CN111250146A - Preparation method of oxygen-enriched BiOI-BiOBr/SBA-16 composite photocatalytic material - Google Patents
Preparation method of oxygen-enriched BiOI-BiOBr/SBA-16 composite photocatalytic material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 title claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 27
- 239000001301 oxygen Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 36
- 229960000892 attapulgite Drugs 0.000 claims abstract description 27
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 22
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 230000004913 activation Effects 0.000 claims abstract description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
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- 238000000227 grinding Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 229940010698 activated attapulgite Drugs 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 239000002957 persistent organic pollutant Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002734 clay mineral Substances 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002386 leaching Methods 0.000 abstract description 3
- 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 abstract description 3
- 229940012189 methyl orange Drugs 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 abstract 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 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 abstract 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 abstract 1
- 235000011151 potassium sulphates Nutrition 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000011941 photocatalyst Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 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
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
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- 150000002009 diols Chemical class 0.000 description 1
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- 238000010893 electron trap Methods 0.000 description 1
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- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
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- 239000002135 nanosheet Substances 0.000 description 1
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- 125000004430 oxygen atom Chemical group O* 0.000 description 1
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Images
Classifications
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- B01J35/39—
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B01J35/613—
-
- B01J35/633—
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention belongs to the technical field of photocatalysis and material chemistry, and particularly discloses a preparation method of an oxygen-enriched BiOI-BiOBr/SBA-16 composite photocatalytic material. The method comprises the steps of taking attapulgite as a raw material, carrying out acid leaching and alkali roasting activation treatment, adding deionized water to obtain a silicon-aluminum source, adding the silicon-aluminum source into a diluted acid solution of F127, polyethylene glycol and potassium sulfate, and carrying out hydrothermal reaction to obtain a precursor of SBA-16. Bismuth nitrate, potassium iodide and sodium bromide are used as raw materials, ethylene glycol is used as a solvent, and a hydrothermal method is adopted to prepare the BiOI-BiOBr composite photocatalytic component. The BiOI-BiOBr active component is directly loaded on the precursor of the carrier SBA-16 by adopting an impregnation method. And (3) obtaining the oxygen-rich BiOI-BiOBr/SBA-16 composite photocatalytic material while generating the SBA-16 carrier through high-temperature roasting. The obtained composite material has good photocatalytic activity and can effectively remove methyl orange in water.
Description
Technical Field
The invention belongs to the technical field of photocatalysis and material chemistry, and particularly relates to a preparation method of an oxygen-enriched BiOI-BiOBr/SBA-16 composite photocatalytic material.
Background
The semiconductor photocatalytic oxidation technology is a green environmental management technology which takes a semiconductor as a catalyst and utilizes light energy to deeply degrade organic pollutants, has the characteristics of low energy consumption, mild reaction conditions, basically harmless degradation products, no secondary pollution and the like, and is an environmental remediation technology for effectively degrading pollutants.
Photocatalysts are the heart of photocatalytic technology. Currently, bismuth oxyhalide (BiOX) (X ═ F, Cl, Br, I) and compounds thereof are a novel photocatalytic material which is widely researched in recent years, and the unique open lamellar structure and indirect transition mode of the bismuth oxyhalide are favorable for effective separation and charge transfer of hole-electron pairs, so that the bismuth oxyhalide (BiOX) and compounds thereof show higher visible light catalytic activity. However, due to the limitation of the inherent energy band structure of the BiOX monomer and the composite material thereof, the visible light catalytic degradation capability of the photocatalyst on organic pollutants is limited, and the application of the photocatalyst in the environmental field is greatly limited. In addition, the BiOX monomer and the composite material powder thereof have the problems of easy agglomeration and difficult recovery after reaction in practical application. Therefore, how to effectively modify and immobilize the BiOX monomer and the composite photocatalyst thereof has positive practical significance for realizing the industrial application of the photocatalytic technology.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: in order to overcome the defects in the prior art, the invention provides a preparation method of an oxygen-enriched BiOI-BiOBr/SBA-16 composite photocatalytic material with excellent adsorption-photocatalytic performance.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of an oxygen-enriched BiOI-BiOBr/SBA-16 composite photocatalytic material with excellent adsorption-photocatalytic performance. The method comprises the following steps:
(1) soaking natural clay mineral attapulgite serving as a raw material in medium-strength inorganic acid at 60 ℃ for 12 hours, performing suction filtration, repeatedly washing the attapulgite with deionized water to be neutral, and drying the attapulgite at 80 ℃ to obtain acidified attapulgite;
wherein the medium strength mineral acid is 6mol/L HCl.
(2) Taking acidified attapulgite as a raw material, uniformly mixing the acidified attapulgite with NaOH solid, and roasting at high temperature for 3-5 hours for activation;
wherein the addition amount of NaOH solid is 1-2 times of the mass of the acidified attapulgite.
(3) Adding deionized water into the activated attapulgite at normal temperature, mechanically stirring for 24 hours, and taking the upper-layer leachate as a silica-alumina source for later use;
the addition amount of the deionized water is 5-10 ml of deionized water added into every 1g of activated attapulgite.
(4) Dissolving surfactant F127, polyethylene glycol and K with lower concentration of inorganic acid2SO4And the obtained mixed solution is ready for use.
Wherein the inorganic acid is HCl with a concentration of 3mol/L, surfactant F127, polyethylene glycol and K2SO4The mass ratio of (1: 1): 0.3 to 0.8.
(5) Mixing the solutions prepared in the steps (3) and (4), stirring for 12h, transferring into a high-pressure reaction kettle, carrying out hydrothermal crystallization at the temperature of 110 ℃ for 12h, carrying out suction filtration on the obtained suspension, washing to be neutral, and drying at the temperature of 80 ℃ to obtain an SBA-16 precursor for later use;
(6) separately adding Bi (NO)3)3·5H2Dissolving O and KI with ethylene glycol, mechanically stirring for 30min, mixing the two solutions, and mechanically stirring again in dark place for 1h to obtain solution ①.
Bi(NO3)3·5H2The mass ratio of O to KI is 2.4-2.9: 1.
(7) separately adding Bi (NO)3)3·5H2Dissolving O and NaBr in ethylene glycol, mechanically stirring for 30min, mixing the two solutions, and stirring againMechanically stir for 1h away from light to give solution ②.
Bi(NO3)3·5H2The mass ratio of O to NaBr is 4-4.5: 1.
(8) And (3) mixing the solutions ① and ② obtained in the steps (6) and (7), mechanically stirring for 1 hour in the dark, adding the SBA-16 precursor prepared in the step (5), and mechanically stirring for 1 hour in the dark again to obtain a suspension.
The addition amount of SBA-16 precursor and Bi (NO)3)3·5H2The mass ratio of O is 0.2-0.7: 1.
(9) Transferring the suspension obtained in the step (8) into a high-pressure reaction kettle, performing hydrothermal crystallization at the temperature of 160 ℃ for 12 hours, cooling to room temperature, performing suction filtration, washing for 2-3 times with absolute ethyl alcohol, drying at the temperature of 80 ℃, and grinding to obtain a BiOI-BiOBr/SBA-16 precursor sample;
(10) and (4) placing the BiOI-BiOBr/SBA-16 precursor sample prepared in the step (9) into a muffle furnace, roasting for 4 hours at different temperatures in an air atmosphere, removing the template agent to generate an SBA-16 carrier, and simultaneously obtaining the oxidation-rich BiOI-BiOBr/SBA-16 composite photocatalytic material.
Wherein the roasting temperature is 400-550 ℃.
The invention has the beneficial effects that: (1) the invention can enlarge the absorption range of the monomer to visible light and inhibit the recombination of photon-generated carriers by compounding the BiOX material with a proper band gap value, thereby achieving the purpose of enhancing the photocatalytic activity. The composite material can be brought into an oxidation-rich state by a high-temperature calcination process, creating iodine or bromine vacancies that can create vacancy defect states in the conduction band of BiOX, which, like active electron traps, aid in the separation of photogenerated carriers. The vacancy can be used as a hole capture center to improve the relative migration rate of a photon-generated carrier, and can also be used for supplementing bromine and iodine vacancies with oxygen atoms to generate an oxygen-enriched compound, so that a local internal electric field is enhanced, the recombination of the photon-generated carrier is obviously inhibited, and the photocatalytic activity is further improved.
(2) The method takes the natural attapulgite as the raw material, prepares the high-stability ordered mesoporous material SBA-16 precursor by a chemical method, does not need to add additional silicon and aluminum sources, has high utilization rate of the raw material and low production cost, widens the application range of the attapulgite, and can be used for producing the mineral-based composite material with high added value.
(3) According to the invention, a BiOI-BiOBr active component is directly loaded on a precursor of a mesoporous material SBA-16 by adopting an impregnation method, and a template agent is removed by a heat treatment method to generate an SBA-16 carrier, and simultaneously, the oxidation-rich BiOI-BiOBr/SBA-16 composite photocatalytic material is obtained.
According to the method, the active component is directly loaded on the precursor of the SBA-16, and the oxygen-enriched BiOI-BiOBr/SBA-16 composite photocatalyst is directly obtained in a one-step roasting mode, so that the solid loading and uniform distribution of the oxygen-enriched BiOI-BiOBr active particles are facilitated, and the photocatalytic activity of the oxygen-enriched BiOI-BiOBr composite photocatalyst is further improved.
(4) The raw materials are cheap and easy to obtain, the preparation method is simple and feasible, the synthesis of the carrier and the modification of the photocatalytic active component can be completed in one step by high-temperature calcination, the use of an organic solvent and the processes of repeated roasting and the like in the conventional treatment method are avoided, the time and the energy are saved, and the environment is not polluted.
(5) The mesoporous material SBA-16 is introduced as a carrier, the contact area of the oxygen-enriched BiOI-BiOBr active component and a target pollutant is increased, and the specific surface area of the composite material can reach 92.70m2Per g, pore volume can reach 0.17cm3More than g, concentrated pore size distribution and good pore performance. Meanwhile, the use of the SBA-16 carrier also solves the problems that the BiOI-BiOBr composite material powder is easy to agglomerate and difficult to recycle after reaction, and has important practical significance for promoting the industrial application of the photocatalytic technology and widening the application range of the photocatalytic technology.
(6) The method takes methyl orange as a target pollutant and evaluates the prepared oxygen-enriched BiOI-BiOBr/SBA-16 composite photocatalyst. Experimental results show that the thermal treatment method of roasting at 450 ℃ for 4 hours is adopted, the prepared oxygen-enriched BiOI-BiOBr/SBA-16 composite material has good photocatalytic activity, and 99.59% of methyl orange in water can be removed by an adsorption-photodegradation combined treatment technology.
Drawings
Fig. 1 is an X-ray diffraction pattern of the photocatalyst prepared, in which (a): x-ray diffraction patterns of acidified attapulgite, SBA-16, BiOI-BiOBr/SBA-16, BiOI and BiOBr; (b) the method comprises the following steps The X-ray diffraction patterns of BiOI-BiOBr-450, BiOI-BiOBr-550, BiOI-BiOBr/SBA-16-450 and BiOI-BiOBr/SBA-16-550.
Fig. 2 is a scanning electron micrograph of the prepared photocatalyst, in which (a): acidifying the attapulgite; (b) the method comprises the following steps SBA-16; (c) the method comprises the following steps BiOI; (d) the method comprises the following steps BiOBr; (e) BiOI-BiOBr-450; (f) BiOI-BiOBr-550; (g) BiOI-BiOBr/SBA-16; (h) the method comprises the following steps BiOI-BiOBr/SBA-16-450; (i) the method comprises the following steps BiOI-BiOBr/SBA-16-550.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
Example 1
A preparation method of an oxygen-enriched BiOI-BiOBr/SBA-16 composite photocatalytic material with excellent adsorption-photocatalytic performance.
Soaking 10.0g attapulgite clay in 80mL of 6mol/L HCl at 60 deg.C for 12h, vacuum filtering, repeatedly washing with deionized water to neutrality, and drying at 80 deg.C to obtain 9.1g acidified attapulgite clay. Grinding the acidified attapulgite and 15.0g NaOH solid, mixing uniformly, and roasting at 600 deg.C for 5 h. Transferring the roasted mixture into a container with stirring, adding 65ml of deionized water, stirring for 24h to fully dissolve soluble aluminosilicate in the mixture, and taking the upper-layer leaching solution as a silica-aluminum source for later use.
1.5g of surfactant F127, 1.5g of polyethylene glycol, 1.3g of 1.3g K were dissolved in 30mL of 3mol/L HCl2SO4. Adding the mixed solution into the silicon-aluminum source, stirring for 12 hours, and transferring into a high-pressure reaction kettle. Carrying out hydrothermal crystallization at 110 ℃ for 12h to obtain a white suspension, carrying out suction filtration, washing and drying at 80 ℃ on the precursor to obtain an SBA-16 precursor for later use.
1.4g of Bi (NO)3)3·5H2Dissolving O in 30ml of ethylene glycol, dissolving 0.5g of KI in 15ml of ethylene glycol, respectively mechanically stirring for 30min, mixing the two solutions, and mechanically stirring again for 1h in the absence of light to obtain a solution ①.
1.6g of Bi (NO)3)3·5H2Dissolving O in 30ml of ethylene glycol, dissolving 0.3g of NaBr in 15ml of ethylene glycol, respectively mechanically stirring for 30min, mixing the two solutions, and mechanically stirring for 1h again in the absence of light to obtain a solution ②.
And mixing the solutions ① and ②, mechanically stirring for 1 hour in a dark place, adding 2.0g of SBA-16 precursor, mechanically stirring for 1 hour in a dark place again to obtain a suspension, transferring the suspension into a high-pressure reaction kettle, performing hydrothermal crystallization for 12 hours at the temperature of 160 ℃, cooling to room temperature, performing suction filtration, washing for 2-3 times with absolute ethyl alcohol, drying at the temperature of 80 ℃, and grinding to obtain a BiOI-BiOBr/SBA-16 precursor sample.
And (3) putting the BiOI-BiOBr/SBA-16 precursor sample into a muffle furnace, and roasting for 4h at 450 ℃ in the air atmosphere to obtain the oxygen-enriched BiOI-BiOBr/SBA-16-450 composite photocatalyst.
Example 2
The BiOI-BiOBr/SBA-16 precursor sample in the example 1 is put into a muffle furnace and roasted for 4h at 550 ℃ in the air atmosphere, and the oxygen-enriched BiOI-BiOBr/SBA-16-550 composite photocatalyst is obtained.
Comparative example 1
Soaking 10.0g attapulgite clay in 80mL of 6mol/L HCl at 60 deg.C for 12h, vacuum filtering, repeatedly washing with deionized water to neutrality, and drying at 80 deg.C to obtain acidified attapulgite.
Comparative example 2
9.1g of the attapulgite acidified according to the method of example 1 and 15.0g of NaOH solid were ground, mixed well and calcined at 600 ℃ for 5 h. Transferring the roasted mixture into a container with stirring, adding 65ml of deionized water, stirring for 24h to fully dissolve soluble aluminosilicate in the mixture, and taking the upper-layer leaching solution as a silica-aluminum source for later use.
1.5g of surfactant F127, 1.5g of polyethylene glycol, 1.3g of 1.3g K were dissolved in 30mL of 3mol/L HCl2SO4. Adding the mixed solution into the silicon-aluminum source, stirring for 12 hours, and transferring into a high-pressure reaction kettle. Hydrothermal crystallization at 110 deg.C for 12 hr to obtain precursor, suction filtering, washing, drying, and roasting at 450 deg.C for 4 hr to remove surfactantAnd obtaining the SBA-16 carrier.
Comparative example 3
1.4g of Bi (NO)3)3·5H2Dissolving O in 30ml of ethylene glycol, dissolving 0.5g of KI in 15ml of ethylene glycol, respectively and mechanically stirring for 30min, mixing the two solutions, mechanically stirring for 1h in a dark place, transferring into a high-pressure reaction kettle, performing hydrothermal crystallization for 12h at the temperature of 160 ℃, cooling to room temperature, performing suction filtration, washing for 2-3 times with absolute ethyl alcohol, drying at the temperature of 80 ℃, and grinding to obtain the BiOI sample.
Comparative example 4
1.6g of Bi (NO)3)3·5H2Dissolving O in 30ml of ethylene glycol, dissolving 0.3g of NaBr in 15ml of ethylene glycol, respectively and mechanically stirring for 30min, mixing the two solutions, mechanically stirring for 1h in a dark place, transferring into a high-pressure reaction kettle, performing hydrothermal crystallization for 12h at the temperature of 160 ℃, cooling to room temperature, performing suction filtration, washing for 2-3 times with absolute ethyl alcohol, drying at the temperature of 80 ℃, and grinding to obtain the BiOBr sample.
Comparative example 5
1.4g of Bi (NO)3)3·5H2Dissolving O in 30ml of ethylene glycol, dissolving 0.5g of KI in 15ml of ethylene glycol, respectively mechanically stirring for 30min, mixing the two solutions, and mechanically stirring again for 1h in the absence of light to obtain a solution ①.
1.6g of Bi (NO)3)3·5H2Dissolving O in 30ml of ethylene glycol, dissolving 0.3g of NaBr in 15ml of ethylene glycol, respectively mechanically stirring for 30min, mixing the two solutions, and mechanically stirring for 1h again in the absence of light to obtain a solution ②.
Mixing the solutions ① and ②, mechanically stirring for 1 hour in the dark place, adding 2.0g of SBA-16 carrier prepared in comparative example 2, mechanically stirring for 1 hour in the dark place again to obtain a suspension, transferring the suspension into a high-pressure reaction kettle, carrying out hydrothermal crystallization for 12 hours at the temperature of 160 ℃, cooling to room temperature, carrying out suction filtration, washing for 2-3 times by using absolute ethyl alcohol, drying at the temperature of 80 ℃, and grinding to obtain a BiOI-BiOBr/SBA-16 sample.
Comparative example 6
1.4g of Bi (NO)3)3·5H2O is dissolved in 30ml of ethylene glycol, 0.5g of KI is dissolved in 15ml of ethylene glycolDissolving diol, respectively mechanically stirring for 30min, mixing the above two solutions, and mechanically stirring again in dark place for 1h to obtain solution ①.
1.6g of Bi (NO)3)3·5H2Dissolving O in 30ml of ethylene glycol, dissolving 0.3g of NaBr in 15ml of ethylene glycol, respectively mechanically stirring for 30min, mixing the two solutions, and mechanically stirring for 1h again in the absence of light to obtain a solution ②.
Mixing the solutions ① and ②, mechanically stirring for 1h in the dark, transferring the mixture into a high-pressure reaction kettle, carrying out hydrothermal crystallization for 12h at 160 ℃ to obtain a required product, cooling the product to room temperature, carrying out suction filtration, washing for 2-3 times with absolute ethyl alcohol, drying at 80 ℃, and grinding to obtain a BiOI-BiOBr sample, putting the sample into a muffle furnace, and roasting for 4h at 450 ℃ to obtain the BiOI-BiOBr-450 sample.
Comparative example 7
The BiOI-BiOBr sample obtained in comparative example 6 was placed in a muffle furnace and calcined at 550 ℃ for 4h to obtain a BiOI-BiOBr-550 sample.
Fig. 1 is an X-ray diffraction pattern of the photocatalyst prepared, in which (a): x-ray diffraction patterns of acidified attapulgite, SBA-16, BiOI-BiOBr/SBA-16, BiOI and BiOBr; (b) the method comprises the following steps The X-ray diffraction patterns of BiOI-BiOBr-450, BiOI-BiOBr-550, BiOI-BiOBr/SBA-16-450 and BiOI-BiOBr/SBA-16-550. As shown in FIG. 1, BiOI-BiOBr/SBA-16-450 has good crystallization, and XRD diffraction peaks thereof can correspond to characteristic peaks of BiOI and BiOBr in tetragonal phases.
Fig. 2 is a scanning electron micrograph of the prepared photocatalyst, in which (a): acidifying the attapulgite; (b) the method comprises the following steps SBA-16; (c) the method comprises the following steps BiOI; (d) the method comprises the following steps BiOBr; (e) BiOI-BiOBr-450; (f) BiOI-BiOBr-550; (g) BiOI-BiOBr/SBA-16; (h) the method comprises the following steps BiOI-BiOBr/SBA-16-450; (i) the method comprises the following steps BiOI-BiOBr/SBA-16-550. As can be seen from figure 2, the grains of the BiOI-BiOBr/SBA-16-450 composite material synthesized by the invention do not have obvious agglomeration phenomenon, the roasting temperature of 450 ℃ does not destroy the original spherical grain structure of the BiOI-BiOBr, and the nanosheets forming the spherical grains are uniformly dispersed.
The properties of the materials obtained in the examples of the invention and the comparative examples are shown in Table 1.
TABLE 1
Claims (10)
1. A preparation method of an oxygen-enriched BiOI-BiOBr/SBA-16 composite photocatalytic material is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) taking a natural clay mineral attapulgite as a raw material, soaking the attapulgite for 12 hours at 60 ℃ by using a medium-strength inorganic acid, performing suction filtration, repeatedly washing the attapulgite to be neutral by using deionized water, and drying the attapulgite at 80 ℃ to obtain an acidified attapulgite;
(2) uniformly mixing the acidified attapulgite with NaOH solid, and roasting at high temperature for 3-5 h for activation;
(3) adding deionized water into the activated attapulgite at normal temperature, mechanically stirring for 24 hours, and taking the upper-layer leachate as a silica-alumina source for later use;
(4) dissolving surfactant F127, polyethylene glycol and K with inorganic acid2SO4And the obtained mixed solution is reserved;
(5) mixing the solutions prepared in the steps (3) and (4), stirring for 12h, transferring into a high-pressure reaction kettle, carrying out hydrothermal crystallization at the temperature of 110 ℃ for 12h, carrying out suction filtration on the obtained suspension, washing to be neutral, and drying at the temperature of 80 ℃ to obtain an SBA-16 precursor for later use;
(6) separately adding Bi (NO)3)3·5H2Dissolving O and KI with ethylene glycol, mechanically stirring for 30min, mixing the two solutions, and mechanically stirring for 1h in a dark place to obtain solution ①;
(7) separately adding Bi (NO)3)3·5H2Dissolving O and NaBr with ethylene glycol, mechanically stirring for 30min, mixing the two solutions, and mechanically stirring for 1h in a dark place again to obtain a solution ②;
(8) mixing the solutions ① and ② obtained in the steps (6) and (7), mechanically stirring for 1h in a dark place, adding the SBA-16 precursor prepared in the step (5), and mechanically stirring for 1h in a dark place again to obtain a suspension;
(9) transferring the suspension obtained in the step (8) into a high-pressure reaction kettle, performing hydrothermal crystallization at the temperature of 160 ℃ for 12 hours, cooling to room temperature, performing suction filtration, washing for 2-3 times with absolute ethyl alcohol, drying at the temperature of 80 ℃, and grinding to obtain a BiOI-BiOBr/SBA-16 precursor sample;
(10) and (4) placing the BiOI-BiOBr/SBA-16 precursor sample prepared in the step (9) into a muffle furnace, roasting for 4 hours at different temperatures in an air atmosphere, removing the template agent to generate an SBA-16 carrier, and simultaneously obtaining the oxidation-rich BiOI-BiOBr/SBA-16 composite photocatalytic material.
2. The method for preparing the oxygen-enriched BiOI-BiOBr/SBA-16 composite photocatalytic material as claimed in claim 1, wherein: the medium strength mineral acid described in step (1) is 6mol/L HCl.
3. The method for preparing the oxygen-enriched BiOI-BiOBr/SBA-16 composite photocatalytic material as claimed in claim 1, wherein: and (3) adding the NaOH solid in the step (2) in an amount which is 1-2 times of the mass of the acidified attapulgite.
4. The method for preparing the oxygen-enriched BiOI-BiOBr/SBA-16 composite photocatalytic material as claimed in claim 1, wherein: the adding amount of the deionized water in the step (3) is 5-10 ml of deionized water added to every 1g of activated attapulgite.
5. The method for preparing the oxygen-enriched BiOI-BiOBr/SBA-16 composite photocatalytic material as claimed in claim 1, wherein: the inorganic acid in the step (4) is 3mol/L HCl; surfactants F127, polyethylene glycol and K2SO4The mass ratio of (1: 1): 0.3 to 0.8.
6. The method for preparing the oxygen-enriched BiOI-BiOBr/SBA-16 composite photocatalytic material as claimed in claim 1, wherein: said Bi (NO) in step (6)3)3·5H2The mass ratio of O to KI is 2.4-2.9: 1.
7. the method for preparing the oxygen-enriched BiOI-BiOBr/SBA-16 composite photocatalytic material as claimed in claim 1, wherein the method comprises the steps ofIn the following steps: said Bi (NO) in step (7)3)3·5H2The mass ratio of O to NaBr is 4-4.5: 1.
8. The method for preparing the oxygen-enriched BiOI-BiOBr/SBA-16 composite photocatalytic material as claimed in claim 1, wherein: the SBA-16 precursor and Bi (NO) in the step (8)3)3·5H2The mass ratio of O is 0.2-0.7: 1.
9. The method for preparing the oxygen-enriched BiOI-BiOBr/SBA-16 composite photocatalytic material as claimed in claim 1, wherein: the roasting temperature in the step (10) is 400-550 ℃.
10. Use of an oxygen-enriched BiOI-BiOBr/SBA-16 composite photocatalytic material prepared according to the method of claim 1, characterized in that: the composite photocatalytic material is used for adsorbing and photodegrading organic pollutants.
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| CN111792700A (en) * | 2020-07-07 | 2020-10-20 | 桂林理工大学 | Application of BiOBr or oxygen vacancy BiOBr in removing algae organic matters and removing method |
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| CN113926421A (en) * | 2021-09-17 | 2022-01-14 | 浙江大学 | Bismuth-loaded inorganic porous iodine adsorption material and macro preparation method thereof |
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