WO2020042125A1 - Lithium bismuthate-bismuth oxide photocatalytic material and preparation method thereof - Google Patents

Lithium bismuthate-bismuth oxide photocatalytic material and preparation method thereof Download PDF

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WO2020042125A1
WO2020042125A1 PCT/CN2018/103369 CN2018103369W WO2020042125A1 WO 2020042125 A1 WO2020042125 A1 WO 2020042125A1 CN 2018103369 W CN2018103369 W CN 2018103369W WO 2020042125 A1 WO2020042125 A1 WO 2020042125A1
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lithium
bismuth oxide
bismuth
libio
solution
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PCT/CN2018/103369
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French (fr)
Chinese (zh)
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黄彦林
刘宣宣
秦杰
魏东磊
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南通纺织丝绸产业技术研究院
苏州大学
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Priority to PCT/CN2018/103369 priority Critical patent/WO2020042125A1/en
Publication of WO2020042125A1 publication Critical patent/WO2020042125A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/18—Arsenic, antimony or bismuth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation

Definitions

  • Lithium bismuthate-bismuth oxide photocatalytic material and preparation method thereof Lithium bismuthate-bismuth oxide photocatalytic material and preparation method thereof
  • the present invention relates to an inorganic photocatalyst material and a preparation method thereof, and particularly to a heterojunction photocatalyst LiBiO 2 / Bi 2 0 3 for degrading organic pollutants and a preparation method thereof.
  • the invention belongs to the technical field of semiconductor material preparation.
  • Bismuth oxide (Bi 2 0 3 ) is widely used in gas sensors, solid oxide fuel cells, optical films, and ceramics because of its excellent properties such as high refractive index, high dielectric constant, and obvious photoluminescence characteristics. Glass manufacturing and other fields.
  • the bismuth oxide Bi 2 0 3 has five isomers of a (monoclinic), (3 (square), Y (body-centered cubic), 6 (face-centered cubic), and e (triclinic) phases. These five isomers Bulk properties vary, especially a-Bi 2 0 3 is a low-temperature phase with a wide absorption wavelength in the visible region (band gap 2.8 eV), and the valence band (VB) of Bi 2 0 3 has strong oxidizing properties. (Compared to the standard hydrogen electrode is 3.13 eV) and is non-toxic and harmless, so it has become a promising photocatalytic material, which can be used for photocatalytic decomposition of water and pollutants.
  • the main disadvantage of the single bismuth oxide Bi 2 0 3 is that the recombination rate of photo-generated electrons and holes is high, and the photocatalytic activity is low. Therefore, more and more researchers are working on the modification of Bi 2 0 3 to reduce the recombination of electrons and holes. In these modification studies, the emphasis is on establishing a heterojunction structure between Bi 2 0 3 and other semiconductors with similar band structures. In recent years, BiOCl / Bi 2 0 3 , BiOBr / Bi 2 0 3 , NaBiO 3 Heterojunction photocatalysts such as / Bi 2 0 3 and NaBiO 3 / BiOCl were synthesized.
  • the present invention provides a simple and easy preparation method, short synthesis period, good photocatalytic activity, and good performance in the visible light region.
  • Heterojunction photocatalyst LiBiO 2 / Bi 2 0 3 which can effectively degrade organic pollutants and its preparation method.
  • the technical solution adopted by the present invention is to provide a lithium bismuth oxide-bismuth oxide photocatalytic material, and bismuth oxide Bi 2 0 3 is supported on lithium bismuth oxide LiBiO 2
  • the technical solution of the present invention also provides a method for preparing a lithium bismuthate-bismuth oxide photocatalytic material, which adopts a hydrothermal method and includes the following steps:
  • the lithium ion Li + containing compound is lithium carbonate Li 2 C0 3, Li 2 lithium sulfate
  • the compound containing bismuth ion Bi 3+ is one of bismuth nitrate Bi (NO 3 ) r 5H 2 0 and bismuth chloride BiCl 3 ; the one containing bismuth ion Bi 3+
  • the molar amount of the compound is 2.2 to 2.6 times the molar amount of the compound containing lithium ion Li + .
  • a preferred solution of step (2) of the present invention is: the reaction temperature is 140 ⁇ 180 ° C, and the reaction time is 10 ⁇ 16 hours.
  • the prepared LiBi0 2 / Bi 2 0 3 photocatalyst has a pure phase, fine particles and uniform distribution, a heterojunction structure promotes the separation of photogenerated electrons and holes, broadens the spectral response range, and has good photocatalytic activity. .
  • the LiBi0 2 / Bi 2 0 3 photocatalyst is prepared from a wide range of raw materials, the preparation process is simple and easy to operate, the preparation conditions are mild and risk-free, the synthesis cycle is short, energy consumption and costs can be reduced, and the chemical properties of the samples prepared And stable optical performance.
  • the present invention is easy for industrial production and is environmentally friendly.
  • the LiBiO 2 / Bi 2 0 3 photocatalyst is a green and safe inorganic photocatalytic material.
  • FIG. 1 is an X-ray powder diffraction pattern of a LiBiO 2 / Bi 2 0 3 sample prepared in Example 1 of the present invention
  • FIG. 2 shows the SEN / ® of the LiBiO 2 / Bi 2 0 3 sample prepared in Example 1 of the present invention
  • FIG. 3 is an ultraviolet-visible absorption spectrum of a LiBiO 2 / Bi 2 0 3 sample prepared in Example 1 of the present invention
  • FIG. 4 is LiBiO 2 / Bi prepared in Example 1 of the present invention 203 samples degradation profile of organic dyes methylene blue in the light;
  • FIG. 5 is a kinetic curve diagram of the degradation of methylene blue dye by the LiBiO 2 / Bi 2 0 3 sample prepared in Example 1 of the present invention
  • FIG. 6 is an X-ray powder diffraction pattern of a LiBiO 2 / Bi 2 0 3 sample prepared in Example 4 of the present invention.
  • Example 7 is a SEN / ® of a LiBiO 2 / Bi 2 0 3 sample prepared in Example 4 of the present invention.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • FIG. 1 is an X-ray powder diffraction pattern of a sample prepared according to the technical solution of this embodiment.
  • XRD test results show that the prepared LiBiO 2 / Bi 2 0 3 crystals are better and appear in many places.
  • the diffraction peaks corresponding to the LiBiO 2 standard PDF card are shown, indicating the formation of the main crystal phase LiBiO 2 , and the incorporation of Bi 2 0 3 does not cause a significant shift of the diffraction peaks of LiBiO 2 , indicating that the Bi 2 0 3 phase exists alone. Without entering the LiBiO 2 lattice, the two form a heterostructure.
  • FIG. 2 it is a SEM (scanning electron microscope) spectrum of a sample LiBi0 2 / Bi 2 0 3 prepared according to the technical solution of this embodiment.
  • the obtained sample exhibits a lamellar distribution, and The sheet is thin and has good dispersion, which is beneficial to the separation of photo-generated carriers.
  • FIG. 3 it is an ultraviolet-visible absorption spectrum diagram of a sample LiBiO 2 / Bi 2 0 3 prepared according to the technical solution of this embodiment. As can be seen from the figure, the sample has absorption in the ultraviolet and visible light regions. This shows that the heterostructure broadens the spectral response range.
  • the sample LiBi0 2 / Bi 2 0 3 prepared in this example was used as a catalyst for photocatalytic degradation of methylene blue, and its activity was evaluated.
  • the light source lamp is a 500-watt cylindrical xenon lamp
  • the reaction tank uses a cylindrical photocatalytic reaction instrument made of borosilicate glass
  • the light source lamp is inserted into the reaction tank, and the condensed water is passed to cool down.
  • the temperature during the reaction was room temperature.
  • the dosage of the catalyst was 100 mg, the solution volume was 250 ml, and the concentration of methylene blue was 10 mg / liter.
  • the catalyst was placed in the reaction solution, and the catalytic time was set to 2400 minutes.
  • FIG. 4 it is a degradation curve of the organic dye methylene blue prepared by the sample LiBiO 2 / Bi 2 0 3 and a blank sample according to the technical solution of this embodiment.
  • the sample photocatalytically degrades methylene blue
  • the degradation rate reached 90% in 120 minutes, indicating that the prepared LiBiO 2 / Bi 2 0 3 material has good photocatalytic activity.
  • FIG. 5 it is a kinetic curve diagram of the degradation of methylene blue by the sample LiBiO 2 / Bi 2 0 3 prepared according to the technical solution of this embodiment. It can be seen from the figure that the sample photocatalytically degrades methylene blue. The kinetic rate constant is 0.02268 minutes- 1 .
  • Lithium sulfate Li 2 SO 4 was magnetically stirred at room temperature for 30 minutes and dissolved in 20 ml of deionized water until it was completely transparent. It was recorded as solution A.
  • Bismuth nitrate Bi ( NO 3 ) 3 -5H 2 0 was dissolved in 20 ml of nitric acid by magnetic stirring at 90 ° C until it was completely transparent and recorded as solution B.
  • phase structure, SEM spectrum, ultraviolet-visible absorption spectrum, degradation rate of methylene blue, and kinetic curve of methylene blue degradation of the sample prepared in this example are similar to those in Example 1.
  • Lithium carbonate Li 2 CO 3 was magnetically stirred at room temperature for 30 minutes and dissolved in 20 ml of nitric acid until completely penetrated. Ming, referred to as A solution, bismuth chloride (: 13 to 80 ° (: were dissolved under magnetic stirring in 20 ml of nitric acid, until completely transparent, as B solution.
  • phase structure, SEM spectrum, UV-visible absorption spectrum, degradation rate of methylene blue, and kinetic curve of methylene blue degradation of the sample prepared in this example are similar to those in Example 1.
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • Lithium carbonate Li 2 CO 3 was magnetically stirred at room temperature for 30 minutes and dissolved in 20 ml of nitric acid until it was completely transparent. Recorded as A solution.
  • Bismuth nitrate Bi (N0 3 ) R 5H 2 0 was dissolved in 20 ml of nitric acid with magnetic stirring at 60 ° C until it was completely transparent and recorded as solution B.
  • FIG. 6 is an X-ray powder diffraction pattern of a sample prepared according to the technical solution of this embodiment.
  • XRD test results show that the prepared LiBiO 2 / Bi 2 0 3 crystals are better and appear in many places.
  • a diffraction peak corresponding to 2 LiBiO standard PDF card described main crystalline phase formed LiBiO 2 while, Bi incorporated 203 did not cause significant diffraction peaks shift LiBiO 2, 203 Description of Bi phase alone Without entering the LiBiO 2 lattice, the two form a heterostructure.
  • Example 7 is a SEM (scanning electron microscope) spectrum of a sample LiBi0 2 / Bi 2 0 3 prepared according to the technical solution of this embodiment. As can be seen from the figure, the obtained sample exhibits a lamellar distribution. Moreover, the sheet is thin and has good dispersibility, which is beneficial to the separation of photo-generated carriers. [0047] The UV-visible absorption spectrum, the degradation rate of methylene blue, and the kinetic curve of methylene blue degradation of the prepared sample were similar to those of Example 1.
  • lithium sulfate Li 2 SO 4 was weighed : 0.003 mol (0.3298 g), and bismuth chloride BiCl 3 was 4 mol of lithium sulfate Li 2 SO The amount is 2.48 times: 0.00744 mol (2.3461 g); Lithium sulfate Li 2 SO 4 is magnetically stirred at room temperature for 30 minutes and dissolved in 20 ml of deionized water until it is completely transparent. It is recorded as solution A, and bismuth chloride (: 1 3 Dissolve in 20 ml of nitric acid with magnetic stirring at 60 ° (:) until it is completely transparent, and record it as solution B.
  • phase structure and SEM spectrum of the sample prepared in this example are similar to those in Example 4.
  • the ultraviolet-visible absorption spectrum, the degradation rate of methylene blue, and the kinetic curve of methylene blue degradation are similar to those in Example 1.
  • Embodiment 6 is a diagrammatic representation of Embodiment 6
  • the phase structure and SEM spectrum of the sample provided in this example are similar to those in Example 4.
  • the ultraviolet-visible absorption spectrum, the degradation rate of methylene blue, and the kinetic curve of methylene blue degradation are similar to those in Example 1.
  • the LiBi0 2 / Bi 2 0 3 heterojunction powder is prepared by a hydrothermal method. The preparation method is simple and easy, and the synthesis period is short. Using the product as a photocatalyst, broadens the spectral response range through a heterostructure, reduces the photo-generated electron-hole recombination rate, has good light absorption in the visible light region, can effectively degrade organic pollutants, and has broad application prospects .

Abstract

A lithium bismuthate-bismuth oxide photocatalytic material and a preparation method thereof, relating to the technical field of inorganic photocatalytic materials. The surface of lithium bismuthate (LiBiO2) is loaded with bismuth oxide (Bi2O3), and an interface of two phases form a heterostructure; wherein a mole ratio of the LiBiO2 to the Bi2O3 is 1:(0.05-0.15). LiBiO2/Bi2O3 heterojunction powder is prepared by means of a hydrothermal method. The preparation method is simple, feasible and short in synthetic period and the prepared material is uniform in particle size distribution, high in purity and good in chemical stability. The product is used as a photocatalyst, can broaden a spectral response range by means of the heterostructure, reduces the recombination rate of photoproduced electrons and holes, shows good light absorption capability in a visible light zone, can effectively degrade organic pollutants, and has a broad application prospect.

Description

一种铋酸锂 -氧化铋光催化材料及其制备方法 技术领域  Lithium bismuthate-bismuth oxide photocatalytic material and preparation method thereof
[0001] 本发明涉及一种无机光催化剂材料及其制备方法， 特别涉及一种用于降解有机 污染物的异质结光催化剂 LiBiO 2/Bi 20 3及其制备方法。 属于半导体材料制备技 术领域。 [0001] The present invention relates to an inorganic photocatalyst material and a preparation method thereof, and particularly to a heterojunction photocatalyst LiBiO 2 / Bi 2 0 3 for degrading organic pollutants and a preparation method thereof. The invention belongs to the technical field of semiconductor material preparation.
背景技术  Background technique
[0002] 高效可见光光催化剂的制备是光催化研究的重要课题之一。 近年来， 各种形貌 和表面结构的光催化剂的制备受到了广泛的关注。 TiO 2作为传统的光催化剂由 于其带隙较宽， 只能吸收波长小于 380纳米的光， 对光的利用效率低。 光催化剂 的光吸收特性对其光催化效率起着重要的作用。 因此， 研究可吸收可见光的光 催化剂至关重要， 以便能够利用太阳光谱的主要部分并实现光催化剂的室内应 用。 [0002] The preparation of highly efficient visible light photocatalysts is one of the important topics in photocatalysis research. In recent years, the preparation of photocatalysts with various morphologies and surface structures has received widespread attention. TiO 2 as a conventional photocatalyst because of its wide band gap, can only absorb light wavelengths less than 380 nm, light utilization efficiency is low. The light absorption characteristics of photocatalysts play an important role in their photocatalytic efficiency. Therefore, it is important to study a photocatalyst that can absorb visible light so that a major part of the solar spectrum can be utilized and indoor applications of the photocatalyst can be realized.
[0003] 氧化铋 （Bi 20 3） 因其具有高折射率、 高介电常数、 明显的光致发光特性等优 异性能而被广泛应用于气体传感器、 固体氧化物燃料电池、 光学薄膜、 陶瓷玻 璃制造等领域。 氧化铋 Bi 20 3具有 a （单斜） 、 （3 （四方） 、 Y （体心立方） 、 6 （ 面心立方） 和 e （三斜） 相五种异构体。 这五种异构体的性能各异， 特别是 a-Bi 2 0 3为低温相， 在可见光区 （带隙 2.8 eV） 具有很宽的吸收波长， Bi 20 3 的价带 （VB） 空穴具有强氧化性 （相对于标准氢电极为 3.13 eV） 而本身又无毒 无害， 因此， 成为一种很有前途的光催化材料， 可用于光催化分解水和污染物 的降解。 [0003] Bismuth oxide (Bi 2 0 3 ) is widely used in gas sensors, solid oxide fuel cells, optical films, and ceramics because of its excellent properties such as high refractive index, high dielectric constant, and obvious photoluminescence characteristics. Glass manufacturing and other fields. The bismuth oxide Bi 2 0 3 has five isomers of a (monoclinic), (3 (square), Y (body-centered cubic), 6 (face-centered cubic), and e (triclinic) phases. These five isomers Bulk properties vary, especially a-Bi 2 0 3 is a low-temperature phase with a wide absorption wavelength in the visible region (band gap 2.8 eV), and the valence band (VB) of Bi 2 0 3 has strong oxidizing properties. (Compared to the standard hydrogen electrode is 3.13 eV) and is non-toxic and harmless, so it has become a promising photocatalytic material, which can be used for photocatalytic decomposition of water and pollutants.
[0004] 但是， 单一氧化铋 Bi 20 3存在的最主要不足是光生电子和空穴的复合率高， 光 催化活性低。 因此， 越来越多的研究者致力于 Bi 20 3的改性以减少电子和空穴的 复合。 在这些改性研究中， 重点在于建立 Bi 20 3与其他具有相似能带结构的半导 体之间的异质结结构， 近年来， BiOCl/Bi 20 3 , BiOBr/Bi 20 3, NaBiO 3/Bi 20 3 ， NaBiO 3/BiOCl等异质结光催化剂被合成， 结果表明， 复合后的光催化剂能有 效的抑制光生电子-空穴的再复合， 大大提高光催化活性。 但目前异质结光催化 剂的合成方法复杂， 且制备周期长。 [0004] However, the main disadvantage of the single bismuth oxide Bi 2 0 3 is that the recombination rate of photo-generated electrons and holes is high, and the photocatalytic activity is low. Therefore, more and more researchers are working on the modification of Bi 2 0 3 to reduce the recombination of electrons and holes. In these modification studies, the emphasis is on establishing a heterojunction structure between Bi 2 0 3 and other semiconductors with similar band structures. In recent years, BiOCl / Bi 2 0 3 , BiOBr / Bi 2 0 3 , NaBiO 3 Heterojunction photocatalysts such as / Bi 2 0 3 and NaBiO 3 / BiOCl were synthesized. The results show that the photocatalysts after recombination can effectively inhibit the recombination of photogenerated electrons and holes, and greatly improve the photocatalytic activity. Heterojunction photocatalysis The synthetic method of the agent is complicated, and the preparation cycle is long.
发明概述  Summary of invention
技术问题  technical problem
问题的解决方案  Problem solution
技术解决方案  Technical solutions
[0005] 本发明针对现有制备 Bi 20 3改性异质结结构光催化材料存在的不足， 提供一种 制备方法简单易行， 合成周期短， 且光催化活性好、 在可见光区具有良好的光 吸收能力， 能有效降解有机污染物的异质结光催化剂 LiBiO 2/Bi 20 3及其制备方 法。 [0005] In view of the shortcomings of the existing preparation of Bi 2 0 3 modified heterojunction structure photocatalytic materials, the present invention provides a simple and easy preparation method, short synthesis period, good photocatalytic activity, and good performance in the visible light region. Heterojunction photocatalyst LiBiO 2 / Bi 2 0 3 which can effectively degrade organic pollutants and its preparation method.
[0006] 为达到以上发明目的， 本发明采用的技术方案是提供一种铋酸锂 -氧化铋光催 化材料， 氧化铋 Bi 20 3负载于铋酸锂 LiBiO 2 [0006] In order to achieve the above object of the invention, the technical solution adopted by the present invention is to provide a lithium bismuth oxide-bismuth oxide photocatalytic material, and bismuth oxide Bi 2 0 3 is supported on lithium bismuth oxide LiBiO 2
表面， 两种相界面形成异质结构； LiBi0 2和 Bi 20 3的摩尔比为 1: (0.05〜 0.15) Surface, the two phases formed heterostructure interface; LiBi0 2 and Bi 2 0 3 molar ratio of 1: (0.05~ 0.15)
[0007] 本发明技术方案还提供一种铋酸锂 -氧化铋光催化材料的制备方法， 采用水热 法， 包括如下步骤： [0007] The technical solution of the present invention also provides a method for preparing a lithium bismuthate-bismuth oxide photocatalytic material, which adopts a hydrothermal method and includes the following steps:
[0008] ( 1) 按 LiBi0 2和 Bi 20 3的摩尔比为 1: (0.05〜 0.15) ， 分别称取含有锂离子 Li[0008] (1) by LiBi0 2 and Bi 2 0 3 molar ratio of 1: (0.05~ 0.15), were weighed containing lithium ions Li
+的化合物和含有铋离子 Bi 3+的化合物； 将含有锂离子 Li +的化合物溶解于硝酸中 或去离子水中， 室温、 搅拌条件下， 得到无色透明溶液 A; 将含有铋离子 Bi 3+的 化合物溶解于硝酸中， 在温度为 60〜 90°C、 搅拌条件下， 得到无色透明溶液 B ; + Compounds and bismuth ion-containing Bi 3+ compounds; compounds containing lithium ions Li + are dissolved in nitric acid or deionized water, and a colorless transparent solution A is obtained at room temperature under stirring conditions; bismuth ion-containing Bi 3+ The compound was dissolved in nitric acid, at a temperature of 60 to 90 ° C, under stirring conditions to obtain a colorless transparent solution B;
[0009] (2) 在室温、 搅拌条件下， 将溶液 A和溶液 B缓慢混合， 再置于反应釜中， 在 温度为 120〜 200°C的条件下反应 8〜 18小时后， 自然冷却至室温； [0009] (2) Slowly mix solution A and solution B at room temperature and under stirring, and then put them in a reaction kettle, and react for 8 to 18 hours at a temperature of 120 to 200 ° C, and then naturally cool to Room temperature
[0010] (3) 将冷却后的产物充分洗涤， 再置于温度为 60〜 80°C的烘箱中烘干， 得到 一种 LiBiO 2/Bi 20 3异质结光催化材料。 [0010] (3) The cooled product is fully washed and then dried in an oven at a temperature of 60 to 80 ° C. to obtain a LiBiO 2 / Bi 2 0 3 heterojunction photocatalytic material.
[0011] 本发明技术方案所述的含有锂离子 Li +的化合物为碳酸锂 Li 2C0 3、 硫酸锂 Li 2 [0011] aspect of the present invention, the lithium ion Li + containing compound is lithium carbonate Li 2 C0 3, Li 2 lithium sulfate
SO 4中的一种； 所述的含有铋离子 Bi 3+的化合物为硝酸铋 Bi(NO 3) r5H 20、 氯化 铋 BiCl 3中的一种； 所述含有铋离子 Bi 3+的化合物的摩尔量为含有锂离子 Li +的化 合物的摩尔量的 2.2〜 2.6倍。 One of SO 4 ; the compound containing bismuth ion Bi 3+ is one of bismuth nitrate Bi (NO 3 ) r 5H 2 0 and bismuth chloride BiCl 3 ; the one containing bismuth ion Bi 3+ The molar amount of the compound is 2.2 to 2.6 times the molar amount of the compound containing lithium ion Li + .
[0012] 本发明步骤 (2) 的一个优选方案是： 反应温度为 140〜 180°C， 反应时间为 10 〜 16小时。 [0012] A preferred solution of step (2) of the present invention is: the reaction temperature is 140 ~ 180 ° C, and the reaction time is 10 ~ 16 hours.
发明的有益效果  The beneficial effects of the invention
有益效果  Beneficial effect
[0013] 与现有技术方案相比， 本发明技术方案的优点在于：  [0013] Compared with the prior art solutions, the technical solutions of the present invention have the following advantages:
[0014] 1 . 制备的 LiBi0 2/Bi 20 3光催化剂物相纯， 颗粒细小且分布均匀， 异质结结构 促进了光生电子-空穴的分离， 拓宽了光谱响应范围， 光催化活性好。 [0014] 1. The prepared LiBi0 2 / Bi 2 0 3 photocatalyst has a pure phase, fine particles and uniform distribution, a heterojunction structure promotes the separation of photogenerated electrons and holes, broadens the spectral response range, and has good photocatalytic activity. .
[0015] 2. 制备的 LiBi0 2/Bi 20 3光催化剂的原材料来源广泛， 制备的过程简单易于操 作， 制备条件温和无风险， 合成周期短， 可降低能耗和成本， 制备的样品化学 性质和光学性能稳定。 [0015] 2. The LiBi0 2 / Bi 2 0 3 photocatalyst is prepared from a wide range of raw materials, the preparation process is simple and easy to operate, the preparation conditions are mild and risk-free, the synthesis cycle is short, energy consumption and costs can be reduced, and the chemical properties of the samples prepared And stable optical performance.
[0016] 3 . 本发明易于工业化生产， 对环境友好， LiBiO 2/Bi 20 3光催化剂是一种绿色 安全的无机光催化材料。 [0016] 3. The present invention is easy for industrial production and is environmentally friendly. The LiBiO 2 / Bi 2 0 3 photocatalyst is a green and safe inorganic photocatalytic material.
对附图的简要说明  Brief description of the drawings
附图说明  BRIEF DESCRIPTION OF THE DRAWINGS
[0017] 图 1为本发明实施例 1所制得的 LiBiO 2/Bi 20 3样品的 X射线粉末衍射图谱；[0017] FIG. 1 is an X-ray powder diffraction pattern of a LiBiO 2 / Bi 2 0 3 sample prepared in Example 1 of the present invention;
[0018] 图 2为本发明实施例 1所制得的 LiBiO 2/Bi 20 3样品的 SEN/® ; [0018] FIG. 2 shows the SEN / ® of the LiBiO 2 / Bi 2 0 3 sample prepared in Example 1 of the present invention;
[0019] 图 3为本发明实施例 1所制得的 LiBiO 2/Bi 20 3样品的紫外 -可见吸收光谱图； [0020] 图 4为本发明实施例 1所制得的 LiBiO 2/Bi 20 3样品在光照时对有机染料亚甲基蓝 的降解曲线； 3 is an ultraviolet-visible absorption spectrum of a LiBiO 2 / Bi 2 0 3 sample prepared in Example 1 of the present invention; [0020] FIG. 4 is LiBiO 2 / Bi prepared in Example 1 of the present invention 203 samples degradation profile of organic dyes methylene blue in the light;
[0021] 图 5为本发明实施例 1所制得的 LiBiO 2/Bi 20 3样品降解亚甲基蓝染料的动力学曲 线图； [0021] FIG. 5 is a kinetic curve diagram of the degradation of methylene blue dye by the LiBiO 2 / Bi 2 0 3 sample prepared in Example 1 of the present invention;
[0022] 图 6为本发明实施例 4所制得的 LiBiO 2/Bi 20 3样品的 X射线粉末衍射图谱；[0022] FIG. 6 is an X-ray powder diffraction pattern of a LiBiO 2 / Bi 2 0 3 sample prepared in Example 4 of the present invention;
[0023] 图 7为本发明实施例 4所制得的 LiBiO 2/Bi 20 3样品的 SEN/®。 7 is a SEN / ® of a LiBiO 2 / Bi 2 0 3 sample prepared in Example 4 of the present invention.
发明实施例  Invention Examples
本发明的实施方式  Embodiments of the invention
[0024] 下面结合附图和实施例对本发明技术方案作进一步描述。  [0024] The technical solution of the present invention is further described below with reference to the accompanying drawings and embodiments.
[0025] 实施例 1 :  [0025] Embodiment 1:
[0026] 按 LiBiO 2和 20 3摩尔比 1:0.05， 分别称取碳酸锂 Li 2CO 3: 0.004mol (0.2956 克） ， 硝酸铋 Bi（N0 3）r5H 20: 0.0088mol （4.2686克） ， 为碳酸锂 Li 2C0 3摩尔 量的 2.2倍； 将碳酸锂 Li 2CO 3于室温下磁力搅拌 30分钟溶解于 20毫升硝酸中， 直 至完全透明， 记为 A溶液， 将硝酸铋 Bi（N0 3）r5H 20于 60°C条件下磁力搅拌溶解 于 20毫升硝酸中， 直至完全透明， 记为 B溶液。 [0026] Press LiBiO 2 and 203 molar ratio of 1: 0.05, were weighed lithium carbonate Li 2 CO 3: 0.004mol (0.2956 G), Bi (N0 3 ) r 5H 2 0 : 0.0088 mol (4.2686 g), which is 2.2 times the molar amount of lithium carbonate Li 2 C0 3 ; Lithium carbonate Li 2 CO 3 was magnetically stirred at room temperature for 30 minutes to dissolve Dissolve in 20 ml of nitric acid until it is completely transparent and record it as solution A. Dissolve bismuth nitrate Bi (N0 3 ) r 5H 2 0 in 20 ml of nitric acid with magnetic stirring at 60 ° C until it is completely transparent and record it as solution B. .
[0027] 将上述 A溶液用滴管慢慢转移到 B溶液中使两种溶液混合， 再加入 20毫升的去 离子水， 在室温下磁力搅拌 30分钟使之充分混合， 记为 C溶液。 将 C溶液转移到 1 00毫升聚四氟乙烯高温反应釜中， 置于鼓风干燥箱中 140。（：恒温反应 16小时。 冷 却至室温后取出反应溶液用去离子水和无水乙醇交替洗涤充分后， 再置于干燥 箱中 60°C烘干， 随后取出即得到 LiBiO 2/Bi 20 3异质结光催化剂。 [0027] The above solution A was slowly transferred into the solution B with a dropper to mix the two solutions, and then 20 ml of deionized water was added, and the mixture was magnetically stirred at room temperature for 30 minutes to be thoroughly mixed, and recorded as solution C. The C solution was transferred to a 100 ml polytetrafluoroethylene high temperature reactor and placed in a blast drying oven 140. (: Constant temperature reaction for 16 hours. After cooling to room temperature, take out the reaction solution, wash it with deionized water and absolute ethanol alternately, and then place it in a dry box at 60 ° C to dry. Then take out to get LiBiO 2 / Bi 2 0 3 Heterojunction Photocatalyst.
[0028] 参见附图 1， 它是按本实施例技术方案所制备样品的 X射线粉末衍射图谱， XR D测试结果显示， 所制备的 LiBiO 2/Bi 20 3结晶较好， 在多处出现了对应于 LiBiO 2 标准 PDF卡片的衍射峰， 说明主体晶相 LiBiO 2的形成， 同时， Bi 20 3的掺入没有 造成 LiBiO 2衍射峰的明显偏移， 说明 Bi 20 3物相单独存在， 没有进入 LiBiO 2晶格 ， 二者形成异质结构。 [0028] Referring to FIG. 1, which is an X-ray powder diffraction pattern of a sample prepared according to the technical solution of this embodiment. XRD test results show that the prepared LiBiO 2 / Bi 2 0 3 crystals are better and appear in many places. The diffraction peaks corresponding to the LiBiO 2 standard PDF card are shown, indicating the formation of the main crystal phase LiBiO 2 , and the incorporation of Bi 2 0 3 does not cause a significant shift of the diffraction peaks of LiBiO 2 , indicating that the Bi 2 0 3 phase exists alone. Without entering the LiBiO 2 lattice, the two form a heterostructure.
[0029] 参见附图 2， 它是按本实施例技术方案所制备样品 LiBi0 2/Bi 20 3 SEM （扫描 电子显微镜） 图谱， 从图中可以看出， 所得样品呈现片层状分布， 且片层较薄 ， 分散性较好， 有利于光生载流子的分离。 [0029] Referring to FIG. 2, it is a SEM (scanning electron microscope) spectrum of a sample LiBi0 2 / Bi 2 0 3 prepared according to the technical solution of this embodiment. As can be seen from the figure, the obtained sample exhibits a lamellar distribution, and The sheet is thin and has good dispersion, which is beneficial to the separation of photo-generated carriers.
[0030] 参见附图 3， 它是按本实施例技术方案所制备样品 LiBiO 2/Bi 20 3的紫外-可见吸 收光谱图， 从图中可以看出， 该样品在紫外及可见光区域有吸收， 说明异质结 构拓宽了光谱响应范围。 [0030] Referring to FIG. 3, it is an ultraviolet-visible absorption spectrum diagram of a sample LiBiO 2 / Bi 2 0 3 prepared according to the technical solution of this embodiment. As can be seen from the figure, the sample has absorption in the ultraviolet and visible light regions. This shows that the heterostructure broadens the spectral response range.
[0031] 以本实施例制备的样品 LiBi0 2/Bi 20 3为催化剂， 用于光催化降解亚甲基蓝， 并 对其活性进行评价。 采用自制光催化反应装置， 光源灯为 500瓦圆柱形形氙灯， 反应槽使用硼硅酸玻璃制成的圆柱形光催化反应仪器， 将光源灯***到反应槽 中， 并通入冷凝水降温， 反应时温度为室温。 催化剂用量 100毫克， 溶液体积 25 0毫升， 亚甲基蓝的浓度为 10毫克 /升。 催化剂置于反应液中， 催化时间设定为 24 0分钟， 打开冷凝水后开始光照， 光照后每隔一段时间取一次样， 离心， 取其上 清液， 用紫外-可见分光光度计在波长 664〜 666纳米处测定亚甲基蓝溶液的吸光 度。 根据朗伯 -比尔定律， 溶液的吸光度与浓度成正比， 因此， 可用吸光度代替 浓度计算去除率， 以此为亚甲基蓝溶液的去除率。 计算公式： 降解率 =（1-C/C Q ）xlOO%=（l-A/A 0）xlOO% , 其中， C Q、 C分别为光催化降解前后的浓度， A。、 A 分别是降解前后的吸光度值。 [0031] The sample LiBi0 2 / Bi 2 0 3 prepared in this example was used as a catalyst for photocatalytic degradation of methylene blue, and its activity was evaluated. Using a self-made photocatalytic reaction device, the light source lamp is a 500-watt cylindrical xenon lamp, the reaction tank uses a cylindrical photocatalytic reaction instrument made of borosilicate glass, the light source lamp is inserted into the reaction tank, and the condensed water is passed to cool down. The temperature during the reaction was room temperature. The dosage of the catalyst was 100 mg, the solution volume was 250 ml, and the concentration of methylene blue was 10 mg / liter. The catalyst was placed in the reaction solution, and the catalytic time was set to 2400 minutes. After the condensation water was turned on, the light was started. After the light was taken, samples were taken at regular intervals, centrifuged, and the supernatant was taken. The absorbance of the methylene blue solution was measured at 664 to 666 nm. According to Lambert-Beer's law, the absorbance of a solution is proportional to the concentration, so the absorbance can be used instead The removal rate was calculated as the concentration, and this was the removal rate of the methylene blue solution. Calculation formula: Degradation rate = (1-C / C Q ) x 100% = (lA / A 0 ) x 100%, where C Q and C are the concentrations before and after photocatalytic degradation, respectively, A. And A are the absorbance values before and after degradation, respectively.
[0032] 参见附图 4， 它是按本实施例技术方案所制备样品 LiBiO 2/Bi 20 3和空白样对有 机染料亚甲基蓝的降解曲线， 从图中可以看出， 该样品光催化降解亚甲基蓝的 降解率 120分钟达到 90%， 说明制备出的 LiBiO 2/Bi 20 3材料具有良好的光催化活 性。 [0032] Referring to FIG. 4, it is a degradation curve of the organic dye methylene blue prepared by the sample LiBiO 2 / Bi 2 0 3 and a blank sample according to the technical solution of this embodiment. As can be seen from the figure, the sample photocatalytically degrades methylene blue The degradation rate reached 90% in 120 minutes, indicating that the prepared LiBiO 2 / Bi 2 0 3 material has good photocatalytic activity.
[0033] 参见附图 5， 它是按本实施例技术方案所制备样品 LiBiO 2/Bi 20 3降解亚甲基蓝 的动力学曲线图， 从图中可以看出， 该样品光催化降解亚甲基蓝的表观动力学 速率常数为 0.02268分钟 -1。 [0033] Referring to FIG. 5, it is a kinetic curve diagram of the degradation of methylene blue by the sample LiBiO 2 / Bi 2 0 3 prepared according to the technical solution of this embodiment. It can be seen from the figure that the sample photocatalytically degrades methylene blue. The kinetic rate constant is 0.02268 minutes- 1 .
[0034] 实施例 2:  Example 2:
[0035] 按 LiBiO 2和 20 3摩尔比 1:0.07， 分别称取硫酸锂 Li 2SO 4: 0.004mol （0.4398克 ） ， 硝酸铋 Bi（NO 3） r5H 20 （为硫酸锂 Li 2S0 4 [0035] Press LiBiO 2 and 203 molar ratio of 1: 0.07, respectively, said lithium Sulfate Li 2 SO 4: 0.004mol (0.4398 g), bismuth nitrate Bi (NO 3) r 5H 2 0 ( lithium sulfate Li 2 S0 4
摩尔量的 2.28倍） ： 0.00912mol （4.4238克） ； 将硫酸锂 Li 2SO 4于室温下磁力搅 拌 30分钟溶解于 20毫升去离子水中， 直至完全透明， 记为 A溶液， 将硝酸铋 Bi（N O 3） 3-5H 20于 90°C条件下磁力搅拌溶解于 20毫升硝酸中， 直至完全透明， 记为 B 溶液。 2.28 times the molar amount): 0.00912 mol (4.4238 g); Lithium sulfate Li 2 SO 4 was magnetically stirred at room temperature for 30 minutes and dissolved in 20 ml of deionized water until it was completely transparent. It was recorded as solution A. Bismuth nitrate Bi ( NO 3 ) 3 -5H 2 0 was dissolved in 20 ml of nitric acid by magnetic stirring at 90 ° C until it was completely transparent and recorded as solution B.
[0036] 将上述 A溶液用滴管慢慢转移到 B溶液中使两种溶液混合， 再加入 20毫升的去 离子水， 在室温下磁力搅拌 30分钟使之充分混合， 记为 C溶液。 将 C溶液转移到 1 00毫升的聚四氟乙烯高温反应釜中， 置于鼓风干燥箱中 140。（：恒温反应 10小时。 冷却至室温后取出反应溶液用去离子水和无水乙醇交替洗涤充分后， 再置于干 燥箱中 70°C烘干， 随后取出即得到 LiBiO 2/Bi 20 3异质结光催化剂。 [0036] The above solution A was slowly transferred to the solution B with a dropper to mix the two solutions, and then 20 ml of deionized water was added, and the mixture was magnetically stirred at room temperature for 30 minutes to be thoroughly mixed, and recorded as solution C. The C solution was transferred to a 100 ml polytetrafluoroethylene high temperature reactor and placed in a blast drying oven 140. (: Constant temperature reaction for 10 hours. After cooling to room temperature, take out the reaction solution and wash it with deionized water and absolute ethanol alternately. Then, place it in a drying box at 70 ° C and dry it. Then take it out to obtain LiBiO 2 / Bi 2 0 3 Heterojunction Photocatalyst.
[0037] 本实施例制备得到的样品的物相结构、 SEM图谱、 紫外-可见吸收光谱、 对亚 甲基蓝的降解率和降解亚甲基蓝的动力学曲线与实施例 1相似。  [0037] The phase structure, SEM spectrum, ultraviolet-visible absorption spectrum, degradation rate of methylene blue, and kinetic curve of methylene blue degradation of the sample prepared in this example are similar to those in Example 1.
[0038] 实施例 3:  Example 3:
[0039] 按 LiBiO 2和 20 3摩尔比 1:0.09， 分别称取碳酸锂 Li 2CO 3: 0.004mol （0.2956 克） ， 氯化铋 BiCl 3为碳酸锂 Li 2CO 3摩尔量的 2.36倍： 0.00944mol （2.9768克）[0039] Press LiBiO 2 and 203 molar ratio of 1: 0.09, were weighed lithium carbonate Li 2 CO 3: 0.004mol (0.2956 g), bismuth chloride BiCl 3 times 2 CO 3 2.36 molar amount of lithium carbonate Li : 0.00944mol (2.9768g)
； 将碳酸锂 Li 2CO 3于室温下磁力搅拌 30分钟溶解于 20毫升硝酸中， 直至完全透 明， 记为 A溶液， 将氯化铋 （：1 3于80°（：条件下磁力搅拌溶解于 20毫升硝酸中， 直至完全透明， 记为 B溶液。 ; Lithium carbonate Li 2 CO 3 was magnetically stirred at room temperature for 30 minutes and dissolved in 20 ml of nitric acid until completely penetrated. Ming, referred to as A solution, bismuth chloride (: 13 to 80 ° (: were dissolved under magnetic stirring in 20 ml of nitric acid, until completely transparent, as B solution.
[0040] 将上述 A溶液用滴管慢慢转移到 B溶液中使两种溶液混合， 再加入 20毫升的去 离子水， 在室温下磁力搅拌 30分钟使之充分混合， 记为 C溶液。 将 C溶液转移到 1 00毫升的聚四氟乙烯高温反应釜中， 置于鼓风干燥箱中 160。（：恒温反应 13小时。 冷却至室温后取出反应溶液用去离子水和无水乙醇交替洗涤充分后， 再置于干 燥箱中 80°C烘干， 随后取出即得到 LiBiO 2/Bi 20 3异质结光催化剂。 [0040] The above solution A was slowly transferred to the solution B with a dropper to mix the two solutions, and then 20 ml of deionized water was added, and the mixture was magnetically stirred at room temperature for 30 minutes to be thoroughly mixed, and recorded as solution C. The C solution was transferred to a 100 ml polytetrafluoroethylene high-temperature reactor and placed in a blast drying oven 160. (: Constant temperature reaction for 13 hours. After cooling to room temperature, take out the reaction solution and wash it with deionized water and absolute ethanol alternately. Then dry it in a drying box at 80 ° C and take it out to obtain LiBiO 2 / Bi 2 0 3 Heterojunction Photocatalyst.
[0041] 本实施例制备得到的样品的物相结构、 SEM图谱、 紫外-可见吸收光谱、 对亚 甲基蓝的降解率和降解亚甲基蓝的动力学曲线与实施例 1相似。  [0041] The phase structure, SEM spectrum, UV-visible absorption spectrum, degradation rate of methylene blue, and kinetic curve of methylene blue degradation of the sample prepared in this example are similar to those in Example 1.
[0042] 实施例 4:  Embodiment 4:
[0043] 按1^ 10 2和：81 20 3摩尔比1:0.10， 分别称取碳酸锂 Li 2CO 3: 0.003mol （0.2217 克） ， 硝酸铋 Bi（NO 3） r5H 20为碳酸锂 Li 2CO 3 [0043] According to 1 ^ 10 2 and: 81 2 0 3 molar ratio of 1: 0.10, lithium carbonate Li 2 CO 3: 0.003 mol (0.2217 g) was weighed, and bismuth nitrate Bi (NO 3 ) r 5H 2 0 was carbonic acid. Li 2 CO 3
摩尔量的 2.4倍： 0.0072mol （3.4925克） ， 将碳酸锂 Li 2CO 3于室温下磁力搅拌 30 分钟溶解于 20毫升硝酸中， 直至完全透明， 记为 A溶液， 将硝酸铋 Bi（N0 3）r5H 2 0于 60°C条件下磁力搅拌溶解于 20毫升硝酸中， 直至完全透明， 记为 B溶液。 2.4 times the molar amount: 0.0072 mol (3.4925 g). Lithium carbonate Li 2 CO 3 was magnetically stirred at room temperature for 30 minutes and dissolved in 20 ml of nitric acid until it was completely transparent. Recorded as A solution. Bismuth nitrate Bi (N0 3 ) R 5H 2 0 was dissolved in 20 ml of nitric acid with magnetic stirring at 60 ° C until it was completely transparent and recorded as solution B.
[0044] 将上述 A溶液用滴管慢慢转移到 B溶液中使两种溶液混合， 再加入 20毫升的去 离子水， 在室温下磁力搅拌 30分钟使之充分混合， 记为 C溶液。 将 C溶液转移到 1 00毫升的聚四氟乙烯高温反应釜中， 置于鼓风干燥箱中 180°C恒温反应 10小时。 冷却至室温后取出反应溶液用去离子水和无水乙醇交替洗涤充分后， 再置于干 燥箱中 60°C烘干， 随后取出即得到 LiBiO 2/Bi 20 3异质结光催化剂。 [0044] The above solution A was slowly transferred to the solution B with a dropper to mix the two solutions, and then 20 ml of deionized water was added, and the mixture was magnetically stirred at room temperature for 30 minutes to be fully mixed, and recorded as solution C. The C solution was transferred to a 100 ml polytetrafluoroethylene high-temperature reactor, and placed in a blast drying oven at a constant temperature of 180 ° C for 10 hours. After cooling to room temperature, the reaction solution was taken out, washed with alternately deionized water and absolute ethanol, and then dried in a drying box at 60 ° C, and then taken out to obtain a LiBiO 2 / Bi 2 0 3 heterojunction photocatalyst.
[0045] 参见附图 6， 它是按本实施例技术方案所制备样品的 X射线粉末衍射图谱， XR D测试结果显示， 所制备的 LiBiO 2/Bi 20 3结晶较好， 在多处出现了对应于 LiBiO 2 标准 PDF卡片的衍射峰， 说明主晶相 LiBiO 2的形成， 同时， Bi 20 3的掺入没有造 成 LiBiO 2衍射峰的明显偏移， 说明 Bi 20 3物相单独存在， 没有进入 LiBiO 2晶格， 二者形成异质结构。 [0045] Referring to FIG. 6, which is an X-ray powder diffraction pattern of a sample prepared according to the technical solution of this embodiment. XRD test results show that the prepared LiBiO 2 / Bi 2 0 3 crystals are better and appear in many places. a diffraction peak corresponding to 2 LiBiO standard PDF card described main crystalline phase formed LiBiO 2 while, Bi incorporated 203 did not cause significant diffraction peaks shift LiBiO 2, 203 Description of Bi phase alone Without entering the LiBiO 2 lattice, the two form a heterostructure.
[0046] 参见附图 7， 它是按本实施例技术方案所制备样品 LiBi0 2/Bi 20 3的 SEM （扫描 电子显微镜） 图谱， 从图中可以看出， 所得样品呈现片层状分布， 且片层较薄 ， 分散性较好， 有利于光生载流子的分离。 [0047] 所制备样品的紫外-可见吸收光谱、 对亚甲基蓝的降解率和降解亚甲基蓝的动 力学曲线与实施例 1相似。 7 is a SEM (scanning electron microscope) spectrum of a sample LiBi0 2 / Bi 2 0 3 prepared according to the technical solution of this embodiment. As can be seen from the figure, the obtained sample exhibits a lamellar distribution. Moreover, the sheet is thin and has good dispersibility, which is beneficial to the separation of photo-generated carriers. [0047] The UV-visible absorption spectrum, the degradation rate of methylene blue, and the kinetic curve of methylene blue degradation of the prepared sample were similar to those of Example 1.
[0048] 实施例 5:  [0048] Embodiment 5:
[0049] 按 !^10 2和：^ 20 3摩尔比1:0.12， 分别称取硫酸锂 Li 2SO 4: 0.003mol （0.3298克 ） ， 氯化铋 BiCl 3为硫酸锂 Li 2SO 4摩尔量的 2.48倍： 0.00744mol （2.3461克） ； 将硫酸锂 Li 2SO 4于室温下磁力搅拌 30分钟溶解于 20毫升去离子水中， 直至完全 透明， 记为 A溶液， 将氯化铋 （：1 3于60°（：条件下磁力搅拌溶解于 20毫升硝酸中 ， 直至完全透明， 记为 B溶液。 [0049] According to ^ 10 2 and: ^ 2 0 3 molar ratio of 1: 0.12, lithium sulfate Li 2 SO 4 was weighed : 0.003 mol (0.3298 g), and bismuth chloride BiCl 3 was 4 mol of lithium sulfate Li 2 SO The amount is 2.48 times: 0.00744 mol (2.3461 g); Lithium sulfate Li 2 SO 4 is magnetically stirred at room temperature for 30 minutes and dissolved in 20 ml of deionized water until it is completely transparent. It is recorded as solution A, and bismuth chloride (: 1 3 Dissolve in 20 ml of nitric acid with magnetic stirring at 60 ° (:) until it is completely transparent, and record it as solution B.
[0050] 将上述 A溶液用滴管慢慢转移到 B溶液中使两种溶液混合， 再加入 20毫升的去 离子水， 在室温下磁力搅拌 30分钟使之充分混合， 记为 C溶液。 将 C溶液转移到 1 00毫升的聚四氟乙烯高温反应釜中， 置于鼓风干燥箱中 160。（：恒温反应 12小时。 冷却至室温后取出反应溶液用去离子水和无水乙醇交替洗涤充分后， 再置于干 燥箱中 70°C烘干， 随后取出即得到 LiBiO 2/Bi 20 3异质结光催化剂。 [0050] The above solution A was slowly transferred to the solution B with a dropper to mix the two solutions, and then 20 ml of deionized water was added, and the mixture was magnetically stirred at room temperature for 30 minutes to be thoroughly mixed, and recorded as solution C. The C solution was transferred to a 100 ml polytetrafluoroethylene high-temperature reactor and placed in a blast drying oven 160. (: Constant temperature reaction for 12 hours. After cooling to room temperature, take out the reaction solution and wash thoroughly with deionized water and absolute ethanol, and then place it in a drying box at 70 ° C to dry. Then take out to obtain LiBiO 2 / Bi 2 0 3 Heterojunction Photocatalyst.
[0051] 本实施例所制备样品的物相结构、 SEM图谱与实施例 4相似， 紫外 -可见吸收光 谱、 对亚甲基蓝的降解率和降解亚甲基蓝的动力学曲线与实施例 1相似。  [0051] The phase structure and SEM spectrum of the sample prepared in this example are similar to those in Example 4. The ultraviolet-visible absorption spectrum, the degradation rate of methylene blue, and the kinetic curve of methylene blue degradation are similar to those in Example 1.
[0052] 实施例 6:  Embodiment 6:
[0053] 按 LiBiO 2和 20 3摩尔比 1:0.15， 分别称取硫酸锂 Li 2SO 4: 0.003mol （0.3298克 ） ， 硝酸铋 Bi（N0 3）r5H 20: 0.0078mol （3.7835克） ， 为硫酸锂 Li 2SO 4摩尔量 的 2.6倍； 将硫酸锂 Li 2SO 4于室温下磁力搅拌 30分钟溶解于 20毫升去离子水中， 直至完全透明， 记为 A溶液， 将硝酸铋 Bi（NO 3） r5H 20于 60°C条件下磁力搅拌溶 解于 20毫升硝酸中， 直至完全透明， 记为 B溶液。 [0053] Press LiBiO 2 and 203 molar ratio of 1: 0.15, respectively, said lithium Sulfate Li 2 SO 4: 0.003mol (0.3298 g), bismuth nitrate Bi (N0 3) r 5H 2 0: 0.0078mol (3.7835 g of ), Which is 2.6 times the molar amount of lithium sulfate Li 2 SO 4 ; Lithium sulfate Li 2 SO 4 is magnetically stirred at room temperature for 30 minutes and dissolved in 20 ml of deionized water until it is completely transparent. It is recorded as solution A, and bismuth nitrate Bi (NO 3 ) r 5H 2 0 was dissolved in 20 ml of nitric acid with magnetic stirring at 60 ° C until it was completely transparent and recorded as solution B.
[0054] 将上述 A溶液用滴管慢慢转移到 B溶液中使两种溶液混合， 再加入 20毫升的去 离子水， 在室温下磁力搅拌 30分钟使之充分混合， 记为 C溶液。 将 C溶液转移到 1 00毫升的聚四氟乙烯高温反应釜中， 置于鼓风干燥箱中 180。（：恒温反应 16小时。 冷却至室温后取出反应溶液用去离子水和无水乙醇交替洗涤充分后， 再置于干 燥箱中 80°C烘干， 随后取出即得到 LiBiO 2/Bi 20 3异质结光催化剂。 [0054] The above solution A was slowly transferred to the solution B with a dropper to mix the two solutions, and then 20 ml of deionized water was added, and the mixture was magnetically stirred at room temperature for 30 minutes to be thoroughly mixed, and recorded as solution C. The C solution was transferred to a 100 ml polytetrafluoroethylene high temperature reactor and placed in a blast drying oven for 180 hours. (: Constant temperature reaction for 16 hours. After cooling to room temperature, take out the reaction solution and wash thoroughly with deionized water and absolute ethanol, and then place it in a drying box at 80 ° C to dry. Then take out to obtain LiBiO 2 / Bi 2 0 3 Heterojunction Photocatalyst.
[0055] 本实施例所提供样品的物相结构、 SEM图谱与实施例 4相似， 紫外 -可见吸收光 谱、 对亚甲基蓝的降解率和降解亚甲基蓝的动力学曲线与实施例 1相似。 [0056] 本发明采用水热法制备 LiBi0 2/Bi 20 3异质结粉末， 制备方法简单易行， 合成周 期短。 将产品用作光催化剂， 通过异质结构拓宽光谱的响应范围， 降低了光生 电子-空穴的复合率， 在可见光区具有良好的光吸收能力， 可有效降解有机污染 物， 具有广阔的应用前景。 [0055] The phase structure and SEM spectrum of the sample provided in this example are similar to those in Example 4. The ultraviolet-visible absorption spectrum, the degradation rate of methylene blue, and the kinetic curve of methylene blue degradation are similar to those in Example 1. [0056] In the present invention, the LiBi0 2 / Bi 2 0 3 heterojunction powder is prepared by a hydrothermal method. The preparation method is simple and easy, and the synthesis period is short. Using the product as a photocatalyst, broadens the spectral response range through a heterostructure, reduces the photo-generated electron-hole recombination rate, has good light absorption in the visible light region, can effectively degrade organic pollutants, and has broad application prospects .

Claims

权利要求书 [权利要求 1] 一种铋酸锂-氧化铋光催化材料， 其特征在于： 氧化铋 Bi 20 3负载于铋 酸锂 LiBiO 2表面， 两种相界面形成异质结构； LiBiO 2fPBi 20 3的摩尔 比为 1: (0.05〜 0.15) 。 [权利要求 2] 一种如权利要求 1所述的铋酸锂 -氧化铋光催化材料的制备方法， 其特 征在于采用水热法， 包括如下步骤： Claim [Claim 1] A lithium bismuth oxide-bismuth oxide photocatalytic material, characterized in that: bismuth oxide Bi 20 3 is supported on the surface of lithium bismuth LiBiO 2 and the two phase interfaces form a heterostructure; LiBiO 2fPBi 20 The molar ratio of 3 is 1: (0.05 to 0.15). [Claim 2] A method for preparing a lithium bismuth-bismuth oxide photocatalytic material according to claim 1, characterized in that a hydrothermal method is adopted, including the following steps:
( 1) 按 LiBi0 2和 Bi 20 3的摩尔比为 1: (0.05〜 0.15) ， 分别称取含有 锂离子 Li +的化合物和含有铋离子 Bi 3+的化合物； 将含有锂离子 Li +的 化合物溶解于硝酸中或去离子水中， 室温、 搅拌条件下， 得到无色透 明溶液 A; 将含有铋离子 BP+ (1) a molar ratio LiBi0 2 and Bi 2 0 3 is 1: (0.05~ 0.15), were weighed compounds containing lithium ions Li + and a compound containing bismuth ion Bi 3+; containing a lithium ion Li + The compound is dissolved in nitric acid or deionized water, and at room temperature and under stirring, a colorless transparent solution A is obtained;
的化合物溶解于硝酸中， 在温度为 60〜 90°C、 搅拌条件下， 得到无色 透明溶液 B ;  The compound was dissolved in nitric acid, and a colorless transparent solution B was obtained at a temperature of 60 to 90 ° C under stirring;
(2) 在室温、 搅拌条件下， 将溶液 A和溶液 B缓慢混合， 再置于反应 釜中， 在温度为 120〜 200°C的条件下反应 8〜 18小时后， 自然冷却至 室温；  (2) Slowly mix solution A and solution B at room temperature and under stirring, and then place them in a reaction kettle, react at a temperature of 120 ~ 200 ° C for 8 ~ 18 hours, and then naturally cool to room temperature;
(3) 将冷却后的产物充分洗涤， 再置于温度为 60〜 80°C的烘箱中烘 干， 得到一种 LiBiO 2/Bi 20 3异质结光催化材料。 (3) The cooled product is fully washed, and then dried in an oven at a temperature of 60 to 80 ° C. to obtain a LiBiO 2 / Bi 2 0 3 heterojunction photocatalytic material.
[权利要求 3] 根据权利要求 2所述的一种铋酸锂-氧化铋光催化材料的制备方法， 其 特征在于： 所述的含有锂离子 Li +的化合物为碳酸锂 Li 2CO 3 、 硫酸锂 Li 2S0 4中的一种。 [Claim 3] The method for preparing a lithium bismuth oxide-bismuth oxide photocatalytic material according to claim 2, characterized in that: the compound containing lithium ion Li + is lithium carbonate Li 2 CO 3 , sulfuric acid One of lithium Li 2 S0 4 .
[权利要求 4] 根据权利要求 2所述的一种铋酸锂-氧化铋光催化材料的制备方法， 其 特征在于： 所述的含有铋离子 Bi 3+的化合物为硝酸铋 Bi(NO 3) r5H 20 、 氯化铋 BiCl 3中的一种。 [Claim 4] The method for preparing a lithium bismuth oxide-bismuth oxide photocatalytic material according to claim 2, characterized in that: the compound containing bismuth ion Bi 3+ is bismuth nitrate Bi (NO 3 ) r 5H 2 0 or BiCl 3 .
[权利要求 5] 根据权利要求 2所述的一种铋酸锂-氧化铋光催化材料的制备方法， 其 特征在于： 所述含有铋离子 Bi 的化合物的摩尔量为含有锂离子 Li + 的化合物的摩尔量的 2.2〜 2.6倍。 [Claim 5] The method for preparing a lithium bismuth oxide-bismuth oxide photocatalytic material according to claim 2, characterized in that the molar amount of the compound containing bismuth ion Bi is a compound containing lithium ion Li + The molar amount is 2.2 to 2.6 times.
[权利要求 6] 根据权利要求 2所述的一种铋酸锂-氧化铋光催化材料的制备方法， 其 特征在于： 步骤 (2) 所述的反应温度为 140〜 180°C， 反应时间为 10 〜 16小时。 [Claim 6] The method for preparing a lithium bismuth oxide-bismuth oxide photocatalytic material according to claim 2, characterized in that: the reaction temperature in step (2) is 140 ~ 180 ° C, and the reaction time is 10 ~ 16 hours.
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