阅读说明：本技术 一种碘氧化铋/碳化硼催化剂及其制备方法和应用 (Bismuth oxyiodide/boron carbide catalyst and preparation method and application thereof ) 是由 魏健 吕一凡 徐东耀 刘雪瑜 段亮 李明月 李丹 于 2020-05-08 设计创作，主要内容包括：本发明提供了一种碘氧化铋/碳化硼催化剂及其制备方法和应用,属于催化材料领域。本发明提供的催化剂,包括碘氧化铋与碳化硼的复合结构,控制碘氧化铋与碳化硼的物质的量之比为1:(0.855～85.5),以使二者结合形成较多的半导体异质结,在对可见光进行响应时发生电子跃迁,通过所述异质结的连接,使得光生电子转移至BiOI一侧,空穴对转移至B<Sub>4</Sub>C一侧,光生电子和空穴对被分离,降低了二者的复合率,从而增加催化反应体系中活性基团的数量,以提高催化活性以及对内分泌干扰物的降解率。将本发明提供的催化剂和硫酸盐氧化技术结合后,对水中的内分泌干扰物BPS的降解率可达95％,对BPA的降解率可达98％。(The invention provides a bismuth oxyiodide/boron carbide catalyst and a preparation method and application thereof, belonging to the field of catalytic materials. The catalyst provided by the invention comprises a composite structure of bismuth oxyiodide and boron carbide, the mass ratio of bismuth oxyiodide to boron carbide is controlled to be 1 (0.855-85.5), so that the bismuth oxyiodide and the boron carbide are combined to form more semiconductor heterojunctions, electron transition occurs in response to visible light, photo-generated electrons are transferred to one side of BiOI through the connection of the heterojunctions, and hole pairs are transferred to B 4 On the side C, the photoproduction electron and the hole pair are separated, and the recombination rate of the photoproduction electron and the hole pair is reduced, so that the number of active groups in a catalytic reaction system is increased, and the catalytic activity and the degradation rate of endocrine disruptors are improved. After the catalyst provided by the invention is combined with the sulfate oxidation technology, the catalyst is applied to waterThe degradation rate of the endocrine disrupter BPS can reach 95 percent, and the degradation rate of BPA can reach 98 percent.)

1. The bismuth oxyiodide/boron carbide catalyst comprises a composite structure of bismuth oxyiodide and boron carbide, wherein a semiconductor heterojunction is formed at the joint of the bismuth oxyiodide and the boron carbide, and the mass ratio of the bismuth oxyiodide to the boron carbide is 1 (0.855-85.5).

2. A method of preparing a bismuth oxyiodide/boron carbide catalyst as claimed in claim 1, comprising the steps of:

(1) mixing a bismuth source, boron carbide and an organic solvent to obtain a suspension;

(2) mixing an iodine source and a solvent to obtain an iodine precursor solution;

(3) mixing the suspension obtained in the step (1) with the iodine precursor solution obtained in the step (2), and carrying out solvothermal reaction to obtain a bismuth oxyiodide/boron carbide catalyst;

the step (1) and the step (2) are not in sequence.

3. The preparation method according to claim 2, wherein the concentration of the bismuth source in the suspension obtained in the step (1) is 0.01 to 10 mol/L.

4. The method according to claim 2 or 3, wherein the bismuth source in the step (1) comprises bismuth nitrate pentahydrate, bismuth chloride, bismuth sulfate, bismuth hydroxide or bismuth subsalicylate.

5. The production method according to claim 2, wherein the mixing of the bismuth source, the boron carbide and the organic solvent in the step (2) includes: adding bismuth source and boron carbide into organic solvent, and then stirring and ultrasonic processing.

6. The method according to claim 2, wherein the ratio of the amount of the bismuth source in the step (1) to the amount of the iodine source in the step (2) is 1 (0.1-10).

7. The method according to claim 2 or 6, wherein the iodine source in the step (2) comprises sodium iodide or potassium iodate.

8. The method of claim 2, wherein the mixing of the suspension and the iodine precursor solution in the step (3) comprises: and dropwise adding the iodine precursor solution into the suspension, and stirring after the dropwise adding is finished.

9. The preparation method according to claim 1, wherein the temperature of the solvothermal reaction in the step (3) is 120-250 ℃, and the time of the solvothermal reaction is 12-36 h.

10. Use of the bismuth oxyiodide/boron carbide catalyst according to claim 1 or the bismuth oxyiodide/boron carbide catalyst prepared by the preparation method according to any one of claims 2 to 9 for removing endocrine disruptors in water.

Technical Field

The invention relates to the field of catalytic materials, in particular to a bismuth oxyiodide/boron carbide catalyst and a preparation method and application thereof.

Background

With the acceleration of urbanization and the advance of industrialization, a large amount of artificially synthesized organic matters are applied to manufacturing industry, so that residual artificially synthesized organic matters enter and are exposed to the environment through various ways, thereby inducing a serious water pollution problem and further seriously harming human health. The endocrine disruptors (ECDs) are exogenous endocrine disrupting chemicals which are released into the environment due to human life and production, enter human bodies or animal bodies, disturb or even destroy the original homeostasis of the human bodies or animal bodies by simulating or inhibiting the metabolic activity of the endocrine systems of the human bodies or animal bodies, cause abnormal effects in various aspects such as reproductive systems, immune systems, nervous systems and the like of the bodies, and seriously harm the health of the human bodies and the animals.

The traditional water treatment technology has limited degradation effect on endocrine disruptors, the cost is high, and most endocrine disruptors have toxic effect on microorganisms in the water treatment technology. At present, the chemical method for effectively degrading endocrine disruptors in water is an oxidation method. The photocatalytic oxidation technology is an environment-friendly water treatment technology, and can safely and efficiently degrade organic pollutants in a water body by directly utilizing the sun under mild reaction conditions, but the catalyst used in the existing photocatalytic oxidation technology has the technical problem of low degradation efficiency of endocrine disruptors, so that the further wide application of the catalyst is limited.

Disclosure of Invention

The invention aims to provide a bismuth oxyiodide/boron carbide catalyst and a preparation method and application thereof. The bismuth oxyiodide/boron carbide catalyst provided by the invention responds to visible light, after electron transition occurs, the recombination rate of photogenerated electrons and holes is low, the catalytic activity is obviously improved, and endocrine disruptors in water can be efficiently degraded.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a bismuth oxyiodide/boron carbide catalyst, which comprises bismuth oxyiodide and boron carbide, wherein a semiconductor heterojunction is formed at the joint of the bismuth oxyiodide and the boron carbide, and the mass ratio of the bismuth oxyiodide to the boron carbide is 1 (0.855-85.5).

The invention also provides a preparation method of the catalyst in the technical scheme, which comprises the following steps:

(1) mixing a bismuth source, boron carbide and an organic solvent to obtain a suspension;

(2) mixing an iodine source and a solvent to obtain an iodine precursor solution;

(3) and (3) mixing the suspension obtained in the step (1) with the iodine precursor solution obtained in the step (2), and carrying out solvothermal reaction to obtain the bismuth oxyiodide/boron carbide catalyst.

Preferably, the concentration of the bismuth source in the suspension obtained in the step (1) is 0.01-10 mol/L.

Preferably, the bismuth source in step (1) comprises bismuth nitrate pentahydrate, bismuth chloride, bismuth sulfate, bismuth hydroxide or bismuth subsalicylate.

Preferably, the mixing of the bismuth source, the boron carbide and the organic solvent in the step (2) comprises: adding bismuth source and boron carbide into organic solvent, and then stirring and ultrasonic processing.

Preferably, the ratio of the amount of the bismuth source in the step (1) to the amount of the iodine source in the step (2) is 1 (0.1 to 10)

Preferably, the iodine source in step (2) comprises sodium iodide or potassium iodate.

Preferably, the mixing of the suspension and the iodine precursor solution in the step (3) comprises: and dropwise adding the iodine precursor solution into the suspension, and stirring after the dropwise adding is finished.

Preferably, the temperature of the solvothermal reaction in the step (3) is 120-250 ℃, and the time of the solvothermal reaction is 12-36 h.

The invention also provides the application of the catalyst in the technical scheme or the catalyst prepared by the preparation method in removing endocrine disruptors in water.

The invention provides a bismuth oxyiodide/boron carbide catalyst, which comprises a composite structure of bismuth oxyiodide and boron carbide, and is prepared by controlling bismuth oxyiodide BiOI and boron carbide B₄The mass ratio of C is 1 (0.855 to 85.5) so that BiOI and B are as much as possible₄C is combined to form more semiconductor heterojunctions, so that the catalytic activity of the catalyst is improved. Under the irradiation of visible light, the catalyst provided by the invention responds to the visible light, generates electron transition and generates electron and hole pairs, the photoproduction electrons are transferred to one side of the BiOI through the connection of a semiconductor heterojunction formed by combining bismuth oxyiodide and boron carbide, and the hole pairs are transferred to B₄On the side C, the photo-generated electron and the hole pair are separated, and the recombination rate of the photo-generated electron and the hole pair is reduced, so that the number of active groups in a catalytic reaction system is increased, the catalytic activity of the catalyst is further improved, and the degradation rate of endocrine disruptors is increased. The results of the examples show that the catalyst provided by the invention can be used for degrading endocrine disruptors in water under normal temperature and pressure and visible light after being combined with a sulfate oxidation technology, so that the energy is saved, the cost is reduced, degradation byproducts are nontoxic and harmless, the degradation rate of the endocrine disruptors BPS in water can reach 95%, and the degradation rate of BPA can reach 98%.

The preparation method of the bismuth oxyiodide/boron carbide catalyst provided by the invention is simple to operate, mild in reaction conditions and suitable for large-scale production.

Drawings

FIG. 1 is an SEM image of a pure BiOI sample;

FIG. 2 is an SEM image of a pure BiOI sample;

FIG. 3 shows BiOI/B prepared in example 1 of the present invention₄SEM picture of catalyst C;

FIG. 4 shows BiOI/B prepared in example 1 of the present invention₄Magnified SEM image of catalyst C;

FIG. 5 shows BiOI/B prepared in example 1 of the present invention₄C catalysisA plot of XPS survey analysis of the agent;

FIG. 6 shows BiOI/B prepared in examples 1, 4 and 6 of the present invention₄C catalyst and pure BiOI and pure B₄XRD pattern of C.

Detailed Description

The invention provides a bismuth oxyiodide/boron carbide catalyst which comprises a composite structure of bismuth oxyiodide and boron carbide, wherein a semiconductor heterojunction is formed at the joint of the bismuth oxyiodide and the boron carbide, and the mass ratio of the bismuth oxyiodide to the boron carbide is 1 (0.855-85.5).

The bismuth oxyiodide/boron carbide catalyst provided by the invention comprises a composite structure of bismuth oxyiodide and boron carbide, and a semiconductor heterojunction is formed at the joint of the bismuth oxyiodide and the boron carbide. In the present invention, the semiconductor heterojunction enables the transfer of the photo-generated electrons in the catalyst to the BiOI side and the transfer of the hole pairs to B₄On the side C, the photo-generated electron and the hole pair are separated, and the recombination rate of the photo-generated electron and the hole pair is reduced, so that the number of active groups in a catalytic reaction system is increased, and the catalytic activity of the catalyst is improved.

In the invention, the bismuth oxyiodide is preferably in a flower sphere shape consisting of nano sheets, and the average grain size of the bismuth oxyiodide is preferably (2-3 μm); the boron carbide is preferably in a diamond column shape, and the average grain size of the boron carbide is preferably (2-3 μm).

In the present invention, the ratio of the amounts of the bismuth oxyiodide and the boron carbide is 1 (0.855 to 85.5), preferably 1 (1 to 20), and more preferably 1 (1.5 to 10). The invention controls the quantity ratio of bismuth oxyiodide to boron carbide in the range, which is beneficial to combining bismuth oxyiodide and boron carbide as much as possible to form more semiconductor heterojunctions, thereby improving the catalytic activity of the catalyst.

When the bismuth oxyiodide/boron carbide catalyst provided by the invention responds to visible light, electron transition occurs to generate electron and hole pairs, the connection of a semiconductor heterojunction formed by combining bismuth oxyiodide and boron carbide enables photo-generated electrons to be transferred to one side of BiOI, and the hole pairs are transferred to B₄C side, photo-generated electron and hole pairs are dividedAnd in the condition that the pH value is 3-10, the peroxydisulfate is used as an electron acceptor, and is activated after the peroxydisulfate reacts with generated photo-generated electrons and holes after the contact, so that a large number of active free radicals are generated, and the active free radicals can react with endocrine disruptors to degrade the endocrine disruptors, thereby efficiently degrading the endocrine disruptors in water.

The invention also provides a preparation method of the bismuth oxyiodide/boron carbide catalyst in the technical scheme, which comprises the following steps:

(1) mixing a bismuth source, boron carbide and an organic solvent to obtain a suspension;

(2) mixing an iodine source and a solvent to obtain an iodine precursor solution;

(3) mixing the suspension obtained in the step (1) with the iodine precursor solution obtained in the step (2), and carrying out solvothermal reaction to obtain a bismuth oxyiodide/boron carbide catalyst;

the step (1) and the step (2) are not in sequence.

The invention mixes bismuth source, boron carbide and organic solvent to obtain suspension. In the present invention, the bismuth source preferably comprises bismuth nitrate pentahydrate, bismuth chloride, bismuth sulfate, bismuth hydroxide or bismuth subsalicylate; in the embodiment of the invention, the bismuth source is bismuth nitrate pentahydrate. The source of the bismuth source is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.

In the present invention, the boron carbide is preferably powdered boron carbide; the particle size of the powdery boron carbide is preferably 1-4 μm, and more preferably 2-3 μm. The source of the boron carbide is not particularly limited in the present invention, and a commercially available product known to those skilled in the art may be used.

In the present invention, the organic solvent is preferably an alcoholic hydroxyl group-containing organic solvent, more preferably methanol, absolute ethanol or ethylene glycol; in the embodiment of the invention, absolute ethyl alcohol is adopted. The source of the organic solvent is not particularly limited in the present invention, and a commercially available product known to those skilled in the art may be used.

In the present invention, the mixture of the bismuth source, boron carbide and organic solvent preferably includes: adding bismuth source and boron carbide into organic solvent, and then stirring and ultrasonic processing. In the present invention, the stirring manner is preferably magnetic stirring; the magnetic stirring time is preferably 20-80 min, more preferably 30-60 min, and further preferably 45 min; the speed of the magnetic stirring is preferably 100-500 r/min, and more preferably 200-300 r/min. In the invention, the time of the ultrasonic treatment is preferably 5-60 min, more preferably 10-40 min, and further preferably 20 min; the power of the ultrasonic wave is preferably 50-100W, and more preferably 70-80W. According to the invention, the stirring mode, time and speed, and the ultrasonic time and power are controlled within the above ranges, so that the bismuth source and the boron carbide are fully mixed, and the combination of subsequently generated bismuth oxyiodide and boron carbide is promoted to form more semiconductor heterojunctions, thereby improving the catalytic activity of the prepared catalyst.

In the invention, the concentration of the bismuth source in the suspension is preferably 0.01-10 mol/L, more preferably 0.05-5 mol/L, and further preferably 0.08-2 mol/L. the concentration of the bismuth source in the suspension is controlled in the above range, so that the bismuth source and boron carbide are fully mixed, the combination of subsequently generated bismuth oxyiodide and boron carbide is promoted to form more semiconductor heterojunctions, and the catalytic activity of the prepared catalyst is improved.

In the present invention, the ratio of the amount of the bismuth source to the amount of the boron carbide substance is preferably 1 (0.855 to 85.5), more preferably 1 (1 to 20), and still more preferably 1 (1.5 to 10). The ratio of the bismuth source to the boron carbide is controlled within the range, so that subsequently formed bismuth oxyiodide is combined with the boron carbide as much as possible to form more semiconductor heterojunctions, the catalytic activity of the catalyst is improved, the phenomenon that when the using amount of the boron carbide is too high, the bismuth oxyiodide generated by the bismuth source is cut and decomposed into nano sheets, the broken flaky bismuth oxyiodide cannot form the heterojunctions with the boron carbide, the catalytic activity of the catalyst is reduced, and meanwhile, the phenomenon that when the using amount of the boron carbide is too low, enough heterojunctions are difficult to form, and the activity of the catalyst is reduced is avoided.

The invention mixes the iodine source and the solvent to obtain the iodine precursor solution. In the present invention, the iodine source preferably comprises sodium iodide or potassium iodate. The source of the iodine source is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.

In the invention, the concentration of the iodine source in the iodine source precursor solution is preferably 0.01-10 mol/L, more preferably 0.05-5 mol/L, and even more preferably 0.1-2 mol/L.

In the present invention, the ratio of the amounts of the bismuth source and the iodine source is 1 (0.1 to 10), more preferably 1 (0.5 to 5), and still more preferably 1:1. The invention controls the ratio of the bismuth source to the iodine source in the range, which is beneficial to generating bismuth oxyiodide with proper particle size and regular shape.

In the invention, the suspension and the iodine precursor solution are prepared in no sequence.

After the suspension and the iodine precursor solution are obtained, the suspension and the iodine precursor solution are mixed and subjected to solvothermal reaction to obtain the bismuth oxyiodide/boron carbide catalyst. In the present invention, the mixing of the suspension and the iodine precursor solution preferably comprises: dropwise adding an iodine precursor solution into the suspension, and stirring after dropwise adding; the dripping speed is preferably 1-4 drops/s, and more preferably 2-3 drops/s. The method controls the dropping speed within the range, and can be beneficial to the full reaction of the bismuth source in the suspension and the iodine precursor solution, thereby obtaining bismuth oxyiodide with good appearance and uniform particle size. In the present invention, the stirring manner is preferably magnetic stirring; the magnetic stirring time is preferably 0.5-2.5 h, more preferably 1-2 h, and further preferably 1.5 h; the speed of the magnetic stirring is preferably 100-500 r/min, and more preferably 200-300 r/min. According to the invention, the stirring mode, time and speed are controlled within the above ranges, so that the materials can be fully mixed, the subsequently formed bismuth oxyiodide is promoted to be combined with boron carbide as much as possible to form more semiconductor heterojunctions, and the catalytic activity of the catalyst is improved.

In the invention, the volume ratio of the suspension to the iodine precursor solution is preferably 1 (0.1-10), more preferably 1 (0.3-5), and even more preferably 1 (0.5-3). The volume ratio of the suspension to the iodine precursor solution is controlled within the range, so that the concentration of subsequently generated bismuth oxyiodide in the solution can be controlled, the subsequently formed bismuth oxyiodide is promoted to be combined with boron carbide as much as possible to form more semiconductor heterojunctions, and the catalytic activity of the catalyst is improved.

In the invention, the temperature of the solvothermal reaction is preferably 120-250 ℃, more preferably 150-200 ℃, and further preferably 180 ℃; the preferable time of the solvothermal reaction is 12-36 h, more preferably 20-30 h, and further preferably 24 h. The temperature and time of the solvothermal reaction are controlled within the range, so that bismuth oxyiodide with good appearance can be obtained, and the generated bismuth oxyiodide and boron carbide are promoted to form more semiconductor heterojunctions, so that the catalytic activity of the catalyst is improved. In the present invention, the solvothermal reaction is preferably carried out under autogenous pressure and stirring conditions, and the stirring rate in the present invention is not particularly limited, and may be a conventional stirring rate. In the invention, the solvothermal reaction process is that a bismuth source and an iodine source firstly undergo double decomposition reaction to generate bismuth oxyiodide, and simultaneously, as the lattice surface of the bismuth oxyiodide continuously grows, a heterojunction is formed after the bismuth oxyiodide contacts boron carbide.

After the solvothermal reaction is finished, the invention preferably carries out solid-liquid separation, washing and drying on the product of the solvothermal reaction in sequence to obtain the bismuth oxyiodide/boron carbide catalyst. The solid-liquid separation method is not particularly limited, and a method known to those skilled in the art may be used. In the present invention, the solid-liquid separation is preferably performed by centrifugation or suction filtration. In the invention, the centrifugal speed is preferably 5000 r/min-10000 r/min, more preferably 7000-9000 r/min; the time for centrifugation is preferably 3-15 min, and more preferably 8-10 min. In the present invention, the filter paper used for the suction filtration is preferably a microporous filter paper having a pore size of less than 0.8 μm. In the present invention, the washing preferably includes a first washing and a second washing which are sequentially performed; the solvent used for the first washing is preferably deionized water, and the solvent used for the second washing is preferably an organic solvent; the organic solvent is preferably an alcoholic hydroxyl group-containing organic solvent, more preferably methanol, absolute ethanol or ethylene glycol. In the present invention, the number of times of the first washing and the second washing is preferably 3 to 10 times, and more preferably 5 times, independently. In the invention, the drying temperature is preferably 30-80 ℃, and more preferably 60 ℃; the drying time is preferably 6-24 hours, and more preferably 12 hours.

The preparation method of the bismuth oxyiodide/boron carbide catalyst provided by the invention is simple to operate, mild in reaction conditions and suitable for large-scale production.

The invention also provides the application of the bismuth oxyiodide/boron carbide catalyst or the bismuth oxyiodide/boron carbide catalyst prepared by the preparation method in removing endocrine disruptors in water.

In the invention, the endocrine disrupter is preferably one or more of bisphenol A, bisphenol S, bisphenol AF, estrone and estradiol-diethylstilbestrol, and the concentration of the endocrine disrupter in water is preferably 0.01-100 mg/L, more preferably 1-50 mg/L.

In the invention, the mass ratio of the peroxydisulfate to the water to be treated containing the endocrine disrupter is preferably 1 (1000-10000), and more preferably 1 (1000-5000).

In the invention, the bismuth oxyiodide/boron carbide catalyst is preferably used for removing endocrine disruptors in water in the presence of peroxydisulfate and at a pH value of 3-10.

In the present invention, the application of the bismuth oxyiodide/boron carbide catalyst in removing endocrine disruptors in water preferably comprises the following steps:

1) mixing the peroxydisulfate with a water sample to be treated containing endocrine disruptors to obtain a mixed solution;

2) adjusting the pH value of the mixed solution obtained in the step 1) to 3-10 to obtain a pretreatment reaction solution;

3) mixing the pretreatment reaction liquid obtained in the step 2) with the bismuth oxyiodide/boron carbide catalyst or the bismuth oxyiodide/boron carbide catalyst prepared by the preparation method to obtain a mixed reaction liquid, and irradiating with visible light.

According to the invention, the peroxodisulfate is preferably mixed with the water sample to be treated containing the endocrine disruptors to obtain the mixed solution. The operation of mixing the persulfate and the water sample to be treated containing the endocrine disruptors is not particularly limited, and the technical scheme for preparing the mixed solution, which is well known by the technical personnel in the field, can be adopted. In the invention, the peroxydisulfate is mixed with the water sample to be treated containing the endocrine disrupter, preferably, the peroxydisulfate is added into the water sample to be treated containing the endocrine disrupter and then stirred. In the invention, the stirring time is preferably 5-60 min, and more preferably 10-30 min; the stirring speed is preferably 100-300 r/min, and more preferably 200 r/min.

In the present invention, the concentration of the hydrogen persulfate in the mixed solution is preferably 0.01 to 0.2 mmol/L, more preferably 0.03 to 0.1 mmol/L, and further preferably 0.05 mmol/L.

In the present invention, the mass ratio of the peroxodisulfate to the endocrine disruptor is preferably 1 (0.02 to 20), more preferably 1 (0.1 to 10), and still more preferably 1 (0.4 to 5). The invention controls the mass ratio of the peroxodisulfate to the endocrine disruptors within the range, is favorable for the peroxodisulfate to be used as an electron acceptor, and is activated after contacting and reacting with electron and hole pairs generated by the bismuth oxyiodide/boron carbide catalyst to generate enough active free radicals, so that more active free radicals react with the endocrine disruptors, and the degradation efficiency is further improved.

After a mixed solution is obtained, the pH value of the mixed solution is preferably adjusted to be 3-10 to obtain a pretreatment reaction solution, in the invention, the pH value of the mixed solution is preferably adjusted to be room temperature under the condition of stirring, the stirring speed is preferably 100-300 r/min, more preferably 200r/min, in the invention, the pH value is more preferably 6-8, and further preferably 7, in the invention, the pH value of the suspension is controlled to be within the range, so that the situation that excessive hydrogen ions and hydroxyl ions in the pretreatment reaction solution react with active free radicals generated by subsequent reaction when the pH value is too high or too low can be avoided, the free radicals are consumed, and the degradation efficiency of the catalyst is reduced.

After the pre-treatment reaction liquid is obtained, the pre-treatment reaction liquid is preferably mixed with the bismuth oxyiodide/boron carbide catalyst prepared by the technical scheme or the bismuth oxyiodide/boron carbide catalyst prepared by the preparation method to obtain a mixed reaction liquid. In the invention, the operation of mixing the pretreated reaction liquid and the bismuth oxyiodide/boron carbide catalyst or the bismuth oxyiodide/boron carbide catalyst prepared by the preparation method is not particularly limited, and the technical scheme of preparing the mixed solution, which is well known to those skilled in the art, can be adopted to realize the full mixing of materials.

In the invention, the concentration of the bismuth oxyiodide/boron carbide catalyst or the bismuth oxyiodide/boron carbide catalyst prepared by the preparation method in the mixed reaction solution is preferably 10-300 mg/L, more preferably 80-200 mg/L, and further preferably 100 mg/L.

After obtaining the mixed reaction solution, the present application preferably irradiates the mixed reaction solution with visible light. In the present invention, the irradiation with visible light is preferably performed at room temperature under stirring; the stirring speed is preferably 100-300 r/min, and more preferably 200 r/min. In the invention, the time of the visible light irradiation is preferably 20-180 min, more preferably 25-90 min, and further preferably 30 min; the light source power of the visible light is preferably 10W-500W, and more preferably 200W-300W.

The invention provides bismuth oxyiodide/boron carbide catalystUnder the irradiation of visible light, the agent responds to the visible light, electron transition is generated, electron and hole pairs are generated, the photo-generated electrons are transferred to the BiOI side through the connection of the heterojunction, and the hole pairs are transferred to the B₄And on the side C, the photoproduction electrons and the holes are separated, the recombination rate of the photoproduction electrons and the holes is reduced, the hydrogen persulfate is used as an electron acceptor under the condition that the pH value is 3-10, the hydrogen persulfate is in contact with the generated photoproduction electrons and the holes and then is activated after reaction, a large number of active free radicals are generated, the active free radicals can react with endocrine disruptors to complete the degradation of the endocrine disruptors, and therefore the endocrine disruptors in water are efficiently degraded under visible light at normal temperature and normal pressure, energy is saved, cost is reduced, and degradation byproducts are nontoxic and harmless.

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.