 1 (not rare earth Er contained)
It measures 48ml ethyl alcohol first and 6ml acetic acid is uniformly mixed to form mixed solvent, disperse 10.2ml butyl titanate in
State in the mixed solvent, (it is 0.1ml/ second that control, which instills rate) addition 3ml deionized water dropwise after stir about 15min, in room temperature
Dry 15h obtains gel to lower stirring 1.5h postposition at 80 DEG C in a vacuum drying oven, and gained gel is transferred in Muffle furnace
It is ground after calcining 2.5h at 500 DEG C and (is denoted as Pure-TiO to get to pure titinium dioxide nano-photocatalyst material2).Referring to figure
1, it is shown as the SEM figure of gained pure titinium dioxide nano-photocatalyst material powder, it can be it is found that gained pure titinium dioxide be received from figure
Rice catalysis material is graininess, and pattern is uniform；
The above-mentioned pure titinium dioxide powder of 0.2g is taken to be scattered in 2g ethyl alcohol, drop coating is in the glass sheet substrate of 6cm*13cm after ball milling 8h
Coating is formed, pure titinium dioxide coating (32 μm of thickness) is dried to obtain, by low concentration mobile phase aldehydes gas degradation experiment, is come
Catalytic activity test under ultraviolet light is carried out to gained pure titinium dioxide coating, the pure titinium dioxide coating quality is 0.1g,
The initial concentration of aldehydes gas is 500ppm, and flow velocity 20sccm, it is 500W xenon lamp that illumination condition is tested in photocatalysis, in this comparative example
The photocatalysis performance of coating of titanium dioxide is shown in Fig. 6, wherein Pure-TiO2For sample described in comparative example 1, degradation efficiency is
61.7%.
Comparative example 2 (not rare earth Er contained)
It measures 48ml ethyl alcohol first and 6ml acetic acid is uniformly mixed to form mixed solvent, disperse 10.2ml butyl titanate in
State in the mixed solvent, (it is 0.1ml/ second that control, which instills rate) addition 3ml deionized water dropwise after stir about 15min, in room temperature
Dry 15h obtains gel to lower stirring 1.5h postposition at 80 DEG C in a vacuum drying oven, and gained gel is transferred in Muffle furnace
It is ground after calcining 2.5h at 500 DEG C and (is denoted as Pure-TiO to get to pure titinium dioxide nano-photocatalyst material2)；
The above-mentioned pure titinium dioxide nano-photocatalyst material of 0.2g is taken to be scattered in 2g ethyl alcohol, glass of the drop coating in 6cm*13cm after ball milling 8h
Coating is formed in glass piece substrate, pure titinium dioxide coating (32 μm of thickness) is dried to obtain, passes through low concentration mobile phase aldehydes gas
Degradation experiment carries out the catalytic activity under visible (λ > 420nm) light to gained pure titinium dioxide coating and tests, and described pure two
Titania coating quality is 0.1g, and the initial concentration of aldehydes gas is 500ppm, flow velocity 20sccm, photocatalysis experiment illumination condition
For 500W xenon lamp, the photocatalysis performance of coating of titanium dioxide is shown in Fig. 7 in this comparative example, wherein Pure-TiO2For described in comparative example 2
Sample, without degradation property.
Comparative example 3 (not rare earth Er contained)
It measures 48ml ethyl alcohol first and 6ml acetic acid is uniformly mixed to form mixed solvent, disperse 10.2ml butyl titanate in
State in the mixed solvent, (it is 0.1ml/ second that control, which instills rate) addition 3ml deionized water dropwise after stir about 15min, in room temperature
Dry 15h obtains gel to lower stirring 1.5h postposition at 80 DEG C in a vacuum drying oven, and gained gel is transferred in Muffle furnace
It is ground after calcining 2.5h at 500 DEG C and (is denoted as Pure-TiO to get to pure titinium dioxide nano-photocatalyst material2)；
The above-mentioned pure titinium dioxide powder of 0.2g is taken to be scattered in 2g ethyl alcohol, drop coating is in the glass sheet substrate of 6cm*13cm after ball milling 8h
Coating is formed, pure titinium dioxide coating (32 μm of thickness) is dried to obtain, is degraded by low concentration mobile phase ortho-xylene gas real
It tests, the catalytic activity under ultraviolet light is carried out to gained pure titinium dioxide coating and is tested, the pure titinium dioxide coating quality is
0.1g, the initial concentration of ortho-xylene gas are 25ppm, and flow velocity 20sccm, it is 500W xenon lamp that illumination condition is tested in photocatalysis, this
The photocatalysis performance of coating of titanium dioxide is shown in Fig. 8 in comparative example, wherein Pure-TiO2For sample described in comparative example 3, degradation efficiency
About 37.3%.
Comparative example 4 (not rare earth Er contained)
It measures 48ml ethyl alcohol first and 6ml acetic acid is uniformly mixed to form mixed solvent, disperse 10.2ml butyl titanate in
State in the mixed solvent, (it is 0.1ml/ second that control, which instills rate) addition 3ml deionized water dropwise after stir about 15min, in room temperature
Dry 15h obtains gel to lower stirring 1.5h postposition at 80 DEG C in a vacuum drying oven, and gained gel is transferred in Muffle furnace
It is ground after calcining 2.5h at 500 DEG C and (is denoted as Pure-TiO to get to pure titinium dioxide nano-photocatalyst material2)；
The above-mentioned pure titinium dioxide powder of 0.2g is taken to be scattered in 2g ethyl alcohol, drop coating is in the glass sheet substrate of 6cm*13cm after ball milling 8h
Coating is formed, pure titinium dioxide coating (32 μm of thickness) is dried to obtain, adjacent aldehydes gas degradation experiment is flowed by low concentration,
To carry out gained pure titinium dioxide coating the catalytic activity test under ultraviolet light, the pure titinium dioxide coating quality is
0.1g, the initial concentration of aldehydes gas are 500ppm, and flow velocity 80sccm, it is 500W xenon lamp that illumination condition is tested in photocatalysis, this is right
The photocatalysis performance of coating of titanium dioxide is shown in Figure 10 in ratio, wherein Pure-TiO2For sample described in comparative example 3, degradation efficiency
About 34.2%.
Comparative example 5 (commercial P25)
0.2g commercialization P25 powder is taken, 2g dehydrated alcohol is added, ball milling 8h obtains titanium dioxide (P25) alcohol dispersion liquid drop coating and exists
Coating is formed in the glass sheet substrate of 6cm*13cm, is dried to obtain P25 coating, is degraded by low concentration mobile phase aldehydes gas real
It tests, the catalytic activity under ultraviolet light is carried out to gained coating and is tested, control coating quality is 0.1g, and the starting of aldehydes gas is dense
Degree is 500ppm, and flow velocity 20sccm, it is 500W xenon lamp that illumination condition is tested in photocatalysis, the light of coating of titanium dioxide in this comparative example
Catalytic performance is shown in Fig. 6, and wherein P25 is sample described in comparative example 5, and degradation efficiency is about 49.0%.
Comparative example 6 (commercial P25)
0.2g commercialization P25 powder is taken, 2g dehydrated alcohol is added, ball milling 8h obtains titanium dioxide (P25) alcohol dispersion liquid drop coating and exists
Coating is formed in the glass sheet substrate of 6cm*13cm, dilute P25 coating (32 μm of thickness) is dried to obtain, passes through low concentration mobile phase second
Aldehyde gas degradation experiment carries out the catalytic activity under visible light (λ > 420nm) to gained coating and tests, controls coating quality
For 0.1g, the initial concentration of aldehydes gas is 500ppm, and flow velocity 20sccm, it is 500W xenon lamp that illumination condition is tested in photocatalysis, this
The photocatalysis performance of coating of titanium dioxide is shown in Fig. 7 in comparative example, and wherein P25 is sample described in comparative example 6, without degradation property.
Comparative example 7 (commercial P25)
0.2g commercialization P25 powder is taken, 2g dehydrated alcohol is added, ball milling 8h obtains titanium dioxide (P25) alcohol dispersion liquid drop coating and exists
Coating is formed in the glass sheet substrate of 6cm*13cm, is dried to obtain dilute P25 coating, is degraded by low concentration mobile phase aldehydes gas
Experiment carries out the catalytic activity under ultraviolet light to gained coating and tests, and control coating quality is 0.1g, the starting of aldehydes gas
Concentration is 500ppm, and flow velocity 80sccm, it is 500W xenon lamp that illumination condition is tested in photocatalysis, coating of titanium dioxide in this comparative example
Photocatalysis performance is shown in Figure 10, and wherein P25 is sample described in comparative example 7, and degradation efficiency is about 27.7%.
Industrial applicability:
Raw material needed for graphene/titania composite material provided by the invention is cheap and easy to get, and preparation process is simple, to experiment item
Part, equipment requirement are lower, and material repeats regeneration.Rare earth Er modifying titanium dioxide material provided by the present invention improves
The photocatalytic activity of semiconductor light-catalyst；And rare earth Er modifying titanium dioxide coating prepared by the present invention can effectively drop
Solve the volatile organic compounds such as acetaldehyde, ortho-xylene gas under current system, and all have under ultraviolet light and visible light compared with
High Photocatalytic Degradation Property.In addition, materials chemistry property is stablized, higher photocatalytic activity repeatedly is remained after circulation,
It has broad application prospects in removal air purification field.
Table 1 is degradation data table of the rare earth Er modifying titanium dioxide material to mobile phase acetaldehyde, ortho-xylene gas:
Claims (15)
1. a kind of preparation method of rare-earth element modified titanium dioxide nano photocatalysis material characterized by comprising
(1) by the uniformly mixing of pure and mild acid, mixed solvent is obtained；
(2) gained in the mixed solvent is dispersed by titanium source and water is added dropwise, obtain mixed solution A；
(3) rare earth source is added in gained mixed solution A again, obtains mixed solution B；
(4) gained mixed solution B is stirred 0.5~5 hour at normal temperature, obtains colloidal sol；
(5) by gained drying sol and calcining, then it is ground, obtain rare-earth element modified titanium dioxide nano photocatalysis material
Material.
2. preparation method according to claim 1, which is characterized in that the alcohol be ethyl alcohol, methanol, isopropanol, ethylene glycol,
At least one of n-butanol, n-hexyl alcohol；The acid is at least one of acetic acid, propionic acid, citric acid.
3. preparation method according to claim 1 or 2, which is characterized in that the titanium source is the compound of hydrolyzable titaniferous,
It is preferred that at least one of isopropyl titanate, butyl titanate, titanium tetrachloride.
4. preparation method according to any one of claim 1-3, which is characterized in that the volume ratio of the water, pure and mild acid
For 1:(5~50): (1~20), preferably 1:(10~20): (2~10), more preferably 1:(5~20): (1~8), most preferably
For 1:(10~15): (2~5).
5. preparation method described in any one of -4 according to claim 1, which is characterized in that the addition rate of the water is 0.01
~0.5ml/ seconds, preferably 0.05~0.5 ml/ seconds, more preferably 0.05~0.1ml/ seconds.
6. preparation method according to any one of claims 1-5, which is characterized in that the rare earth source be containing Yb, Er,
In the soluble rare-earth salt of at least one of Tm, Pr, Ho element, preferably rare earth nitrades, rare earth nitrades hydrate
It is at least one.
7. preparation method according to claim 1 to 6, which is characterized in that the titanium source and the molar ratio of water are
1:(3~50).
8. preparation method described in any one of -7 according to claim 1, which is characterized in that mole in the rare earth source and titanium source
Than for (0.001~0.10): 1, preferably (0.0025~0.015): 1.
9. preparation method according to claim 1 to 8, which is characterized in that the temperature of the stirring is 20~30
DEG C, the time is 0.5~5 hour.
10. preparation method according to claim 1 to 9, which is characterized in that the temperature of the drying be 40~
120 DEG C, the time is 5~30 hours；The temperature of the calcining is 200~800 DEG C, and the time is 0.5~5.5 hour.
11. a kind of rare-earth element modified titanium dioxide of preparation method preparation according to claim 1 to 10 is received
Rice catalysis material, which is characterized in that rare earth element and two in the rare-earth element modified titanium dioxide nano photocatalysis material
The molar ratio of titanium oxide is (0.001~0.10): 1, preferably (0.0015~0.015): 1.
12. rare-earth element modified titanium dioxide nano photocatalysis material according to claim 11, which is characterized in that described
The partial size of rare-earth element modified titanium dioxide nano photocatalysis material is 3~40nm, preferably 8~15 nm.
13. a kind of catalysis material by the rare-earth element modified titanium dioxide nano material preparation of claim 11 or 12 applies
Layer.
14. rare-earth element modified titanium dioxide nano material is in photocatalytic degradation volatility described in a kind of claim 11 or 12
Application in organic compound, which is characterized in that the rare-earth element modified titanium dioxide nano photocatalysis material 320~
1100nm wavelength, the lower degradation and removal that can be achieved to volatile organic compounds VOCs of 50~1000W power light irradiation；It is preferred that
Ground, the volatile organic compounds VOCs are formaldehyde, in acetaldehyde, benzene, toluene, ortho-xylene, alkene, alkynes, aromatic hydrocarbon
At least one, concentration are 1~1000ppm.
15. described in rare-earth element modified titanium dioxide nano material and claim 13 described in a kind of claim 11 or 12
Regeneration method after the catalysis material coating inactivation of rare-earth element modified titanium dioxide nano material preparation, feature exist
In by the rare-earth element modified titanium dioxide nano photocatalysis material or rare-earth element modified nano titania material after inactivation
The catalysis material painting of material preparation is placed in air atmosphere, is irradiated 0.5~5 hour under the ultraviolet light of 50~1000W, so that
Rare-earth element modified titanium dioxide nano photocatalysis material after inactivation can restore its photo-catalysis capability.
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| CN110394172A (en) * | 2019-07-23 | 2019-11-01 | 山东师范大学 | Ytterbium and thulium doped strontium titanate semiconductor material, preparation method and application |
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| CN112717916A (en) * | 2020-12-30 | 2021-04-30 | 江苏安纳泰环保科技有限公司 | Rare earth monoatomic-supported two-dimensional flaky titanium oxide composite photocatalytic material and preparation method and application thereof |
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| CN114570348B (en) * | 2022-03-02 | 2024-03-12 | 济南大学 | Titanium dioxide-based nano composite photocatalyst for photocatalytic degradation by irradiation of visible light and application thereof |
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