CN105536765A - Shell-based boron-doped titanium dioxide composite photocatalyst and preparation method thereof - Google Patents
Shell-based boron-doped titanium dioxide composite photocatalyst and preparation method thereof Download PDFInfo
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- CN105536765A CN105536765A CN201510973652.8A CN201510973652A CN105536765A CN 105536765 A CN105536765 A CN 105536765A CN 201510973652 A CN201510973652 A CN 201510973652A CN 105536765 A CN105536765 A CN 105536765A
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- titanium dioxide
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 104
- 239000002131 composite material Substances 0.000 title claims abstract description 100
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 30
- 239000008367 deionised water Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000725 suspension Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004327 boric acid Substances 0.000 claims abstract description 16
- 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
- 238000005406 washing Methods 0.000 claims abstract description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 50
- 241000276489 Merlangius merlangus Species 0.000 claims description 38
- 239000000376 reactant Substances 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 7
- 241001417490 Sillaginidae Species 0.000 claims description 6
- 238000005703 Whiting synthesis reaction Methods 0.000 claims description 6
- 238000010306 acid treatment Methods 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000000047 product Substances 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 16
- 239000002244 precipitate Substances 0.000 abstract description 5
- 239000000843 powder Substances 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract 2
- 239000011541 reaction mixture Substances 0.000 abstract 2
- 230000004298 light response Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 62
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 56
- 230000001699 photocatalysis Effects 0.000 description 41
- 238000007146 photocatalysis Methods 0.000 description 37
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 24
- 238000012360 testing method Methods 0.000 description 23
- 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 20
- 229940012189 methyl orange Drugs 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 14
- 229910052796 boron Inorganic materials 0.000 description 14
- 238000010521 absorption reaction 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 11
- 230000001476 alcoholic effect Effects 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 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
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 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
- 241000237536 Mytilus edulis Species 0.000 description 5
- 238000007605 air drying Methods 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 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
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 235000020638 mussel Nutrition 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004506 ultrasonic cleaning 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000011835 investigation Methods 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
- 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
- 238000005070 sampling Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000010936 titanium Substances 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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 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
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion 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
- 238000001514 detection method Methods 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
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 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
- 230000000630 rising effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- -1 titanium dioxide compound Chemical class 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
Classifications
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- 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
-
- 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
-
- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention discloses a shell-based boron-doped titanium dioxide composite photocatalyst and a preparation method thereof. The preparation method comprises the following steps: titanate is dissolved in an organic solvent, such that a light yellow solution is obtained; boric acid and shell powder is added into deionized water, and the mixture is well mixed, such that a suspension liquid is obtained; under a fast stirring condition, the light yellow solution is gradually dropped into the suspension liquid; stirring is continued until titanate is fully hydrolyzed, such that an initial reaction solution is obtained; the initial reaction solution is placed in a high-temperature high-pressure reaction kettle, and is subjected to a hydrothermal reaction for 2-12h under a temperature of 140-180 DEG C, such that a reaction mixture is obtained; the reaction mixture is subjected to centrifugal separation, and a precipitate is collected; washing and drying are carried out, such that a preliminarily finished product is obtained; the preliminarily finished product is fully ground and calcined, and is naturally cooled to room temperature, such that the shell-based boron-doped titanium dioxide composite photocatalyst is obtained. The method is simple to operate, and is environment-friendly. The photocatalyst has high activity, and can be recycled. The photocatalyst has a wide light response range.
Description
Technical field
The present invention relates to a kind of photochemical catalyst, be specifically related to a kind of shell base boron-doped titanium dioxide composite photo-catalyst and preparation method thereof.
Background technology
Photochemical catalyst is a kind of important green material, a kind of water technology of rising in recent years that to take semi-conducting material as the photocatalytic oxidation of catalyst be.With conventional method ratio, the method oxidation efficiency is high, stable and non-secondary pollution, and the organic pollution in waste water from dyestuff can be decomposed into CO by it
2, H
2o, N
2, Cl
-deng inorganic matter Small molecular, thus there is good application prospect.
TiO
2nano material because of the photochemical catalyst that it has good chemical stability, low cost, the feature such as nontoxic become most application potential, but due to TiO
2greater band gap, energy gap is 3.2ev, needs ultraviolet light (λ≤387.5nm) just can excite its catalytic activity, thus significantly limit its application; In addition nano-TiO
2there is shortcomings such as reclaiming difficulty, utilization difficulty again when using as photochemical catalyst, this severely limits TiO
2the application & development of nano material in wastewater treatment.
For solving nano-TiO
2recycle this problem difficult, publication number is the preparation method that the Chinese patent literature of CN101352675A discloses a kind of shell powder supported active nano titanic oxide, this preparation method comprises: be dissolved in organic solvent by least one in the alkoxide of predecessor titanate esters, titanium, titanate, Ti
4+concentration be 0.01 ~ 6.0mol/L, drip appropriate water and hydrolyst under vigorous stirring, make pH=3.5 ~ 6.5 of solution, vigorous stirring forms yellowish transparent TiO
2colloidal sol, ageing is stand-by; Get shell powder supported (carrying method is spin coating, dipping, plasma spraying or thermal spraying) this TiO of activation
2colloidal sol, 70 ~ 100 DEG C of oven dry, distilled water rinses repeatedly, then in 70 ~ 100 DEG C of oven dry, in muffle furnace with 400 ~ 500 DEG C of roastings (control heating rate for 1 ~ 10K/min, after being warmed up to 300 DEG C, constant temperature; Then 400 ~ 500 DEG C are warming up to, then constant temperature), namely obtain the immobilized nano-TiO of oyster shell whiting
2.
But the method does not improve TiO
2bandgap range, the photoresponse scope of expansion photochemical catalyst not yet in effect, can not efficiency utilization visible region energy, and this makes the obtained photochemical catalyst of the method be difficult to large-scale promotion in actual applications.
Need ultraviolet light (λ≤387.5nm) just can excite TiO for solving in use procedure
2this problem of catalytic activity, publication number is the synthetic method that the Chinese patent literature of CN104645952A discloses a kind of boron doped nano titanium dioxide, this synthetic method comprises: be dissolved in by 13-15ml butyl titanate in 60-70ml absolute ethyl alcohol, heat to 50-70 DEG C, be forced into 5-8MPa, vigorous stirring, slowly drips and is dissolved with H
3bO
3deionized water, stir 3-6h butyl titanate is fully hydrolyzed, then put into teflon-lined stainless steel autoclave, when being forced into 10-15MPa, 200-240 DEG C maintain 12-48h, rapid water-cooled, to 2-8 DEG C, is depressurized to normal pressure; Product after filtration, ethanol and deionized water washing, at room temperature dry 24h, then in 90-100 DEG C of vacuum drying 5-10h, obtained B
2tiO
2catalyst.
But this synthetic method is comparatively loaded down with trivial details, harsh complicated to experiment condition, the TiO of generation
2very easily reunite, and unresolved TiO
2recycle this defect of difficulty.
Prepare the method all comparatively very complicated of nanometer titanium dioxide compound photocatalyst at present, and the composite photo-catalyst catalytic efficiency of preparation is lower, therefore in order to expand nano-TiO
2the use scale of this photochemical catalyst, in the urgent need to developing new simple and easy, efficient technology of preparing and method.
Summary of the invention
Present invention also offers a kind of shell base boron-doped titanium dioxide composite photo-catalyst, the photocatalytic activity of this composite photo-catalyst is high, can repeat to reclaim and utilize, and response range is wide, can play its photocatalytic activity under excited by visible light.
Meanwhile, present invention also offers a kind of preparation method of shell base boron-doped titanium dioxide composite photo-catalyst, this preparation method is simple to operate, avoids titanate esters long-term exposure in preparation process in the environment, to cause operating personnel uncomfortable.
A kind of shell base boron-doped titanium dioxide composite photo-catalyst, is prepared from by following preparation method:
(1) titanate esters is scattered in organic solvent, obtains yellow solution;
(2) boric acid, oyster shell whiting are joined in deionized water, mix, obtain suspension;
(3) under rapid mixing conditions, described yellow solution is dropwise added drop-wise in described suspension, continues to stir until titanate esters is fully hydrolyzed, obtain initial reaction solution;
(4) described initial reaction solution is inserted in high-temperature high-pressure reaction kettle, at 140 ~ 180 DEG C, naturally cool to room temperature after hydro-thermal reaction 2 ~ 12h, obtain reactant mixture;
(5) by described reactant mixture centrifugation, get precipitation, washing is dry, obtains just finished product;
(6) described just finished product is fully ground rear calcining, naturally cool to room temperature;
Final acquisition described shell base boron-doped titanium dioxide composite photo-catalyst.
The present invention utilizes hydro-thermal method (carrying out in high-temperature high-pressure reaction kettle) to be doped in nano titanium oxide by the calcium constituent in boron element, oyster shell whiting, form the compound of a kind of novel perovskite and titanium dioxide, the composite photo-catalyst obtained not only is made to have better anatase crystal, effectively improve the photocatalysis performance of nano titanium oxide, under the prerequisite reaching peer-level photocatalysis efficiency, containing less B/TiO in composite photo-catalyst of the present invention
2, effectively reduce B/TiO
2synthetic quantity, reduce manufacturing cost; And accelerate boron doped nano titanium dioxide and be attached to process on oyster shell whiting, take time and effort unlike the immersion load of routine, spraying load even load method; Boron doped nano titanium dioxide is not only load on oyster shell whiting, but also there occurs with the calcium in oyster shell whiting and crosslinked generate perovskite, in conjunction with more firm; Also greatly simplify preparation process, avoid titanate esters to expose in the environment for a long time in preparation process, the bad smell preventing titanate esters from distributing causes operating personnel uncomfortable, and preparation process is environmental protection more simultaneously.
And calcining can improve the ratio of anatase crystal titanium dioxide in composite photo-catalyst, anatase crystal titanium dioxide is conducive to the photocatalysis performance improving composite photo-catalyst.
Particularly, the preparation method of a kind of shell base of the present invention boron-doped titanium dioxide composite photo-catalyst comprises the following steps:
(1) titanate esters is scattered in organic solvent, obtains yellow solution;
In the present invention, described titanate esters can select the titanyl organic matters such as butyl titanate, metatitanic acid orthocarbonate or tetraethyl titanate as the predecessor generating titanium dioxide.Described organic solvent can select at least one in absolute methanol, absolute ethyl alcohol, anhydrous propyl alcohol, anhydrous isopropyl alcohol, anhydrous butanols or dry isobutanol, is preferably absolute ethyl alcohol.
As preferably, the mixed proportion of described titanate esters and organic solvent is (3:1) ~ (1:1).
(2) boric acid, oyster shell whiting are joined in deionized water, mix, obtain suspension;
In the present invention, described oyster shell whiting general reference lives in the molluscan outer embrane of waterside, can adopt at least one in oyster shell, mussel shell, spiral shell shell or clam shell.
For increasing oyster shell whiting to the load area of nano titanium oxide, as preferably, first acid treatment (or directly doing acid treatment to shell) being carried out to described oyster shell whiting, and then joining in deionized water.The main component of shell is calcium carbonate, carry out acid treatment to oyster shell whiting (or shell) contribute to corrosion calcium carbonate thus form hole, increase the specific area of shell, make the cellulosic be originally buried in calcium carbonate expose simultaneously, increase the load area of nano titanium oxide further.
As preferred further, described acid treatment is: dilution heat of sulfuric acid shell being placed in 0.1 ~ 2M soaks 6 ~ 24h, then by rinsed with deionized water to neutral post-drying, being ground into particle diameter is 100 ~ 400 object oyster shell whitings.
Nonmetalloid (boron element) doping effectively can expand the response range of nano titanium oxide, makes composite photo-catalyst can the light energy of efficiency utilization visible region, also need not can play its photocatalytic activity by ultraviolet excitation.
In the present invention, the mass ratio of described boric acid and oyster shell whiting is (1:2) ~ (2:1), most preferably is 1:1.The present invention finds, when suitably improving the doping of boron element (in prior art, the doping of boron element is only 0.1% (accounting for photochemical catalyst gross weight) left and right), the corresponding increase of ratio of anatase crystal nano titanium oxide, and the content of perovskite also increases thereupon, catalytic efficiency also increases.
(3) under rapid mixing conditions, described yellow solution is dropwise added drop-wise in described suspension, continues to stir until titanate esters is fully hydrolyzed, obtain initial reaction solution;
As preferably, stir speed (S.S.) maintains 300 ~ 600rpm, and the rate of addition of yellow solution maintains 20-50 and drips/minute.
Stir speed (S.S.) and rate of addition can affect the composite effect of composite photo-catalyst, and stirring stir speed (S.S.) is crossed slowly or dripped too fast meeting and causes butyl titanate to condense in solution surface, cannot be hydrolyzed under aqueous environment.
(4) described initial reaction solution is inserted in high-temperature high-pressure reaction kettle, at 140 ~ 180 DEG C, naturally cool to room temperature after hydro-thermal reaction 2 ~ 12h, obtain reactant mixture; As preferably, described initial reaction solution is inserted in high-temperature high-pressure reaction kettle, at 180 DEG C, naturally cools to room temperature after hydro-thermal reaction 12h, obtain reactant mixture.
(5) by described reactant mixture centrifugation, get precipitation, washing is dry, obtains just finished product;
(6) described just finished product is fully ground rear calcining, naturally cool to room temperature, obtain described shell base boron-doped titanium dioxide composite photo-catalyst.
Find through uv-visible absorption spectra (UV-vis) test, calcining can widen the photoresponse scope of composite photo-catalyst, improves composite photo-catalyst photocatalysis efficiency under visible light.
As preferably, after fully being ground by described first finished product, at 550 ~ 750 DEG C, calcine 1 ~ 5h; As further preferably, after described first finished product is fully ground, at 600 ~ 700 DEG C, calcine 1 ~ 2h, most preferably be and calcine 1h at 700 DEG C.
Calcination process needs suitable calcining heat, otherwise absorbance can be caused to decline, and this may be because composite photo-catalyst is reunited seriously under the calcining heat of 400 DEG C-550 DEG C; And crystal formation conversion very likely occurs nano titanium oxide under calcining heat more than 750 DEG C, anatase crystal nano titanium oxide ratio is caused to reduce.
Compared with prior art, beneficial effect of the present invention is:
The present invention utilizes hydro-thermal method to be doped in nano titanium oxide by the calcium constituent in boron element, oyster shell whiting, form the compound of a kind of novel perovskite and titanium dioxide, the composite photo-catalyst obtained not only is made to have better anatase crystal, effectively improve the photocatalysis performance of nano titanium oxide, under the prerequisite reaching peer-level photocatalysis efficiency, containing less B/TiO in composite photo-catalyst of the present invention
2, effectively reduce B/TiO
2synthetic quantity, reduce manufacturing cost; And accelerate boron doped nano titanium dioxide and be attached to process on oyster shell whiting, take time and effort unlike the immersion load of routine, spraying load even load method; Boron doped nano titanium dioxide is not only load on oyster shell whiting, but also there occurs with the calcium in oyster shell whiting and crosslinked generate perovskite, in conjunction with more firm; Also greatly simplify preparation process, avoid titanate esters to expose in the environment for a long time in preparation process, the bad smell preventing titanate esters from distributing causes operating personnel uncomfortable, and preparation process is environmental protection more simultaneously.
Accompanying drawing explanation
Fig. 1 is field emission scanning electron microscope (FE-SEM) figure of shell base boron-doped titanium dioxide composite photo-catalyst in the embodiment of the present invention 1;
Fig. 2 is Fourier transform infrared spectroscopy (FT-IR) figure of shell base boron-doped titanium dioxide composite photo-catalyst in the embodiment of the present invention 1;
Wherein, %Transmittance represents light transmittance (%), Wavenumbers (cm
-1) represent wave number (cm
-1), lower same;
Fig. 3 is X-ray diffraction (XRD) figure of shell base boron-doped titanium dioxide composite photo-catalyst in the embodiment of the present invention 1;
Wherein, 2Theta (degree) represents the incident angle of the x-ray of twice, and Intensity (a.u.) represents the intensity after diffraction;
Fig. 4 is B/TiO prepared by embodiment 1 ~ 4
2b/TiO prepared by/shell composite photo-catalyst and comparative example 1
2photochemical catalyst is to the photocatalysis efficiency of methyl orange;
Wherein, B-TiO
2represent B/TiO
2photochemical catalyst, B/TiO
2/ shell (1:0.5) represents B/TiO
2/ shell composite photo-catalyst (mass ratio of boric acid and oyster shell whiting is 1:0.5), B/TiO
2/ shell (1:1) represents B/TiO
2/ shell composite photo-catalyst (mass ratio of boric acid and oyster shell whiting is 1:1), B/TiO
2/ shell (1:2) represents B/TiO
2/ shell composite photo-catalyst (mass ratio of boric acid and oyster shell whiting is 1:2), B/TiO
2/ shell (1:4) represents B/TiO
2/ shell composite photo-catalyst (mass ratio of boric acid and oyster shell whiting is 1:4); MOremoving (%) represents methyl orange degradation rate (%), and T (min) represents degradation time (min), lower same;
Fig. 5 a is B/TiO prepared by embodiment 1,8 ~ 10 and comparative example 3 ~ 5
2/ shell composite photo-catalyst is to the photocatalysis efficiency of methyl orange;
Fig. 5 b is B/TiO prepared by embodiment 1 and embodiment 11
2/ shell composite photo-catalyst is to the photocatalysis efficiency of methyl orange;
Wherein, Absorbance represents absorbance, lower same;
Fig. 6 a is B/TiO
2/ shell composite photo-catalyst and commercially available nano titanium oxide P25 are to the photocatalysis efficiency comparison diagram of activated red X-3B; Wherein, X-3BRemoving (%) represents the degradation rate (%) of activated red X-3B;
Fig. 6 b is B/TiO
2/ shell composite photo-catalyst and commercially available nano titanium oxide P25 are to the photocatalysis efficiency comparison diagram of methyl orange;
Fig. 6 c is B/TiO
2/ shell composite photo-catalyst and the photoresponse scope comparison diagram without the first finished product calcined, commercially available nano titanium oxide P25;
Fig. 7 a is that methyl orange initial concentration is to B/TiO
2the impact of/shell composite photo-catalyst activity;
Wherein, MO represents methyl orange;
When Fig. 7 b is reaction 15min, methyl orange initial concentration and B/TiO2/ shell composite photo-catalyst are to the linear relationship between the degradation rate of methyl orange;
Wherein, c/mg.L
-1represent methyl orange initial concentration;
Fig. 8 a is that the initial pH of solution is to B/TiO
2the impact of/shell composite photo-catalyst activity;
Fig. 8 b is that the initial pH of solution is on the impact of nano titanium oxide P25 activity;
Fig. 9 is B/TiO
2/ shell composite photo-catalyst and nano titanium oxide P25 are to the degradation effect manually preparing dyeing waste water containing reactive brilliant red x-3b.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Embodiment 1
A preparation method for shell base boron-doped titanium dioxide composite photo-catalyst, comprises the following steps:
(1) dilution heat of sulfuric acid mussel shell being placed in 0.5M soaks 24h, and by rinsed with deionized water to neutral post-drying, being ground into particle diameter is 150 object oyster shell whitings, for subsequent use;
(2) 7.5ml butyl titanate is dissolved in 5ml absolute ethyl alcohol, fully stirs, mix, obtain butyl titanate alcoholic solution;
(3) by 1.5g boric acid (H
3bO
3), the oyster shell whiting of 1.5g step (1) joins in 60ml deionized water, mixes, obtains suspension;
(4) under rapid mixing conditions, be dropwise added drop-wise in suspension by butyl titanate alcoholic solution, stir speed (S.S.) maintains 400rpm, and rate of addition maintains 30 droplets/minute; Continuing to stir 30min makes butyl titanate fully be hydrolyzed, and obtains initial reaction solution;
(5) be placed in by initial reaction solution with teflon-lined stainless steel high temperature autoclave, 180 DEG C maintain 12 hours, naturally cool to room temperature, obtain reactant mixture;
(6) by described reactant mixture in the centrifugal 3min of 13000rpm, get precipitation, precipitation first used absolute ethyl alcohol ultrasonic (concussion) to clean 3 times and distinguish centrifugal treating afterwards, then use washed with de-ionized water 3 times, and quick forced air drying at being placed in 90 DEG C, obtain just finished product;
(7) put into crucible after fully being ground by first finished product mortar, be placed in Muffle furnace and calcine, 700 DEG C maintain 1h, naturally cool to room temperature, and obtained shell base boron-doped titanium dioxide composite photo-catalyst is (hereinafter referred to as B/TiO
2/ shell composite photo-catalyst).
Gained B/TiO
2form, the size of/shell composite photo-catalyst are observed by field emission electron flying-spot microscope, and thing phase and functional group analysis thereof then adopt x-ray diffractometer and Fourier infrared spectrograph to measure, and the result of test is shown in Fig. 1 respectively, Fig. 2 and Fig. 3.
As seen from Figure 1, B/TiO
2be adsorbed on securely on oyster shell whiting carrier, and passed through doping and the load of oyster shell whiting, B/TiO
2particle is effectively scatter, and is conducive to improving its photocatalysis performance.
As seen from Figure 2, under 700 DEG C of calcination conditions, the burned consumption of the organic principle in oyster shell whiting, leaves loose porous calcareous shell.3600-2900cm
-1the wide absworption peak occurred comes from B/TiO
2oh group on/shell composite photo-catalyst, absworption peak is more weak is due to made B/TiO
2in/shell composite photo-catalyst structure, the ordered arrangement of-OH is subject to the impact of B.At 1630cm
-1the strong absworption peak that place occurs is caused, at 1420cm by adsorbed water molecule-OH flexural vibrations
-1, 872cm
-1and 713cm
-1at place for CO3
2-the vibration peak of ion.Result shows B/TiO
2exist containing a large amount of hydroxyls in/shell composite photo-catalyst, the hydroxyl due to particle surface has better Charger transfer effect, therefore can contribute to improving B/TiO
2the photocatalysis performance of/shell composite photo-catalyst.
As seen from Figure 3, B/TiO
2/ shell composite photo-catalyst contains the anatase crystal nano titanium oxide of larger proportion, perovskite simultaneously also containing larger proportion, show that boron doped nano titanium dioxide is not only load on oyster shell whiting, but also there occurs crosslinked with the calcium in oyster shell whiting, make the combination of boron doped nano titanium dioxide and oyster shell whiting more firm.
Embodiment 2
A preparation method for shell base boron-doped titanium dioxide composite photo-catalyst, comprises the following steps:
(1) dilution heat of sulfuric acid mussel shell being placed in 0.5M soaks 12h, and by rinsed with deionized water to neutral post-drying, being ground into particle diameter is 200 object oyster shell whitings, for subsequent use;
(2) 6ml butyl titanate is dissolved in 2.5ml absolute ethyl alcohol, fully stirs, mix, obtain butyl titanate alcoholic solution;
(3) by 1.5g boric acid, the oyster shell whiting of 0.75g step (1) joins in 40ml deionized water, mixes, obtains suspension;
(4) under rapid mixing conditions, be dropwise added drop-wise in suspension by butyl titanate alcoholic solution, stir speed (S.S.) maintains 300rpm, and rate of addition maintains 20 droplets/minute; Continuing to stir 15min makes butyl titanate fully be hydrolyzed, and obtains initial reaction solution;
(5) be placed in by initial reaction solution with teflon-lined stainless steel high temperature autoclave, 180 DEG C maintain 12 hours, naturally cool to room temperature, obtain reactant mixture;
(6) by described reactant mixture in the centrifugal 6min of 10000rpm, get precipitation, will precipitate first by absolute ethyl alcohol ultrasonic cleaning 3 times centrifugal treating respectively afterwards, then use washed with de-ionized water 3 times, and quick forced air drying at being placed in 90 DEG C, finished product at the beginning of obtaining;
(7) put into crucible after fully being ground by first finished product mortar, be placed in Muffle furnace and calcine, 700 DEG C maintain 1h, naturally cool to room temperature, obtained B/TiO
2/ shell composite photo-catalyst.
Embodiment 3
A preparation method for shell base boron-doped titanium dioxide composite photo-catalyst, comprises the following steps:
(1) dilution heat of sulfuric acid mussel shell being placed in 2M soaks 6h, and by rinsed with deionized water to neutral post-drying, being ground into particle diameter is 400 object oyster shell whitings, for subsequent use;
(2) 9ml butyl titanate is dissolved in 10ml absolute ethyl alcohol, fully stirs, mix, obtain butyl titanate alcoholic solution;
(3) by 1.5g boric acid, the oyster shell whiting of 3g step (1) joins in 60ml deionized water, mixes, obtains suspension;
(4) under rapid mixing conditions, be dropwise added drop-wise in suspension by butyl titanate alcoholic solution, stir speed (S.S.) maintains 500rpm, and rate of addition maintains 50 droplets/minute; Continuing to stir 60min makes butyl titanate fully be hydrolyzed, and obtains initial reaction solution;
(5) be placed in by initial reaction solution with teflon-lined stainless steel high temperature autoclave, 180 DEG C maintain 12 hours, naturally cool to room temperature, obtain reactant mixture;
(6) by described reactant mixture in the centrifugal 3min of 15000rpm, get precipitation, will precipitate first by absolute ethyl alcohol ultrasonic cleaning 3 times centrifugal treating respectively afterwards, then use washed with de-ionized water 3 times, and quick forced air drying at being placed in 60 DEG C, finished product at the beginning of obtaining;
(7) put into crucible after fully being ground by first finished product mortar, be placed in Muffle furnace and calcine, 700 DEG C maintain 1h, naturally cool to room temperature, obtained B/TiO
2/ shell composite photo-catalyst.
Embodiment 4
A preparation method for shell base boron-doped titanium dioxide composite photo-catalyst, comprises the following steps:
(1) dilution heat of sulfuric acid mussel shell being placed in 0.1M soaks 24h, and by rinsed with deionized water to neutral post-drying, being ground into particle diameter is 300 object oyster shell whitings, for subsequent use;
(2) 8ml butyl titanate is dissolved in 8ml absolute ethyl alcohol, fully stirs, mix, obtain butyl titanate alcoholic solution;
(3) by 1.5g boric acid, the oyster shell whiting of 6g step (1) joins in 50ml deionized water, mixes, obtains suspension;
(4) under rapid mixing conditions, be dropwise added drop-wise in suspension by butyl titanate alcoholic solution, stir speed (S.S.) maintains 600rpm, and rate of addition maintains 40 droplets/minute; Continuing to stir 45min makes butyl titanate fully be hydrolyzed, and obtains initial reaction solution;
(5) be placed in by initial reaction solution with teflon-lined stainless steel high temperature autoclave, 180 DEG C maintain 12 hours, naturally cool to room temperature, obtain reactant mixture;
(6) by described reactant mixture in the centrifugal 3min of 15000rpm, get precipitation, will precipitate first by absolute ethyl alcohol ultrasonic cleaning 3 times centrifugal treating respectively afterwards, then use washed with de-ionized water 3 times, and quick forced air drying at being placed in 60 DEG C, finished product at the beginning of obtaining;
(7) put into crucible after fully being ground by first finished product mortar, be placed in Muffle furnace and calcine, 700 DEG C maintain 1h, naturally cool to room temperature, obtained B/TiO
2/ shell composite photo-catalyst.
Comparative example 1
A preparation method for boron doped nanometer titanium dioxide photocatalyst, comprises the following steps:
(1) butyl titanate measuring 7.5ml is dissolved in 5ml absolute ethyl alcohol, fully stirs, mixes, and obtains butyl titanate alcoholic solution;
(2) take 1.5g boric acid to be dissolved in 60ml deionized water, mix, obtain suspension;
(3) under rapid mixing conditions, be dropwise added drop-wise in suspension by butyl titanate alcoholic solution, stir speed (S.S.) maintains 400rpm, and rate of addition maintains 30 droplets/minute; Continuing to stir 30min makes butyl titanate fully be hydrolyzed, and obtains initial reaction solution;
(4) be placed in by initial reaction solution with teflon-lined stainless steel high temperature autoclave, 180 DEG C maintain 12 hours, naturally cool to room temperature, obtain reactant mixture;
(5) by described reactant mixture in the centrifugal 3min of 13000rpm, get precipitation, will precipitate first by absolute ethyl alcohol ultrasonic cleaning 3 times centrifugal treating respectively afterwards, then use washed with de-ionized water 3 times, and quick forced air drying at being placed in 90 DEG C, finished product at the beginning of obtaining;
(6) put into crucible after fully being ground by first finished product mortar, be placed in Muffle furnace and calcine, 700 DEG C maintain 1h, naturally cool to room temperature, and obtained boron doped nanometer titanium dioxide photocatalyst is (hereinafter referred to as B/TiO
2photochemical catalyst).
Test example 1
Detect B/TiO prepared by embodiment 1 ~ 4
2/ shell composite photo-catalyst, and B/TiO prepared by comparative example 1
2photochemical catalyst is to the photocatalysis efficiency of methyl orange.
Each for 160mg photochemical catalyst sample is joined respectively in 160mL methyl orange solution (20mg/L), first at dark place ultrasonic disperse 5min, ensure to be uniformly dispersed, keep afterwards carrying out photocatalytic degradation under magnetic agitation state; In course of reaction, every 5min sampling once, centrifugal 10min under 12000r/min immediately after taking-up, gets supernatant and measures its absorbance at maximum absorption wavelength (463nm) place.Testing result is shown in Fig. 4.
As seen from Figure 4, the B/TiO of embodiment 1 ~ 4 preparation
2the photocatalysis efficiency of/shell composite photo-catalyst to methyl orange is all better than B/TiO
2photochemical catalyst, wherein, the B/TiO of embodiment 1
2the photocatalysis efficiency of/shell composite photo-catalyst to methyl orange is the highest, show that the photocatalysis efficiency of the mass ratio of preparation process mesoboric acid and oyster shell whiting on composite photo-catalyst has remarkable impact, if oyster shell whiting addition is too much, oyster shell whiting can form screening effect to photochemical catalyst.
Embodiment 5 ~ 7
The preparation method identical with embodiment 1 is adopted to prepare B/TiO
2/ shell composite photo-catalyst, but the calcining heat in step (6) changes 650 DEG C, 750 DEG C, 800 DEG C into.
Embodiment 8
The preparation method identical with embodiment 1 is adopted to prepare B/TiO
2/ shell composite photo-catalyst, but the calcination time in step (6) changes 5 hours into.
Comparative example 2 ~ 4
The preparation method identical with embodiment 1 is adopted to prepare B/TiO
2/ shell composite photo-catalyst, but the calcining heat in step (6) changes 500 DEG C, 550 DEG C, 850 DEG C into.
Test example 2
Adopt the B/TiO that the method identical with test example 1 detects embodiment 1, prepared by embodiment 5 ~ 7, comparative example 2 ~ 4
2/ shell composite photo-catalyst is to the photocatalysis efficiency of methyl orange, and testing result is shown in Fig. 5 a.
From Fig. 5 a, calcining heat in 550 to 750 degree Celsius range, B/TiO
2there is higher absorbance, show that photocatalysis performance is better; Wherein when calcining heat is at 700 degrees Celsius, not only photocatalysis performance is best, and photoresponse scope is significantly widened.
The B/TiO adopting the method identical with test example 1 to detect embodiment 1 and embodiment 8 to prepare
2/ shell composite photo-catalyst is to the photocatalysis efficiency of methyl orange, and testing result is shown in Fig. 5 b.
From Fig. 5 b, extend calcination time, be conducive to the raising of photocatalysis performance.But after calcining heat reaches a certain value (700 degrees Celsius), calcination time just need not be long, as long as calcine 1 hour.
Test example 3
(1) B/TiO of comparing embodiment 1 preparation
2/ shell composite photo-catalyst and commercially available nano titanium oxide P25 are to the photocatalysis efficiency of activated red X-3B; Specifically comprise:
1. taking B/TiO2/ shell photochemical catalyst prepared by 0.6g is dissolved in activated red X-3B (maximum absorption wavelength the is 538nm) solution that 300ml concentration is 100mg/L in the dark state, taking 0.3g nano titanium oxide P25 is dissolved in activated red X-3B (maximum absorption wavelength the is 538nm) solution that 300ml concentration is 100mg/L in the dark state, forming active ingredient nano titanium oxide concentration is respectively the suspension of 1g/L, the ultrasonic 5min in dark place, to ensure to be uniformly dispersed;
2. 250w high-pressure sodium lamp is utilized to carry out photocatalysis test under keeping 200r/min magnetic agitation state, reaction 50min, in course of reaction, every 5min sampling once;
3. centrifugal 8min under 12000r/min immediately after taking out, gets supernatant and measures its light absorption value through ultraviolet specrophotometer at maximum absorption wavelength 538nm place, calculate percent of decolourization, map, see Fig. 6 a through Origin9.0.
From Fig. 6 a, compared with nano titanium oxide P25, B/TiO prepared by the present invention
2/ shell composite photo-catalyst has higher photocatalysis efficiency to activated red X-3B (maximum absorption wavelength is 538nm).
(2) B/TiO adopting the Measures compare comparing embodiment 1 identical with test example 1 to prepare
2/ shell composite photo-catalyst and commercially available nano titanium oxide P25 are to the photocatalysis efficiency of 20mg/L methyl orange solution (maximum absorption wavelength 463nm), and testing result is shown in Fig. 6 b.
From Fig. 6 b, compared with nano titanium oxide P25, B/TiO prepared by the present invention
2/ shell composite photo-catalyst has higher photocatalysis efficiency to methyl orange (maximum absorption wavelength 463nm).
As can be seen from Fig. 6 a and Fig. 6 b, because the maximum absorption wavelength of methyl orange is at about 463nm, and the maximum absorption wavelength of activated red X-3B is at about 538nm, and the maximum absorption wavelength of activated red X-3B, can the B/TiO for preparing of the present invention further from ultra-violet (UV) band
2/ shell composite photo-catalyst has wider photoresponse scope, and photocatalysis effect is better.
B/TiO prepared by the present invention
2/ shell composite photo-catalyst is comparatively large due to particle, cannot carry out uv-visible absorption spectra test, and B/TiO
2in/shell composite photo-catalyst, actual effectively light degradation composition is B/TiO
2, therefore B/TiO
2uv-visible absorption spectra test result can represent B/TiO
2the uv-visible absorption spectra test result of/shell composite photo-catalyst.To nano titanium oxide P25 and B/TiO
2carry out ultraviolet-visible spectrum (UV-vis) test and find (see Fig. 6 c), B/TiO
2have wider photoresponse scope than nano titanium oxide P25, this is consistent with the conclusion of Fig. 6 a and Fig. 6 b.
Test example 4
Detection substrate initial concentration is to B/TiO
2the impact of/shell composite photo-catalyst activity, specifically comprises:
Respectively compound concentration be 10,20,30,40, the methyl orange solution of 50mg/L, B/TiO
2the concentration of/shell composite photo-catalyst is 2g/L, carries out light-catalyzed reaction, draws the relation of methyl orange clearance and light application time.In course of reaction, carry out primary sample every 5min, centrifugal 10min under 12000r/min immediately after taking-up, gets supernatant and measures its absorbance in maximum absorption wave strong point.Testing result is shown in Fig. 7 a and Fig. 7 b.
From Fig. 7 a and Fig. 7 b, when methyl orange concentration is lower, B/TiO
2/ shell composite photo-catalyst has higher photocatalysis efficiency within the unit interval, and show that photocatalysis efficiency is relevant with reactant initial concentration, initial concentration is lower, and photocatalysis efficiency is higher; Illustrate that photocatalysis technology is the effective means of process low concentration pollutant.
Test example 5
Investigate initial soln pH to B/TiO
2the impact of/shell composite photo-catalyst activity, specifically comprises:
Getting five parts of concentration is the methyl orange solution of 20mg/L, uses H respectively
2sO
4regulate the pH value to 2,4,6,8,10,12 of methyl orange solution with NaOH solution, then drop into B/TiO to every part of methyl orange solution
2/ shell composite photo-catalyst is to B/TiO
2final concentration is 1g/L, and light falls 50 minutes, draws different pH value to B/TiO
2the impact of/shell composite photo-catalyst activity, investigates and the results are shown in Figure 8a;
Similarly, getting three parts of concentration is the methyl orange solution of 20mg/L, uses H respectively for other two parts
2sO
4regulate the pH value to 2,7,12 of methyl orange solution with NaOH solution, then dropping into nano titanium oxide P25 to final concentration to every part of methyl orange solution is 1g/L, and light falls 50 minutes, draws different pH value to B/TiO
2the impact of/shell composite photo-catalyst activity; Investigation the results are shown in Figure 8b.
From Fig. 8 a and 8b, B/TiO
2/ shell composite photo-catalyst photocatalysis efficiency in acid condition higher (reaching the highest when pH=2), this is because acid medium is conducive to dissolved oxygen and excitation electron effect generates the extremely strong OH of oxidisability, make the Be very effective of Photodegradation of Methyl Orange.And when methyl orange solution be faintly acid or neutral time, the pH value of solution is little on photocatalysis efficiency impact, B/TiO
2the photocatalysis efficiency of/shell composite photo-catalyst is than low under acid medium; And when methyl orange solution alkalescence strengthens gradually, B/TiO
2the photocatalysis efficiency of/shell composite photo-catalyst but improves gradually, and this may improve relevant with the concentration of OH in solution gradually; And because nano titanium oxide P25 needs acid medium competence exertion catalytic performance, therefore in the basic conditions, B/TiO
2the catalytic performance of/shell composite photo-catalyst is better than nano titanium oxide P25.
Test example 6
Preparation manually prepares dyeing waste water containing reactive brilliant red x-3b, and filling a prescription is: reactive brilliant red x-3b 20mg/L, glucose 860mg/L, acetic acid (99.9%) 0.150ml/L, urea 108mg/L, KH
2pO
467mg/L, NaHCO
3840mg/L, MgSO
47H
2o38mg/L, CaCl
221mg/L, FeCl
36H
2o7mg/L.The method identical with test example 1 is adopted to test B/TiO of the present invention
2the photocatalysis efficiency of/shell composite photo-catalyst and the above-mentioned dyeing waste water of nano titanium oxide p25, investigates B/TiO of the present invention
2/ shell composite photo-catalyst and nano titanium oxide p25 are to the degradation effect manually preparing dyeing waste water containing reactive brilliant red x-3b; Investigation the results are shown in Figure 9.
As seen from Figure 9, compared with nano titanium oxide p25, B/TiO of the present invention
2/ shell composite photo-catalyst improves greatly to the above-mentioned degradation rate manually preparing dyeing waste water containing reactive brilliant red x-3b.
Claims (10)
1. a shell base boron-doped titanium dioxide composite photo-catalyst, is characterized in that, is prepared from by following preparation method:
(1) titanate esters is scattered in organic solvent, obtains yellow solution;
(2) boric acid, oyster shell whiting are joined in deionized water, mix, obtain suspension;
(3) under rapid mixing conditions, described yellow solution is dropwise added drop-wise in described suspension, continues to stir until titanate esters is fully hydrolyzed, obtain initial reaction solution;
(4) described initial reaction solution is inserted in high-temperature high-pressure reaction kettle, at 140 ~ 180 DEG C, naturally cool to room temperature after hydro-thermal reaction 2 ~ 12h, obtain reactant mixture;
(5) by described reactant mixture centrifugation, get precipitation, washing is dry, obtains just finished product;
(6) described just finished product is fully ground rear calcining, naturally cool to room temperature;
Final acquisition described shell base boron-doped titanium dioxide composite photo-catalyst.
2. shell base boron-doped titanium dioxide composite photo-catalyst as claimed in claim 1, it is characterized in that, in step (1), the volume ratio of described titanate esters and organic solvent is (3:1) ~ (1:1).
3. shell base boron-doped titanium dioxide composite photo-catalyst as claimed in claim 1, is characterized in that, in step (2), first carry out acid treatment to described oyster shell whiting, and then join in deionized water.
4. shell base boron-doped titanium dioxide composite photo-catalyst as claimed in claim 3, it is characterized in that, described acid treatment is: dilution heat of sulfuric acid shell being placed in 0.1 ~ 2M soaks 6 ~ 24h, then by rinsed with deionized water to neutral post-drying, being ground into particle diameter is 100 ~ 400 object oyster shell whitings.
5. the shell base boron-doped titanium dioxide composite photo-catalyst as described in claim 1 or 3 or 4, is characterized in that, in step (2), the mass ratio of described 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, it is characterized in that, in step (2), the mass ratio of described boric acid and oyster shell whiting is (1:2) ~ (2:1).
7. shell base boron-doped titanium dioxide composite photo-catalyst as claimed in claim 1, it is characterized in that, in step (3), stir speed (S.S.) maintains 300 ~ 600rpm, and the rate of addition of yellow solution maintains 20-50 and drips/minute.
8. shell base boron-doped titanium dioxide composite photo-catalyst as claimed in claim 1, it is characterized in that, in step (4), described initial reaction solution is inserted in high-temperature high-pressure reaction kettle, at 160 ~ 180 DEG C, naturally cool to room temperature after hydro-thermal reaction 8 ~ 12h, obtain reactant mixture.
9. shell base boron-doped titanium dioxide composite photo-catalyst as claimed in claim 1, is characterized in that, in step (6), after fully being ground by described first finished product, at 550 ~ 750 DEG C, calcines 1 ~ 5h.
10. a preparation method for shell base boron-doped titanium dioxide composite photo-catalyst, is characterized in that, comprise the following steps:
(1) titanate esters is dissolved in organic solvent, obtains yellow solution;
(2) boric acid, oyster shell whiting are joined in deionized water, mix, obtain suspension;
(3) under rapid mixing conditions, described yellow solution is dropwise added drop-wise in described suspension, continues to stir until titanate esters is fully hydrolyzed, obtain initial reaction solution;
(4) described initial reaction solution is inserted in high-temperature high-pressure reaction kettle, at 140 ~ 180 DEG C, naturally cool to room temperature after hydro-thermal reaction 2 ~ 12h, obtain reactant mixture;
(5) by described reactant mixture centrifugation, get precipitation, washing is dry, obtains just finished product;
(6) described just finished product is fully ground rear calcining, naturally cool to room temperature, obtain described shell base boron-doped titanium dioxide composite photo-catalyst.
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| CN106072776A (en) * | 2016-07-28 | 2016-11-09 | 华巧波 | A kind of health type electronic cigarette is cotton |
| CN106108115A (en) * | 2016-07-28 | 2016-11-16 | 华巧波 | A kind of health-care type electronic smoke cigarette is cotton |
| CN108325547A (en) * | 2018-03-14 | 2018-07-27 | 杭州电子科技大学 | Composite photo-catalyst shell base boron-doped titanium dioxide and preparation method thereof |
| CN111659365A (en) * | 2020-06-02 | 2020-09-15 | 天津大学 | Preparation method of photocatalyst for degrading methylene blue by using shell powder loaded with titanium dioxide in core-shell structure |
| CN111686776A (en) * | 2020-06-18 | 2020-09-22 | 吉林建筑大学 | Titanium dioxide-shell powder composite material and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106072776A (en) * | 2016-07-28 | 2016-11-09 | 华巧波 | A kind of health type electronic cigarette is cotton |
| CN106108115A (en) * | 2016-07-28 | 2016-11-16 | 华巧波 | A kind of health-care type electronic smoke cigarette is cotton |
| CN108325547A (en) * | 2018-03-14 | 2018-07-27 | 杭州电子科技大学 | Composite photo-catalyst shell base boron-doped titanium dioxide and preparation method thereof |
| CN111659365A (en) * | 2020-06-02 | 2020-09-15 | 天津大学 | Preparation method of photocatalyst for degrading methylene blue by using shell powder loaded with titanium dioxide in core-shell structure |
| CN111686776A (en) * | 2020-06-18 | 2020-09-22 | 吉林建筑大学 | Titanium dioxide-shell powder composite material and preparation method and application thereof |
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