CN105728055B - A kind of TiO2The preparation method of/AER composite photo-catalysts - Google Patents
A kind of TiO2The preparation method of/AER composite photo-catalysts Download PDFInfo
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- CN105728055B CN105728055B CN201610069585.1A CN201610069585A CN105728055B CN 105728055 B CN105728055 B CN 105728055B CN 201610069585 A CN201610069585 A CN 201610069585A CN 105728055 B CN105728055 B CN 105728055B
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 61
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000011347 resin Substances 0.000 claims abstract description 55
- 229920005989 resin Polymers 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000008367 deionised water Substances 0.000 claims abstract description 44
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 44
- 238000001035 drying Methods 0.000 claims abstract description 30
- 230000035484 reaction time Effects 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000010936 titanium Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000019441 ethanol Nutrition 0.000 claims abstract description 9
- 125000005909 ethyl alcohol group Chemical group 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 238000007654 immersion Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 7
- 239000003957 anion exchange resin Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 description 17
- 238000004042 decolorization Methods 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 12
- 238000007146 photocatalysis Methods 0.000 description 11
- 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 9
- 238000001179 sorption measurement Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000005286 illumination Methods 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 5
- 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 5
- 229940012189 methyl orange Drugs 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008187 granular material Substances 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
- 238000006552 photochemical reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 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
- 229940126678 chinese medicines Drugs 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
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000011065 in-situ storage Methods 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
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910001868 water Inorganic materials 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses a kind of TiO2The preparation method of/AER composite photo-catalysts, comprises the following steps：(1) AER resins pre-process；(2) 0.99 5.96mL butyl titanate is added in 30mL absolute ethyl alcohols, stirring forms transparent yellow solution A；Pretreated AER is added in solution A, continues to stir；Amount n (the Ti of the titanium atom material4+) with resin in hydroxylated material amount n (OH‑) ratio be 1:1‑6；(3) solidliquid mixture is transferred to the reactor of 50mL polytetrafluoroethyllining lining, is placed in thermostatic drying chamber, the reaction time is 6 24h；(4) room temperature is naturally cooled to, is alternately washed, dried with absolute ethyl alcohol and deionized water, TiO is made2/ AER composite photo-catalysts.Complex light photochemical catalyst stability of the present invention is good, and photocatalyst activity is high, and reusability is strong, and catalytic activity is excellent.
Description
Technical field
The present invention relates to catalyst technical field, and in particular to a kind of TiO2The preparation method of/AER composite photo-catalysts.
Background technology
Semiconductor TiO2Because it has, nontoxic, photocatalytic activity is high, oxidability is strong, catabolite CO2And H2O etc. is excellent
Point is widely used in numerous areas such as dye wastewater treatments.Due to powdered TiO2Easily reunite when in use, and react rear overhang
It is floating to be not readily separated, reclaim in the solution, by TiO2It is fixed on different carriers and is prepared into loaded photocatalyst and turns into current light
The study hotspot of catalytic field.TiO2After immobilized, can solve the problems, such as its easy reunion, difficult recovery in actual applications, but
Contaminant molecule and TiO2Surface contact probability reduces, and this influences the degradation rate of catalyst, makes support type to a certain extent
The activity reduction of photochemical catalyst.To obtain good using effect, by TiO2It is carried on stronger with having to target contaminant
Adsorption and enrichment performance, do not influenceing TiO2There is stronger binding ability on the premise of activity therewith, be easy to the carrier of solid-liquor separation
On.
717 type strong-base anion-exchange resins are that pale yellow transparent spheroid, highly basic group exchange capacity are big, adsorption capacity
By force.Anion can be with its highly basic base exchange and being combined in the form of chemical bond, and adsorption activity group can enter to contaminant molecule
Row enrichment, and then improve photocatalytic activity.
At present, a kind of high TiO of photocatalyst activity is lacked2The preparation method of/AER composite photo-catalysts.
The content of the invention
To solve the above problems, it is an object of the invention to provide a kind of high TiO of photocatalyst activity2/ AER is compound
The preparation method of photochemical catalyst.
To realize above-mentioned technical purpose, the technical solution adopted by the present invention is as follows：A kind of TiO of the present invention2/ AER is compound
The preparation method of photochemical catalyst, comprises the following steps：
(1) AER resins pre-process；
(2) 0.99-5.96mL butyl titanate is added in 30mL absolute ethyl alcohols, stirring forms transparent faint yellow molten
Liquid A；Pretreated AER is added in solution A, continues to stir；Amount n (the Ti of the titanium atom material4+) with resin in hydroxyl
Amount n (the OH of substratess matter-) ratio be 1:1-6；
(3) solidliquid mixture is transferred to the reactor of 50mL polytetrafluoroethyllining lining, is placed in thermostatic drying chamber, is reacted
Time is 6-24h；
(4) room temperature is naturally cooled to, is alternately washed, dried with absolute ethyl alcohol and deionized water, TiO is made2/ AER is compound
Photochemical catalyst.
Further, in step (1), the resin is cleaned to colourless rear immersion 24-30h, separation with deionized water；Successively
4-6h is soaked in the NaOH of the 4-5% with 2-4 times of volume, is washed with deionized water to neutrality；Soaked with the 3-4%HCl of 2-4 times of volume
4-6h is steeped, deionized water is washed till neutrality；The 4-5%NaOH immersion 8-10h of 2-4 times of volume, then be washed with deionized water to neutrality；
It is that 80 DEG C of thermostatic drying chambers are dried for standby in temperature, by resin from Cl-Type is converted into OH-Type.
Further, in step (1), the resin is cleaned to colourless rear immersion 24h, separation with deionized water；Exist successively
4h is soaked with 5% NaOH of 2 times of volumes, is washed with deionized water to neutrality；4h, deionization are soaked with the 4%HCl of 2 times of volumes
It is washed to neutrality；8h is soaked using the 5%NaOH of 2 times of volumes, then is washed with deionized water to neutrality；It is that 80 DEG C of constant temperature are done in temperature
Dry case is dried for standby, by resin from Cl-Type is converted into OH-Type.
Further, in step (2), the resin is 717 type strong-base anion-exchange resins.
Further, in step (2), 0.99-5.96mL butyl titanate, stirring are added in 30mL absolute ethyl alcohols
15-30min forms transparent yellow solution A；
Pretreated AER is added in solution A, continues to stir 30-60min；Amount n (the Ti of the titanium atom material4 +) with resin in hydroxylated material amount n (OH-) ratio be 1:1-6.
Further, in step (3), solidliquid mixture is transferred to the reactor of 50mL polytetrafluoroethyllining lining, put
In temperature be reaction time 6-24h in 150 DEG C of thermostatic drying chambers.
Further, in step (3), solidliquid mixture is transferred to the reactor of 50mL polytetrafluoroethyllining lining,
It is reaction time 18h in 150 DEG C of thermostatic drying chambers to be placed in temperature.
Further, in step (4), room temperature is naturally cooled to, 3-6 is alternately washed with absolute ethyl alcohol and deionized water
It is secondary；110 DEG C of thermostatic drying chambers dry 10-13h, and TiO is made2/ AER composite photo-catalysts.
Beneficial effect：Complex light photochemical catalyst stability of the present invention is good, and photocatalyst activity is high, and reusability is strong, urges
Change good activity.
Compared with prior art, the invention has the advantages that：
(1) loaded photocatalyst of the invention not only realizes TiO2It is immobilized on solid globules AER, and ensure
The strong absorption properties of AER resins.Composite is due to AER absorption property and TiO2Photocatalysis is mutually cooperateed with and shown
Excellent photocatalytic activity.
(2) TiO loaded on resin2Particle part covering resin surface, this structure can preferably cooperate with AER trees
The absorption property and TiO of fat2Photocatalysis, accelerate rate of photocatalytic oxidation, improve reaction efficiency.
Brief description of the drawings
Fig. 1 is the pure AER and TiO of the present invention2/ AER XRD；
Fig. 2 be the present invention a-N1, b-N2, c-N4, d-N6 (10000 ×) SEM photograph；
Fig. 3 is the EDS spectrograms of the AER surfaces spheric granules of the present invention；
Fig. 4 is the pure AER and TiO of the present invention2/ AER FT-IR figures；
Fig. 5 is different n (Ti4+)/n (OH of the present invention-) TiO2/ AER decolouring curve；
Fig. 6 is the TiO of the differential responses time of the present invention2/ AER decolouring curve；
Fig. 7 is the TiO of the differential responses time of the present invention2/ AER XRD；
Fig. 8 is the collection of illustrative plates of the reusability of the different photochemical catalysts of the present invention.
Embodiment
The present invention is further illustrated by the following examples.It should be understood that these embodiments are the explainations of the present invention
And citing, the scope of the present invention is not limited in any form.
Embodiment 1
Reagent and instrument
201 × 7 (717) type strong-base anion-exchange resins (Shanghai Ling Feng chemical reagent Co., Ltd), 36% dense salt
Sour (AR, Shanghai Bo He fine chemicals Co., Ltd), sodium hydroxide, absolute ethyl alcohol (AR, the limited public affairs of Chinese medicines group chemical reagent
Department), and tetra-n-butyl titanate (CP, >=98.0%, Chemical Reagent Co., Ltd., Sinopharm Group), methyl orange (AR, Shanghai reagent three
Factory).
Electric drying oven with forced convection (Shanghai Yiheng Scientific Instruments Co., Ltd)；754PC ultraviolet-uisible spectrophotometers (Shanghai
Ao Pule Instrument Ltd.)；D8 series of X-ray powder diffractometer (German Brooker company), Hitachi's S-4800 high-resolution field
Launch ESEM (HIT)；FTIR-650 FTISs (Tianjin Gangdong development in science and technology share
Co., Ltd)；YZ-GHX-A photochemical reactions instrument (Dong Luyang Industrial Co., Ltd.s of Shenzhen).
A kind of TiO of the present invention2The preparation method of/AER composite photo-catalysts, comprises the following steps：
(1) AER resins pre-process；The resin is cleaned to colourless rear immersion 24h, separation with deionized water；Successively with 2
The 5% NaOH immersion 4h of times volume, are washed with deionized water to neutrality；4h, deionized water are soaked with the 4%HCl of 2 times of volumes
It is washed till neutrality；8h is soaked using the 5%NaOH of 2 times of volumes, then is washed with deionized water to neutrality；It is 80 DEG C of freeze-day with constant temperature in temperature
Case is dried for standby, by resin from Cl-Type is converted into OH-Type.
(2) 5.96mL butyl titanate is added in 30mL absolute ethyl alcohols, stirring 15min forms transparent faint yellow molten
Liquid A；Pretreated AER is added in solution A, continues to stir 30min；Amount n (the Ti of the titanium atom material4+) and resin
Amount n (the OH of middle hydroxylated material-) ratio be 1:1；
(3) solidliquid mixture is transferred to the reactor of 50mL polytetrafluoroethyllining lining, temperature is placed in and is done for 150 DEG C of constant temperature
In dry case, reaction time 18h；
(4) room temperature is naturally cooled to, with absolute ethyl alcohol and deionized water alternately washing 3 times；110 DEG C of thermostatic drying chambers are dried
12h, TiO is made2/ AER composite photo-catalysts, sample N1 is made.
Embodiment 2
The difference of embodiment 2 and embodiment 1 is：
A kind of TiO of the present invention2The preparation method of/AER composite photo-catalysts, comprises the following steps：
In step (1), the pretreatment of AER resins；The resin is cleaned to colourless rear immersion 26h with deionized water, point
From；5h is being soaked with 4% NaOH of 2.5 times of volumes successively, is being washed with deionized water to neutrality；Soaked with the 3%HCl of 3 times of volumes
5h is steeped, deionized water is washed till neutrality；The 4.5%NaOH immersion 9h of 3 times of volumes, then be washed with deionized water to neutrality；It is in temperature
80 DEG C of thermostatic drying chambers are dried for standby, and resin is converted into OH- types from Cl- types.
In step (2), 2.98mL butyl titanate is added in 30mL absolute ethyl alcohols, stirring 20min forms transparent
Yellow solution A；Pretreated AER is added in solution A, continues to stir 40min；The amount n of the titanium atom material
(Ti4+) with resin in hydroxylated material amount n (OH-) ratio be 1:2；
In step (3), solidliquid mixture is transferred to the reactor of 50mL polytetrafluoroethyllining lining, being placed in temperature is
In 150 DEG C of thermostatic drying chambers, reaction time 18h；
In step (4), room temperature is naturally cooled to, with absolute ethyl alcohol and deionized water alternately washing 4 times；110 DEG C of constant temperature
Drying box dries 10h, and TiO is made2/ AER composite photo-catalysts, sample N2 is made.
Embodiment 3
The difference of embodiment 3 and embodiment 1 is：
A kind of TiO of the present invention2The preparation method of/AER composite photo-catalysts, comprises the following steps：
In step (1), the pretreatment of AER resins；The resin is cleaned to colourless rear immersion 30h with deionized water, point
From；6h is being soaked with 5% NaOH of 4 times of volumes successively, is being washed with deionized water to neutrality；Soaked with the 4%HCl of 4 times of volumes
6h, deionized water are washed till neutrality；The 5%NaOH immersion 10h of 4 times of volumes, then be washed with deionized water to neutrality；It it is 80 DEG C in temperature
Thermostatic drying chamber is dried for standby, by resin from Cl-Type is converted into OH-Type.
In step (2), 0.99mL butyl titanate is added in 30mL absolute ethyl alcohols, stirring 30min forms transparent
Yellow solution A；
Pretreated AER is added in solution A, continues to stir 60min；Amount n (the Ti of the titanium atom material4+)
With the amount n (OH of hydroxylated material in resin-) ratio be 1:4；The resin is 717 type strong-base anion-exchange resins.
In step (3), solidliquid mixture is transferred to the reactor of 50mL polytetrafluoroethyllining lining, being placed in temperature is
In 150 DEG C of thermostatic drying chambers, reaction time 18h；
In step (4), room temperature is naturally cooled to, with absolute ethyl alcohol and deionized water alternately washing 6 times；110 DEG C of constant temperature
Drying box dries 12h, and TiO is made2/ AER composite photo-catalysts, sample N4 is made.
Embodiment 4
The difference of embodiment 4 and embodiment 1 is：
A kind of TiO of the present invention2The preparation method of/AER composite photo-catalysts, comprises the following steps：
In step (1), the pretreatment of AER resins；Resin is cleaned to colourless rear immersion 24h, separation with deionized water；Successively
4h is soaked with the 5%NaOH of 2 times of volumes, is washed with deionized water to neutrality；4h, deionized water are soaked with the 4%HCl of 2 times of volumes
It is washed till neutrality；8h is soaked using the 5%NaOH of 2 times of volumes, then is washed with deionized water to neutrality；It is 80 DEG C of freeze-day with constant temperature in temperature
Case is dried for standby.
In step (2), 0.99mL butyl titanate is added in 30mL absolute ethyl alcohols, stirring 15min forms transparent
Yellow solution A；Pretreated AER is added in solution A, continues to stir 30min；The amount n of the titanium atom material
(Ti4+) with resin in hydroxylated material amount than n (OH-) it is 1:6；
In step (3), solidliquid mixture is transferred to the reactor of 50mL polytetrafluoroethyllining lining, being placed in temperature is
In 150 DEG C of thermostatic drying chambers, reaction time 18h；
In step (4), room temperature is naturally cooled to, with absolute ethyl alcohol and deionized water alternately washing 3 times；110 DEG C of constant temperature
Drying box dries 12h, and TiO is made2/ AER composite photo-catalysts, sample N6 is made.
Embodiment 5
The difference of embodiment 5 and embodiment 3 is：
A kind of TiO of the present invention2The preparation method of/AER composite photo-catalysts, comprises the following steps：
In step (3), solidliquid mixture is transferred to the reactor of 50mL polytetrafluoroethyllining lining, being placed in temperature is
In 150 DEG C of thermostatic drying chambers, reaction time 6h,
In step (4), room temperature is naturally cooled to, with absolute ethyl alcohol and deionized water alternately washing 6 times；110 DEG C of constant temperature
Drying box dries 12h, and TiO is made2/ AER composite photo-catalysts, sample T6 is made.
Embodiment 6
The difference of embodiment 6 and embodiment 3 is：
A kind of TiO of the present invention2The preparation method of/AER composite photo-catalysts, comprises the following steps：
In step (3), solidliquid mixture is transferred to the reactor of 50mL polytetrafluoroethyllining lining, being placed in temperature is
In 150 DEG C of thermostatic drying chambers, reaction time 12h,
In step (4), room temperature is naturally cooled to, with absolute ethyl alcohol and deionized water alternately washing 6 times；110 DEG C of constant temperature
Drying box dries 12h, and TiO is made2/ AER composite photo-catalysts, sample T12 is made.
Embodiment 7
The difference of embodiment 7 and embodiment 3 is：
A kind of TiO of the present invention2The preparation method of/AER composite photo-catalysts, comprises the following steps：
In step (3), solidliquid mixture is transferred to the reactor of 50mL polytetrafluoroethyllining lining, being placed in temperature is
In 150 DEG C of thermostatic drying chambers, reaction time 18h,
In step (4), room temperature is naturally cooled to, with absolute ethyl alcohol and deionized water alternately washing 6 times；110 DEG C of constant temperature
Drying box dries 13h, and TiO is made2/ AER composite photo-catalysts, sample T18 is made.
Embodiment 8
The difference of embodiment 8 and embodiment 3 is：
A kind of TiO of the present invention2The preparation method of/AER composite photo-catalysts, comprises the following steps：
In step (3), solidliquid mixture is transferred to the reactor of 50mL polytetrafluoroethyllining lining, being placed in temperature is
In 150 DEG C of thermostatic drying chambers, reaction time 24h,
In step (4), room temperature is naturally cooled to, with absolute ethyl alcohol and deionized water alternately washing 6 times；110 DEG C of constant temperature
Drying box dries 12h, and TiO is made2/ AER composite photo-catalysts, sample T24 is made.
Experiment 1
The XRD analysis of sample
As shown in figure 1, pure AER and TiO for the present invention2/ AER XRD；Fig. 1 is pure AER and n (Ti4+)/n(OH-)
=1:4th, the TiO of 18h synthesis is reacted2The XRD of/AER composite photo-catalysts.TiO2/ AER XRD spectrum 2 θ=25.3 °,
There is characteristic diffraction peak at 38.1 °, 48.0 °, 54.1 ° and 62.6 °, with standard XRD pattern (PDFNo21-1272) to approved for distribution
Anatase TiO is now corresponded to respectively2(101), (004), (200), (105) and (204) crystal face, illustrate the TiO of Anatase2
It is carried on resin.TiO is loaded2AER characteristic peak do not change, illustrate to have loaded TiO2Resin anion (R.A.) structure
It is not destroyed, the composite of this structure has both TiO2With AER characteristic, produce both and mutually act synergistically and then carry
Highlight catalytic active is possibly realized.
Experiment 2
Sem analysis
By the TiO of sample N1, N2, N4, N6 made from embodiment 1 to embodiment 42/ AER composite photo-catalysts carry out SEM
Analysis, obtains the structure shown in Fig. 2；As shown in Fig. 2 it is N1 (a), N2 (b), N4 (c) of the invention, N6 (d) (10000 ×)
SEM photograph.From scheming a~d, with n (Ti4+)/n(OH-) reduction, the TiO loaded on AER2Particle is fewer.A,
TiO in b figures2Occurs the obvious, agglomeration of part between particle, the TiO that resin surface generates in d2Particle is less, schemes resin in c
On loaded more spherical TiO2Particle, be evenly distributed, do not reunite each other, its diameter between 1~2 μm, TiO2Particle is simultaneously
Resin surface is not completely covered, this structure is advantageous to the absorption property and TiO of AER in light-catalyzed reaction2Photocatalysis make
With mutual collaboration.
Experiment 3
EDS is analyzed
As shown in figure 3, the EDS spectrograms of the resin surface spheric granules for the present invention.There was only Ti, O element peak in Fig. 3,
There is no other elements peak, and the atomic percent of titanium and oxygen is about 1:2, thus may determine that AER area loads is TiO2,
Obtained product is TiO2/AER。
Experiment 4
FT-IR is analyzed
As shown in figure 4, AER and TiO for the present invention2The FT-IR collection of illustrative plates of/AER composite photo-catalysts.AER is in 3435cm-1、1642cm-1Absworption peak be respectively belonging to the stretching vibration of resin-OH and carbonyl, have been moved to 3429cm in the composite-1
And 1627cm-1, illustrate that metallic atom has coordination bonding with the oxygen atom on hydroxyl and carbonyl, show TiO2It is not letter with interlaminar resin
Single physical absorption but combined in a manner of chemical bond.Due to the presence of chemical bond, TiO2It is difficult for drop-off, so composite
Stability is preferable during reuse.
Experiment 5
Photocatalysis is tested
50mg/L methyl orange solution 50mL is pipetted in cylindrical light catalytic reaction cell, being put into magneton, adds 0.04g
Photochemical catalyst, insert in photochemical reaction instrument, open fan, 1h is stirred under dark condition, reach adsorption-desorption balance.After
Continuous ventilation stirring, using 300W high-pressure sodium lamps as light source, carries out light-catalyzed reaction, light source circulating cooling water cooling.Every
Its absorbance at maximum absorption wavelength (464nm) place is measured by sampling in 20min.By the linear relationship (A of absorbance and concentration
=0.01855+0.06732C, R2=0.9988, A are concentration, and C is absorbance), obtain corresponding concentration value.In photocatalytic process
The percent of decolourization (η) of methyl orange solution：η=(A0-At)/A0=(C0-Ct)/C0, C0, Ct, A0 and At represent that MO is molten respectively in formula
The initial concentration of liquid, t concentration, initial absorbance and t absorbance.
The reusability of photochemical catalyst
To investigate photochemical catalyst AER, TiO2/AER、TiO2Reusability, reacted solution is removed, again plus
The methyl orange solution 50mL for entering 50mg/L carries out photocatalysis experiment, so 5 results repeatedly, as shown in figure 8, for the present invention not
With the collection of illustrative plates of the reusability of photochemical catalyst.TiO2The percent of decolourization of methyl orange solution is reduced to by original 76.92%
63.22%, decline 13.70%；Composite photo-catalyst TiO2/ AER percent of decolourization is declined by less than 3%.Illustrate TiO2With chemical bonding
Mode load to the loaded photocatalyst obtained on resin be not only easy to from the dye solution reacted separate and reclaim,
And compared with powder TiO2Stablize, repeat practical.
And AER only has 5.24% when using for second to the percent of decolourization of methyl orange, illustrate experiment of the resin in first time
In basically reached saturation state；With composite photo-catalyst TiO2/ AER (percent of decolourization when using second is 95.41%,
Understand that the decolouring of methyl orange is not that AER simple suction-operated causes in solution compared with only have dropped 0.66%) contrast for the first time
, but the TiO being first then supported by AER adsorption and enrichments2Particle photocatalytic degradation.
TiO2/ AER photocatalytic activity
As shown in figure 5, the photochemical catalyst TiO for the present invention2, decolouring to methyl orange solution of N1, N2, N4, N6, AER it is bent
Line (- 60~0min is adsorption process).When adsorbing 1h, AER is up to 73.14% to the percent of decolourization of methyl orange solution；With light
According to progress, add AER solution percent of decolourization to be basically unchanged, illustrate that AER does not have photocatalysis performance, decolouring is under dark condition
Caused by absorption.Add TiO2Solution adsorption bleaching rate minimum only 12.24%；Under illumination, its percent of decolourization increasing degree is maximum,
Illustrate TiO2Absorption property it is very weak, the photocatalysis being mainly shown as under illumination.
Suction before sample N1, N2, N4 and N6 illumination of composite photo-catalyst made from the embodiment of the present invention 1 to embodiment 4
Attached percent of decolourization is between AER and TiO2Between, and with n (Ti4+)/n(OH-) reduction and increase.Because AER surfaces are born
The TiO of load2Particle occupies the adsorption potential of amount of activated group, TiO2Load capacity it is higher, the exposed surface of resin is fewer, thus inhale
Attached percent of decolourization is smaller.
With the progress of illumination, the percent of decolourization of methyl orange solution is but with n (Ti4+)/n(OH-) reduction in first increase after
The trend of reduction, as n (Ti4+)/n(OH-)=1:Reach when 4 and be up to 96.06%.N1, N2 are due to TiO2Intergranular reunion,
Photocatalytic activity center number is reduced because being wrapped, and influences the photocatalysis performance of composite；And a large amount of TiO2Particle covers
Cover in resin surface, can hinder the absorption property of resin again, be decreased obviously the adsorption bleaching rate of photochemical catalyst.N6 is because of resin table
The TiO in face2The less adsorbed methyl orange molecule that can not degrade in time of particle, can also influence photochemical catalyst to a certain extent
Activity.And the TiO loaded on N4 resins2Particle part covering resin surface, but photocatalytic activity highest, illustrate this structure
AER absorption property and TiO can preferably be cooperateed with2Photocatalysis, accelerate rate of photocatalytic oxidation, improve reaction effect
Rate.
As shown in fig. 6, the TiO of the differential responses time synthesis for the present invention2The decolouring curves of/AER to methyl orange solution.
When 1h is adsorbed under dark condition, composite photo-catalyst is essentially identical to the percent of decolourization of methyl orange solution in 4.Afterwards with illumination
Carry out, percent of decolourization gradually increases；After illumination 2h, the increased amplitudes of T18 are maximum.When being 18h between illustrating when reacted, generation
TiO2/ AER photocatalytic activity highests.
As shown in fig. 7, the XRD for sample T6, T12, T18, T24 made from embodiments of the invention 5 to embodiment 8.
When reaction time is 6h (T6), the TiO in sample2Substantially exist in the form of impalpable structure；Reaction time extends to 12h
(T12), there is obvious Anatase TiO2Generation；Anatase diffraction maximum becomes obvious and sharp when reaction time is 18h (T12)
Sharp, i.e., within a certain period of time, the reaction time is longer, the anatase structured TiO of the load on resin2Crystal formation is better.But the reaction time
For 24h when (T24) diffraction peak intensity slightly weaken.TiO can be influenceed because the reaction time is long2Crystal formation, make complex light photocatalysis
Agent activity reduces, the TiO of T18 resin surfaces load2Crystal formation is best, photocatalyst activity highest, and the reaction time is 18h for most
The good reaction time.
By solvent-thermal method, using a series of positive four butyl ester of metatitanic acid different n (Ti that have been titanium source in fabricated in situ on carrier AER4 +)/n (OH-), the TiO of differential responses time2/ AER composite photo-catalysts, optimal synthesis technologic parameter are n (Ti4+)/n(OH-)
=1:4th, reaction time 18h.XRD, SEM, EDS and FT-IR analysis result shows, anatase structured TiO2Particle is with chemistry
The mode of bonding is carried on AER, and resin structure is not destroyed, TiO2Particle part covering AER surfaces.
This loaded photocatalyst not only realizes TiO2It is immobilized on solid globules AER, and ensure that AER's
Strong absorption property.Composite is due to AER absorption property and TiO2Photocatalysis, which mutually cooperates with, to show excellent light and urges
Change activity.The TiO after reusing 5 times2/ AER is declined by less than 3% to the percent of decolourization of methyl orange by 96.09%, illustrates TiO2/
AER stability in photocatalytic process is good, and reusability is strong.
General principle, principal character and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, the present invention
Claimed scope is by appended claims, specification and its equivalent thereof.
Claims (8)
- A kind of 1. TiO2The preparation method of/AER composite photo-catalysts, it is characterised in that comprise the following steps：（1）AER resins pre-process；（2）0.99-5.96mL butyl titanate is added in 30mL absolute ethyl alcohols, stirring forms transparent yellow solution A； Pretreated AER resins are added in solution A, continue to stir；The amount n (Ti) of titanium atom material and hydroxyl in AER resins The amount n (- OH) of material ratio is 1:1-6, obtain solidliquid mixture；（3）Solidliquid mixture is transferred to the reactor of 50mL polytetrafluoroethyllining lining, is placed in thermostatic drying chamber, the reaction time For 6-24h；（4）Room temperature is naturally cooled to, is alternately washed, dried with absolute ethyl alcohol and deionized water, TiO is made2/ AER composite photocatalysts Agent.
- 2. TiO according to claim 12The preparation method of/AER composite photo-catalysts, it is characterised in that：Step（1）In, The AER resins are cleaned to colourless rear immersion 24-30h, separation with deionized water；Successively again with the 4-5%'s of 2-4 times of volume NaOH soaks 4-6h, is washed with deionized water to neutrality；4-6h is soaked with the 3-4%HCl of 2-4 times of volume, during deionized water is washed till Property；8-10h is soaked with the 4-5%NaOH of 2-4 times of volume, then is washed with deionized water to neutrality；It is 80 DEG C of thermostatic drying chambers in temperature It is dried for standby, by AER resins from Cl-Type is converted into-OH types.
- 3. TiO according to claim 12The preparation method of/AER composite photo-catalysts, it is characterised in that：Step（1）In, The AER resins are cleaned to colourless rear immersion 24h, separation with deionized water；Soaked again with 5% NaOH of 2 times of volumes successively 4h, it is washed with deionized water to neutrality；4h is soaked with the 4%HCl of 2 times of volumes, deionized water is washed till neutrality；Use the 5% of 2 times of volumes NaOH soaks 8h, then is washed with deionized water to neutrality；It is that 80 DEG C of thermostatic drying chambers are dried for standby in temperature, by AER resins from Cl- Type is converted into-OH types.
- 4. TiO according to claim 12The preparation method of/AER composite photo-catalysts, it is characterised in that：In step（2） In, the AER resins are 717 type strong-base anion-exchange resins.
- 5. TiO according to claim 12The preparation method of/AER composite photo-catalysts, it is characterised in that：In step（2） In, 0.99-5.96mL butyl titanate is added in 30mL absolute ethyl alcohols, stirring 15-30min forms transparent faint yellow molten Liquid A；Pretreated AER is added in solution A, continues to stir 30-60min；The amount n (Ti) of the titanium atom material with The amount n (- OH) of hydroxylated material ratio is 1 in AER resins:1-6.
- 6. TiO according to claim 12The preparation method of/AER composite photo-catalysts, it is characterised in that：In step（3） In, solidliquid mixture is transferred to the reactor of 50mL polytetrafluoroethyllining lining, is placed in temperature as in 150 DEG C of thermostatic drying chambers, Reaction time is 6-24h.
- 7. TiO according to claim 12The preparation method of/AER composite photo-catalysts, it is characterised in that：In step（3） In, solidliquid mixture is transferred to the reactor of 50mL polytetrafluoroethyllining lining, is placed in temperature as in 150 DEG C of thermostatic drying chambers, Reaction time is 18h.
- 8. according to the TiO described in any one of claim 1 to 72The preparation method of/AER composite photo-catalysts, it is characterised in that： Step（4）In, room temperature is naturally cooled to, with absolute ethyl alcohol and deionized water alternately washing 3-6 times；110 DEG C of thermostatic drying chambers are done Dry 10-13h, TiO is made2/ AER composite photo-catalysts.
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