CN112774706B - Bismuth oxide carbonate/sepiolite composite photocatalyst and preparation method thereof - Google Patents
Bismuth oxide carbonate/sepiolite composite photocatalyst and preparation method thereof Download PDFInfo
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- 239000004113 Sepiolite Substances 0.000 title claims abstract description 102
- 229910052624 sepiolite Inorganic materials 0.000 title claims abstract description 102
- 235000019355 sepiolite Nutrition 0.000 title claims abstract description 102
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- GACUIHAEKGVEIC-UHFFFAOYSA-L [Bi+2]=O.C([O-])([O-])=O Chemical compound [Bi+2]=O.C([O-])([O-])=O GACUIHAEKGVEIC-UHFFFAOYSA-L 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000243 solution Substances 0.000 claims abstract description 48
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 12
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- GQLMQWWBIJYOFC-UHFFFAOYSA-M [Br-].C(CCCCCCCCCCCCCCC)[N+](C)(C)C.C(CO)O Chemical compound [Br-].C(CCCCCCCCCCCCCCC)[N+](C)(C)C.C(CO)O GQLMQWWBIJYOFC-UHFFFAOYSA-M 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims 4
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 12
- 238000001179 sorption measurement Methods 0.000 abstract description 10
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- 238000005215 recombination Methods 0.000 abstract description 8
- 230000031700 light absorption Effects 0.000 abstract description 4
- 230000033558 biomineral tissue development Effects 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 description 19
- 230000015556 catabolic process Effects 0.000 description 17
- 230000001699 photocatalysis Effects 0.000 description 9
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 9
- 229940043267 rhodamine b Drugs 0.000 description 9
- 239000002957 persistent organic pollutant Substances 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- MGLUJXPJRXTKJM-UHFFFAOYSA-L bismuth subcarbonate Chemical compound O=[Bi]OC(=O)O[Bi]=O MGLUJXPJRXTKJM-UHFFFAOYSA-L 0.000 description 6
- 229940036358 bismuth subcarbonate Drugs 0.000 description 6
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 6
- CCEKXLJXSBYSEB-UHFFFAOYSA-N ethane-1,2-diol;hydrobromide Chemical compound Br.OCCO CCEKXLJXSBYSEB-UHFFFAOYSA-N 0.000 description 6
- 238000005286 illumination Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
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- 238000007254 oxidation reaction Methods 0.000 description 4
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- 239000000126 substance Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
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- 230000005684 electric field Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 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 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
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- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
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- 150000001622 bismuth compounds Chemical class 0.000 description 1
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- 239000011247 coating layer Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
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- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052610 inosilicate Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
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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
- 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
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- 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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- 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
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- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- 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
- C02F2101/38—Organic compounds containing nitrogen
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- 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)
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- Organic Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
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- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention relates to a bismuth oxide carbonate/sepiolite composite photocatalyst and a preparation method thereof. The invention firstly dissolves Cetyl Trimethyl Ammonium Bromide (CTAB) in Ethylene Glycol (EG) to prepare CTAB-EG solution as a template agent and a reducing agent, then adds bismuth nitrate-ferric nitrate solution, adjusts the pH value of the mixed solution by using strong alkali solution, then adds purified sepiolite, fully mixes and transfers the mixed solution into a polytetrafluoroethylene autoclave for hydrothermal reaction to generate the porous bismuth oxide carbonate/sepiolite composite photocatalyst with controllable appearance. Through oxidizing and decomposing EG or CTAB under hydrothermal condition to generate carbonate radical, and loading and growing bismuth oxide carbonate on sepiolite under the combined actions of CTAB surface activity, template action and sepiolite interface effect, the structure and morphology of the bismuth oxide carbonate can be effectively controlled, the recombination rate of energy band gap and photogenerated carriers can be reduced, the visible light absorption utilization rate and the adsorption performance on organic matters can be improved, and thus the photocatalytic degradation performance and mineralization capacity of the bismuth oxide carbonate can be improved.
Description
Technical Field
The invention belongs to the technical field of photocatalytic degradation of organic pollutants, and particularly relates to a bismuth oxide carbonate/sepiolite composite photocatalyst and a preparation method thereof.
Background
The rapid development of industrial and agricultural production and the continuous improvement of living standard of people lead to the increasing of organic pollutants discharged to the environment and the increasing of water environment pollution. Heretofore, various treatment techniques have been developed to cope with the increasingly serious organic pollution such as adsorption, flocculation, electrochemical methods, chemical reagent oxidation methods, ozone oxidation, fenton oxidation, photo Fenton oxidation, photocatalytic degradation, and the like. In a plurality of treatment methods, the photocatalytic degradation can utilize light energy to oxidize and decompose organic pollutants at normal temperature, has the advantages of strong capability of degrading the organic pollutants, complete degradation, high speed and no secondary pollution, and particularly, the visible photocatalytic degradation can fully utilize natural light sources, so that the treatment cost is low. The semiconductor mesoporous structure photocatalytic material has a superior porous structure and a larger specific surface area, is favorable for light reflection and refraction, and can greatly improve the utilization rate of light; and the larger specific surface area can provide enough active sites and places for pollutant molecule adsorption, and promote the efficient mass transfer of pollutant substances, thereby improving the catalytic degradation effect of the pollutant, and therefore, the method becomes a focus and a hot spot for research and development of environmental protection workers. At present, the photocatalyst which is the most deeply and widely researched, developed and applied is titanium dioxide, and has the advantages of good chemical stability, strong capability of resisting chemical pollutants, environmental friendliness and the like. However, the band gap is higher than 3.2eV, so that electron/hole pairs can be effectively excited and generated only under the irradiation of ultraviolet rays (lambda is less than or equal to 387.5 nm), and the defects that the electron/hole pair recombination rate is high, the titanium dioxide powder is difficult to separate when suspended in a solution, and the popularization and application of the titanium dioxide powder are greatly limited. Therefore, developing a photocatalyst which has high light utilization rate, particularly good catalytic degradation effect on visible light, low price and no toxicity is a key for promoting the application of the photocatalytic degradation technology in the treatment of organic pollutants.
In recent years, bismuth-based semiconductor materials, e.g. BiFeO 3 、BiVO 4 、Bi 2 WO 6 、Bi 2 MoO 6 BiOX, etc., has relatively high photocatalytic performance due to the fact that the internal electric field generated by polarization is favorable for separating photo-generated electrons from holes, and has become an important point for the development of environmental protection workers due to the fact that bismuth compounds are nontoxic and have little pollution to the environment. Wherein bismuth oxide carbonate (Bi 2 O 2 CO 3 ) Is a typical Aurivillius-type oxide belonging to the tetragonal system and having a unique structure of [ Bi ] 2 O 2 ] 2+ And CO 3 2- The layered structure formed by alternate layers, the internal electric field generated by polarization is beneficial to the separation of photoinduced electrons and holes, thereby improving Bi 2 O 2 CO 3 Is used for the photocatalytic performance of the catalyst. But the band gap value is between 3.2 and 3.5eV, the absorption rate to visible light is low, the recombination rate of photo-generated carrier particles (hole/electron pairs) is high, the quantum efficiency is low, and the popularization and application of the photo-generated carrier particles are greatly limited. Therefore, proper measures must be taken to improve the structure and morphology of the material, reduce the energy band gap, and improve the absorptivity and quantum efficiency of light and the adsorption performance of pollutants, thereby improving the photocatalytic degradation performance of the pollutants.
Sepiolite (Sepiolite) is a magnesium-containing porous inosilicate mineral, has unique nano-structure pore diameter, larger pore volume and specific surface area, strong adsorption capacity, light weight and good chemical stability, and particularly, a large number of acid-base centers exist in the Sepiolite, so that other materials can form and grow on the Sepiolite, and the purposes of regulating and controlling the structure and the morphology of the generated material are achieved. Thus, in situ generation of the photocatalyst in the presence of sepiolite is adoptedBi as an agent 2 O 2 CO 3 Thus preparing bismuth oxide carbonate/sepiolite (Bi) 2 O 2 CO 3 Sepiolite) composite photocatalyst, and is expected to improve Bi produced 2 O 2 CO 3 The structure and the morphology of the material are reduced, the energy gap band is reduced, the absorption rate of visible light and the absorption performance of pollution are improved, and the aim of improving the photocatalytic activity is fulfilled. Heretofore, there has not been Bi 2 O 2 CO 3 A study report of the Sepiolite composite photocatalyst.
Disclosure of Invention
In view of Bi 2 O 2 CO 3 The invention has the advantages of lamellar structure, no toxicity and the like, has the defects of high energy band gap, low light absorptivity, high recombination rate of photo-generated carriers, low photocatalysis efficiency and the like, and aims to provide a Bi 2 O 2 CO 3 The Sepiolite composite photocatalyst has excellent structural morphology, lower energy gap band and photon-generated carrier recombination rate, higher visible light absorption utilization rate and quantum efficiency, good adsorption performance on organic matters and excellent photocatalytic degradation performance.
Another object of the present invention is to provide a Bi 2 O 2 CO 3 Preparation method of Sepiolite composite photocatalyst, which generates Bi in situ in the presence of Sepiolite 2 O 2 CO 3 Can be used for Bi 2 O 2 CO 3 The structure and the morphology of the product are effectively controlled, the preparation method is simple and convenient, the process is easy to control, the three wastes are less discharged, the manufacturing cost is lower, and the large-scale production is easy to realize; the method specifically comprises the following steps:
(1) Adding cetyl trimethyl ammonium bromide into ethylene glycol, and stirring ultrasonically for 20-40 min to prepare a cetyl trimethyl ammonium bromide-ethylene glycol solution with the concentration of 0.125-0.25 mol/L, and marking the solution as solution A;
(2) Bismuth nitrate pentahydrate and ferric nitrate nonahydrate are added into deionized water at the same time according to the mol ratio of 1:0.9-1.0, and are stirred for 20-40 min by ultrasonic to be dissolved and prepared into bismuth nitrate-ferric nitrate mixed solution, which is marked as solution B, wherein Bi is contained in the solution B 3+ The concentration is 0.02 to 0.033mol/L, fe 3+ Concentration of0.018 to 0.033mol/L;
(3) Slowly dripping the solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 15-30 min, then adjusting the pH to 10-10.5, and continuously ultrasonically stirring at room temperature for 3-4 h to obtain a mixture C;
(4) Adding purified sepiolite into the mixture C obtained in the step (3) according to the mass ratio of the sepiolite to the bismuth nitrate pentahydrate of 0.082-0.41:1, and stirring for 40-80 min by ultrasonic to obtain a mixture D;
(5) Transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 3-6 h at 180-250 ℃; cooling to room temperature, filtering, washing the filter residue with deionized water and ethanol for 2-5 times, and drying at 100-120deg.C to constant weight to obtain Bi 2 O 2 CO 3 Sepiolite composite photocatalyst.
Further, in the step (3), a strong alkali solution with the pH of 8-12 mol/L is adopted for adjusting the pH, and the strong alkali is KOH or NaOH.
Further, in the step (4), the purified sepiolite is treated by the following method: grinding sepiolite, sieving with 200-300 mesh sieve, soaking with 1-2 mol/L hydrochloric acid at 75-85deg.C under reflux for 0.5-1 hr, filtering, and washing with distilled water to neutrality; then preparing a mixture of sepiolite and 10mmol/L hexadecyl trimethyl ammonium bromide, i.e. CTAB solution with the solid-to-liquid ratio (g/mL) of 1:40-60, carrying out ultrasonic treatment for 0.5-1 h, filtering, washing with distilled water, drying to constant weight at 80-100 ℃, grinding, sieving with a 800-1000 mesh sieve, and taking the undersize for later use.
Further, in the step (5), the high-pressure reaction kettle is a polytetrafluoroethylene lining high-pressure reaction kettle.
Further, the ultrasonic stirring is ultrasonic auxiliary mechanical stirring, and the ultrasonic power is 200-250W.
Further, the reagents used, cetyl trimethylammonium bromide, ethylene glycol, bismuth nitrate pentahydrate, ferric nitrate nonahydrate, KOH, naOH, ethanol and hydrochloric acid, were all analytically pure.
The invention relates to a bismuth oxide carbonate/sepiolite composite photocatalyst and a preparation method thereof. It is prepared by dissolving hexadecyl trimethyl ammonium bromide in glycolDissolving bismuth nitrate and ferric nitrate in deionized water to prepare bismuth nitrate-ferric nitrate mixed solution, then dripping the bismuth nitrate-ferric nitrate mixed solution into the template agent-reducing agent solution, regulating the pH value of the mixed solution by using a strong alkali solution, and fully stirring to obtain a mixture; and then adding the treated purified sepiolite into the mixture, fully mixing, and transferring the mixture into an autoclave with a polytetrafluoroethylene lining for hydrothermal reaction to obtain the porous bismuth oxide carbonate/sepiolite composite photocatalyst with good morphology based on sepiolite. Oxidative decomposition of ethylene glycol or cetyltrimethylammonium bromide under hydrothermal conditions to produce carbonate by bismuth nitrate and ferric nitrate, and with Bi 3+ Bismuth oxide carbonate is generated under alkaline condition, and is loaded and grown on sepiolite under the combined actions of the surface activity of hexadecyl trimethyl ammonium bromide and the template effect and the stronger interfacial effect of sepiolite. The morphology and the structure of the generated bismuth oxide carbonate are well controlled, the recombination rate of energy band gaps and photo-generated carriers is reduced, the visible light absorption utilization rate and the adsorption performance on organic matters are improved, and the photocatalytic degradation performance on organic pollution is obviously improved.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) Cetyl trimethyl ammonium bromide or ethylene glycol solution is used as a template agent and a reducing agent, bismuth nitrate and ferric nitrate are oxidized and decomposed under hydrothermal conditions to obtain carbonate, and the amount of the carbonate in the reaction process can be effectively controlled, so that Bi is controlled 2 O 2 CO 3 Is formed at a forming speed of (2); the structure and the morphology of the composite photocatalyst are effectively regulated and controlled through the surface activity or the template effect of hexadecyl trimethyl ammonium bromide and ethylene glycol and the interfacial effect of sepiolite.
(2) Bi prepared by the invention 2 O 2 CO 3 The Sepiolite composite photocatalyst has a porous structure, and the specific surface area of the catalyst is free of Bi generated by Sepiolite 2 O 2 CO 3 Large; the adsorption capacity to organic matters is enhanced through the synergistic effect with sepiolite.
(3) The preparation of the inventionBi of (2) 2 O 2 CO 3 Bi in Sepiolite composite photocatalyst 2 O 2 CO 3 Is generated in the presence of sepiolite and grows by taking sepiolite as a support, and the fusion property and the stability of the sepiolite and the support are good; sepiolite not only promotes and regulates Bi loaded on the sepiolite by the special pore canal structure 2 O 2 CO 3 The formation of the structure and the morphology of the material reduces the energy band gap and the recombination rate of photo-generated electrons and holes, and sepiolite and Bi 2 O 2 CO 3 The synergistic effect enhances the absorption of organic pollutants and the absorption and utilization rate of light, and improves the photocatalytic degradation performance of the organic pollutants.
(4) The product of the invention has excellent visible light catalytic degradation performance and good mineralization capability on organic pollutants, and has good photocatalytic decoloration performance on organic dye wastewater; safe and nontoxic, convenient recovery and good recycling performance, and is suitable for treating various organic pollution wastewater.
(5) The preparation method has the advantages of simple preparation process, easy control of the process, less three-waste emission, lower manufacturing cost, and easy realization of large-scale production due to the conventional equipment, and has wide application prospect.
Drawings
FIG. 1 is a synthetic route diagram of bismuth subcarbonate/sepiolite composite photocatalyst.
FIG. 2 shows a bismuth subcarbonate/sepiolite composite photocatalyst (m (Bi 2 O 2 CO 3 ) XRD pattern of: (Sepilolite) =1:0.4).
FIG. 3 shows a bismuth subcarbonate/sepiolite composite photocatalyst (m (Bi 2 O 2 CO 3 ) SEM image of: (Sepilolite) =1:0.4).
FIG. 4 shows a bismuth subcarbonate/sepiolite composite photocatalyst (m (Bi 2 O 2 CO 3 ) Photocatalytic degradation efficiency profile for: (Sepilolite) =1:0.4).
FIG. 5 shows a bismuth subcarbonate/sepiolite composite photocatalyst (m (Bi 2 O 2 CO 3 ) Cyclic usage effect graph of: (Sepilolite) =1:0.4).
Note that: m (Bi) 2 O 2 CO 3 ) The mass ratio of bismuth oxide carbonate to sepiolite is shown in the specification of m.
Detailed Description
The invention will be described in further detail with reference to the drawings and the specific examples, but the invention is not limited thereto.
Example 1
(1) Adding 5.47g of cetyltrimethylammonium bromide into 120mL of ethylene glycol, and stirring ultrasonically for 20min to prepare a cetyltrimethylammonium bromide-ethylene glycol solution A with the concentration of 0.125 mol/L;
(2) Respectively taking 2.94g of bismuth nitrate pentahydrate with the content of 99.0 percent and 2.46g of ferric nitrate nonahydrate with the content of 98.5 percent, adding into 300mL of deionized water at the same time, and stirring for 20min by ultrasonic to dissolve to obtain Bi 3+ The concentration is 0.02mol/L, fe 3+ Bismuth nitrate-ferric nitrate mixed solution B with the concentration of 0.020 mol/L;
(3) Slowly dripping the mixed solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 15min, then adjusting the pH to 10.5 by using 10mol/L KOH solution, and continuously ultrasonically stirring for 4h at room temperature to obtain a mixture C;
(4) Adding 0.24g of purified sepiolite into the mixture C obtained in the step (3), and stirring for 40min by ultrasonic to obtain a mixture D;
(5) Transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 3 hours at the temperature of 250 ℃; cooling to room temperature, filtering, washing filter residues with deionized water and ethanol for 3 times respectively, and drying at 120 ℃ to constant weight to obtain 1.75g of bismuth oxide carbonate/sepiolite composite photocatalyst.
Example 2
(1) Adding 5.47g of cetyltrimethylammonium bromide into 100mL of ethylene glycol, and stirring ultrasonically for 25min to prepare a cetyltrimethylammonium bromide-ethylene glycol solution A with the concentration of 0.15 mol/L;
(2) Respectively taking 2.94g of bismuth nitrate pentahydrate with the content of 99.0 percent and 2.41g of ferric nitrate nonahydrate with the content of 98.5 percent, simultaneously adding the bismuth nitrate pentahydrate and the ferric nitrate nonahydrate into 240mL of deionized water, and stirring the mixture for 25 minutes by ultrasonic to dissolve the bismuth nitrate pentahydrate and the ferric nitrate nonahydrate into Bi 3+ The concentration is 0.025mol/L, fe 3+ Bismuth nitrate-ferric nitrate mixed solution B with the concentration of 0.024 mol/L;
(3) Slowly dripping the mixed solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 20min, then adjusting the pH to 10.3 by using 12mol/L KOH solution, and continuously ultrasonically stirring for 3.5h at room temperature to obtain a mixture C;
(4) Adding 0.29g of purified sepiolite into the mixture C obtained in the step (3), and stirring for 50min by ultrasonic to obtain a mixture D;
(5) Transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 4 hours at 230 ℃; cooling to room temperature, filtering, washing filter residues with deionized water and ethanol for 4 times, and drying at 115 ℃ to constant weight to obtain 1.78g of bismuth oxide carbonate/sepiolite composite photocatalyst.
Example 3
(1) Adding 5.47g of cetyltrimethylammonium bromide into 75mL of ethylene glycol, and stirring ultrasonically for 30min to prepare a cetyltrimethylammonium bromide-ethylene glycol solution A with the concentration of 0.20 mol/L;
(2) Respectively taking 2.94g of bismuth nitrate pentahydrate with the content of 99.0 percent and 2.34g of ferric nitrate nonahydrate with the content of 98.5 percent, adding into 200mL of deionized water at the same time, and stirring for 25min by ultrasonic to dissolve to obtain Bi 3+ The concentration is 0.030mol/L, fe 3+ Bismuth nitrate-ferric nitrate mixed solution B with the concentration of 0.0285 mol/L;
(3) Slowly dripping the mixed solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 25min, then adjusting the pH to 10.1 by using 11mol/L KOH solution, and continuously ultrasonically stirring at room temperature for 3h to obtain a mixture C;
(4) Adding 0.59g of purified sepiolite into the mixture C obtained in the step (3), and stirring for 60min by ultrasonic to obtain a mixture D;
(5) Transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 4.5 hours at 220 ℃; cooling to room temperature, filtering, washing filter residues with deionized water and ethanol for 3 times respectively, and drying at 110 ℃ to constant weight to obtain 2.04g of bismuth oxide carbonate/sepiolite composite photocatalyst.
Samples were taken and their phases were measured on a D8 advanced X-powder diffractometer (40 kV,40mA, bruce AXS, germany) and scanned at 10℃to 80℃using the MDI Jade 5.0 analyte phase, resultsAs shown in fig. 2. As can be seen from FIG. 2, bi 2 O 2 CO 3 The Sepiolite XRD diffraction patterns are 23.9 degrees, 30.3 degrees, 32.7 degrees and 48.9 degrees with Bi 2 O 2 CO 3 Standard card (JCPDS No. 41-1488) is well matched, and diffraction peak of 26.6 degrees and sepiolite (080) crystal face structure show that the product is Bi 2 O 2 CO 3 Sepiolite complex.
Bi prepared in the absence of sepiolite was measured using a S-4800 type field emission scanning electron microscope (FESEM, hitachi Co., japan) 2 O 2 CO 3 And the morphology of the sample of this example, the results are shown in FIG. 3. As can be seen from FIG. 3 (a), bi is produced in the absence of sepiolite 2 O 2 CO 3 Is composed of long granular particles with different sizes; as can be seen from FIG. 3 (b), bi is produced in the presence of sepiolite 2 O 2 CO 3 The Sepiolite composite photocatalyst is porous large particles formed by stacking fine spherical particles. This indicates that the presence of sepiolite alters the coating layer Bi 2 O 2 CO 3 The crystal structure of the catalyst is beneficial to improving the photoelectrochemical property of the photocatalyst, such as improving the light absorption performance, reducing the energy band gap, the recombination rate of photo-generated electrons and holes, and the like, and improving the adsorption capacity to pollutants.
Determination of Bi by means of a specific surface area-pore volume analyzer (BELSORP-mini II, microtracBEL, japan) 2 O 2 CO 3 Is 49.01m 2 /g，Bi 2 O 2 CO 3 The specific surface area of the Sepiolite composite photocatalyst is 77.86m 2 And/g. The diffuse reflection ultraviolet-visible spectrum (UV-vis DRS) was measured by a UV-2550 scanning ultraviolet-visible spectrophotometer (Shimadzu, japan), and Bi was calculated 2 O 2 CO 3 And Bi (Bi) 2 O 2 CO 3 Band gap E of Sepiolite sample g 3.39eV and 3.14eV, respectively, indicating Bi 2 O 2 CO 3 Bi formed by compounding with sepiolite 2 O 2 CO 3 E of Sepiolite composite photocatalyst g Obviously reduces the sepiolite existence, obviously improves the structure of the composite photocatalyst, reduces the energy of the composite photocatalystBand gap.
Example 4
(1) Adding 5.47g of cetyltrimethylammonium bromide into 60mL of ethylene glycol, and stirring ultrasonically for 40min to prepare a cetyltrimethylammonium bromide-ethylene glycol solution A with the concentration of 0.25 mol/L;
(2) Respectively taking 2.94g of bismuth nitrate pentahydrate with the content of 99.0 percent and 2.21g of ferric nitrate nonahydrate with the content of 98.5 percent, adding the bismuth nitrate pentahydrate and the ferric nitrate nonahydrate into 182mL of deionized water at the same time, and stirring for 25min by ultrasonic to dissolve Bi 3+ The concentration is 0.033mol/L, fe 3+ Bismuth nitrate-ferric nitrate mixed solution B with the concentration of 0.030 mol/L;
(3) Slowly dripping the mixed solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 30min, then adjusting the pH to 10.0 by using 8mol/L KOH solution, and continuously ultrasonically stirring for 3.5h at room temperature to obtain a mixture C;
(4) Adding 0.88g of purified sepiolite into the mixture C obtained in the step (3), and stirring for 70min by ultrasonic to obtain a mixture D;
(5) Transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 5 hours at 210 ℃; cooling to room temperature, filtering, washing filter residues with deionized water and ethanol for 5 times respectively, and drying at 105 ℃ to constant weight to obtain 2.33g of bismuth oxide carbonate/sepiolite composite photocatalyst.
Example 5
1) Adding 5.47g of cetyltrimethylammonium bromide into 110mL of ethylene glycol, and stirring ultrasonically for 25min to prepare a cetyltrimethylammonium bromide-ethylene glycol solution A with the concentration of 0.14 mol/L;
(2) Respectively taking 2.94g of bismuth nitrate pentahydrate with the content of 99.0 percent and 2.46g of ferric nitrate nonahydrate with the content of 98.5 percent, adding the bismuth nitrate pentahydrate and the ferric nitrate nonahydrate into 182mL of deionized water at the same time, and stirring the mixture for 25 minutes by ultrasonic to dissolve the bismuth nitrate pentahydrate and the ferric nitrate nonahydrate into Bi 3+ The concentration is 0.033mol/L, fe 3+ Bismuth nitrate-ferric nitrate mixed solution B with the concentration of 0.033mol/L;
(3) Slowly dripping the mixed solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 25min, then adjusting the pH to 10.2 by using 8mol/L NaOH solution, and continuously ultrasonically stirring for 4h at room temperature to obtain a mixture C;
(4) Adding 1.21g of purified sepiolite into the mixture C obtained in the step (3), and stirring for 80min by ultrasonic to obtain a mixture D;
(5) Transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 5.5 hours at 200 ℃; cooling to room temperature, filtering, washing filter residues with deionized water and ethanol for 2 times respectively, and drying at 100 ℃ to constant weight to obtain 2.64g of bismuth oxide carbonate/sepiolite composite photocatalyst.
Example 6
1) Adding 5.47g of cetyltrimethylammonium bromide into 100mL of ethylene glycol, and stirring ultrasonically for 35min to prepare a cetyltrimethylammonium bromide-ethylene glycol solution A with the concentration of 0.15 mol/L;
(2) Respectively taking 2.94g of bismuth nitrate pentahydrate with the content of 99.0 percent and 2.34g of ferric nitrate nonahydrate with the content of 98.5 percent, simultaneously adding the bismuth nitrate pentahydrate and the ferric nitrate nonahydrate into 220mL of deionized water, and stirring ultrasonically for 25min to dissolve Bi 3+ The concentration is 0.027mol/L, fe 3+ Bismuth nitrate-ferric nitrate mixed solution B with the concentration of 0.026 mol/L;
(3) Slowly dripping the mixed solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 30min, then adjusting the pH to 10.5 by using a 12mol/L NaOH solution, and continuously ultrasonically stirring for 3.5h at room temperature to obtain a mixture C;
(4) Adding 1.18g of purified sepiolite into the mixture C obtained in the step (3), and stirring for 80min by ultrasonic waves to obtain a mixture D;
(5) Transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 6 hours at 180 ℃; cooling to room temperature, filtering, washing filter residues with deionized water and ethanol for 4 times, and drying at 100deg.C to constant weight to obtain 2.67g of bismuth subcarbonate/sepiolite composite photocatalyst.
Examples 7 to 9 are examples of photocatalytic degradation performance tests
Example 7
The photocatalytic performance test conditions were as follows: bismuth oxide carbonate/sepiolite composite photocatalyst (Bi) prepared in example 3 using a 300W xenon lamp as a light source at room temperature 2 O 2 CO 3 /Sepiolite，m(Bi 2 O 2 CO 3 ) M (sepiolite) =1:0.4) and in the absence of sepiolitePreparation of bismuth oxide carbonate (Bi) in the presence of the same conditions 2 O 2 CO 3 ) The degradation rate of rhodamine B (RhB) was used as an evaluation index for the test sample. The specific operation steps are as follows: a clean 100mL jacketed beaker was charged with 50mg of photocatalyst sample and 50mL of 60mg/L RhB solution, each kept at equal distance from the light source. Standing for 30min in the dark to ensure that the adsorption and desorption of RhB on the surface of the sample reach equilibrium; degradation is carried out under 300W xenon lamp illumination, and sampling is carried out every 15min in the degradation process, and the sampling volume is 2mL. The samples were poured into a centrifuge tube and centrifuged to obtain a supernatant, the concentration of the supernatant was measured at 554nm by a UV-3600 ultraviolet-visible spectrophotometer (Shimazu, japan), and the degradation rates at different degradation times were calculated, and a degradation graph was obtained by plotting the degradation rates versus time, as shown in FIG. 4. Taking a water sample with illumination for 90min, measuring total organic carbon in a TOC-LCPH type total organic carbon analyzer (Shimadzu, japan), and calculating the degradation rate of the total organic carbon.
As can be seen from fig. 4, the adsorption/desorption equilibrium is reached in the dark room for 30min, the RhB concentration is reduced by about 5.8%; when the photocatalyst is not added for illumination for 90min, the self-degradation rate is very small; in sample Bi 2 O 2 CO 3 /Sepiolite(m(Bi 2 O 2 CO 3 ) M (Sepilolite) =1:0.4) is catalyst illumination 90min, and the degradation rate of Rh B reaches 99.1%; and Bi is used as 2 O 2 CO 3 As a catalyst, the degradation rate of RhB reaches 62.5% after 90min of irradiation. Therefore, bi 2 O 2 CO 3 /Sepiolite(m(Bi 2 O 2 CO 3 ) M (Sepilolite) =1:0.4) has excellent photocatalytic degradation performance on RhB.
Bi after 90min of measurement irradiation 2 O 2 CO 3 /Sepiolite(m(Bi 2 O 2 CO 3 ) M (Sepilolite) =1:0.4) and Bi 2 O 2 CO 3 The Total Organic Carbon (TOC) removal rates were 71.23% and 29.76%, respectively. Therefore, bi 2 O 2 CO 3 /Sepiolite(m(Bi 2 O 2 CO 3 ) M (Sepilolite) =1:0.4) has excellent mineralization ability to RhB.
Example 8
Bi after degradation 2 O 2 CO 3 The Sepiolite composite photocatalyst was separated and recovered and used as the photocatalyst for the next round of experiments. The experimental conditions and procedures and test methods were the same as in example 7. The cycle was repeated 5 times, and the change in degradation rate was as shown in FIG. 5.
As can be seen from FIG. 5, the recycling is 5 times, bi 2 O 2 CO 3 The catalytic degradation rate of the composite photocatalyst of the/Sepiolite on the RhB is reduced from 99.1% of the 1 st time to 94.7% of the 5 th time, and is reduced by only 4.4%. The results show that the Bi prepared by the invention 2 O 2 CO 3 The Sepiolite composite photocatalyst has excellent recovery and recycling performance.
Example 9
This example is an example of photocatalytic decolorization performance, and the test conditions are as follows: 10mg of Methyl Orange (MO), methylene Blue (MB) and Fluorescein (FS) were dissolved in 1L of distilled water to prepare a simulated mixed solution (MO-MB-FS), respectively, to prepare a bismuth oxide carbonate/sepiolite composite photocatalyst (Bi) prepared in example 3 2 O 2 CO 3 /Sepiolite，m(Bi 2 O 2 CO 3 ) Bismuth oxide carbonate (Bi) prepared under the same conditions in the presence of m (Sepilolite) =1:0.4) 2 O 2 CO 3 ) Is a photocatalyst sample. A clean 200mL jacketed beaker was charged with 100mg of the photocatalyst sample and 100mL of MO-MB-FS solution. Standing in the dark for 30min, then carrying out degradation under 300W xenon lamp illumination, sampling every 15min in the degradation process, sampling 2mL in volume, and measuring the chromaticity of the solution by a dilution fold method after centrifugal separation, wherein the result is shown in Table 1.
TABLE 1 variation of solution chromaticity with time of illumination
The results in Table 1 show that Bi 2 O 2 CO 3 The Sepiolite has excellent photocatalytic decoloring capability on mixed dye solution, can be completely decolored after being irradiated for 90min, and is obviously superior to Bi without Sepiolite 2 O 2 CO 3 . The foregoing is merely a preferred embodiment of the invention, and various modifications and changes may be made thereto by those skilled in the art in light of the above teachings, for example, combinations of parts and process conditions may be made within the scope of the parts and process conditions presented herein, and similar such changes and modifications are intended to fall within the spirit of the invention.
Claims (5)
1. The preparation method of the bismuth oxide/sepiolite composite photocatalyst is characterized in that bismuth oxide is generated on line in the presence of sepiolite to form a porous material of which sepiolite is coated by bismuth oxide based on sepiolite, and the mass ratio of the bismuth oxide to the sepiolite is 1:0.16-0.78, and the preparation method comprises the following steps:
(1) Adding cetyl trimethyl ammonium bromide into ethylene glycol, and stirring ultrasonically for 20-40 min to prepare a cetyl trimethyl ammonium bromide-ethylene glycol solution with the concentration of 0.125-0.25 mol/L, and marking the solution as a solution A;
(2) Bismuth nitrate pentahydrate and ferric nitrate nonahydrate are simultaneously added into deionized water according to the mol ratio of 1:0.9-1.0, and are ultrasonically stirred for 20-40 min to be dissolved and prepared into bismuth nitrate-ferric nitrate mixed solution, which is marked as solution B, wherein Bi is contained in the solution B 3+ The concentration is 0.02-0.033 mol/L, fe 3+ The concentration is 0.018-0.033 mol/L;
(3) Slowly dripping the solution B prepared in the step (2) into the solution A prepared in the step (1), ultrasonically stirring for 15-30 min, then adjusting the pH to 10-10.5, and continuously ultrasonically stirring at room temperature for 3-4 h to obtain a mixture C;
(4) Adding purified sepiolite into the mixture C obtained in the step (3) according to the mass ratio of the sepiolite to bismuth nitrate pentahydrate of 0.082-0.41:1, and carrying out ultrasonic stirring for 40-80 min to obtain a mixture D, wherein the purified sepiolite is treated by adopting the following method: grinding sepiolite, sieving with a 200-300 mesh sieve, soaking with 1-2 mol/L hydrochloric acid at 75-85 ℃ under reflux for 0.5-1 h, filtering, and washing with distilled water to neutrality; then preparing a mixture of sepiolite and 8-10 mmol/L hexadecyl trimethyl ammonium bromide, namely CTAB solution with a solid-to-liquid ratio of 1:40-60 g/mL, carrying out ultrasonic treatment for 0.5-1 h, filtering, washing with distilled water, drying to constant weight at 80-100 ℃, grinding, sieving with a 800-1000 mesh sieve, and taking a screen lower product for later use;
(5) Transferring the mixture D prepared in the step (4) into a high-pressure reaction kettle, and reacting for 3-6 h at 180-250 ℃; cooling to room temperature, filtering, washing filter residues with deionized water and ethanol for 2-5 times respectively, and drying at 100-120 ℃ to constant weight to obtain the bismuth oxide carbonate/sepiolite composite photocatalyst.
2. The preparation method of the bismuth oxide carbonate/sepiolite composite photocatalyst according to claim 1, wherein in the step (3), a strong alkali solution with the pH of 8-12 mol/L is adopted for adjusting the pH, and the strong alkali is KOH or NaOH.
3. The method for preparing bismuth oxide carbonate/sepiolite composite photocatalyst according to claim 1, wherein in the step (5), the high-pressure reaction kettle is a polytetrafluoroethylene lining high-pressure reaction kettle.
4. The preparation method of the bismuth oxide carbonate/sepiolite composite photocatalyst according to claim 1, wherein the ultrasonic stirring is ultrasonic-assisted mechanical stirring, and the ultrasonic power is 200-250W.
5. The method for preparing bismuth oxide carbonate/sepiolite composite photocatalyst according to any one of claims 1 to 4, wherein the reagents used are cetyl trimethylammonium bromide, ethylene glycol, bismuth nitrate pentahydrate, ferric nitrate nonahydrate, KOH, naOH, ethanol and hydrochloric acid.
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