CN105536765B - A kind of shell base boron-doped titanium dioxide composite photo-catalyst and preparation method thereof - Google Patents
A kind of shell base boron-doped titanium dioxide composite photo-catalyst and preparation method thereof Download PDFInfo
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- CN105536765B CN105536765B CN201510973652.8A CN201510973652A CN105536765B CN 105536765 B CN105536765 B CN 105536765B CN 201510973652 A CN201510973652 A CN 201510973652A CN 105536765 B CN105536765 B CN 105536765B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 158
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 96
- 239000002131 composite material Substances 0.000 title claims abstract description 93
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 49
- 241000276489 Merlangius merlangus Species 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011541 reaction mixture Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 239000000725 suspension Substances 0.000 claims abstract description 19
- 239000004327 boric acid Substances 0.000 claims abstract description 17
- 238000001556 precipitation Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 47
- 239000003054 catalyst Substances 0.000 claims description 21
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 5
- 238000010306 acid treatment Methods 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 16
- 230000007613 environmental effect Effects 0.000 abstract description 2
- PQMFVUNERGGBPG-UHFFFAOYSA-N (6-bromopyridin-2-yl)hydrazine Chemical compound NNC1=CC=CC(Br)=N1 PQMFVUNERGGBPG-UHFFFAOYSA-N 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 37
- 238000007146 photocatalysis Methods 0.000 description 36
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 36
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 35
- 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 22
- 229940012189 methyl orange Drugs 0.000 description 22
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 238000001354 calcination Methods 0.000 description 17
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 14
- 229910052796 boron Inorganic materials 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 11
- 238000001514 detection method Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000013078 crystal Substances 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 6
- 230000001476 alcoholic effect Effects 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 125000005909 ethyl alcohol group Chemical group 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 238000007605 air drying Methods 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- XWZDJOJCYUSIEY-UHFFFAOYSA-L disodium 5-[(4,6-dichloro-1,3,5-triazin-2-yl)amino]-4-hydroxy-3-phenyldiazenylnaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].Oc1c(N=Nc2ccccc2)c(cc2cc(cc(Nc3nc(Cl)nc(Cl)n3)c12)S([O-])(=O)=O)S([O-])(=O)=O XWZDJOJCYUSIEY-UHFFFAOYSA-L 0.000 description 5
- 238000004043 dyeing Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000012423 maintenance Methods 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 241000237536 Mytilus edulis Species 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 235000020638 mussel Nutrition 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- -1 titanium Alkoxide Chemical class 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 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
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000007836 KH2PO4 Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 230000007935 neutral effect 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000012216 screening 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
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000005303 weighing 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a kind of shell base boron-doped titanium dioxide composite photo-catalysts and preparation method thereof.The preparation method includes：Titanate esters are dissolved in organic solvent, obtain yellow solution；Boric acid, oyster shell whiting are added in deionized water, are uniformly mixed, obtains suspension；Under rapid mixing conditions, yellow solution is added drop-wise in suspension dropwise, continue stirring until titanate esters be fully hydrolyzed, obtain initial reaction solution；Initial reaction solution is inserted in high-temperature high-pressure reaction kettle, the cooled to room temperature after 2~12h of hydro-thermal reaction at 140~180 DEG C, obtain reaction mixture；Reaction mixture is centrifuged, takes precipitation, washs drying, obtains just finished product；It is calcined after first finished product is fully ground, cooled to room temperature, obtains shell base boron-doped titanium dioxide composite photo-catalyst.Method is easy to operate, and environmental protection, photocatalyst activity is high, can recycle, photoresponse scope is wide.
Description
Technical field
The present invention relates to a kind of photochemical catalysts, and in particular to a kind of shell base boron-doped titanium dioxide composite photo-catalyst and its
Preparation method.
Background technology
Photochemical catalyst is a kind of important green material, and the photocatalytic oxidation using semi-conducting material as catalyst is
A kind of water technology of rising in recent years.With conventional method ratio, this method oxidation efficiency is high, stable and non-secondary pollution, it
Organic pollution in waste water from dyestuff can be decomposed into CO2, H2O, N2, Cl-Inorganic matters small molecule is waited, thus with preferable
Application prospect.
TiO2Nano material is because it has the characteristics that good chemical stability, low cost, nontoxic to become most application latent
The photochemical catalyst of power, but due to TiO2Greater band gap, energy gap 3.2ev need ultraviolet light (λ≤387.5nm) that could excite
Its catalytic activity, thus significantly limit its application；In addition nano-TiO2It is tired to there is recycling when being used as photochemical catalyst
Hardly possible reuses the shortcomings of difficulty, and this severely limits TiO2Application of the nano material in terms of wastewater treatment and development.
To solve nano-TiO2This difficult problem is recycled, the Chinese patent literature of Publication No. CN101352675A is public
A kind of preparation method of shell powder supported active nano titanic oxide is opened, which includes：By predecessor titanate esters, titanium
Alkoxide, at least one of titanate be dissolved in organic solvent, Ti4+Concentration for 0.01~6.0mol/L, be vigorously stirred down
Suitable water and hydrolyst is added dropwise, makes pH=3.5~6.5 of solution, is vigorously stirred to form yellowish transparent TiO2Colloidal sol,
Ageing is for use；Take shell powder supported (carrying method is spin coating, dipping, plasma spraying or thermal spraying) TiO of activation2It is molten
Glue, 70~100 DEG C of drying, distilled water rinse repeatedly, then at 70~100 DEG C of drying, with 400~500 DEG C of roastings in muffle furnace
(heating rate is controlled as 1~10K/min, after being warming up to 300 DEG C, constant temperature；Then heat to 400~500 DEG C, then constant temperature), i.e.,
Obtain the nano-TiO of oyster shell whiting immobilization2。
But this method does not improve TiO2Bandgap range, the photoresponse scope not yet in effect for expanding photochemical catalyst, it is impossible to high
For effect using visible light region energy, this makes photochemical catalyst made from this method be difficult to large-scale promotion in practical applications.
To solve to need ultraviolet light (λ≤387.5nm) that TiO could be excited during use2This problem of catalytic activity, it is public
The number of opening is that the Chinese patent literature of CN104645952A discloses a kind of synthetic method of boron doped nano titanium dioxide, the synthesis
Method includes：13-15ml butyl titanates are dissolved in 60-70ml absolute ethyl alcohols, are heated up to 50-70 DEG C, are forced into 5-8MPa, it is acute
Strong stirring, is slowly added dropwise dissolved with H3BO3Deionized water, stirring 3-6h be fully hydrolyzed butyl titanate, be then placed in poly- four
In the stainless steel autoclave of vinyl fluoride liner, in the case of being forced into 10-15MPa, 200-240 DEG C maintains 12-48h, fast
Fast water cooling is depressurized to normal pressure to 2-8 DEG C；Product is filtered, ethyl alcohol and deionized water wash, and is dried at room temperature for for 24 hours, Ran Houyu
90-100 DEG C of vacuum drying 5-10h, is made B2TiO2Catalyst.
However the synthetic method is relatively complicated, harsh to experiment condition complicated, the TiO of generation2Easily reunite, and do not solve
Certainly TiO2Recycle this difficult defect.
The all relatively complicated complexity of method of nanometer titanium dioxide compound photocatalyst is prepared at present, and the complex light prepared is urged
Agent catalytic efficiency is relatively low, therefore in order to expand nano-TiO2The use scale of this photochemical catalyst, there is an urgent need to develop new
Simply, efficient technology of preparing and method.
The content of the invention
The present invention also provides a kind of shell base boron-doped titanium dioxide composite photo-catalyst, the light of the composite photo-catalyst is urged
It is high to change activity, can repeat to recycle and utilize, and response range is wide, its photocatalysis work can be played under excited by visible light
Property.
Meanwhile the present invention also provides a kind of preparation method of shell base boron-doped titanium dioxide composite photo-catalyst, the systems
Preparation Method is easy to operate, and avoiding titanate esters, exposure in the environment, causes operating personnel uncomfortable for a long time in preparation process.
A kind of shell base boron-doped titanium dioxide composite photo-catalyst, is prepared by following preparation method：
(1) titanate esters are scattered in organic solvent, obtain yellow solution；
(2) boric acid, oyster shell whiting are added in deionized water, are uniformly mixed, obtain suspension；
(3) under rapid mixing conditions, the yellow solution is added drop-wise to dropwise in the suspension, it is straight to continue stirring
It is fully hydrolyzed to titanate esters, obtains initial reaction solution；
(4) the initial reaction solution is inserted in high-temperature high-pressure reaction kettle, at 140~180 DEG C hydro-thermal reaction 2~
Cooled to room temperature after 12h obtains reaction mixture；
(5) reaction mixture is centrifuged, takes precipitation, wash drying, obtain just finished product；
(6) calcined after the first finished product is fully ground, cooled to room temperature；
Finally obtain the shell base boron-doped titanium dioxide composite photo-catalyst.
The present invention is using hydro-thermal method (in high-temperature high-pressure reaction kettle carry out) by the calcium constituent doping in boron element, oyster shell whiting
Into nano-titanium dioxide, the compound of a kind of new perovskite and titanium dioxide is formed, not only so that the complex light obtained
Catalyst has better anatase crystal, effectively increases the photocatalysis performance of nano-titanium dioxide, is reaching peer-level
On the premise of photocatalysis efficiency, less B/TiO is contained in composite photo-catalyst of the invention2, effectively reduce B/TiO2Conjunction
Cheng Liang reduces manufacture cost；And the process that boron doped nano titanium dioxide is attached on oyster shell whiting is accelerated, unlike routine
Impregnate load, spraying load even load method takes time and effort；Boron doped nano titanium dioxide is not only to load on oyster shell whiting,
But also crosslinking generation perovskite has occurred with the calcium in oyster shell whiting, with reference to more firm；Preparation step is also greatly simplified simultaneously
Suddenly, avoiding titanate esters, exposure in the environment, prevents the bad smell that titanate esters distribute from causing operator for a long time in preparation process
Member is uncomfortable, and preparation process is more environmentally friendly.
Moreover, calcining can improve the ratio of anatase crystal titanium dioxide in composite photo-catalyst, anatase crystal two
Titanium oxide is conducive to improve the photocatalysis performance of composite photo-catalyst.
Specifically, a kind of preparation method of shell base boron-doped titanium dioxide composite photo-catalyst of the present invention includes following step
Suddenly：
(1) titanate esters are scattered in organic solvent, obtain yellow solution；
In the present invention, the titanate esters can select the titanyls such as butyl titanate, metatitanic acid orthocarbonate or tetraethyl titanate to have
Predecessor of the machine object as generation titanium dioxide.The organic solvent can select absolute methanol, absolute ethyl alcohol, anhydrous propyl alcohol,
At least one of anhydrous isopropyl alcohol, anhydrous butanol or dry isobutanol are preferably absolute ethyl alcohol.
Preferably, the titanate esters and the mixed proportion of organic solvent are (3:1)~(1:1).
(2) boric acid, oyster shell whiting are added in deionized water, are uniformly mixed, obtain suspension；
In the present invention, the oyster shell whiting refers to the molluscan outer embrane for living in waterside, and oyster shell may be employed, make a gift of
At least one of shell, spiral case or clam shell.
It is load area of the increase oyster shell whiting to nano-titanium dioxide, preferably, first being carried out to the oyster shell whiting at sour
It manages (or acid treatment directly is done to shell), is then then added in deionized water.The main component of shell is calcium carbonate, to shell
Powder (or shell), which carries out acid treatment, helps to corrode calcium carbonate so as to form hole, increases the specific surface area of shell, while makes original
The cellulosic exposure being first buried in calcium carbonate further increases the load area of nano-titanium dioxide.
As further preferred, the acid treatment is：Shell is placed in the dilution heat of sulfuric acid of 0.1~2M impregnate 6~
For 24 hours, then after being rinsed with deionized water to neutrality dry, be ground into the oyster shell whiting that grain size is 100~400 mesh.
Nonmetalloid (boron element) adulterates the response range that can effectively expand nano-titanium dioxide so that complex light is urged
Agent can efficiently utilize the light energy of visible light region, its photocatalytic activity can be also played without ultraviolet excitation.
In the present invention, the mass ratio of the boric acid and oyster shell whiting is (1:2)~(2:1) it is most preferably, 1:1.Present invention hair
It is existing, when properly increasing boron element (doping of boron element is only 0.1% (accounting for photochemical catalyst total weight) left and right in the prior art)
Doping when, the ratio of anatase crystal nano-titanium dioxide accordingly increases, and the content of perovskite also increases therewith, urges
Change efficiency also to increase.
(3) under rapid mixing conditions, the yellow solution is added drop-wise to dropwise in the suspension, it is straight to continue stirring
It is fully hydrolyzed to titanate esters, obtains initial reaction solution；
Preferably, stir speed (S.S.) maintains 300~600rpm, the rate of addition of yellow solution maintain 20-50 drops/
Minute.
Stir speed (S.S.) and rate of addition can influence the composite effect of composite photo-catalyst, and stirring stir speed (S.S.) is excessively slow or is added dropwise
It is too fast that butyl titanate can be caused to be condensed in solution surface, it can not be hydrolyzed under aqueous environment.
(4) the initial reaction solution is inserted in high-temperature high-pressure reaction kettle, at 140~180 DEG C hydro-thermal reaction 2~
Cooled to room temperature after 12h obtains reaction mixture；Preferably, the initial reaction solution is inserted into high temperature high pressure reverse
It answers in kettle, the cooled to room temperature after hydro-thermal reaction 12h at 180 DEG C, obtains reaction mixture.
(5) reaction mixture is centrifuged, takes precipitation, wash drying, obtain just finished product；
(6) calcined after the first finished product is fully ground, cooled to room temperature obtains the shell base boron-doping titanium dioxide
Titanium composite photo-catalyst.
It tests and finds through uv-visible absorption spectra (UV-vis), calcining can widen the photoresponse of composite photo-catalyst
Scope improves the photocatalysis efficiency of composite photo-catalyst under visible light.
Preferably, after the first finished product is fully ground, 1~5h is calcined at 550~750 DEG C；As further excellent
Choosing after the first finished product is fully ground, 1~2h is calcined at 600~700 DEG C, most preferably calcines 1h at 700 DEG C.
Calcination process needs suitable calcining heat, otherwise absorbance can be caused to decline, this may be because complex light is urged
Agent is reunited seriously under 400 DEG C -550 DEG C of calcining heat；And the nano-titanium dioxide pole under 750 DEG C or more of calcining heat
Crystal form conversion is likely to occur, causes the reduction of anatase crystal nano-titanium dioxide ratio.
Compared with prior art, beneficial effects of the present invention are：
Calcium constituent in boron element, oyster shell whiting is doped in nano-titanium dioxide by the present invention using hydro-thermal method, forms one
The compound of the new perovskite of kind and titanium dioxide, not only so that the composite photo-catalyst obtained has better anatase crystalline substance
Type effectively increases the photocatalysis performance of nano-titanium dioxide, on the premise of peer-level photocatalysis efficiency is reached, the present invention
Composite photo-catalyst in contain less B/TiO2, effectively reduce B/TiO2Synthetic quantity, reduce manufacture cost；And add
Fast boron doped nano titanium dioxide is attached to the process on oyster shell whiting, unlike conventional immersion load, spraying load even load
Method takes time and effort；Boron doped nano titanium dioxide is not only to load on oyster shell whiting, but also is sent out with the calcium in oyster shell whiting
Crosslinking generation perovskite is given birth to, with reference to more firm；Preparation process is also greatly simplified simultaneously, avoids titanate esters in preparation process
Medium-term and long-term exposure in the environment, prevents the bad smell that titanate esters distribute from causing operating personnel uncomfortable, preparation process is more
Environmental protection.
Description of the drawings
Fig. 1 is the field emission scanning electron microscope of shell base boron-doped titanium dioxide composite photo-catalyst in the embodiment of the present invention 1
(FE-SEM) figure；
Fig. 2 is the Fourier transform infrared light of shell base boron-doped titanium dioxide composite photo-catalyst in the embodiment of the present invention 1
Compose (FT-IR) figure；
Wherein, %Transmittance represents light transmittance (%), Wavenumbers (cm-1) represent wave number (cm-1), under
Together；
Fig. 3 is the X-ray diffraction (XRD) of shell base boron-doped titanium dioxide composite photo-catalyst in the embodiment of the present invention 1
Figure；
Wherein, 2Theta (degree) represents the incident angle of twice of x-ray, and Intensity (a.u.) represents diffraction
Intensity afterwards；
Fig. 4 is B/TiO prepared by Examples 1 to 42B/TiO prepared by/shell composite photo-catalyst and comparative example 12Light
Catalyst is to the photocatalysis efficiency of methyl orange；
Wherein, B-TiO2Represent B/TiO2Photochemical catalyst, B/TiO2/ shell (1:0.5) B/TiO is represented2/ shell complex light
(mass ratio of boric acid and oyster shell whiting is 1 to catalyst:0.5), B/TiO2/ shell (1:1) B/TiO is represented2/ shell composite photocatalyst
(mass ratio of boric acid and oyster shell whiting is 1 for agent:1), B/TiO2/ shell (1:2) B/TiO is represented2/ shell composite photo-catalyst (boric acid
Mass ratio with oyster shell whiting is 1:2), B/TiO2/ shell (1:4) B/TiO is represented2/ shell composite photo-catalyst (boric acid and shell
The mass ratio of powder is 1:4)；MO removing (%) represent methyl orange degradation rate (%), and T (min) represents degradation time (min),
Similarly hereinafter；
Fig. 5 a are B/TiO prepared by embodiment 1,8~10 and comparative example 3~52/ shell composite photo-catalyst is to methyl
The photocatalysis efficiency of orange；
Fig. 5 b are B/TiO prepared by embodiment 1 and embodiment 112Photocatalysis of/shell the composite photo-catalyst to methyl orange
Efficiency；
Wherein, Absorbance represents absorbance, similarly hereinafter；
Fig. 6 a are B/TiO2/ shell composite photo-catalyst urges the light of activated red X-3B with commercially available nano-titanium dioxide P25
Change efficiency and compare figure；Wherein, X-3B Removing (%) represent the degradation rate (%) of activated red X-3B；
Fig. 6 b are B/TiO2/ shell composite photo-catalyst imitates the photocatalysis of methyl orange with commercially available nano-titanium dioxide P25
Rate compares figure；
Fig. 6 c are B/TiO2/ shell composite photo-catalyst and the first finished product without calcining, commercially available nano-titanium dioxide P25
Photoresponse scope compares figure；
Fig. 7 a are methyl orange initial concentration to B/TiO2The influence of/shell composite photo-catalyst activity；
Wherein, MO represents methyl orange；
Drop of the methyl orange initial concentration with B/TiO2/ shells composite photo-catalyst to methyl orange when Fig. 7 b are reaction 15min
Linear relationship between solution rate；
Wherein, c/mg.L-1Represent methyl orange initial concentration；
Fig. 8 a are the initial pH of solution to B/TiO2The influence of/shell composite photo-catalyst activity；
Fig. 8 b are influences of the initial pH of solution to nano-titanium dioxide P25 activity；
Fig. 9 is B/TiO2/ shell composite photo-catalyst and nano-titanium dioxide P25 are manually prepared to containing reactive brilliant red x-3b
The degradation effect of dyeing waste water.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and detailed description.
Embodiment 1
A kind of preparation method of shell base boron-doped titanium dioxide composite photo-catalyst, comprises the following steps：
(1) mussel shell is placed in the dilution heat of sulfuric acid of 0.5M and impregnated for 24 hours, dried after being rinsed with deionized water to neutrality,
The oyster shell whiting that grain size is 150 mesh is ground into, it is spare；
(2) 7.5ml butyl titanates are dissolved in 5ml absolute ethyl alcohols, be sufficiently stirred, be uniformly mixed, obtain butyl titanate alcohol
Solution；
(3) by 1.5g boric acid (H3BO3), the oyster shell whiting of 1.5g steps (1) is added in 60ml deionized waters, is uniformly mixed,
Obtain suspension；
(4) under rapid mixing conditions, butyl titanate alcoholic solution is added drop-wise in suspension dropwise, stir speed (S.S.) maintains
400rpm, rate of addition maintain 30 drops/minute；Continuing stirring 30min is fully hydrolyzed butyl titanate, and it is molten to obtain initial reaction
Liquid；
(5) initial reaction solution is placed in the stainless steel high temperature autoclave with polytetrafluoroethyllining lining, 180 DEG C
Maintain 12 it is small when, cooled to room temperature, obtain reaction mixture；
(6) reaction mixture is centrifuged into 3min in 13000rpm, takes precipitation, by precipitation first with absolute ethyl alcohol ultrasound
Centrifugal treating, then cleaned 3 times with deionized water respectively after (concussion) is cleaned 3 times, is placed in quick forced air drying at 90 DEG C, obtains
First finished product；
(7) it is put into after first finished product is fully ground with mortar in crucible, is placed in Muffle furnace and calcines, 700 DEG C of maintenance 1h, from
It is so cooled to room temperature, shell base boron-doped titanium dioxide composite photo-catalyst (hereinafter referred to as B/TiO is made2/ shell composite photocatalyst
Agent).
Gained B/TiO2Form, the size of/shell composite photo-catalyst are observed by field emission electron flying-spot microscope,
Object phase and its functional group analysis are then measured using x-ray diffractometer and Fourier infrared spectrograph, the result difference of test
See Fig. 1, Fig. 2 and Fig. 3.
As seen from Figure 1, B/TiO2It has been firmly adsorbed on shell powder carrier, and by the doping and load of oyster shell whiting,
B/TiO2Particle is effectively scatter, and is conducive to improve its photocatalysis performance.
From Figure 2 it can be seen that under 700 DEG C of calcination conditions, the organic principle in oyster shell whiting is burned consumption, leaves loose porous
Calcareous shell.3600-2900cm-1The wide absworption peak occurred is derived from B/TiO2On/shell composite photo-catalyst
Hydroxyl group, weaker absworption peak is due to made B/TiO2The ordered arrangement of-OH is subject in/shell composite photo-catalyst structure
The influence of B.In 1630cm-1The strong absworption peak that place occurs is as caused by adsorbed water molecule-OH bending vibrations, in 1420cm-1, 872cm-1And 713cm-1Etc. be CO32-The vibration peak of ion.The result shows that B/TiO2Contain in/shell composite photo-catalyst
Substantial amounts of hydroxyl exists, and since the hydroxyl of particle surface has better electric charge transfer effect, can help to improve B/
TiO2The photocatalysis performance of/shell composite photo-catalyst.
As seen from Figure 3, B/TiO2/ shell composite photo-catalyst contains the anatase crystal nanometer titanium dioxide of larger proportion
Titanium, while the also perovskite containing larger proportion, it is not only to load on oyster shell whiting to show boron doped nano titanium dioxide, and
It and is also crosslinked with the calcium in oyster shell whiting so that the combination of boron doped nano titanium dioxide and oyster shell whiting is more firm.
Embodiment 2
A kind of preparation method of shell base boron-doped titanium dioxide composite photo-catalyst, comprises the following steps：
(1) mussel shell is placed in the dilution heat of sulfuric acid of 0.5M and impregnates 12h, dried after being rinsed with deionized water to neutrality,
The oyster shell whiting that grain size is 200 mesh is ground into, it is spare；
(2) 6ml butyl titanates are dissolved in 2.5ml absolute ethyl alcohols, be sufficiently stirred, be uniformly mixed, obtain butyl titanate alcohol
Solution；
(3) by 1.5g boric acid, the oyster shell whiting of 0.75g steps (1) is added in 40ml deionized waters, is uniformly mixed, is obtained
Suspension；
(4) under rapid mixing conditions, butyl titanate alcoholic solution is added drop-wise in suspension dropwise, stir speed (S.S.) maintains
300rpm, rate of addition maintain 20 drops/minute；Continuing stirring 15min is fully hydrolyzed butyl titanate, and it is molten to obtain initial reaction
Liquid；
(5) initial reaction solution is placed in the stainless steel high temperature autoclave with polytetrafluoroethyllining lining, 180 DEG C
Maintain 12 it is small when, cooled to room temperature, obtain reaction mixture；
(6) reaction mixture is centrifuged into 6min in 10000rpm, takes precipitation, precipitation is first clear with absolute ethyl alcohol ultrasound
Centrifugal treating is distinguished after washing 3 times, then is cleaned 3 times with deionized water, is placed in quick forced air drying at 90 DEG C, obtains just finished product；
(7) it is put into after first finished product is fully ground with mortar in crucible, is placed in Muffle furnace and calcines, 700 DEG C of maintenance 1h, from
It is so cooled to room temperature, B/TiO is made2/ shell composite photo-catalyst.
Embodiment 3
A kind of preparation method of shell base boron-doped titanium dioxide composite photo-catalyst, comprises the following steps：
(1) mussel shell is placed in the dilution heat of sulfuric acid of 2M and impregnates 6h, dried after being rinsed with deionized water to neutrality, crushed
It is spare into the oyster shell whiting that grain size is 400 mesh；
(2) 9ml butyl titanates are dissolved in 10ml absolute ethyl alcohols, be sufficiently stirred, be uniformly mixed, it is molten to obtain butyl titanate alcohol
Liquid；
(3) by 1.5g boric acid, the oyster shell whiting of 3g steps (1) is added in 60ml deionized waters, is uniformly mixed, is suspended
Liquid；
(4) under rapid mixing conditions, butyl titanate alcoholic solution is added drop-wise in suspension dropwise, stir speed (S.S.) maintains
500rpm, rate of addition maintain 50 drops/minute；Continuing stirring 60min is fully hydrolyzed butyl titanate, and it is molten to obtain initial reaction
Liquid；
(5) initial reaction solution is placed in the stainless steel high temperature autoclave with polytetrafluoroethyllining lining, 180 DEG C
Maintain 12 it is small when, cooled to room temperature, obtain reaction mixture；
(6) reaction mixture is centrifuged into 3min in 15000rpm, takes precipitation, precipitation is first clear with absolute ethyl alcohol ultrasound
Centrifugal treating is distinguished after washing 3 times, then is cleaned 3 times with deionized water, is placed in quick forced air drying at 60 DEG C, obtains just finished product；
(7) it is put into after first finished product is fully ground with mortar in crucible, is placed in Muffle furnace and calcines, 700 DEG C of maintenance 1h, from
It is so cooled to room temperature, B/TiO is made2/ shell composite photo-catalyst.
Embodiment 4
A kind of preparation method of shell base boron-doped titanium dioxide composite photo-catalyst, comprises the following steps：
(1) mussel shell is placed in the dilution heat of sulfuric acid of 0.1M and impregnated for 24 hours, dried after being rinsed with deionized water to neutrality,
The oyster shell whiting that grain size is 300 mesh is ground into, it is spare；
(2) 8ml butyl titanates are dissolved in 8ml absolute ethyl alcohols, be sufficiently stirred, be uniformly mixed, it is molten to obtain butyl titanate alcohol
Liquid；
(3) by 1.5g boric acid, the oyster shell whiting of 6g steps (1) is added in 50ml deionized waters, is uniformly mixed, is suspended
Liquid；
(4) under rapid mixing conditions, butyl titanate alcoholic solution is added drop-wise in suspension dropwise, stir speed (S.S.) maintains
600rpm, rate of addition maintain 40 drops/minute；Continuing stirring 45min is fully hydrolyzed butyl titanate, and it is molten to obtain initial reaction
Liquid；
(5) initial reaction solution is placed in the stainless steel high temperature autoclave with polytetrafluoroethyllining lining, 180 DEG C
Maintain 12 it is small when, cooled to room temperature, obtain reaction mixture；
(6) reaction mixture is centrifuged into 3min in 15000rpm, takes precipitation, precipitation is first clear with absolute ethyl alcohol ultrasound
Centrifugal treating is distinguished after washing 3 times, then is cleaned 3 times with deionized water, is placed in quick forced air drying at 60 DEG C, obtains just finished product；
(7) it is put into after first finished product is fully ground with mortar in crucible, is placed in Muffle furnace and calcines, 700 DEG C of maintenance 1h, from
It is so cooled to room temperature, B/TiO is made2/ shell composite photo-catalyst.
Comparative example 1
A kind of preparation method of boron doped nanometer titanium dioxide photocatalyst, comprises the following steps：
(1) butyl titanate for measuring 7.5ml is dissolved in 5ml absolute ethyl alcohols, is sufficiently stirred, and is uniformly mixed, is obtained metatitanic acid
Butyl ester alcoholic solution；
(2) weigh 1.5g boric acid to be dissolved in 60ml deionized waters, be uniformly mixed, obtain suspension；
(3) under rapid mixing conditions, butyl titanate alcoholic solution is added drop-wise in suspension dropwise, stir speed (S.S.) maintains
400rpm, rate of addition maintain 30 drops/minute；Continuing stirring 30min is fully hydrolyzed butyl titanate, and it is molten to obtain initial reaction
Liquid；
(4) initial reaction solution is placed in the stainless steel high temperature autoclave with polytetrafluoroethyllining lining, 180 DEG C
Maintain 12 it is small when, cooled to room temperature, obtain reaction mixture；
(5) reaction mixture is centrifuged into 3min in 13000rpm, takes precipitation, precipitation is first clear with absolute ethyl alcohol ultrasound
Centrifugal treating is distinguished after washing 3 times, then is cleaned 3 times with deionized water, is placed in quick forced air drying at 90 DEG C, obtains just finished product；
(6) it is put into after first finished product is fully ground with mortar in crucible, is placed in Muffle furnace and calcines, 700 DEG C of maintenance 1h, from
It is so cooled to room temperature, boron doped nanometer titanium dioxide photocatalyst (hereinafter referred to as B/TiO is made2Photochemical catalyst).
Detect example 1
Detect B/TiO prepared by Examples 1 to 42B/TiO prepared by/shell composite photo-catalyst and comparative example 12Light
Catalyst is to the photocatalysis efficiency of methyl orange.
Each photochemical catalyst samples of 160mg are added separately in 160mL methyl orange solutions (20mg/L), are first surpassed at dark
Sound disperses 5min, ensures to be uniformly dispersed, and keeps carrying out photocatalytic degradation under magnetic agitation state afterwards；In reaction process, every
5min is sampled once, is centrifuged 10min under 12000r/min immediately after taking-up, is taken supernatant at maximum absorption wavelength (463nm)
Place measures its absorbance.Testing result is shown in Fig. 4.
From fig. 4, it can be seen that B/TiO prepared by Examples 1 to 42/ shell composite photo-catalyst is to the photocatalysis efficiency of methyl orange
It is superior to B/TiO2Photochemical catalyst, wherein, the B/TiO of embodiment 12/ shell composite photo-catalyst is to the photocatalysis efficiency of methyl orange
Highest shows that the mass ratio of boric acid and oyster shell whiting has notable shadow to the photocatalysis efficiency of composite photo-catalyst in preparation process
It rings, if oyster shell whiting addition is excessive, oyster shell whiting can form screening effect to photochemical catalyst.
Embodiment 5~7
B/TiO is prepared using preparation method same as Example 12/ shell composite photo-catalyst, but in step (6)
Calcining heat is changed to 650 DEG C, 750 DEG C, 800 DEG C.
Embodiment 8
B/TiO is prepared using preparation method same as Example 12/ shell composite photo-catalyst, but in step (6)
Calcination time be changed to 5 it is small when.
Comparative example 2~4
B/TiO is prepared using preparation method same as Example 12/ shell composite photo-catalyst, but in step (6)
Calcining heat is changed to 500 DEG C, 550 DEG C, 850 DEG C.
Detect example 2
The B/TiO prepared using the method detection embodiment 1 identical with detection example 1, embodiment 5~7, comparative example 2~42/
Shell composite photo-catalyst is shown in Fig. 5 a to the photocatalysis efficiency of methyl orange, testing result.
By Fig. 5 a as it can be seen that calcining heat is in 550 to 750 degree Celsius ranges, B/TiO2With higher absorbance, show
Photocatalysis performance is preferable；Wherein when calcining heat is at 700 degrees Celsius, not only photocatalysis performance is best, and photoresponse scope is shown
Work is widened.
The B/TiO prepared using the method detection embodiment 1 identical with detection example 1 and embodiment 82/ shell complex light is urged
Agent is shown in Fig. 5 b to the photocatalysis efficiency of methyl orange, testing result.
By Fig. 5 b as it can be seen that extending calcination time, be conducive to the raising of photocatalysis performance.But when calcining heat reaches a certain value
After (700 degrees Celsius), calcination time just need not be long, as long as calcining 1 is small.
Detect example 3
(1) B/TiO prepared by comparing embodiment 12/ shell composite photo-catalyst is with commercially available nano-titanium dioxide P25 to work
The photocatalysis efficiency of the red X-3B of property；It specifically includes：
1. the B/TiO2/ shells photochemical catalyst for weighing 0.6g preparations is dissolved in 300ml concentration for 100mg/L in the dark state
Activated red X-3B (a length of 538nm of maximum absorption wave) solution in, it is molten in the dark state to weigh 0.3g nano-titanium dioxides P25
In activated red X-3B (a length of 538nm of the maximum absorption wave) solution for being 100mg/L in 300ml concentration, effective ingredient is respectively formed
Nano-titanium dioxide concentration be 1g/L suspension, dark place ultrasound 5min, with guarantee be uniformly dispersed；
2. keeping carrying out photocatalysis test using 250w high-pressure sodium lamps under 200r/min magnetic agitation states, 50min is reacted,
In reaction process, every 5min samplings once；
3. centrifuging 8min under 12000r/min immediately after taking out, take supernatant through ultraviolet specrophotometer in absorption maximum
Its light absorption value is measured at wavelength 538nm, percent of decolourization is calculated, maps through Origin9.0, see Fig. 6 a.
By Fig. 6 a as it can be seen that compared with nano-titanium dioxide P25, the B/TiO of the invention prepared2/ shell composite photo-catalyst
There is higher photocatalysis efficiency to activated red X-3B (a length of 538nm of maximum absorption wave).
(2) B/TiO that compared with using the method identical with detection example 1 prepared by comparing embodiment 12/ shell composite photocatalyst
Agent is with commercially available nano-titanium dioxide P25 to the photocatalysis efficiency of 20mg/L methyl orange solutions (maximum absorption wavelength 463nm), detection
The result is shown in Fig. 6 b.
By Fig. 6 b as it can be seen that compared with nano-titanium dioxide P25, the B/TiO of the invention prepared2/ shell composite photo-catalyst
There is higher photocatalysis efficiency to methyl orange (maximum absorption wavelength 463nm).
From Fig. 6 a and Fig. 6 b as can be seen that since the maximum absorption wavelength of methyl orange is in 463nm or so, and active red X-
The maximum absorption wavelength of 3B of the invention can be made in 538nm or so, the maximum absorption wavelength of activated red X-3B further from ultra-violet (UV) band
Standby B/TiO2/ shell composite photo-catalyst has broader photoresponse scope, and photocatalysis effect is more preferable.
B/TiO prepared by the present invention2/ shell composite photo-catalyst can not carry out ultraviolet-ray visible absorbing since particle is larger
Spectrum test, and B/TiO2Actually active light degradation ingredient is B/TiO in/shell composite photo-catalyst2, therefore B/TiO2Purple
Outside-visible absorption spectra test result can represent B/TiO2The uv-visible absorption spectra test of/shell composite photo-catalyst
As a result.To nano-titanium dioxide P25 and B/TiO2It carries out ultraviolet-visible spectrum (UV-vis) and tests discovery (see Fig. 6 c), B/TiO2
There is broader photoresponse scope than nano-titanium dioxide P25, this is consistent with the conclusion of Fig. 6 a and Fig. 6 b.
Detect example 4
Detection substrate initial concentration is to B/TiO2The influence of/shell composite photo-catalyst activity, specifically includes：
Respectively compound concentration for 10,20,30,40, the methyl orange solution of 50mg/L, B/TiO2/ shell composite photo-catalyst
Concentration for 2g/L, carry out light-catalyzed reaction, draw the relation of methyl orange removal rate and light application time.In reaction process, every
5min carries out primary sample, and 10min is centrifuged under 12000r/min immediately after taking-up, and supernatant is taken to be surveyed in maximum absorption wave strong point
Measure its absorbance.Testing result is shown in Fig. 7 a and Fig. 7 b.
By Fig. 7 a and Fig. 7 b as it can be seen that when methyl orange concentration is relatively low, B/TiO2/ shell composite photo-catalyst is in the unit interval
It is interior that there is higher photocatalysis efficiency, show that photocatalysis efficiency is related with reactant initial concentration, initial concentration is lower, photocatalysis
Efficiency is higher；It is the effective means for handling low concentration pollutant to illustrate photocatalysis technology.
Detect example 5
Initial soln pH is investigated to B/TiO2The influence of/shell composite photo-catalyst activity, specifically includes：
The methyl orange solution that five parts of concentration is taken to be 20mg/L, uses H respectively2SO4The pH of methyl orange solution is adjusted with NaOH solution
Then value puts into B/TiO to 2,4,6,8,10,12 to every part of methyl orange solution2/ shell composite photo-catalyst is to B/TiO2It is dense eventually
It spends for 1g/L, light drops 50 minutes, draws different pH value to B/TiO2Knot is investigated in the influence of/shell composite photo-catalyst activity
Fruit sees Fig. 8 a；
Similarly, the methyl orange solution that three parts of concentration is taken to be 20mg/L, in addition uses H for two parts respectively2SO4With NaOH solution tune
The pH value of methyl orange solution is saved to 2,7,12, then puts into nano-titanium dioxide P25 to final concentration of to every part of methyl orange solution
1g/L, light drop 50 minutes, draw different pH value to B/TiO2The influence of/shell composite photo-catalyst activity；Investigate the result is shown in
Fig. 8 b.
By Fig. 8 a and 8b as it can be seen that B/TiO2The photocatalysis efficiency of/shell composite photo-catalyst in acid condition it is higher (
Reach highest during pH=2), this is because acid medium is conducive to dissolved oxygen and excitation electronic action generation oxidisability is extremely strong
OH so that the significant effect of Photodegradation of Methyl Orange.And when methyl orange solution is faintly acid or is neutral, the pH value of solution urges light
Changing efficiency influences little, B/TiO2The photocatalysis efficiency ratio of/shell composite photo-catalyst is low under acid medium；And work as methyl
When orange solution alkaline gradually enhances, B/TiO2The photocatalysis efficiency of/shell composite photo-catalyst but gradually steps up, this may with it is molten
The concentration of OH gradually steps up related in liquid；And since nano-titanium dioxide P25 needs acid medium competence exertion catalytic
Can, therefore in alkaline conditions, B/TiO2The catalytic performance of/shell composite photo-catalyst is better than nano-titanium dioxide P25.
Detect example 6
It prepares and containing reactive brilliant red x-3b manually prepares dyeing waste water, be formulated and be：Reactive brilliant red x-3b 20mg/L, glucose
860mg/L, acetic acid (99.9%) 0.150ml/L, urea 108mg/L, KH2PO467mg/L, NaHCO3840mg/L, MgSO4·
7H2O 38mg/L, CaCl221mg/L, FeCl3·6H2O 7mg/L.Using the method test present invention's identical with detection example 1
B/TiO2The photocatalysis efficiency of/shell composite photo-catalyst and the above-mentioned dyeing waste waters of nano-titanium dioxide p25 investigates the present invention's
B/TiO2/ shell composite photo-catalyst and nano-titanium dioxide p25 are to manually preparing the drop of dyeing waste water containing reactive brilliant red x-3b
Solve effect；The result is shown in Fig. 9 for investigation.
As seen from Figure 9, compared with nano-titanium dioxide p25, B/TiO of the invention2/ shell composite photo-catalyst is to above-mentioned
The degradation rate that dyeing waste water is manually prepared containing reactive brilliant red x-3b greatly improves.
Claims (10)
1. a kind of shell base boron-doped titanium dioxide composite photo-catalyst, which is characterized in that be prepared by following preparation method：
(1) titanate esters are scattered in organic solvent, obtain yellow solution；
(2) boric acid, oyster shell whiting are added in deionized water, are uniformly mixed, obtain suspension；
(3) under rapid mixing conditions, the yellow solution is added drop-wise to dropwise in the suspension, continues stirring until titanium
Acid esters is fully hydrolyzed, and obtains initial reaction solution；
(4) the initial reaction solution is inserted in high-temperature high-pressure reaction kettle, at 140~180 DEG C after 2~12h of hydro-thermal reaction
Cooled to room temperature obtains reaction mixture；
(5) reaction mixture is centrifuged, takes precipitation, wash drying, obtain just finished product；
(6) calcined after the first finished product is fully ground, cooled to room temperature；
Finally obtain the shell base boron-doped titanium dioxide composite photo-catalyst.
2. shell base boron-doped titanium dioxide composite photo-catalyst as described in claim 1, which is characterized in that in step (1), institute
The volume ratio for stating titanate esters and organic solvent is (3:1)~(1:1).
3. shell base boron-doped titanium dioxide composite photo-catalyst as described in claim 1, which is characterized in that in step (2), first
Acid treatment is carried out to the oyster shell whiting, is then then added in deionized water.
4. shell base boron-doped titanium dioxide composite photo-catalyst as claimed in claim 3, it is characterised in that：Shell is placed in
Impregnate 6 in the dilution heat of sulfuric acid of 0.1~2M~for 24 hours, it then is dried after being rinsed with deionized water to neutrality, is ground into grain size as 100
The oyster shell whiting of~400 mesh.
5. the shell base boron-doped titanium dioxide composite photo-catalyst as described in claim 1 or 3 or 4, which is characterized in that step
(2) in, the mass ratio of the boric acid and oyster shell whiting is (1:4)~(2:1).
6. shell base boron-doped titanium dioxide composite photo-catalyst as claimed in claim 5, which is characterized in that in step (2), institute
The mass ratio for stating boric acid and oyster shell whiting is (1:2)~(2:1).
7. shell base boron-doped titanium dioxide composite photo-catalyst as described in claim 1, which is characterized in that in step (3), stir
It mixes rate and maintains 300~600rpm, the rate of addition of yellow solution maintains 20-50 drops/minute.
8. shell base boron-doped titanium dioxide composite photo-catalyst as described in claim 1, which is characterized in that, will in step (4)
The initial reaction solution is inserted in high-temperature high-pressure reaction kettle, is naturally cooled at 160~180 DEG C after 8~12h of hydro-thermal reaction
Room temperature obtains reaction mixture.
9. shell base boron-doped titanium dioxide composite photo-catalyst as described in claim 1, which is characterized in that, will in step (6)
After the first finished product is fully ground, 1~5h is calcined at 550~750 DEG C.
10. a kind of preparation method of shell base boron-doped titanium dioxide composite photo-catalyst, which is characterized in that comprise the following steps：
(1) titanate esters are dissolved in organic solvent, obtain yellow solution；
(2) boric acid, oyster shell whiting are added in deionized water, are uniformly mixed, obtain suspension；
(3) under rapid mixing conditions, the yellow solution is added drop-wise to dropwise in the suspension, continues stirring until titanium
Acid esters is fully hydrolyzed, and obtains initial reaction solution；
(4) the initial reaction solution is inserted in high-temperature high-pressure reaction kettle, at 140~180 DEG C after 2~12h of hydro-thermal reaction
Cooled to room temperature obtains reaction mixture；
(5) reaction mixture is centrifuged, takes precipitation, wash drying, obtain just finished product；
(6) calcined after the first finished product is fully ground, cooled to room temperature obtains the shell base boron-doped titanium dioxide and answers
Closing light catalyst.
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