CN105728055A - Preparation method of TiO2-AER composite photocatalyst - Google Patents
Preparation method of TiO2-AER composite photocatalyst Download PDFInfo
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- CN105728055A CN105728055A CN201610069585.1A CN201610069585A CN105728055A CN 105728055 A CN105728055 A CN 105728055A CN 201610069585 A CN201610069585 A CN 201610069585A CN 105728055 A CN105728055 A CN 105728055A
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- Prior art keywords
- aer
- tio
- resin
- deionized water
- catalyst
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 52
- 229920005989 resin Polymers 0.000 claims abstract description 49
- 239000008367 deionised water Substances 0.000 claims abstract description 43
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000001035 drying Methods 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000010936 titanium Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 79
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 48
- 230000004044 response Effects 0.000 claims description 27
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 14
- 229910052719 titanium Inorganic materials 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 7
- 239000003957 anion exchange resin Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- -1 polytetrafluoroethylene Polymers 0.000 abstract description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract 1
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 21
- 238000010521 absorption reaction Methods 0.000 description 12
- 239000008187 granular material Substances 0.000 description 12
- 238000004042 decolorization Methods 0.000 description 10
- 238000007146 photocatalysis Methods 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000005286 illumination Methods 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 6
- 229940012189 methyl orange Drugs 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004061 bleaching Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B01J35/39—
Abstract
The invention discloses a preparation method of a TiO2-AER composite photocatalyst.The preparation method comprises the following steps that 1, AER resin is preprocessed; 2, 0.99-5.96 mL of tetrabutyl titanate is added into 30 mL of absolute ethyl alcohol, the mixture is stirred to form a transparent faint yellow solution A, the preprocessed AER resin is added into the solution A, stirring is continuously performed, and the ratio of the amount-of-substance n (Ti<4+>) of titanium atoms to the amount-of-substance n (OH<->) of hydroxy in the resin is 1:(1-6); 3, the solid-liquid mixture is transferred into a 50-mL reaction kettle provided with a polytetrafluoroethylene lining, the reaction kettle is put in a constant-temperature drying box, and reacting is performed for 6-24 h; 4, the reaction kettle is naturally cooled until the temperature is lowered to room temperature, alternate washing is performed with absolute ethyl alcohol and deionized water, drying is performed, and then the TiO2-AER composite photocatalyst is prepared.The composite photocatalyst is good in stability, high in activity and reusability and good in catalytic activity.
Description
Technical field
The present invention relates to catalyst technical field, be specifically related to a kind of TiO2The preparation side of/AER composite photo-catalyst
Method.
Background technology
Quasiconductor TiO2Because of its have nontoxic, photocatalytic activity is high, oxidability is strong, catabolite is CO2With
H2The advantages such as O are widely used at numerous areas such as dye wastewater treatment.Due to powder TiO2The easiest
Reunite, and be suspended in solution after reaction and be not readily separated, reclaim, by TiO2It is fixed on different carriers and is prepared as
Loaded photocatalyst becomes the study hotspot of current photocatalysis field.TiO2After immobilized, can solve its
Easily reunion in actual application, difficult recovery problem, but contaminant molecule and TiO2Surface contact probability reduces, this
Affect the degradation rate of catalyst to a certain extent, make the activity reduction of loaded photocatalyst.For obtaining
Good using effect, by TiO2It is carried on to have and target contaminant is had stronger adsorption and enrichment performance, not
Affect TiO2There is stronger binding ability on the premise of activity therewith, be prone on the carrier of solid-liquor separation.
717 type strong-base anion-exchange resins are that pale yellow transparent spheroid, highly basic group exchange capacity are big, inhale
Attached ability is strong.Anion can be with its highly basic base exchange being combined with the form of chemical bond, adsorption activity group
Contaminant molecule can be enriched with, and then improve photocatalytic activity.
At present, the TiO that a kind of photocatalyst activity is high is lacked2The preparation method of/AER composite photo-catalyst.
Summary of the invention
For solving the problems referred to above, it is an object of the invention to provide the TiO that a kind of photocatalyst activity is high2/AER
The preparation method of composite photo-catalyst.
For realizing above-mentioned technical purpose, the technical solution used in the present invention is as follows: a kind of TiO of the present invention2/AER
The preparation method of composite photo-catalyst, comprises the steps:
(1) AER resin pretreatment；
(2) adding the butyl titanate of 0.99-5.96mL in 30mL dehydrated alcohol, stirring is formed transparent
Yellow solution A；Pretreated AER is joined in solution A, continues stirring；Described titanium atom thing
Amount n (the Ti of matter4+) with the amount n (OH of hydroxylated material in resin-) ratio be 1:1-6；
(3) solidliquid mixture is proceeded to the teflon-lined reactor of 50mL, is placed in freeze-day with constant temperature
In case, the response time is 6-24h；
(4) naturally cool to room temperature, with dehydrated alcohol and deionized water alternately washing, be dried, prepare TiO2/AER
Composite photo-catalyst.
Further, in step (1), described resin deionized water cleans and soaks 24-30h after colourless,
Separate；Soaking 4-6h with the NaOH of the 4-5% of 2-4 times of volume successively, be washed with deionized water to neutrality；
Soaking 4-6h with the 3-4%HCl of 2-4 times of volume, deionized water is washed till neutrality；The 4-5%NaOH of 2-4 times of volume
Soak 8-10h, then be washed with deionized water to neutrality；It is 80 DEG C of thermostatic drying chamber dry for standby in temperature, will
Resin is from Cl-Type is converted into OH-Type.
Further, in step (1), described resin deionized water cleans and soaks 24h after colourless, point
From；Soaking 4h with the NaOH of the 5% of 2 times of volumes successively, be washed with deionized water to neutrality；With 2 times of bodies
Long-pending 4%HCl soaks 4h, and deionized water is washed till neutrality；The 5%NaOH using 2 times of volumes soaks 8h, then
It is washed with deionized water to neutrality；It is 80 DEG C of thermostatic drying chamber dry for standby in temperature, by resin from Cl-Type converts
For OH-Type.
Further, in step (2), described resin is 717 type strong-base anion-exchange resins.
Further, in step (2), 30mL dehydrated alcohol adds the metatitanic acid of 0.99-5.96mL
Four butyl esters, stirring 15-30min forms transparent yellow solution A；
Pretreated AER is joined in solution A, continues stirring 30-60min；Described titanium atom material
Amount n (Ti4+) it is 1:1-6 with the ratio of amount n (OH-) of hydroxylated material in resin.
Further, in step (3), solidliquid mixture is proceeded to the teflon-lined of 50mL
Reactor, is placed in temperature is 150 DEG C of thermostatic drying chambers, and the response time is 6-24h.
Further, in step (3), solidliquid mixture is proceeded to the polytetrafluoroethyllining lining of 50mL
Reactor, be placed in temperature is 150 DEG C of thermostatic drying chambers, the response time is 18h.
Further, in step (4), naturally cool to room temperature, replace with dehydrated alcohol and deionized water
Wash 3-6 time；110 DEG C of thermostatic drying chambers are dried 10-13h, prepare TiO2/ AER composite photo-catalyst.
Beneficial effect: complex light photocatalyst good stability of the present invention, photocatalyst activity is high, reuses
Property strong, be catalyzed good activity.
Compared with prior art, present invention have the advantage that
(1) loaded photocatalyst of the present invention not only achieves TiO2Immobilized in solid globules AER,
And ensure that the strong absorption property of AER resin.Composite is due to the absorption property of AER and TiO2Light is urged
Change effect is mutually collaborative shows excellent photocatalytic activity.
(2) TiO of load on resin2Granule part covering resin surface, this structure can be the most collaborative
The absorption property of AER resin and TiO2Photocatalysis, accelerate rate of photocatalytic oxidation, improve reaction efficiency.
Accompanying drawing explanation
Fig. 1 is pure AER and TiO of the present invention2The XRD figure of/AER；
Fig. 2 is the a-N1 of the present invention, the SEM photograph of b-N2, c-N4, d-N6 (10000 ×)；
Fig. 3 is the EDS spectrogram of the AER surface spheroidal particle of the present invention；
Fig. 4 is pure AER and TiO of the present invention2The FT-IR figure of/AER；
Fig. 5 is different n (Ti4+)/n (OH of the present invention-) TiO2The decolouring curve of/AER；
Fig. 6 is the TiO of the differential responses time of the present invention2The decolouring curve of/AER；
Fig. 7 is the TiO of the differential responses time of the present invention2The XRD figure of/AER；
Fig. 8 is the collection of illustrative plates of the reusability of the different photocatalysts of the present invention.
Detailed description of the invention
Further illustrate the present invention by the following examples.It should be understood that these embodiments are the present invention
Explaination and citing, limit the scope of the present invention the most in any form.
Embodiment 1
Reagent and instrument
201 × 7 (717) type strong-base anion-exchange resins (Shanghai Ling Feng chemical reagent company limited),
36% concentrated hydrochloric acid (AR, Shanghai Bo He fine chemicals company limited), sodium hydroxide, dehydrated alcohol (AR,
Chemical Reagent Co., Ltd., Sinopharm Group), and tetra-n-butyl titanate (CP, >=98.0%, the chemistry examination of traditional Chinese medicines group
Agent company limited), methyl orange (AR, Shanghai reagent three factory).
Electric drying oven with forced convection (Shanghai Yiheng Scientific Instruments Co., Ltd)；754PC UV, visible light spectrophotometric
Meter (Shanghai Ao Pule Instrument Ltd.)；D8 series of X-ray powder diffractometer (Brooker company of Germany),
Hitachi S-4800 high-resolution field emission scanning electron microscope (HIT)；FTIR-650 Fourier transformation is red
External spectrum instrument (Tianjin Gangdong Technology Development Co., Ltd.)；YZ-GHX-A photochemical reaction instrument (Shenzhen
Dong Luyang Industrial Co., Ltd.).
A kind of TiO of the present invention2The preparation method of/AER composite photo-catalyst, comprises the steps:
(1) AER resin pretreatment；Described resin deionized water cleans and soaks 24h after colourless, separates；
Soaking 4h with the NaOH of the 5% of 2 times of volumes successively, be washed with deionized water to neutrality；With 2 times of volumes
4%HCl soaks 4h, and deionized water is washed till neutrality；Use 2 times of volumes 5%NaOH soak 8h, then spend from
Son is washed to neutrality；It is 80 DEG C of thermostatic drying chamber dry for standby in temperature, by resin from Cl-Type is converted into OH-
Type.
(2) adding the butyl titanate of 5.96mL in 30mL dehydrated alcohol, stirring 15min is formed transparent
Yellow solution A；Pretreated AER is joined in solution A, continues stirring 30min；Described titanium
Amount n (the Ti of atom species4+) with the amount n (OH of hydroxylated material in resin-) ratio be 1:1；
(3) solidliquid mixture proceeds to the teflon-lined reactor of 50mL, and being placed in temperature is 150 DEG C
In thermostatic drying chamber, the response time is 18h；
(4) room temperature is naturally cooled to, with dehydrated alcohol and deionized water alternately washing 3 times；110 DEG C of constant temperature
Drying baker is dried 12h, prepares TiO2/ AER composite photo-catalyst, prepares sample N1.
Embodiment 2
Embodiment 2 is with the difference of embodiment 1:
A kind of TiO of the present invention2The preparation method of/AER composite photo-catalyst, comprises the steps:
In step (1), AER resin pretreatment；Described resin deionized water cleans and soaks after colourless
26h, separates；Soaking 5h with the NaOH of the 4% of 2.5 times of volumes successively, be washed with deionized water to neutrality；
Soaking 5h with the 3%HCl of 3 times of volumes, deionized water is washed till neutrality；The 4.5%NaOH of 3 times of volumes soaks 9h,
It is washed with deionized water again to neutrality；It is 80 DEG C of thermostatic drying chamber dry for standby in temperature, by resin from Cl-type
It is converted into OH-type.
In step (2), 30mL dehydrated alcohol adds the butyl titanate of 2.98mL, stir 20min
Form transparent yellow solution A；Pretreated AER is joined in solution A, continues stirring 40min；
Amount n (the Ti of described titanium atom material4+) with the amount n (OH of hydroxylated material in resin-) ratio be 1:2；
In step (3), solidliquid mixture is proceeded to the teflon-lined reactor of 50mL, puts
In temperature is 150 DEG C of thermostatic drying chambers, the response time is 18h；
In step (4), naturally cool to room temperature, with dehydrated alcohol and deionized water alternately washing 4 times；
110 DEG C of thermostatic drying chambers are dried 10h, prepare TiO2/ AER composite photo-catalyst, prepares sample N2.
Embodiment 3
Embodiment 3 is with the difference of embodiment 1:
A kind of TiO of the present invention2The preparation method of/AER composite photo-catalyst, comprises the steps:
In step (1), AER resin pretreatment；Described resin deionized water cleans and soaks after colourless
30h, separates；Soaking 6h with the NaOH of the 5% of 4 times of volumes successively, be washed with deionized water to neutrality；With
The 4%HCl of 4 times of volumes soaks 6h, and deionized water is washed till neutrality；The 5%NaOH of 4 times of volumes soaks 10h,
It is washed with deionized water again to neutrality；It is 80 DEG C of thermostatic drying chamber dry for standby in temperature, by resin from Cl-Type turns
Turn to OH-Type.
In step (2), 30mL dehydrated alcohol adds the butyl titanate of 0.99mL, stir 30min
Form transparent yellow solution A；
Pretreated AER is joined in solution A, continues stirring 60min；The amount of described titanium atom material
n(Ti4+) with the amount n (OH of hydroxylated material in resin-) ratio be 1:4；Described resin be 717 type strong basicities cloudy from
Sub-exchange resin.
In step (3), solidliquid mixture is proceeded to the teflon-lined reactor of 50mL, puts
In temperature is 150 DEG C of thermostatic drying chambers, the response time is 18h；
In step (4), naturally cool to room temperature, with dehydrated alcohol and deionized water alternately washing 6 times；
110 DEG C of thermostatic drying chambers are dried 12h, prepare TiO2/ AER composite photo-catalyst, prepares sample N4.
Embodiment 4
Embodiment 4 is with the difference of embodiment 1:
A kind of TiO of the present invention2The preparation method of/AER composite photo-catalyst, comprises the steps:
In step (1), AER resin pretreatment；Resin deionized water cleans and soaks 24h after colourless,
Separate；Soak 4h with the 5%NaOH of 2 times of volumes successively, be washed with deionized water to neutrality；With 2 times of volumes
4%HCl soaks 4h, and deionized water is washed till neutrality；Use 2 times of volumes 5%NaOH soak 8h, then spend from
Son is washed to neutrality；It is 80 DEG C of thermostatic drying chamber dry for standby in temperature.
In step (2), 30mL dehydrated alcohol adds the butyl titanate of 0.99mL, stir 15min
Form transparent yellow solution A；Pretreated AER is joined in solution A, continues stirring 30min；
Amount n (the Ti of described titanium atom material4+) with the amount of hydroxylated material in resin than n (OH-) it is 1:6；
In step (3), solidliquid mixture is proceeded to the teflon-lined reactor of 50mL, puts
In temperature is 150 DEG C of thermostatic drying chambers, the response time is 18h；
In step (4), naturally cool to room temperature, with dehydrated alcohol and deionized water alternately washing 3 times；
110 DEG C of thermostatic drying chambers are dried 12h, prepare TiO2/ AER composite photo-catalyst, prepares sample N6.
Embodiment 5
Embodiment 5 is with the difference of embodiment 3:
A kind of TiO of the present invention2The preparation method of/AER composite photo-catalyst, comprises the steps:
In step (3), solidliquid mixture is proceeded to the teflon-lined reactor of 50mL, puts
In temperature is 150 DEG C of thermostatic drying chambers, the response time is 6h,
In step (4), naturally cool to room temperature, with dehydrated alcohol and deionized water alternately washing 6 times；
110 DEG C of thermostatic drying chambers are dried 12h, prepare TiO2/ AER composite photo-catalyst, prepares sample T6.
Embodiment 6
Embodiment 6 is with the difference of embodiment 3:
A kind of TiO of the present invention2The preparation method of/AER composite photo-catalyst, comprises the steps:
In step (3), solidliquid mixture is proceeded to the teflon-lined reactor of 50mL, puts
In temperature is 150 DEG C of thermostatic drying chambers, the response time is 12h,
In step (4), naturally cool to room temperature, with dehydrated alcohol and deionized water alternately washing 6 times；
110 DEG C of thermostatic drying chambers are dried 12h, prepare TiO2/ AER composite photo-catalyst, prepares sample T12.
Embodiment 7
Embodiment 7 is with the difference of embodiment 3:
A kind of TiO of the present invention2The preparation method of/AER composite photo-catalyst, comprises the steps:
In step (3), solidliquid mixture is proceeded to the teflon-lined reactor of 50mL, puts
In temperature is 150 DEG C of thermostatic drying chambers, the response time is 18h,
In step (4), naturally cool to room temperature, with dehydrated alcohol and deionized water alternately washing 6 times；
110 DEG C of thermostatic drying chambers are dried 13h, prepare TiO2/ AER composite photo-catalyst, prepares sample T18.
Embodiment 8
Embodiment 8 is with the difference of embodiment 3:
A kind of TiO of the present invention2The preparation method of/AER composite photo-catalyst, comprises the steps:
In step (3), solidliquid mixture is proceeded to the teflon-lined reactor of 50mL, puts
In temperature is 150 DEG C of thermostatic drying chambers, the response time is 24h,
In step (4), naturally cool to room temperature, with dehydrated alcohol and deionized water alternately washing 6 times；
110 DEG C of thermostatic drying chambers are dried 12h, prepare TiO2/ AER composite photo-catalyst, prepares sample T24.
Test 1
The XRD analysis of sample
As it is shown in figure 1, be pure AER and TiO of the present invention2The XRD figure of/AER；Fig. 1 be pure AER and
n(Ti4+)/n (OH-)=1:4, the TiO of reaction 18h synthesis2The XRD figure of/AER composite photo-catalyst.TiO2/AER
XRD figure spectrum at 2 θ=25.3 °, 38.1 °, 48.0 °, 54.1 ° and 62.6 °, occur in that feature is spread out
Penetrate peak, find corresponding Anatase TiO respectively with standard XRD pattern (PDFNo21-1272) comparison2(101),
(004), (200), (105) and (204) crystal face, the TiO of Anatase is described2It is carried on resin.Load
TiO2The characteristic peak of AER do not change, illustrate to have loaded TiO2Resin anion (R.A.) structure not by
Destroying, the composite of this structure has both TiO2With the characteristic of AER, both are made to produce mutual synergism
And then raising photocatalytic activity is possibly realized.
Test 2
Sem analysis
By the TiO of sample N1, N2, N4, N6 that embodiment 1 to embodiment 4 prepares2/ AER composite photocatalyst
Agent carries out sem analysis, obtains the structure shown in Fig. 2；As in figure 2 it is shown, be the N1 (a) of the present invention, N2 (b),
The SEM photograph of N4 (c), N6 (d) (10000 ×).From figure a～d, along with n (Ti4+)/n(OH-) subtract
Little, the TiO of the upper load of AER2Granule is the fewest.TiO in a, b figure2Occur substantially, partly between granule
Agglomeration, the TiO that in d, resin surface generates2Granule is less, has loaded on resin more spherical in figure c
TiO2Granule, be evenly distributed, do not reunite, its diameter between 1～2 μm, TiO2Granule is the completeest
All standing resin surface, this structure is conducive to absorption property and the TiO of AER in light-catalyzed reaction2Light urge
Change effect is the most collaborative.
Test 3
EDS analyzes
As it is shown on figure 3, be the EDS spectrogram of the resin surface spheroidal particle of the present invention.Fig. 3 only has Ti, O
Element peak, there is no other element peaks, and the atomic percent of titanium and oxygen be about 1:2, thus may determine that
AER area load is TiO2, the product obtained is TiO2/AER。
Test 4
FT-IR analyzes
As shown in Figure 4, for AER and TiO of the present invention2The FT-IR collection of illustrative plates of/AER composite photo-catalyst.AER
At 3435cm-1、1642cm-1Absworption peak be respectively belonging to the stretching vibration of resin-OH and carbonyl, compound
Material has been moved to 3429cm-1And 1627cm-1, illustrate that metallic atom has with the oxygen atom on hydroxyl and carbonyl and join
Position bonding, shows TiO2It not simple physical absorption with interlaminar resin but be combined in the way of chemical bond.By
In the existence of chemical bond, TiO2Difficult drop-off, so composite stability during reusing is preferable.
Test 5
Photocatalysis is tested
Pipette the methyl orange solution 50mL of 50mg/L in cylindrical light catalytic reaction cell, put into magneton,
Add 0.04g photocatalyst, insert in photochemical reaction instrument, open fan, under dark condition, stir 1h,
Reach adsorption-desorption balance.Continue stirring of ventilating, using 300W high voltage mercury lamp as light source, carry out photocatalysis
Reaction, light source circulating cooling water cooling.Every 20min sampling and measuring its at maximum absorption wavelength (464nm)
The absorbance at place.By absorbance and concentration linear relationship (A=0.01855+0.06732C, R2=0.9988,
A is concentration, and C is absorbance), obtain corresponding concentration value.The percent of decolourization of methyl orange solution in photocatalytic process
(η): η=(A0-At)/A0=(C0-Ct)/C0, in formula, C0, Ct, A0 and At represent MO solution respectively
Initial concentration, t concentration, initial absorbance and t absorbance.
The reusability of photocatalyst
For investigating photocatalyst AER, TiO2/AER、TiO2Reusability, reacted solution is removed,
The methyl orange solution 50mL rejoining 50mg/L carries out photocatalysis experiment, the most repeatedly 5 results, as
Shown in Fig. 8, for the collection of illustrative plates of reusability of the different photocatalysts of the present invention.TiO2To methyl orange solution
Percent of decolourization is reduced to 63.22% by original 76.92%, declines 13.70%；Composite photo-catalyst TiO2/ AER's
Percent of decolourization is declined by less than 3%.TiO is described2The support type light obtained on resin is loaded in the way of chemical bonding
Catalyst is not only easy to separate from the dye solution reacted and reclaim, and relatively powder body TiO2Stablize,
Repeat practical.
And the percent of decolourization of methyl orange is only had 5.24% when second time uses by AER, illustrate that resin is primary
Experiment has basically reached saturation；With composite photo-catalyst TiO2/ AER (taking off when using second time
Color rate is 95.41%, only have dropped 0.66% relatively for the first time) contrast understands, and in solution, the decolouring of methyl orange is also
It not that the simple adsorption of AER causes, but the TiO being first then supported by AER adsorption and enrichment2?
Grain photocatalytic degradation.
TiO2The photocatalytic activity of/AER
As it is shown in figure 5, be the photocatalyst TiO of the present invention2, N1, N2, N4, N6, AER molten to methyl orange
The decolouring curve (-60～0min is adsorption process) of liquid.When adsorbing 1h, methyl orange solution is taken off by AER
Color rate is 73.14% to the maximum；With the carrying out of illumination, the solution percent of decolourization adding AER is basically unchanged, and AER is described
Not having photocatalysis performance, decolouring is that the absorption under dark condition causes.Add TiO2Solution adsorption bleaching rate
Minimum only has 12.24%；Under illumination, its percent of decolourization increasing degree is maximum, and TiO is described2Absorption property the most weak,
Mainly show as the photocatalysis under illumination.
Sample N1, N2, N4 and the N6 of the composite photo-catalyst that the embodiment of the present invention 1 to embodiment 4 prepares
Adsorption bleaching rate before illumination is between AER and TiO2Between, and along with n (Ti4+)/n(OH-) reduction and increase.
This is because, the TiO of AER area load2Granule occupies the adsorption potential of amount of activated group, TiO2Load capacity
The highest, the exposed surface of resin is the fewest, therefore adsorption bleaching rate is the least.
Along with the carrying out of illumination, the percent of decolourization of methyl orange solution is but along with n (Ti4+)/n(OH-) reduction in first increasing
The trend reduced after big, as n (Ti4+)/n(OH-Reach to be 96.06% to the maximum during)=1:4.N1, N2 are due to TiO2
Intergranular reunion, photocatalytic activity center number reduces because being wrapped, and affects the photocatalysis of composite
Performance；And a large amount of TiO2Granule covers at resin surface, can hinder again the absorption property of resin, make light urge
The adsorption bleaching rate of agent is decreased obviously.N6 is because of the TiO of resin surface2Less can not the degraded in time of granule is inhaled
Attached methyl orange molecule, the most also can affect the activity of photocatalyst.And load on N4 resin
TiO2Granule part covering resin surface, but photocatalytic activity is the highest, illustrates that this structure can be the most collaborative
The absorption property of AER and TiO2Photocatalysis, accelerate rate of photocatalytic oxidation, improve reaction efficiency.
As shown in Figure 6, the TiO synthesized for the differential responses time of the present invention2Methyl orange solution is taken off by/AER
Color curve.When adsorbing 1h under dark condition, the composite photo-catalyst percent of decolourization base to methyl orange solution in 4
This is identical.Afterwards with the carrying out of illumination, percent of decolourization is gradually increased；After illumination 2h, the amplitude that T18 increases is
Greatly.Time between illustrating when reacted for 18h, the TiO of generation2/ AER photocatalytic activity is the highest.
As it is shown in fig. 7, be embodiments of the invention 5 to embodiment 8 prepare sample T6, T12, T18,
The XRD figure of T24.When response time is 6h (T6), the TiO in sample2Substantially deposit with impalpable structure form
?；Response time extend to 12h (T12), have obvious Anatase TiO2Generate；Response time is
During 18h (T12), anatase diffraction maximum becomes obvious and sharp-pointed, and the most within a certain period of time, the response time is the longest,
The anatase structured TiO of load on resin2Crystal formation is the best.But (T24) diffraction maximum is strong when the response time is 24h
Degree slightly weakens.TiO can be affected owing to the response time is long2Crystal formation, makes complex light photocatalyst activity reduce,
The TiO of T18 resin surface load2Crystal formation is best, and photocatalyst activity is the highest, the response time be 18h be optimal
Response time.
By solvent-thermal method, come from carrier AER fabricated in situ with positive four butyl esters of metatitanic acid for titanium a series of not
Same n (Ti4+)/n (OH-), the TiO of differential responses time2/ AER composite photo-catalyst, optimal synthesis technique is joined
Number is n (Ti4+)/n (OH-)=1:4, response time are 18h.XRD, SEM, EDS and FT-IR analysis result
Show, anatase structured TiO2Granule is carried on AER in the way of chemical bonding, resin structure not by
Destroy, TiO2Granule part covers AER surface.
This loaded photocatalyst not only achieves TiO2Immobilized in solid globules AER, and ensure that
The strong absorption property of AER.Composite is due to the absorption property of AER and TiO2Table is mutually worked in coordination with in photocatalysis
Reveal excellent photocatalytic activity.TiO after reusing 5 times2/ AER to the percent of decolourization of methyl orange by 96.09%
It is declined by less than 3%, TiO is described2/ AER is good stability in photocatalytic process, and reusability is strong.
The ultimate principle of the present invention, principal character and advantages of the present invention have more than been shown and described.The industry
Skilled person will appreciate that, the present invention is not restricted to the described embodiments, in above-described embodiment and description
The principle that the present invention is simply described described, without departing from the spirit and scope of the present invention, the present invention
Also have various changes and modifications, claimed scope by appending claims, description and
Its equivalent defines.
Claims (8)
1. a TiO2The preparation method of/AER composite photo-catalyst, it is characterised in that comprise the steps:
(1) AER resin pretreatment；
(2) adding the butyl titanate of 0.99-5.96mL in 30mL dehydrated alcohol, stirring is formed transparent
Yellow solution A；Pretreated AER is joined in solution A, continues stirring；Described titanium atom thing
Amount n (the Ti of matter4+) with the amount n (OH of hydroxylated material in resin-) ratio be 1:1-6；
(3) solidliquid mixture is proceeded to the teflon-lined reactor of 50mL, is placed in freeze-day with constant temperature
In case, the response time is 6-24h；
(4) naturally cool to room temperature, with dehydrated alcohol and deionized water alternately washing, be dried, prepare TiO2/AER
Composite photo-catalyst.
TiO the most according to claim 12The preparation method of/AER composite photo-catalyst, it is characterised in that:
In step (1), described resin deionized water cleans and soaks 24-30h after colourless, separates；Successively with
The NaOH of the 4-5% of 2-4 times of volume soaks 4-6h, is washed with deionized water to neutrality；With 2-4 times of volume
3-4%HCl soaks 4-6h, and deionized water is washed till neutrality；The 4-5%NaOH of 2-4 times of volume soaks 8-10h,
It is washed with deionized water again to neutrality；It is 80 DEG C of thermostatic drying chamber dry for standby in temperature, by resin from Cl-Type turns
Turn to OH-Type.
TiO the most according to claim 12The preparation method of/AER composite photo-catalyst, it is characterised in that:
In step (1), described resin deionized water cleans and soaks 24h after colourless, separates；Successively with 2
The NaOH of the 5% of times volume soaks 4h, is washed with deionized water to neutrality；Soak with the 4%HCl of 2 times of volumes
4h, deionized water is washed till neutrality；Use 2 times of volumes 5%NaOH soak 8h, then be washed with deionized water in
Property；It is 80 DEG C of thermostatic drying chamber dry for standby in temperature, by resin from Cl-Type is converted into OH-Type.
TiO the most according to claim 12The preparation method of/AER composite photo-catalyst, it is characterised in that:
In step (2), described resin is 717 type strong-base anion-exchange resins.
TiO the most according to claim 12The preparation method of/AER composite photo-catalyst, it is characterised in that:
In step (2), 30mL dehydrated alcohol adds the butyl titanate of 0.99-5.96mL, stirring
15-30min forms transparent yellow solution A；
Pretreated AER is joined in solution A, continues stirring 30-60min；Described titanium atom material
Amount n (Ti4+) with the amount n (OH of hydroxylated material in resin-) ratio be 1:1-6.
TiO the most according to claim 12The preparation method of/AER composite photo-catalyst, it is characterised in that:
In step (3), solidliquid mixture is proceeded to the teflon-lined reactor of 50mL, is placed in temperature
In degree is 150 DEG C of thermostatic drying chambers, the response time is 6-24h.
TiO the most according to claim 12The preparation method of/AER composite photo-catalyst, it is characterised in that:
In step (3), solidliquid mixture is proceeded to the teflon-lined reactor of 50mL, is placed in temperature
In degree is 150 DEG C of thermostatic drying chambers, the response time is 18h.
8. according to the TiO described in any one of claim 1 to 72The preparation method of/AER composite photo-catalyst,
It is characterized in that: in step (4), naturally cool to room temperature, alternately wash with dehydrated alcohol and deionized water
Wash 3-6 time；110 DEG C of thermostatic drying chambers are dried 10-13h, prepare TiO2/ AER composite photo-catalyst.
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