阅读说明：本技术 一种MOF改性沸石负载BiOX/TiO2光催化材料及其制备方法 (MOF modified zeolite loaded BiOX/TiO2Photocatalytic material and preparation method thereof ) 是由 李刚 王静 于 2021-10-12 设计创作，主要内容包括：本发明公开了一种MOF改性沸石负载BiOX/TiO-(2)光催化材料,包括以下原料,按摩尔份数计：天然沸石50-100份、MOF材料10-30份、BiOX/TiO-(2)光催化剂10-60份,其中BiOX/TiO-(2)摩尔比为0.01-100。本发明采用上述一种MOF改性沸石负载复合光催化剂的光催化材料,解决了光催化剂回收困难、易随污水流失的问题,该法反应时间短、成本低、操作简单,易于工业化生产。(The invention discloses a MOF modified zeolite loaded BiOX/TiO 2 The 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/TiO 2 10-60 parts of photocatalyst, wherein BiOX/TiO 2 The 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.)

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.

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/TiO₂20 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/TiO₂20 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/TiO₂20 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.