阅读说明：本技术 卤氧化硅铋材料及其制备方法与应用 (Halogen silicon oxide bismuth material and preparation method and application thereof ) 是由 韩晔红 闫宏远 苑亚楠 王明伟 韩丹丹 杨春柳 于 2020-06-02 设计创作，主要内容包括：本发明提供了一种卤氧化硅铋材料及其制备方法与应用,卤氧化硅铋材料的通式为BiSiOX<Sub>a</Sub>I<Sub>b</Sub>,其中,X=Cl或Br,0.5≤a≤2,0≤b≤1,其采用如下方法制得：以铋的无机盐为反应原料,以硅烷化低共溶溶剂或硅烷化离子液体为反应溶剂,将反应原料溶解于反应溶剂后,在pH为7~9下于70~80℃溶剂热反应18~24h,固液分离、洗涤、干燥后即得。本发明所制得的卤氧化硅铋材料比表面积大,吸附性能好,提升光生电子和空穴的分离效率,延长载流子的寿命,光催化活性高,氧化能力强,具有良好的稳定性和可重复利用性,可用于吸附催化去除环境水中多种内分泌干扰物,具有广泛的应用前景。(The invention provides a silicon-bismuth oxyhalide material and a preparation method and application thereof, wherein the general formula of the silicon-bismuth oxyhalide material is BiSiOX a I b Wherein X = Cl or Br, a is more than or equal to 0.5 and less than or equal to 2, and b is more than or equal to 0 and less than or equal to 1, and the catalyst is prepared by the following method: taking inorganic salt of bismuth as a reaction raw material, taking a silanized low co-solvent or silanized ionic liquid as a reaction solvent, dissolving the reaction raw material in the reaction solvent, carrying out solvothermal reaction for 18-24 h at 70-80 ℃ under the condition that the pH value is 7-9, and carrying out solid-liquid separation, washing and drying. The silicon-bismuth oxyhalide material prepared by the method has the advantages of large specific surface area, good adsorption performance, high photocatalytic activity, strong oxidation capacity and good photocatalytic activity, improves the separation efficiency of photo-generated electrons and holes, prolongs the service life of current carriers, and has the advantages of high photocatalytic activity and good oxidation capacityGood stability and reusability, can be used for adsorbing and catalyzing and removing various endocrine disruptors in environmental water, and has wide application prospect.)

1. The halogen-silicon oxide bismuth material is characterized in that the general formula is BiSiOX_aI_bWherein, X = Cl or Br, a is more than or equal to 0.5 and less than or equal to 2, and b is more than or equal to 0 and less than or equal to 1.

2. The bismuth silicon oxyhalide material of claim 1, wherein the morphology of the bismuth silicon oxyhalide material is flower-like.

3. The bismuth silicon oxyhalide material of claim 1, wherein the bismuth silicon oxyhalide material has a specific surface area of > 20m²/g。

4. The preparation method of the bismuth oxyhalide material as claimed in claim 1, wherein inorganic salt of bismuth is used as a reaction raw material, a silanized low co-solvent or silanized ionic liquid is used as a reaction solvent, the reaction raw material is dissolved in the reaction solvent, then the solvothermal reaction is carried out for 18-24 h at 70-80 ℃ under the pH value of 7-9, and the solid-liquid separation, washing and drying are carried out to obtain the bismuth oxyhalide material.

5. The method for preparing a bismuth silicon oxyhalide material as claimed in claim 4, wherein the inorganic salt of bismuth and KI are used as reaction raw materials.

6. The method for preparing the bismuth silicon oxyhalide material as claimed in claim 5, wherein the molar ratio of KI to the inorganic salt of bismuth is 0-1: 1.

7. The method for preparing the bismuth silicon oxyhalide material according to claim 4 or 5, wherein the hydrogen bond acceptor in the silanized low cosolvent comprises at least one of 1-allyl-3-silicopropyl triethoxy imidazole or 1-allyl-3- (triethoxy silicon) propyl imidazole chloride, the hydrogen bond donor comprises at least one of ethylene glycol or glycerol, and the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1: 2-4.

8. The method of preparing a bismuth silicon oxyhalide material according to claim 4 or 5, wherein the silanization ionic liquid is prepared by using a silanization reagent and imidazole, and the silanization reagent comprises (3-chloropropyl) trimethoxysilane, (3-bromopropyl) trimethoxysilane or (3-chloropropyl) triethoxysilane; the imidazole includes imidazole-1-acetic acid, 1-methylimidazole, 1-ethylimidazole or 1-allylimidazole.

9. The method of claim 4 or 5, wherein the molar ratio of the inorganic salt of bismuth to the reaction solvent is 1: 0.5-2.

10. Use of the bismuth oxyhalide material of claim 1 for photocatalysis.

Technical Field

The invention relates to a catalytic material, in particular to a silicon-bismuth oxyhalide material and a preparation method and application thereof.

Background

With the increasing environmental pollution, a large number of environmental endocrine disruptors are continuously released into the environment from human life and corresponding production processes. Although the concentration of endocrine disruptors in the environment is very low, the endocrine disruptors have the characteristics of difficult degradation, wide pollution range, durability and the like, can enter organisms through diet, contact and other ways, and have great influence on the living of the organisms and the health of human beings. Therefore, the monitoring and removal of environmental endocrine disruptors has become a priority in the current fields of health and hygiene and environmental science.

The photocatalytic degradation technology can decompose various organic matters which are difficult to degrade in a water body into small molecular organic matters which are easy to treat and further degrade, has the characteristics of high purification efficiency, small secondary pollution, high reaction speed, simplicity and convenience in operation and the like, and has a good application prospect in the field of efficient and green removal of endocrine disruptors. In recent years, photocatalytic materials have been the focus of research in material science, and common photocatalytic materials include metal oxides, metal sulfides, monocrystalline silicon, bismuthates, inorganic carbides, selenides, and the like. However, the commonly used photocatalytic materials have large band gap energy, only can utilize the ultraviolet light part in sunlight, and the utilization rate of the sunlight energy is less than 5%, so that the defect severely limits the application range of the photocatalytic materials. In order to solve the problem of low utilization rate of the existing photocatalytic material to sunlight, a novel semiconductor photocatalytic material with visible light response becomes one of the key points of research of researchers in recent years.

Disclosure of Invention

The invention aims to provide a silicon-bismuth oxyhalide material to solve the problems that the existing photocatalytic material is low in sunlight utilization rate and the photocatalytic performance needs to be improved.

The second purpose of the invention is to provide a preparation method of the silicon-bismuth oxyhalide material.

The invention also aims to provide an application of the silicon-bismuth oxyhalide material in photocatalysis.

One of the objects of the invention is achieved by:

a silicon-bismuth oxyhalide material with a general formula of BiSiOx_aI_bWherein, X = Cl or Br, a is more than or equal to 0.5 and less than or equal to 2, and b is more than or equal to 0 and less than or equal to 1.

The shape of the halogen silicon oxide bismuth material is a flower-like structure; preferably, the morphology of the bismuth silicon oxyhalide material is a flower-like structure formed by nano-sheets or nano-fibers.

Preferably, the specific surface area of the halogen silicon oxide bismuth material is more than 20m²/g。

The halogen silicon oxide bismuth material is prepared by the following method: taking inorganic salt of bismuth as a reaction raw material, taking a silanized low co-solvent or silanized ionic liquid as a reaction solvent, dissolving the reaction raw material in the reaction solvent, carrying out solvothermal reaction for 18-24 h at 70-80 ℃ under the condition that the pH value is 7-9, and carrying out solid-liquid separation, washing and drying.

Preferably, inorganic salts of bismuth and KI are used as reaction raw materials at the same time.

The inorganic salt of bismuth can be selected from inorganic bismuth salts commonly used in the field, and preferably, the inorganic salt of bismuth is bismuth nitrate.

The hydrogen bond acceptor in the silanization low cosolvent comprises at least one of 1-allyl-3-silicon propyl triethoxy imidazole or 1-allyl-3- (triethoxy silicon) propyl imidazole chloride, and the hydrogen bond donor comprises at least one of ethylene glycol or glycerol; the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1: 2-4.

The silanization ionic liquid is prepared from a silanization reagent and imidazole, wherein the silanization reagent comprises (3-chloropropyl) trimethoxy silane, (3-bromopropyl) trimethoxy silane or (3-chloropropyl) triethoxy silane and the like; the imidazole includes imidazole-1-acetic acid, 1-ethylimidazole, 1-allylimidazole, etc.

Preferably, the molar ratio of the inorganic salt of bismuth to the reaction solvent is 1: 0.5-2.

Preferably, the molar ratio of the KI to the inorganic salt of bismuth is 0-1: 1, and when the KI and the inorganic salt of bismuth are used as reaction raw materials, the molar ratio x of the KI to the inorganic salt of bismuth is within the range of 0< x < 1; preferably, the molar ratio of the KI to the inorganic salt of bismuth is 1-3: 3.

The second purpose of the invention is realized by the following steps:

a preparation method of a silicon-bismuth oxyhalide material comprises the steps of taking inorganic salt of bismuth as a reaction raw material, taking a silanized low-cosolvent solvent or a silanized ionic liquid as a reaction solvent, dissolving the reaction raw material in the reaction solvent, carrying out solvothermal reaction for 18-24 hours at 70-80 ℃ under the condition that the pH value is 7-9, carrying out solid-liquid separation, washing and drying to obtain the silicon-bismuth oxyhalide material.

Preferably, inorganic salts of bismuth and KI are used as reaction raw materials at the same time.

Preferably, the inorganic salt of bismuth may be selected from inorganic bismuth salts commonly used in the art, and preferably, the inorganic salt of bismuth is bismuth nitrate.

The hydrogen bond acceptor in the silanization low cosolvent comprises at least one of 1-allyl-3-silicon propyl triethoxy imidazole or 1-allyl-3- (triethoxy silicon) propyl imidazole chloride, and the hydrogen bond donor comprises at least one of ethylene glycol or glycerol; the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1: 2-4.

The silanization ionic liquid is prepared from a silanization reagent and imidazole, wherein the silanization reagent comprises at least one of (3-chloropropyl) trimethoxy silane, (3-bromopropyl) trimethoxy silane or (3-chloropropyl) triethoxy silane; the imidazole includes at least one of imidazole-1-acetic acid, 1-methylimidazole, 1-ethylimidazole, 1-allylimidazole, or the like.

Preferably, the molar ratio of the inorganic salt of bismuth to the reaction solvent is 1: 0.5-2; preferably 1: 1-2.

Preferably, the molar ratio of the KI to the inorganic salt of bismuth is 0-1: 1, and when the KI and the inorganic salt of bismuth are used as reaction raw materials, the molar ratio x of the KI to the inorganic salt of bismuth is within the range of 0< x < 1; preferably, the molar ratio of the KI to the inorganic salt of bismuth is 1-3: 3.

Specifically, adding inorganic salt of bismuth into a reaction solvent, stirring until the inorganic salt is fully dissolved, adjusting the pH to 7-9 by using ammonia water, ultrasonically removing air in the solution, and reacting for 18-24 hours at 70-80 ℃ by using a solvothermal reaction method under the protection of nitrogen.

Specifically, adding inorganic salt of bismuth into a reaction solvent, and stirring until the inorganic salt of bismuth is fully dissolved to obtain a solution A; adding KI into a reaction solvent, and stirring until the KI is fully dissolved to obtain a solution B; and fully mixing the solution A and the solution B, adjusting the pH value to 7-9 by adopting ammonia water, removing air in the solution by ultrasonic, and reacting for 18-24 hours at 70-80 ℃ by adopting a solvothermal reaction method under the protection of nitrogen.

The third purpose of the invention is realized by the following steps:

the silicon bismuth oxyhalide material is used as a photocatalyst and applied to photocatalysis, in particular to application of endocrine disruptors in photocatalytic degradation environment.

The method has the advantages that the specific solvent is adopted to synthesize the silicon-bismuth oxyhalide material, the method is simple, the condition is mild, the prepared silicon-bismuth oxyhalide material has large specific surface area and good adsorption performance, the separation efficiency of photo-generated electrons and holes is improved, the service life of carriers is prolonged, the photocatalytic activity is high, the oxidizing capability is strong, the stability and the reusability are good, the silicon-bismuth oxyhalide material can be used for adsorbing and catalyzing and removing various endocrine disruptors in environmental water, and the application prospect is wide.

Drawings

Fig. 1 is an XRD characterization pattern of the photocatalyst prepared in example 1 of the present invention.

FIG. 2 is an XPS characterization of the photocatalyst prepared in example 1 of the present invention.

FIG. 3 is an SEM photograph of a photocatalyst prepared in example 1 of the present invention.

FIG. 4 is a BET characterization plot of the photocatalyst prepared in example 1 of the present invention.

Fig. 5 is a XRD characterization contrast chart of the photocatalysts prepared in example 3 of the present invention and comparative example 3.

Fig. 6 is an XPS characterization contrast chart of photocatalysts prepared in examples 3 and 4 of the present invention.

FIG. 7 is a BET characterization plot of the photocatalyst of example 5 of the present invention.

FIG. 8 is an SEM representation of the photocatalyst of example 5 of the present invention.

FIG. 9 is a graph comparing the removal rate curves of forchlorfenuron in examples 1, 3 and 5 of the present invention and comparative examples 2 and 3.

FIG. 10 is a graph comparing the removal rate curves of the catalysts of examples 1 and 2 of the present invention and comparative example 1 for forchlorfenuron.

Detailed Description

The invention is further illustrated by the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention in any way.

Procedures and methods not described in detail in the following examples are conventional methods well known in the art, and the reagents used in the examples are either analytically or chemically pure and are either commercially available or prepared by methods well known to those of ordinary skill in the art. The following examples all achieve the objects of the present invention.