CN104888777A - Preparation method of attapulgite clay -TiO2-Cu2O compound visible photocatalyst - Google Patents
Preparation method of attapulgite clay -TiO2-Cu2O compound visible photocatalyst Download PDFInfo
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- CN104888777A CN104888777A CN201510167537.1A CN201510167537A CN104888777A CN 104888777 A CN104888777 A CN 104888777A CN 201510167537 A CN201510167537 A CN 201510167537A CN 104888777 A CN104888777 A CN 104888777A
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- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 116
- 229960000892 attapulgite Drugs 0.000 title claims abstract description 95
- 239000004927 clay Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 11
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title abstract 5
- 238000003756 stirring Methods 0.000 claims abstract description 55
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000000227 grinding Methods 0.000 claims abstract description 20
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 16
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 41
- 238000000967 suction filtration Methods 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 31
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 21
- 238000010306 acid treatment Methods 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 206010013786 Dry skin Diseases 0.000 claims description 11
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003483 aging Methods 0.000 claims description 9
- 238000010908 decantation Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract 2
- 238000001914 filtration Methods 0.000 abstract 2
- 238000005086 pumping Methods 0.000 abstract 2
- VMKYLARTXWTBPI-UHFFFAOYSA-N copper;dinitrate;hydrate Chemical compound O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O VMKYLARTXWTBPI-UHFFFAOYSA-N 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 8
- YCIHPQHVWDULOY-FMZCEJRJSA-N (4s,4as,5as,6s,12ar)-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide;hydrochloride Chemical compound Cl.C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O YCIHPQHVWDULOY-FMZCEJRJSA-N 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000010849 Ion Exchange Activity Effects 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
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- 238000005842 biochemical reaction Methods 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
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- 230000008878 coupling Effects 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JAUGGEIKQIHSMF-UHFFFAOYSA-N dialuminum;dimagnesium;dioxido(oxo)silane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O JAUGGEIKQIHSMF-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of an attapulgite clay -TiO2-Cu2O compound visible photocatalyst. The method comprises the following steps: 1)preparation of acidified attapulgite clay; 2)preparation of an attapulgite clay -TiO2 catalysis material: adding a tetrabutyl titanate-ethanol solution in the acidified attapulgite clay through an in-situ sol-gel technology, uniformly stirring, adding an ethanol-water solution drop by drop, stirring, aging, performing pumping filtration, drying, grinding and calcining to prepare the attapulgite clay -TiO2 catalysis material; and 3)preparation of the attapulgite clay -TiO2-Cu2O compound photocatalyst: adding a copper nitrate hydrate solution in the attapulgite clay -TiO2-Cu2O catalysis material, adding a sodium hydroxide solution, stirring, reducing by hydrazine hydrate, stirring, performing pumping filtration, washing, drying, grinding, calcining to prepare the -TiO2-Cu2O compound visible photocatalyst.
Description
Technical field
The present invention relates to photochemical catalyst preparing technical field, be specifically related to a kind of attapulgite clay-TiO
2-Cu
2the preparation method of the compound visible light catalyst of O.
Background technology
The bactericidal properties medicine that antibiotic is the most frequent as people's daily life contact, consumption is maximum, through the lipophilic group of cell membrane, can have higher stability, be easy to produce bioaccumulation.Containing the material seriously suppressed biochemical reaction in some waste water, biochemical process is faced severe challenge.By light-catalysed method, within the enough reaction time, toxic organic compound can be mineralized into CO
2and H
2o, and may cheapness be utilized and the sunshine of green, be solve current environment deterioration and an important channel of energy crisis.
TiO
2because of its stable chemical nature, hypotoxicity, the feature that cheap and easy to get, photocatalytic activity is higher, become one of study hotspot of current catalysis material.But, TiO
2energy gap own is wider, the ultraviolet light of an absorbing wavelength λ < 387nm, and it is poor to organic adsorption capacity, and quantum efficiency is low, and the easy compound of light induced electron and electron hole, makes its disposal efficiency not high.Researcher adopts and changes microstructure CN103641165A, composite structural design CN101914248A, adsorptive support load, ACTA Scientiae Circumstantiae, 2001,21 (1): 123 ~ 125; Silicate journal, 2006,34 (7): 823 ~ 826; Journal of Hazardous Materials, 2010,176:884 ~ 892, carried noble metal Chemical Engineering Journal, 2013,5:1877 ~ 1885, ion doping Applied Catalysis A:General, 2011,399:252 ~ 261; Chemical Engineering Journal, the methods such as 2011,172:615 ~ 622 are to TiO
2modify, strengthen its response to visible ray, make full use of sunshine, improve photocatalytic degradation efficiency.Wherein in the majority with semiconductors coupling modification.
Attapulgite clay, take attapulgite as a kind of porous type chain layered hydrous rich magnesium alumino metasilicate salt clay mineral of main component, there is porous, specific area is large, strong ion exchange activity, " heat endurance, adsorptivity, rheological characteristic, mass transfer performances " are good, the features such as mechanical strength is high, application cost is low, being the excellent carrier of metal oxide catalyst, is again the good adsorbing medium of metal ion.
Current shortage is a kind of to be had the visible light-responded and attapulgite clay-TiO that catalytic degradation efficiency is high
2-Cu
2the preparation method of the compound visible light catalyst of O.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind ofly to be had the visible light-responded and attapulgite clay-TiO that catalytic degradation efficiency is high
2-Cu
2the preparation method of the compound visible light catalyst of O.
To achieve these goals, the present invention is achieved through the following technical solutions: the invention provides a kind of attapulgite clay-TiO
2-Cu
2the preparation method of the compound visible light catalyst of O, comprises the following steps:
(1) preparation of Acid-treatment Palygorskite Clays: by attapulgite clay dispersion in deionized water, stir, decantation removes sand; Attapulgite clay is soaked in watery hydrochloric acid, through stirring and dispersion, obtained Acid-treatment Palygorskite Clays;
(2) attapulgite clay-TiO
2the preparation of catalysis material: butyl titanate-ethanolic solution is joined in the attapulgite clay of acidifying by original position sol-gel technology, stir, drip ethanol-water solution, stirring, ageing, suction filtration, drying, grinding, roasting, obtained attapulgite clay-TiO
2catalysis material;
(3) attapulgite clay-TiO
2-Cu
2the preparation of O composite photo-catalyst: nitrate trihydrate copper solution is joined attapulgite clay-TiO
2in catalysis material, add sodium hydroxide solution, stir, adopt hydrazine hydrate to reduce, stirring, suction filtration, washing, drying, grinding, roasting, obtained attapulgite clay-TiO
2-Cu
2the compound visible light catalyst of O.
Further, in step (1), attapulgite clay is dispersed in the deionized water of 30 ~ 50 times amount, stirs, remove the silt being deposited in bottom with decantation, repeat 3 times, suction filtration; The ratio of attapulgite clay and dilute hydrochloric acid solution is 1g:10mL, is joined by attapulgite clay in dilute hydrochloric acid solution, stirs, gets upper strata mixture, suction filtration, washing, drying, obtained Acid-treatment Palygorskite Clays;
In step (2), butyl titanate is dissolved in ethanol, under agitation join in Acid-treatment Palygorskite Clays, then drip ethanol-water solution with the speed of 1 drop/sec, nitre acid for adjusting pH is 3 ~ 5, stir 2 ~ 5h, ageing 24h, suction filtration, 50 ~ 80 DEG C of dryings, Muffle furnace 300 ~ 600 DEG C of roasting 3 ~ 6h are put into, obtained attapulgite clay-TiO after grinding
2catalysis material;
In step (3), nitrate trihydrate copper liquor is joined attapulgite clay-TiO
2in catalysis material, add sodium hydroxide solution, stir 30min, drip hydrazine hydrate solution; stir 2 ~ 5h, suction filtration, and spend deionized water, 50 ~ 80 DEG C of vacuum drying; after grinding under nitrogen protection, 250 ~ 400 DEG C of roasting 3 ~ 6h in tube furnace, obtained attapulgite clay-TiO
2-Cu
2the compound visible light catalyst of O.
Further, in step (1), dilute hydrochloric acid solution concentration is 0.1 ~ 1mol/L, and mixing time is 2 ~ 3h.
Further, in step (2), ethanol-water solution volume ratio is 60 ~ 80%, attapulgite clay: butyl titanate: ethanol: the ratio of ethanol-water solution is 1g:1 ~ 5mL:5mL:10mL.
Further, in step (3), Cu and Ti amount of substance is than being 1:1 ~ 5, and the concentration of sodium hydroxide solution is 3 ~ 6mol/L, and the concentration of hydrazine hydrate solution is 1 ~ 4mol/L.
Beneficial effect: the present invention makes the original TiO only to ultraviolet light response
2after compound, have response at visible region, catalytic degradation efficiency is high, can utilize Visible Light Induced Photocatalytic organic matter, simultaneously load TiO
2and Cu
2o two kinds of semiconducting compounds, catalyst component activity is high.
Compared with prior art, tool of the present invention has the following advantages:
(1) utilize the feature that attapulgite clay porous, specific area are large, organic matter is had to good absorption property, increase photochemical catalyst and contact with organic, improve photocatalysis effect;
(2) attapulgite clay mechanical strength is high, and be the excellent carrier of metal oxide catalyst, raw material is easily bought, and application cost is low, has widened the range of application of attapulgite clay simultaneously.
Accompanying drawing explanation
Fig. 1 is the attapulgite clay-TiO of preparation in attapulgite clay ATP and embodiment 3
2-Cu
2the EDS figure of O;
Fig. 2 is the attapulgite clay-TiO of preparation in attapulgite clay TAP and embodiment 3
2-Cu
2the XRD figure of O.
Detailed description of the invention
Further illustrate technical solution of the present invention below in conjunction with specific embodiment, these embodiments can not be interpreted as it is restriction to technical solution.
A kind of attapulgite clay-TiO of the present invention
2-Cu
2the preparation method of the compound visible light catalyst of O, comprises the following steps:
(1) preparation of Acid-treatment Palygorskite Clays: be dispersed in by attapulgite clay in the deionized water of 30 ~ 50 times amount, stirs, and removes the silt being deposited in bottom, repeat 3 times, suction filtration with decantation; The ratio of attapulgite clay and dilute hydrochloric acid solution is 1g:10mL, is joined by attapulgite clay in dilute hydrochloric acid solution, stirs, gets upper strata mixture, suction filtration, washing, drying, obtained Acid-treatment Palygorskite Clays; Dilute hydrochloric acid solution concentration is 0.1 ~ 1mol/L, and mixing time is 2 ~ 3h.
(2) attapulgite clay-TiO
2the preparation of catalysis material: butyl titanate is dissolved in ethanol, under agitation join in Acid-treatment Palygorskite Clays, then ethanol-water solution is dripped with the speed of 1 drop/sec, nitre acid for adjusting pH is 3 ~ 5, stirs 2 ~ 5h, ageing 24h, suction filtration, 50 ~ 80 DEG C of dryings, put into Muffle furnace 300 ~ 600 DEG C of roasting 3 ~ 6h after grinding, obtained attapulgite clay-TiO
2catalysis material; Ethanol-water solution volume ratio is 60 ~ 80%, attapulgite clay: butyl titanate: ethanol: the ratio of ethanol-water solution is 1g:1 ~ 5mL:5mL:10mL.
(3) attapulgite clay-TiO
2-Cu
2the preparation of O composite photo-catalyst: nitrate trihydrate copper liquor is joined attapulgite clay-TiO
2in catalysis material, add sodium hydroxide solution, stir 30min, drip hydrazine hydrate solution; stir 2 ~ 5h, suction filtration, and spend deionized water, 50 ~ 80 DEG C of vacuum drying; after grinding under nitrogen protection, 250 ~ 400 DEG C of roasting 3 ~ 6h in tube furnace, obtained attapulgite clay-TiO
2-Cu
2the compound visible light catalyst of O.Cu and Ti amount of substance is than being 1:1 ~ 5, and the concentration of sodium hydroxide solution is 3 ~ 6mol/L, and the concentration of hydrazine hydrate solution is 1 ~ 4mol/L.
Embodiment 1
(1) 5g attapulgite clay is dispersed in the deionized water of 150mL, stirs, remove the silt being deposited in bottom with decantation, repeat 3 times, suction filtration; In attapulgite clay, add 0.1mol/L hydrochloric acid 50mL, stir 2h and get upper strata mixture, suction filtration, washing, 80 DEG C of dryings, obtain Acid-treatment Palygorskite Clays;
(2) 2mL butyl titanate is dissolved in 10mL ethanolic solution, join in 2g Acid-treatment Palygorskite Clays under slow stirring, then 80% ethanol-water solution of 20mL is dripped with the speed of 1 drop/sec, nitric acid regulates pH=3, stirs 2h, ageing 24h, suction filtration, 50 DEG C of dryings, put into Muffle furnace 300 DEG C of roasting 3h, obtain attapulgite clay-TiO after grinding
2catalysis material;
(3) 0.274g Cu (NO is taken
3)
23H
2o is dissolved in 50mL water, under agitation joins the attapulgite clay-TiO of step (2)
2in catalysis material, add the sodium hydroxide solution 5mL of 3mol/L, stir 30min, drip the hydrazine hydrate solution 5mL of 1mol/L; stir 2h, suction filtration, and spend deionized water; 50 DEG C of vacuum drying, 250 DEG C of roasting 3h in tube furnace under nitrogen protection after grinding, obtain attapulgite clay-TiO
2-Cu
2o composite photo-catalyst.
Embodiment 2
Embodiment 2 is with the difference of embodiment 1: in step (1), be dispersed in the deionized water of 200mL by 5g attapulgite clay, stirs, and removes the silt being deposited in bottom, repeat 3 times, suction filtration with decantation; In attapulgite clay, add 0.2mol/L hydrochloric acid 50mL, stir 2.5h and get upper strata mixture, suction filtration, washing, 80 DEG C of dryings, obtain Acid-treatment Palygorskite Clays;
In step (2), 6mL butyl titanate is dissolved in 10mL ethanolic solution, join in 2g Acid-treatment Palygorskite Clays under slow stirring, then drip 75% ethanol-water solution of 20mL with the speed of 1 drop/sec, nitric acid regulates pH=4, stir 3h, ageing 24h, suction filtration, 60 DEG C of dryings, put into Muffle furnace 400 DEG C of roasting 4h after grinding, obtain attapulgite clay-TiO
2catalysis material;
In step (3), take 1.372g Cu (NO
3)
23H
2o is dissolved in 50mL water, under agitation joins step 2) ATP-TiO
2in catalysis material, add the sodium hydroxide solution 5mL of 4mol/L, stir 30min, drip the hydrazine hydrate solution 5mL of 2mol/L; stir 3h, suction filtration, and spend deionized water; 60 DEG C of vacuum drying, 300 DEG C of roasting 4h in tube furnace under nitrogen protection after grinding, obtain attapulgite clay-TiO
2-Cu
2o composite photo-catalyst.
Embodiment 3
Embodiment 3 is with the difference of embodiment 1: in step (1), be dispersed in the deionized water of 200mL by 5g attapulgite clay, stirs, and removes the silt being deposited in bottom, repeat 3 times, suction filtration with decantation; In attapulgite clay, add 0.5mol/L hydrochloric acid 50mL, stir 3h and get upper strata mixture, suction filtration, washing, 80 DEG C of dryings, obtain Acid-treatment Palygorskite Clays;
In step (2), 8mL butyl titanate is dissolved in 10mL ethanolic solution, join in 2g Acid-treatment Palygorskite Clays under slow stirring, then drip 70% ethanol-water solution of 20mL with the speed of 1 drop/sec, nitric acid regulates pH=4, stir 4h, ageing 24h, suction filtration, 70 DEG C of dryings, put into Muffle furnace 500 DEG C of roasting 5h after grinding, obtain attapulgite clay-TiO
2catalysis material;
In step (3), take 2.743g Cu (NO
3)
23H
2o is dissolved in 50mL water, under agitation joins step 2) ATP-TiO
2in catalysis material, add the sodium hydroxide solution 5mL of 5mol/L, stir 30min, drip the hydrazine hydrate solution 5mL of 3mol/L; stir 4h, suction filtration, and spend deionized water; 70 DEG C of vacuum drying, 350 DEG C of roasting 5h in tube furnace under nitrogen protection after grinding, obtain attapulgite clay-TiO
2-Cu
2o composite photo-catalyst.
As illustrated in figs. 1 and 2, Fig. 1 is the attapulgite clay-TiO of preparation in Acid-treatment Palygorskite Clays ATP and embodiment 3
2-Cu
2the EDS figure of O, as can be seen from Figure 1, through TiO
2and Cu
2in the catalyst of O load, the content showed increased of Ti element and Cu element, original composition Si, Al, Mg of ATP obviously reduce, and TiO is described
2and Cu
2these two kinds of semiconductors of O have successfully loaded on attapulgite clay.
Fig. 2 is the attapulgite clay-TiO of preparation in Acid-treatment Palygorskite Clays ATP and embodiment 3
2-Cu
2the XRD figure of O, as can be seen from Figure 2,8.20 ° are positioned in ATP collection of illustrative plates, 21.24 °, the diffraction maximum that 34.34 ° of places of grade occur, respectively at (110) of attapulgite (JCPDS NO.21-0958), (121), (002) crystal face coincide, and attapulgite clay rod stone composition is more; Be positioned at 13.50 °, 16.08 °, 19.64 °, 20.67 °, the diffraction maximum that 26.69 ° of places of grade occur, respectively at SiO
2(011) of (JCPDS NO.51-1380), (220), (400), (301), (101) crystal face coincide, and illustrates that this attapulgite clay contains a small amount of quartz.Through TiO
2and Cu
2in the catalyst of O load, occur being positioned at 25.35 °, the diffraction maximum that 48.09 ° of places of grade occur, respectively at TiO
2(101) of (JCPDS NO.65-5714), (200) crystal face coincide, and is typical anatase; Be positioned at 29.63 °, 36.47 °, 42.42 °, the diffraction maximum that 61.58 ° of places of grade occur, respectively at Cu
2(110) of O (JCPDS NO.21-3288), (111), (200), (220) crystal face coincide, and the diffraction maximum of attapulgite and quartz obviously weakens simultaneously, and TiO is described
2and Cu
2these two kinds of semiconductors of O have successfully loaded on attapulgite clay.
Embodiment 4
Embodiment 4 is with the difference of embodiment 1: in step (1), be dispersed in the deionized water of 250mL by 5g attapulgite clay, stirs, and removes the silt being deposited in bottom, repeat 3 times, suction filtration with decantation; In attapulgite clay, add 1mol/L hydrochloric acid 50mL, stir 3h and get upper strata mixture, suction filtration, washing, 80 DEG C of dryings, obtain Acid-treatment Palygorskite Clays;
In step (2), 10mL butyl titanate is dissolved in 10mL ethanolic solution, join in 2g Acid-treatment Palygorskite Clays under slow stirring, then drip 60% ethanol-water solution of 20mL with the speed of 1 drop/sec, nitric acid regulates pH=5, stir 5h, ageing 24h, suction filtration, 80 DEG C of dryings, put into Muffle furnace 600 DEG C of roasting 6h after grinding, obtain attapulgite clay-TiO
2catalysis material;
In step (3), take 6.858g Cu (NO
3)
23H
2o is dissolved in 50mL water, under agitation joins the ATP-TiO of step (2)
2in catalysis material, add the sodium hydroxide solution 5mL of 5mol/L, stir 30min, drip the hydrazine hydrate solution 5mL of 4mol/L; stir 5h, suction filtration, and spend deionized water; 80 DEG C of vacuum drying, 400 DEG C of roasting 6h in tube furnace under nitrogen protection after grinding, obtain attapulgite clay-TiO
2-Cu
2o composite photo-catalyst.
Test 1
50mg photochemical catalyst is joined in the quartz test tube of the 20mg/L quadracycline solution filling 50mL, 30min is stirred under subdued light conditions, then under 500w xenon lamp, photocatalytic degradation experiment is carried out, 5mL is sampled every 20min, centrifugal, remove catalyst, get supernatant and survey absorbance, according to Lambert-Beer's law, calculate the degradation rate of quadracycline.Light-catalyzed reaction 90min, the degradation rate of quadracycline is 61.3%.
Test 2
According to method described in test 1, catalyst obtained in embodiment 2 is carried out light degradation experiment, light-catalyzed reaction 90min, the degradation rate of quadracycline is 78.2%.
Test 3
According to method described in test 1, catalyst obtained in embodiment 3 is carried out light degradation experiment, light-catalyzed reaction 90min, the degradation rate of quadracycline is 88.7%.
Test 4
According to method described in test 1, catalyst obtained in embodiment 4 is carried out light degradation experiment, light-catalyzed reaction 90min, the degradation rate of quadracycline is 74.5%.
The present invention makes the original TiO only to ultraviolet light response
2after compound, have response at visible region, catalytic degradation efficiency is high, can utilize Visible Light Induced Photocatalytic organic matter, simultaneously load TiO
2and Cu
2o two kinds of semiconducting compounds, catalyst component activity is high.
Compared with prior art, tool of the present invention has the following advantages:
(1) utilize the feature that attapulgite clay porous, specific area are large, organic matter is had to good absorption property, increase photochemical catalyst and contact with organic, improve photocatalysis effect;
(2) attapulgite clay mechanical strength is high, and be the excellent carrier of metal oxide catalyst, raw material is easily bought, and application cost is low, has widened the range of application of attapulgite clay simultaneously.
More than show and describe general principle of the present invention, principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and description just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and application claims protection domain is defined by appending claims, description and equivalent thereof.
Claims (5)
1. an attapulgite clay-TiO
2-Cu
2the preparation method of the compound visible light catalyst of O, is characterized in that comprising the following steps:
(1) preparation of Acid-treatment Palygorskite Clays: by attapulgite clay dispersion in deionized water, stir, decantation removes sand; Attapulgite clay is soaked in watery hydrochloric acid, through stirring and dispersion, obtained Acid-treatment Palygorskite Clays;
(2) attapulgite clay-TiO
2the preparation of catalysis material: butyl titanate-ethanolic solution is joined in the attapulgite clay of acidifying by original position sol-gel technology, stir, drip ethanol-water solution, stirring, ageing, suction filtration, drying, grinding, roasting, obtained attapulgite clay-TiO
2catalysis material;
(3) attapulgite clay-TiO
2-Cu
2the preparation of O composite photo-catalyst: nitrate trihydrate copper solution is joined attapulgite clay-TiO
2in catalysis material, add sodium hydroxide solution, stir, adopt hydrazine hydrate to reduce, stirring, suction filtration, washing, drying, grinding, roasting, obtained attapulgite clay-TiO
2-Cu
2the compound visible light catalyst of O.
2. attapulgite clay-TiO according to claim 1
2-Cu
2the preparation method of the compound visible light catalyst of O, is characterized in that:
In step (1), attapulgite clay is dispersed in the deionized water of 30 ~ 50 times amount, stirs, remove the silt being deposited in bottom with decantation, repeat 3 times, suction filtration; The ratio of attapulgite clay and dilute hydrochloric acid solution is 1g:10mL, is joined by attapulgite clay in dilute hydrochloric acid solution, stirs, gets upper strata mixture, suction filtration, washing, drying, obtained Acid-treatment Palygorskite Clays;
In step (2), butyl titanate is dissolved in ethanol, under agitation join in Acid-treatment Palygorskite Clays, then drip ethanol-water solution with the speed of 1 drop/sec, nitre acid for adjusting pH is 3 ~ 5, stir 2 ~ 5h, ageing 24h, suction filtration, 50 ~ 80 DEG C of dryings, Muffle furnace 300 ~ 600 DEG C of roasting 3 ~ 6h are put into, obtained attapulgite clay-TiO after grinding
2catalysis material;
In step (3), nitrate trihydrate copper liquor is joined attapulgite clay-TiO
2in catalysis material, add sodium hydroxide solution, stir 30min, drip hydrazine hydrate solution; stir 2 ~ 5h, suction filtration, and spend deionized water, 50 ~ 80 DEG C of vacuum drying; after grinding under nitrogen protection, 250 ~ 400 DEG C of roasting 3 ~ 6h in tube furnace, obtained attapulgite clay-TiO
2-Cu
2the compound visible light catalyst of O.
3. attapulgite clay-TiO according to claim 2
2-Cu
2the preparation method of the compound visible light catalyst of O, is characterized in that: in step (1), and dilute hydrochloric acid solution concentration is 0.1 ~ 1mol/L, and mixing time is 2 ~ 3h.
4. attapulgite clay-TiO according to claim 2
2-Cu
2the preparation method of the compound visible light catalyst of O, is characterized in that: in step (2), and ethanol-water solution volume ratio is 60 ~ 80%, attapulgite clay: butyl titanate: ethanol: the ratio of ethanol-water solution is 1g:1 ~ 5mL:5mL:10mL.
5. attapulgite clay-TiO according to claim 2
2-Cu
2the preparation method of the compound visible light catalyst of O, is characterized in that: in step (3), Cu and Ti amount of substance is than being 1:1 ~ 5, and the concentration of sodium hydroxide solution is 3 ~ 6mol/L, and the concentration of hydrazine hydrate solution is 1 ~ 4mol/L.
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Application publication date: 20150909 |