CN113751033A - MOF modified zeolite loaded BiOX/TiO2Photocatalytic material and preparation method thereof - Google Patents
MOF modified zeolite loaded BiOX/TiO2Photocatalytic material and preparation method thereof Download PDFInfo
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000000463 material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims description 23
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 59
- 239000010457 zeolite Substances 0.000 claims abstract description 59
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 230000001699 photocatalysis Effects 0.000 claims abstract description 40
- 239000011941 photocatalyst Substances 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
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- 238000005406 washing Methods 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 11
- 229910052678 stilbite Inorganic materials 0.000 claims description 9
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
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- 239000002244 precipitate Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052908 analcime Inorganic materials 0.000 claims description 3
- 229910001603 clinoptilolite Inorganic materials 0.000 claims description 3
- 229910052680 mordenite Inorganic materials 0.000 claims description 3
- 238000009776 industrial production Methods 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000012621 metal-organic framework Substances 0.000 description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000010865 sewage Substances 0.000 description 15
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- 239000000126 substance Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 5
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- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
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Images
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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- B01J35/39—
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a MOF modified zeolite loaded BiOX/TiO2The photocatalytic material comprises the following raw materials in parts by mole: 50-100 parts of natural zeolite, 10-30 parts of MOF material and BiOX/TiO210-60 parts of photocatalyst, wherein BiOX/TiO2The molar ratio is 0.01-100. The invention adopts the photocatalytic material of the MOF modified zeolite supported composite photocatalyst, and solves the problems that the photocatalyst is difficult to recover and is easy to lose along with sewageThe method has the advantages of short reaction time, low cost, simple operation and easy industrial production.
Description
Technical Field
The invention relates to the technical field of ecological environment-friendly materials, in particular to MOF modified zeolite loaded BiOX/TiO2A photocatalytic material and a preparation method thereof.
Background
Chemical Oxygen demand (cod) (chemical Oxygen demand) refers to the amount of oxidant consumed in oxidizing organic and some reducing substances in water with a strong oxidant under certain conditions, expressed as mg/L of Oxygen. High chemical oxygen demand means that the water contains a large amount of reducing substances, mainly organic pollutants. The sources of these organic pollutants may be pesticides, chemical plants, organic fertilizers, etc. If not treated, a plurality of organic pollutants can be adsorbed by bottom mud at the water bottom and deposited, and can cause lasting toxic action on aquatic organisms within a plurality of years. After massive death of aquatic life, the ecosystem in the river is destroyed. If people eat organisms in water, a large amount of toxins in the organisms are absorbed and accumulated in the bodies, and the toxins often have carcinogenic, teratogenic and mutagenic effects. In addition, irrigation with contaminated water also affects plants and crops and causes a great risk to health.
After industrial wastewater and municipal sewage are subjected to biochemical treatment, the effluent still contains organic matters with certain concentration, and the main chemical oxygen demand of the effluent after biochemical treatment is formed. Along with the continuous improvement of industrial waste water and municipal sewage discharge standard, the play water COD of biochemical treatment system often is difficult to discharge to reach standard, and the reuse of reclaimed water demand is also continuously expanding moreover, also objectively need increase advanced treatment unit after industrial waste water and municipal sewage biochemical treatment. The advanced treatment technology of wastewater and sewage mainly comprises three technologies of adsorption, membrane separation, advanced oxidation and the like. The adsorption technology can economically and effectively remove odor, decolor and separate heavy metal and organic pollutants, but the adsorbent has higher cost, is not easy to regenerate and has secondary pollution. The membrane separation technology has wide separation objects, good effluent quality, but high investment and operation cost, and produces high-concentration sewage. Advanced oxidation technology mainly utilizes oxidizing agent and free radical oxidation to degrade organic pollutants. The free radicals can perform rapid chain reaction with most organic matters, hardly selectively degrade organic pollutants, have high reaction speed and do not generate secondary pollution. Wherein the photocatalysis technology can generate strong oxidizing free radicals such as hydroxyl free radicals, superoxide free radicals and the like under the illumination condition, and can effectively react hydrocarbons, halogenated organic matters, surfactants, dyes and agricultural chemicalsThe main organic pollutants of medicine, phenols, aromatic hydrocarbons and the like are degraded and finally mineralized into CO2And H2O, and atoms of halogen X, S, P contained in the organic pollutants are respectively converted into X–、SO4 2–、PO4 3–Plasma is adopted to achieve the aim of completely eliminating organic pollutants.
TiO2The photocatalyst is a typical n-type semiconductor material, has the advantages of good light corrosion resistance, acid and alkali resistance, high stability, low price and the like, and is the most widely applied photocatalyst at present. However, TiO2Can only absorb ultraviolet light with the wavelength less than 390nm, and the proportion of the ultraviolet light in the sunlight is less than 5 percent, so the sunlight utilization rate is low; besides, the photoproduction electron-hole is easy to recombine, the quantum efficiency is low, and TiO is enabled2The photocatalytic effect is limited. Bismuth oxyhalide (BiOX) photocatalysts have received much attention because of their advantages such as excellent stability, good electron transport properties, no photo-corrosion, and high activity. BiOX has an anisotropic layer structure, [ Bi ]2O2]2+Is inserted between layers X-Layer of [ Bi ]2O2]2+And X-The internal electric field formed between the layers can effectively separate photo-generated electrons from holes, and the quantum efficiency is improved. By reacting BiOX with TiO2The heterojunction is formed by compounding, so that the energy level spacing can be obviously reduced, and the range of exciting light is expanded to a visible light region; the sunlight utilization rate is improved, meanwhile, the recombination of photon-generated carriers is prevented, and the photocatalysis efficiency is obviously improved.
Because the photocatalytic material is powdery, when the photocatalytic material is used for purifying pollutants in water, the photocatalytic material is difficult to recover through sedimentation, and the photocatalyst is wasted. At present, most of the researches are carried out by taking natural zeolite as a carrier to load the traditional semiconductor material, and the natural zeolite has rich reserves and low price; the specific surface area is large, and the performance of pre-enriching organic pollutants is excellent; the pore size distribution is relatively uniform, which is beneficial to molecular diffusion; in its unique aluminosilicate tetrahedral structure, negative and positive charges do not spatially overlap, resulting in strong electrostatic attraction. Thus, zeolite is a desirable catalyst support. However, the channels of the natural zeolite are often blocked by other impurities, the degree of mutual communication among the channels is poor, and the number of active sites is small, so that the problems of low adsorption rate and long adsorption time of the natural zeolite on organic pollutants exist. Metal-organic framework (MOF) is a crystalline porous material with a periodic network structure formed by connecting inorganic metal ions or ion clusters and organic ligands with each other through self-assembly. The porous framework crystal structure is a promising zeolite-like material, and can be complexed with various rigid bridging organic ligands through different metal ions to design and synthesize metal-organic frameworks with different pore diameters, so that the MOFs material has infinite structure change, and can be functionalized according to performance requirements such as catalytic reaction or adsorption by carrying some functional modification groups on the ligands, thereby showing great application potential in the field of photocatalysis. The zeolite modified by the MOF has larger specific surface area and unobstructed pore channel structure, and is beneficial to the adsorption and circulation of organic pollutants; can provide more active sites, is more beneficial to the loading of the inorganic photocatalyst, enhances the acting force between the zeolite and the inorganic photocatalyst, and prevents the photocatalyst from losing along with the flowing of sewage in the sewage treatment process.
Disclosure of Invention
The invention aims to provide a MOF modified zeolite supported BiOX/TiO2The photocatalytic material and the preparation method thereof solve the problems that the photocatalyst is difficult to recover and is easy to lose along with sewage, and the method has short reaction time, low cost, simple operation and easy industrial production.
In order to achieve the aim, the invention provides a MOF modified zeolite supported BiOX/TiO2The photocatalytic material comprises the following raw materials in parts by mole:
50-100 parts of natural zeolite, 10-30 parts of MOF material and BiOX/TiO210-60 parts of photocatalyst, wherein BiOX/TiO2The molar ratio is 0.01-100.
Preferably, the natural zeolite is one or more of natural stilbite, clinoptilolite, mordenite or analcime.
Preferably, the natural zeolite is natural stilbite.
MOF modified zeolite loaded BiOX/TiO2The preparation method of the photocatalytic material comprises the following steps:
(1) pretreatment of natural zeolite: washing natural zeolite with deionized water by multiple oscillation, soaking in HCl solution with concentration of 0.01-3mol/L for 1-6h, washing, and drying to obtain pretreated natural zeolite;
(2) preparation of MOF-modified zeolite: dissolving 2-amino terephthalic acid in N, N-dimethylformamide and anhydrous methanol, adding isopropyl titanate and pretreated natural zeolite, uniformly stirring, transferring to a high-pressure reaction kettle, heating to 120 ℃ for reaction at 250 ℃ for 12-36 hours, cooling to room temperature, and washing with N, N-dimethylformamide and anhydrous methanol for three times to obtain MOF modified zeolite;
(3) preparing a photocatalytic material: adding KX into the mixed solution of deionized water and absolute ethyl alcohol, stirring for 20min, according to n (BiOX) n (TiO)2) Adding TiO in the proportion of 0.01-1002Stirring uniformly, then adding Bi (NO)3)3·5H2And (2) adding MOF modified zeolite into the O glycol solution after uniformly stirring, transferring the mixed solution into a high-pressure reaction kettle, heating to the temperature of 120 ℃ and 250 ℃ for reaction for 12-36 hours, cooling to room temperature, performing centrifugal separation on the obtained precipitate, alternately washing for several times by using absolute ethyl alcohol and distilled water, and performing vacuum drying at the temperature of 80 ℃ to obtain a finished product.
Preferably, KX in step (3) is one of KCl, KBr and KI.
Preferably, the volume ratio of the deionized water to the absolute ethyl alcohol in the step (3) is 1: 1.
Aiming at the discharge requirements of industrial wastewater and municipal sewage and the reuse requirements of reclaimed water, the invention provides an MOF modified zeolite supported BiOX/TiO for effectively reducing the COD value in water2A photocatalytic material and a preparation method thereof. The natural zeolite is repeatedly shaken and washed by deionized water and is soaked by HCl solution with certain concentration so as to dissolve impurities blocked in zeolite pore channels and play a role in dredging the pore channels; meanwhile, the HCl solution has small radius H+Replace zeoliteCations with large radius originally in the channels, e.g. Na+、Ca2+And Mg2+And the like, so that the effective space of the pore channel is widened to provide active sites for the growth of the MOF on the surface. Soaking the activated zeolite in 2-amino terephthalic acid, N-dimethylformamide and anhydrous methanol, adding isopropyl titanate, transferring to a high-pressure reaction kettle, and carrying out hydrothermal reaction to graft an MOF material on the surface of the zeolite to obtain an MOF modified zeolite catalyst carrier, wherein the specific surface area of the zeolite is 30.2m before modification2The/g is increased to 136.9m2(ii) in terms of/g. Then the catalyst carrier is immersed in KX and Bi (NO)3)3And TiO2Carrying out hydrothermal reaction in the mixed ethanol solution to obtain MOF modified zeolite loaded BiOX/TiO2A photocatalytic material.
Therefore, the MOF modified zeolite loaded BiOX/TiO is adopted in the invention2The photocatalytic material and the preparation method thereof have the following beneficial effects:
(1) the invention takes natural zeolite as raw material, and dissolves impurities in pore channels by an acid dissolution method, thereby enlarging the pore channel space of the zeolite;
(2) the MOF material is grafted on the surface of zeolite by adopting a high-temperature liquid phase method to obtain the MOF modified zeolite photocatalyst carrier, so that the specific surface area and the active sites of the carrier are improved, the composite efficiency of the carrier and an inorganic photocatalyst is increased, and the adsorption quantity and the adsorption speed of organic pollutants are increased;
(3) BiOX/TiO is synthesized by adopting a hydrothermal method2Photocatalyst and its load on modified carrier, BiOX/TiO2The composite photocatalyst has a specific TiO ratio2The light absorption range is widened to a visible light region due to the lower energy level spacing, and due to the laminated structure of BiOX, the effective separation of electrons and holes is realized, the quantum efficiency is improved, and the photocatalytic performance is obviously improved;
(4) the method solves the problems of difficult recovery of the photocatalyst and easy loss along with sewage through the charge of the photocatalyst on the modified zeolite, and has the advantages of short reaction time, low cost, simple operation and easy industrial production.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is BiOX/TiO2SEM picture of (a), wherein (a) BiOCl and (b) TiO2、(c)BiOCl/0.1TiO2、(d)BiOCl/0.5TiO2；
FIG. 2 shows N of the sample2Adsorption isotherms;
FIG. 3 is a graph of the degradation profile of a sample to acid Red B;
FIG. 4 is a graph of the UV-VIS absorption spectrum of degraded acid Red B of example 2, wherein the sequence of the lines at 500 in the graph corresponds to the sequence indicated by the arrows in the graph.
Detailed Description
The invention provides a MOF modified zeolite loaded BiOX/TiO2The photocatalytic material comprises the following raw materials in parts by mole:
50-100 parts of natural zeolite, 10-30 parts of MOF material and BiOX/TiO210-60 parts of photocatalyst, wherein BiOX/TiO2The molar ratio is 0.01-100.
The natural zeolite is one or more of natural stilbite, clinoptilolite, mordenite or analcime.
MOF modified zeolite loaded BiOX/TiO2The preparation method of the photocatalytic material comprises the following steps:
(1) pretreatment of natural zeolite: washing natural zeolite with deionized water by multiple oscillation, soaking in HCl solution with concentration of 0.01-3mol/L for 1-6h, washing, and drying to obtain pretreated natural zeolite;
(2) preparation of MOF-modified zeolite: dissolving 2-amino terephthalic acid in N, N-dimethylformamide and anhydrous methanol, adding isopropyl titanate and pretreated natural zeolite, uniformly stirring, transferring to a high-pressure reaction kettle, heating to 120 ℃ for reaction at 250 ℃ for 12-36 hours, cooling to room temperature, and washing with N, N-dimethylformamide and anhydrous methanol for three times to obtain MOF modified zeolite;
(3) preparing a photocatalytic material: adding KX into a mixed solution of deionized water and absolute ethyl alcohol with a volume ratio of 1:1, stirring for 20min according to the ratio of n (BiOX) to n (TiO)2) Adding TiO in the proportion of 0.01-1002Stirring uniformly, then adding Bi (NO)3)3·5H2And (2) adding MOF modified zeolite into the O glycol solution after uniformly stirring, transferring the mixed solution into a high-pressure reaction kettle, heating to the temperature of 120 ℃ and 250 ℃ for reaction for 12-36 hours, cooling to room temperature, performing centrifugal separation on the obtained precipitate, alternately washing for several times by using absolute ethyl alcohol and distilled water, and performing vacuum drying at the temperature of 80 ℃ to obtain a finished product.
Further, KX in the step (3) is one of KCl, KBr and KI.
The technical solution of the present invention is further illustrated by the accompanying drawings and examples.
Example 1
MOF modified zeolite loaded BiOX/TiO2The photocatalytic material comprises the following raw materials in parts by mole:
70 parts of natural stilbite, 10 parts of MOF material and BiOX/TiO 220 parts of photocatalyst, wherein BiOX/TiO2The molar ratio was 10.
MOF modified zeolite loaded BiOX/TiO2The preparation method of the photocatalytic material comprises the following steps:
(1) pretreatment of natural zeolite: washing natural zeolite with deionized water by multiple oscillation, soaking the natural zeolite in HCl solution with the concentration of 0.1mol/L for 3 hours, washing and drying to obtain pretreated natural zeolite;
(2) preparation of MOF-modified zeolite: dissolving 2-amino terephthalic acid in N, N-dimethylformamide and anhydrous methanol, adding isopropyl titanate and pretreated natural zeolite, uniformly stirring, transferring to a high-pressure reaction kettle, heating to 120 ℃, reacting for 16 hours, cooling to room temperature, and washing with N, N-dimethylformamide and anhydrous methanol for three times to obtain MOF modified zeolite;
(3) preparing a photocatalytic material: adding KX into a mixed solution of deionized water and absolute ethyl alcohol with a volume ratio of 1:1, stirring for 20min according to the ratio of n (BiOX) to n (TiO)2) TiO is added in a proportion of 102Stirring uniformly, then adding Bi (NO)3)3·5H2Stirring in glycol solution of OAnd after the mixture is uniform, adding MOF modified zeolite, transferring the mixed solution into a high-pressure reaction kettle, heating to 160 ℃ for reaction for 12 hours, cooling to room temperature, performing centrifugal separation on the obtained precipitate, alternately washing with absolute ethyl alcohol and distilled water for several times, and performing vacuum drying at 80 ℃ to obtain a finished product.
The microstructure is shown in FIG. 1(c), and when comparing FIGS. 1(a) and (b), TiO was found2And growing on the surface of the BiOCl to form a heterostructure. As can be seen from fig. 2, the amount of nitrogen adsorbed by zeolite was significantly increased after MOF modification, but the amount of nitrogen adsorbed was slightly decreased after photocatalyst loading. The degradation effect on the ARB is studied under visible light, and the result is shown in figure 3, and the degradation rate on the ARB is 89% after illumination for 80 min. The effect of degrading COD in sewage is reduced from 20000mg/L to 400 mg/L.
Example 2
MOF modified zeolite loaded BiOX/TiO2The photocatalytic material comprises the following raw materials in parts by mole:
60 parts of natural stilbite, 20 parts of MOF material and BiOX/TiO 220 parts of photocatalyst, wherein BiOX/TiO2The molar ratio was 20.
MOF modified zeolite loaded BiOX/TiO2The preparation method of the photocatalytic material comprises the following steps:
(1) pretreatment of natural zeolite: washing natural zeolite with deionized water by multiple oscillation, soaking the natural zeolite in HCl solution with the concentration of 0.1mol/L for 5 hours, washing and drying to obtain pretreated natural zeolite;
(2) preparation of MOF-modified zeolite: dissolving 2-amino terephthalic acid in N, N-dimethylformamide and anhydrous methanol, adding isopropyl titanate and pretreated natural zeolite, uniformly stirring, transferring to a high-pressure reaction kettle, heating to 150 ℃, reacting for 12 hours, cooling to room temperature, and washing with N, N-dimethylformamide and anhydrous methanol for three times to obtain MOF modified zeolite;
(3) preparing a photocatalytic material: adding KX into a mixed solution of deionized water and absolute ethyl alcohol with a volume ratio of 1:1, stirring for 20min according to the ratio of n (BiOX) to n (TiO)2) TiO is added in a proportion of 20 ═ c2Stirring uniformly, thenAdding Bi (NO)3)3·5H2And (2) adding MOF modified zeolite into the O glycol solution, uniformly stirring, transferring the mixed solution into a high-pressure reaction kettle, heating to 150 ℃ for reaction for 12 hours, cooling to room temperature, carrying out centrifugal separation on the obtained precipitate, alternately washing with absolute ethyl alcohol and distilled water for several times, and carrying out vacuum drying at 80 ℃ to obtain the finished product.
The microstructure is shown in FIG. 1(d), and when comparing FIGS. 1(a) and (b), TiO was found2And growing on the surface of the BiOCl to form a heterostructure. As can be seen from fig. 2, the amount of nitrogen adsorbed by zeolite was significantly increased after MOF modification, but the amount of nitrogen adsorbed was slightly decreased after photocatalyst loading. The degradation effect on the ARB is studied under visible light, and the result is shown in figure 3, and the degradation rate on the ARB is 95% after 80min of illumination. The effect of degrading COD in sewage is reduced from 20000mg/L to 100 mg/L.
Example 3
MOF modified zeolite loaded BiOX/TiO2The photocatalytic material comprises the following raw materials in parts by mole:
65 parts of natural stilbite, 15 parts of MOF material and BiOX/TiO 220 parts of photocatalyst, wherein BiOX/TiO2The molar ratio is 1.
MOF modified zeolite loaded BiOX/TiO2The preparation method of the photocatalytic material comprises the following steps:
(1) pretreatment of natural zeolite: washing natural zeolite with deionized water by multiple oscillation, soaking the natural zeolite in HCl solution with the concentration of 0.1mol/L for 5 hours, washing and drying to obtain pretreated natural zeolite;
(2) preparation of MOF-modified zeolite: dissolving 2-amino terephthalic acid in N, N-dimethylformamide and anhydrous methanol, adding isopropyl titanate and pretreated natural zeolite, uniformly stirring, transferring to a high-pressure reaction kettle, heating to 180 ℃, reacting for 20 hours, cooling to room temperature, and washing with N, N-dimethylformamide and anhydrous methanol for three times to obtain MOF modified zeolite;
(3) preparing a photocatalytic material: adding KX into a mixed solution of deionized water and absolute ethyl alcohol in a volume ratio of 1:1, stirring for 20min according to n (B)iOX):n(TiO2) TiO is added in proportion of 12Stirring uniformly, then adding Bi (NO)3)3·5H2And (2) adding MOF modified zeolite into the O glycol solution, uniformly stirring, transferring the mixed solution into a high-pressure reaction kettle, heating to 180 ℃ for reaction for 12 hours, cooling to room temperature, carrying out centrifugal separation on the obtained precipitate, alternately washing with absolute ethyl alcohol and distilled water for several times, and carrying out vacuum drying at 80 ℃ to obtain the finished product.
As can be seen from fig. 2, the amount of nitrogen adsorbed by zeolite was significantly increased after MOF modification, but the amount of nitrogen adsorbed was slightly decreased after photocatalyst loading. The degradation effect on the ARB is studied under visible light, and the result is shown in figure 3, and the degradation rate on the ARB is 80% after illumination for 80 min. The effect of degrading COD in sewage is reduced from 20000mg/L to 700 mg/L.
Example 4
MOF modified zeolite loaded BiOX/TiO2The photocatalytic material comprises the following raw materials in parts by mole:
75 parts of natural stilbite, 10 parts of MOF material and BiOX/TiO215 parts of photocatalyst, wherein BiOX/TiO2The molar ratio is 1.
MOF modified zeolite loaded BiOX/TiO2The preparation method of the photocatalytic material comprises the following steps:
(1) pretreatment of natural zeolite: washing natural zeolite with deionized water by multiple oscillation, soaking the natural zeolite in HCl solution with the concentration of 0.1mol/L for 5 hours, washing and drying to obtain pretreated natural zeolite;
(2) preparation of MOF-modified zeolite: dissolving 2-amino terephthalic acid in N, N-dimethylformamide and anhydrous methanol, adding isopropyl titanate and pretreated natural zeolite, uniformly stirring, transferring to a high-pressure reaction kettle, heating to 200 ℃, reacting for 20 hours, cooling to room temperature, and washing with N, N-dimethylformamide and anhydrous methanol for three times to obtain MOF modified zeolite;
(3) preparing a photocatalytic material: adding KX into a mixed solution of deionized water and absolute ethyl alcohol with a volume ratio of 1:1, stirring for 20min according to the ratio of n (BiOX) to n (TiO)2) Ratio of 1Adding TiO2Stirring uniformly, then adding Bi (NO)3)3·5H2And (2) adding MOF modified zeolite into the O glycol solution, uniformly stirring, transferring the mixed solution into a high-pressure reaction kettle, heating to 200 ℃ for reaction for 12 hours, cooling to room temperature, carrying out centrifugal separation on the obtained precipitate, alternately washing with absolute ethyl alcohol and distilled water for several times, and carrying out vacuum drying at 80 ℃ to obtain the finished product.
As can be seen from fig. 2, the amount of nitrogen adsorbed by zeolite was significantly increased after MOF modification, but the amount of nitrogen adsorbed was slightly decreased after photocatalyst loading. The degradation effect on the ARB is studied under visible light, and the result is shown in figure 3, and the degradation rate on the ARB is 68% after 80min of illumination. The effect of degrading COD in sewage is reduced from 20000mg/L to 950 mg/L.
Therefore, the MOF modified zeolite loaded BiOX/TiO is adopted in the invention2The photocatalytic material and the preparation method thereof solve the problems that the photocatalyst is difficult to recover and is easy to lose along with sewage, and the method has short reaction time, low cost, simple operation and easy industrial production.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the invention without departing from the spirit and scope of the invention.
Claims (6)
1. MOF modified zeolite loaded BiOX/TiO2The photocatalytic material is characterized by comprising the following raw materials in parts by mole:
50-100 parts of natural zeolite, 10-30 parts of MOF material and BiOX/TiO210-60 parts of photocatalyst, wherein BiOX/TiO2The molar ratio is 0.01-100.
2. The MOF-modified zeolite-supported BiOX/TiO of claim 12Photocatalytic material characterized byThe method comprises the following steps: the natural zeolite is one or more of natural stilbite, clinoptilolite, mordenite or analcime.
3. The MOF-modified zeolite-supported BiOX/TiO of claim 22A photocatalytic material characterized by: the natural zeolite is natural stilbite.
4. A MOF-modified zeolite supported BiOX/TiO as claimed in any one of claims 1 to 32The preparation method of the photocatalytic material is characterized by comprising the following steps of:
(1) pretreatment of natural zeolite: washing natural zeolite with deionized water by multiple oscillation, soaking in HCl solution with concentration of 0.01-3mol/L for 1-6h, washing, and drying to obtain pretreated natural zeolite;
(2) preparation of MOF-modified zeolite: dissolving 2-amino terephthalic acid in N, N-dimethylformamide and anhydrous methanol, adding isopropyl titanate and pretreated natural zeolite, uniformly stirring, transferring to a high-pressure reaction kettle, heating to 120 ℃ for reaction at 250 ℃ for 12-36 hours, cooling to room temperature, and washing with N, N-dimethylformamide and anhydrous methanol for three times to obtain MOF modified zeolite;
(3) preparing a photocatalytic material: adding KX into the mixed solution of deionized water and absolute ethyl alcohol, stirring for 20min, according to n (BiOX) n (TiO)2) Adding TiO in the proportion of 0.01-1002Stirring uniformly, then adding Bi (NO)3)3·5H2And (2) adding MOF modified zeolite into the O glycol solution after uniformly stirring, transferring the mixed solution into a high-pressure reaction kettle, heating to the temperature of 120 ℃ and 250 ℃ for reaction for 12-36 hours, cooling to room temperature, performing centrifugal separation on the obtained precipitate, alternately washing for several times by using absolute ethyl alcohol and distilled water, and performing vacuum drying at the temperature of 80 ℃ to obtain a finished product.
5. The MOF-modified zeolite-supported BiOX/TiO of claim 42The preparation method of the photocatalytic material is characterized by comprising the following steps: and (4) KX in the step (3) is one of KCl, KBr and KI.
6. The MOF-modified zeolite-supported BiOX/TiO of claim 42The preparation method of the photocatalytic material is characterized by comprising the following steps: the volume ratio of the deionized water to the absolute ethyl alcohol in the step (3) is 1: 1.
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