阅读说明：本技术 一种W18O49/BiOX复合光催化材料及其制备方法 (W18O49BiOX composite photocatalytic material and preparation method thereof ) 是由 庄艳丽 张显华 董丽敏 单连伟 于 2020-06-03 设计创作，主要内容包括：本发明提供了一种W<Sub>18</Sub>O<Sub>49</Sub>/BiOX复合光催化材料及其制备方法,涉及材料制备技术领域,所述W<Sub>18</Sub>O<Sub>49</Sub>/BiOX复合光催化材料的制备方法包括以下步骤:向醇溶液中加入氯化钨粉末,待所述氯化钨粉末完全溶解后,向氯化钨醇溶液中加入十六烷基三甲基溴化铵的醇溶液,搅拌均匀后得到第一混合溶液；将所述第一混合溶液加入到反应釜中加热,并经过洗涤、干燥后,得到W<Sub>18</Sub>O<Sub>49</Sub>纳米线；将所述W<Sub>18</Sub>O<Sub>49</Sub>纳米线溶解在醇溶剂中,得到W<Sub>18</Sub>O<Sub>49</Sub>纳米线溶液,将所述W<Sub>18</Sub>O<Sub>49</Sub>纳米线溶液加入到硝酸铋醇溶液中,混合均匀后得到第二混合溶液；将所述第二混合溶液加入到金属卤化物溶液中,加热搅拌、洗涤、干燥后,得到W<Sub>18</Sub>O<Sub>49</Sub>/BiOX复合光催化材料。本发明W<Sub>18</Sub>O<Sub>49</Sub>/BiOX复合光催化材料能够有效地分离光生载流子,提高催化效率。(The invention provides a W 18 O 49 A/BiOX composite photocatalytic material and a preparation method thereof relate to the technical field of material preparation, and the W is 18 O 49 The preparation method of the/BiOX composite photocatalytic material comprises the following steps of adding tungsten chloride powder into an alcohol solution, and adding chlorine into the solution after the tungsten chloride powder is completely dissolvedAdding an alcohol solution of cetyl trimethyl ammonium bromide into the tungsten oxide alcohol solution, and uniformly stirring to obtain a first mixed solution; adding the first mixed solution into a reaction kettle, heating, washing and drying to obtain W 18 O 49 A nanowire; the W is 18 O 49 Dissolving the nano-wire in an alcohol solvent to obtain W 18 O 49 Nanowire solution of the W 18 O 49 Adding the nanowire solution into the bismuth nitrate alcohol solution, and uniformly mixing to obtain a second mixed solution; adding the second mixed solution into a metal halide solution, heating, stirring, washing and drying to obtain W 18 O 49 The BiOX composite photocatalytic material. Invention W 18 O 49 The BiOX composite photocatalytic material can effectively separate photon-generated carriers and improve the catalytic efficiency.)

1. W₁₈O₄₉The preparation method of the BiOX composite photocatalytic material is characterized by comprising the following steps:

adding tungsten chloride powder into an alcohol solution, adding an alcohol solution of cetyl trimethyl ammonium bromide into the tungsten chloride alcohol solution after the tungsten chloride powder is completely dissolved, and uniformly stirring to obtain a first mixed solution;

step two, adding the first mixed solution into a reaction kettle for heating, and washing and drying to obtain W₁₈O₄₉A nanowire;

step three, mixing the W₁₈O₄₉Dissolving the nano-wire in an alcohol solvent to obtain W₁₈O₄₉Nanowire solution of the W₁₈O₄₉Adding the nanowire solution into the bismuth nitrate alcohol solution, and uniformly mixing to obtain a second mixed solution;

step four, adding the second mixed solution into a metal halide solution, heating, stirring, washing and drying to obtain W₁₈O₄₉The BiOX composite photocatalytic material.

2. W according to claim 1₁₈O₄₉The preparation method of the/BiOX composite photocatalytic material is characterized in that the heating condition in the step two is heating for 12-48 hours at the temperature of 160-180 ℃.

3. W according to claim 1₁₈O₄₉The preparation method of the/BiOX composite photocatalytic material is characterized in that the drying conditions in the second step and the fourth step are drying at the temperature of 60-90 ℃ for 12-24 hours.

4. W according to claim 1₁₈O₄₉The preparation method of the/BiOX composite photocatalytic material is characterized in that the bismuth nitrate alcoholic solution in the third step is prepared by ultrasonically dispersing bismuth nitrate pentahydrate in an alcoholic solventAnd (5) obtaining the product.

5. W according to claim 4₁₈O₄₉The preparation method of the/BiOX composite photocatalytic material is characterized in that the metal halide solution in the fourth step is prepared by dissolving metal halide in deionized water and heating to 60-90 ℃ for dissolution.

6. W according to claim 5₁₈O₄₉The preparation method of the/BiOX composite photocatalytic material is characterized in that the molar ratio of the bismuth nitrate pentahydrate to the metal halide is 1: 1.

7. W according to claim 5 or 6₁₈O₄₉The preparation method of the/BiOX composite photocatalytic material is characterized in that the metal halide is selected from KI, KCl, KBr, NaI, NaCl or NaBr.

8. W according to claim 1₁₈O₄₉The preparation method of the BiOX composite photocatalytic material is characterized in that the heating and stirring conditions in the fourth step are that the reaction is carried out for 1-4 hours at the temperature of 70-90 ℃.

9. W₁₈O₄₉A/BiOX composite photocatalytic material prepared by using the W as defined in any one of claims 1 to 8₁₈O₄₉The preparation method of the BiOX composite photocatalytic material.

10. W according to claim 9₁₈O₄₉the/BiOX composite photocatalytic material is characterized in that the W is₁₈O₄₉W in/BiOX composite photocatalytic material₁₈O₄₉The proportion of the component is 0.5-10 wt%.

Technical Field

The invention relates to the technical field of material preparation, in particular to W₁₈O₄₉A BiOX composite photocatalytic material and a preparation method thereof.

Background

The semiconductor photocatalytic oxidation technology is a modern novel water treatment technology, is a reaction process for realizing efficient degradation of pollutants in water, low-toxicity conversion of heavy metals, effective catalytic reduction of carbon dioxide, hydrogen production and oxygen production by water electrolysis and the like by utilizing the energy of natural light or artificial indoor light, and has attracted wide attention in society. Among the reported semiconductor materials, TiO₂The material is widely researched due to no toxicity, low cost, higher chemical stability and stronger oxidation capacity, but due to the larger forbidden bandwidth (-3.2eV), the material can only show photocatalytic response under the irradiation of ultraviolet light, and the irradiation of the ultraviolet light only accounts for about 5% of the solar spectrum, so that the efficient utilization of sunlight is greatly limited. Therefore, developing efficient, sustainable and stable visible light driving photocatalytic materials and applying the materials to degrade organic pollutants become one of the trends of research and development in the field of photocatalysis.

In recent years, researchers have conducted a great deal of research and application on visible light catalytic materials, and the third-order bismuth oxyhalide compound BiOX (X ═ F, Cl, Br, I) has received extensive attention and research due to its unique anisotropic layered structure and its high-efficiency photocatalytic effect exhibited in the aspect of efficient solar energy utilization, but the application of the simple BiOX material in the actual photocatalytic field is limited due to its own defects such as high charge carrier recombination rate, low electrical conductivity, and low active sites.

Disclosure of Invention

The invention solves the problem of how to prepare W₁₈O₄₉A BiOX composite photocatalytic material.

To solve the above problems, the present invention provides a W₁₈O₄₉The preparation method of the BiOX composite photocatalytic material comprises the following steps:

adding tungsten chloride powder into an alcohol solution, adding an alcohol solution of cetyl trimethyl ammonium bromide into the tungsten chloride alcohol solution after the tungsten chloride powder is completely dissolved, and uniformly stirring to obtain a first mixed solution;

step two, adding the first mixed solution into a reaction kettle for heating, and washing and drying to obtain W₁₈O₄₉A nanowire;

step three, mixing the W₁₈O₄₉Dissolving the nano-wire in an alcohol solvent to obtain W₁₈O₄₉Nanowire solution of the W₁₈O₄₉Adding the nanowire solution into the bismuth nitrate alcohol solution, and uniformly mixing to obtain a second mixed solution;

step four, adding the second mixed solution into a metal halide solution, heating, stirring, washing and drying to obtain W₁₈O₄₉The BiOX composite photocatalytic material.

Optionally, the heating condition in the second step is heating at 160-180 ℃ for 12-48 h.

Optionally, the drying conditions in step two and step four are drying at a temperature of 60-90 ℃ for 12-24 h.

Optionally, the bismuth nitrate alcoholic solution in step three is prepared by ultrasonically dispersing bismuth nitrate pentahydrate in an alcohol solvent.

Optionally, the metal halide solution in the fourth step is prepared by dissolving the metal halide in deionized water and heating to 60-90 ℃ for dissolution.

Optionally, the molar ratio of the bismuth nitrate pentahydrate to the metal halide is 1: 1.

Optionally, the metal halide is selected from KI, KCl, KBr, NaI, NaCl, or NaBr.

Optionally, the heating and stirring conditions in the fourth step are that the reaction is carried out for 1-4 hours at the temperature of 70-90 ℃.

Compared with the prior art, the W provided by the invention₁₈O₄₉Preparation method of/BiOX composite photocatalytic material₁₈O₄₉The nanometer material has strong organic matter adsorption capacity, and the W is prepared through chemical deposition process₁₈O₄₉the/BiOI binary composite material constructs a heterojunction with matched energy bands, can effectively separate photon-generated carriers, improves the catalytic efficiency and improves the utilization rate of visible light.

In order to solve the technical problem, the invention also provides a W₁₈O₄₉A BiOX composite photocatalytic material prepared by the method₁₈O₄₉The preparation method of the BiOX composite photocatalytic material.

Optionally, the W₁₈O₄₉W in/BiOX composite photocatalytic material₁₈O₄₉The proportion of the component is 0.5-10 wt%.

W in the invention₁₈O₄₉Advantages of/BiOX composite photocatalytic material over prior art and the W₁₈O₄₉The advantages of the preparation method of the/BiOX composite photocatalytic material relative to the prior art are the same, and the detailed description is omitted.

Drawings

FIG. 1 shows W in an embodiment of the present invention₁₈O₄₉A flow chart of a preparation method of the BiOX composite photocatalytic material;

FIG. 2 shows W in an embodiment of the present invention₁₈O₄₉A photocatalytic degradation graph of the BiOX composite photocatalytic material for rhodamine B;

FIG. 3 shows W in an embodiment of the present invention₁₈O₄₉A fluorescence spectrogram of the BiOX composite photocatalytic material;

FIG. 4 is an embodiment of the present inventionIn the example W₁₈O₄₉Schematic diagram of photocatalytic degradation principle of the BiOX composite photocatalytic material.

Detailed Description

In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.

In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. The description of the term "some specific embodiments" means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. Throughout this specification, the schematic representations of the terms used above do not necessarily refer to the same implementation or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

As shown in fig. 1, an embodiment of the present invention provides a W₁₈O₄₉The preparation method of the BiOX composite photocatalytic material comprises the following steps:

step one, adding tungsten chloride (WCl) into an alcohol solution₆) Adding an alcoholic solution of cetyl trimethyl ammonium bromide into the tungsten chloride alcoholic solution after the tungsten chloride powder is completely dissolved, and uniformly stirring to obtain a first mixed solution, wherein the solution turns yellow-green after the tungsten chloride powder is added into the alcoholic solution, and when no tungsten chloride powder exists in the solution, the tungsten chloride is completely dissolved;

step two, adding the first mixed solution into a reaction kettle for heating, and washing and drying to obtain W₁₈O₄₉A nanowire;

step three, mixing the W₁₈O₄₉Dissolving the nano-wire in an alcohol solvent to obtain W₁₈O₄₉A nanowire solution prepared by dissolving the aboveW₁₈O₄₉Adding the nanowire solution into the bismuth nitrate alcohol solution, and uniformly mixing to obtain a second mixed solution;

step four, adding the second mixed solution into a metal halide solution, heating, stirring, washing and drying to obtain the flaky W₁₈O₄₉The BiOX composite photocatalytic material.

In the embodiment, the concentration of the mixed solution of tungsten chloride and alcohol is less than 1.5g/100mL, which is beneficial to the formation of superfine nanowires, and W with small agglomeration and good dispersibility can be formed₁₈O₄₉A nanowire. If the concentration of the mixed solution of tungsten chloride and alcohol is higher than 1.5g/100mL, the synthesized W is sea urchin-shaped₁₈O₄₉Rather than nanowires. Therefore, in this example, by adjusting the ratio of alcohol to tungsten chloride, different amounts of W can be prepared₁₈O₄₉A nanowire.

Preferably, the heating condition in the second step is heating at the temperature of 160-180 ℃ for 12-48 h. This condition favors W₁₈O₄₉And (4) generating the nanowire.

Preferably, the drying conditions in step two and step four are drying at a temperature of 60-90 ℃ for 12-24 h.

Preferably, the bismuth nitrate alcoholic solution in the third step is prepared by ultrasonically dispersing bismuth nitrate pentahydrate in an alcohol solvent, and ultrasonic treatment enables the dispersing effect to be better and the mixing to be more uniform.

Preferably, the metal halide solution in the fourth step is prepared by dissolving the metal halide in deionized water and heating to 60-90 ℃ for dissolution. In some specific embodiments, the metal halide is selected from KI, KCl, KBr, NaI, NaCl, or NaBr, and is low cost and readily available.

Preferably, the molar ratio of the bismuth nitrate pentahydrate to the metal halide is 1:1, such that W is produced₁₈O₄₉The BiOX composite photocatalytic material has good photocatalytic effect. The molar ratio of the bismuth nitrate pentahydrate to the metal halide is the mass ratio of the bismuth nitrate pentahydrate to the metal halide.

Preferably, the heating and stirring conditions in the fourth step are that the reaction is carried out for 1-4 hours at the temperature of 70-90 ℃, and the mixing is more uniform.

In some specific embodiments, W₁₈O₄₉The preparation method of the BiOX composite photocatalytic material comprises the following steps:

adding tungsten chloride powder into an alcoholic solution at room temperature, magnetically stirring, adding an alcoholic solution of cetyl trimethyl ammonium bromide into the alcoholic solution of tungsten chloride after the tungsten chloride powder is completely dissolved, and uniformly stirring to obtain a first mixed solution, wherein after the tungsten chloride powder is added into the alcoholic solution, the solution turns yellow-green, and when no tungsten chloride powder exists in the solution, the tungsten chloride is completely dissolved;

step two, adding the first mixed solution into a reaction kettle with a polytetrafluoroethylene lining, heating for 12-48h at the temperature of 160-180 ℃, repeatedly carrying out centrifugal washing in a centrifugal machine by using absolute ethyl alcohol, wherein the rotating speed of the centrifugal machine is 9000r/min-10000r/min, the washing times are 5-20 times, and finally drying for 12-24h at the temperature of 60-90 ℃ to obtain W₁₈O₄₉A nanowire;

step three, mixing the W₁₈O₄₉Dissolving the nano-wire in an alcohol solvent to obtain W₁₈O₄₉Nanowire solution of the W₁₈O₄₉Adding the nanowire solution into the bismuth nitrate alcohol solution, and uniformly mixing to obtain a second mixed solution;

step four, adding the second mixed solution into a metal halide solution, reacting for 1-4 hours at the temperature of 70-90 ℃, repeatedly carrying out centrifugal washing in a centrifugal machine by using absolute ethyl alcohol, wherein the rotating speed of the centrifugal machine is 9000r/min-10000r/min, the washing times are 5-20 times, and finally drying for 12-24 hours at the temperature of 60-90 ℃ to obtain the flaky W₁₈O₄₉The BiOX composite photocatalytic material.

W₁₈O₄₉The large number of oxygen vacancies present in nanowires, which enhance photocatalytic activity by narrowing the band gap and providing active sites, still affect photo-generated electron hole recombination itself at high ratesTo its own photocatalytic properties. W in the present embodiment₁₈O₄₉Preparation method of/BiOX composite photocatalytic material₁₈O₄₉The nanometer material has strong organic matter adsorption capacity, and the W is prepared through chemical deposition process₁₈O₄₉the/BiOI binary composite material constructs a heterojunction with matched energy bands, can effectively separate photon-generated carriers, improves the catalytic efficiency and improves the utilization rate of visible light.

In order to solve the technical problem, the invention also provides a W₁₈O₄₉A BiOX composite photocatalytic material prepared by the method₁₈O₄₉The preparation method of the BiOX composite photocatalytic material.

Preferably, said W₁₈O₄₉W in/BiOX composite photocatalytic material₁₈O₄₉The proportion of the component is 0.5-10 wt%. On the one hand, if W₁₈O₄₉The content of (A) is more, so that not only can accumulation and accumulation of light be caused, the absorption and transmission of light be hindered or a shielding effect is formed to reduce reaction sites, but also only the adsorption effect of the synthesized composite photocatalytic material can be caused, and further the photocatalytic performance of the composite photocatalytic material is influenced. On the other hand, if W is contained in the composite photocatalytic material₁₈O₄₉In a small amount of W₁₈O₄₉Only a small number of reaction sites are formed, which also hinders the photocatalytic reaction. Therefore, within the proportion range, the composite photocatalytic material has better photocatalytic performance.

W in the invention₁₈O₄₉Advantages of/BiOX composite photocatalytic material over prior art and the W₁₈O₄₉The advantages of the preparation method of the/BiOX composite photocatalytic material relative to the prior art are the same, and the detailed description is omitted.