CN105797760A - A kind of Bi2O2CO3-WO3 composite photocatalyst and preparation method thereof - Google Patents

A kind of Bi2O2CO3-WO3 composite photocatalyst and preparation method thereof Download PDF

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CN105797760A
CN105797760A CN201610235977.0A CN201610235977A CN105797760A CN 105797760 A CN105797760 A CN 105797760A CN 201610235977 A CN201610235977 A CN 201610235977A CN 105797760 A CN105797760 A CN 105797760A
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composite photocatalyst
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吕华
张涵
刘玉民
光景
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Henan Normal University
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Abstract

本发明公开了一种Bi2O2CO3‑WO3复合光催化剂及其制备方法，属于无机环保光催化材料技术领域。本发明的技术方案要点为：（1）将钨酸钠和氯化钠加入到去离子水中配成混合溶液，用盐酸调节混合溶液的pH值为0.5‑1，转移至水热反应釜并放入微波消解仪中于180℃微波反应10‑30min，冷却、洗涤、干燥得到WO3粉末；（2）配制硝酸铋水溶液并加入尿素和WO3粉体形成混合溶液；（3）在室温的条件下将混合溶液搅拌1h后转移至水热反应釜并放入微波消解仪中于180‑200℃微波反应10‑30min，待反应结束冷却至常温后经离心、洗涤、干燥制得Bi2O2CO3‑WO3复合光催化剂。本发明制得的复合光催化剂有效提高了太阳光的利用率和光催化活性。

The invention discloses a Bi 2 O 2 CO 3 -WO 3 composite photocatalyst and a preparation method thereof, belonging to the technical field of inorganic environment-friendly photocatalytic materials. The key points of the technical scheme of the present invention are: (1) Add sodium tungstate and sodium chloride into deionized water to form a mixed solution, adjust the pH value of the mixed solution to 0.5-1 with hydrochloric acid, transfer it to a hydrothermal reaction kettle and put Put it into a microwave digestion apparatus and react with microwave at 180°C for 10-30min, cool, wash and dry to obtain WO 3 powder; (2) Prepare bismuth nitrate aqueous solution and add urea and WO 3 powder to form a mixed solution; (3) Condition at room temperature Stir the mixed solution for 1 hour, then transfer it to a hydrothermal reaction kettle and put it into a microwave digestion apparatus for microwave reaction at 180-200°C for 10-30 minutes. After the reaction is completed, it is cooled to room temperature and then centrifuged, washed and dried to obtain Bi 2 O 2 CO 3 ‑WO 3 composite photocatalyst. The composite photocatalyst prepared by the invention effectively improves the utilization rate of sunlight and photocatalytic activity.

Description

一种Bi2O2CO3-WO3复合光催化剂及其制备方法A kind of Bi2O2CO3-WO3 composite photocatalyst and preparation method thereof

技术领域 technical field

本发明属于无机环保光催化材料技术领域，具体涉及一种Bi2O2CO3-WO3复合光催化剂及其制备方法。 The invention belongs to the technical field of inorganic environment - friendly photocatalytic materials, and in particular relates to a Bi2O2CO3 - WO3 composite photocatalyst and a preparation method thereof.

背景技术 Background technique

近年来，利用半导体材料光催化氧化降解污水中的有机物已经成为一个活跃的研究方向，人们对一些半导体氧化物的光催化性能进行了较为深入的研究。在众多的半导体光催化材料中，Bi2O2CO3光催化剂具有催化活性高、稳定性好、价格便宜和无毒等优良性能，被认为是最具有潜在应用价值的光催化材料。 In recent years, the use of semiconductor materials to photocatalytically oxidize and degrade organic matter in sewage has become an active research direction, and people have conducted in-depth research on the photocatalytic properties of some semiconductor oxides. Among many semiconductor photocatalytic materials, Bi 2 O 2 CO 3 photocatalyst has excellent properties such as high catalytic activity, good stability, low price and non-toxicity, and is considered to be the photocatalytic material with the most potential application value.

但Bi2O2CO3禁带宽度为3.4eV，只有在紫外线下才能激发其催化活性。在到达地面的太阳能中，这一波段的能量尚不足5%，而可见光部分的比例却占到太阳能的45%左右。此外，Bi2O2CO3光催化剂在光催化过程中光生电子和空穴容易复合，催化效率低。因此，如何拓宽Bi2O2CO3光催化剂光谱响应范围、提高其光量子效率成为光催化学科研究的重点和难点。研究表明，WO3的禁带宽度为2.77eV，是一种具有可见光响应能力的光催化材料。然而，目前尚没有相关文献关于Bi2O2CO3-WO3复合光催化剂的报道。 However, the bandgap of Bi 2 O 2 CO 3 is 3.4eV, and its catalytic activity can only be excited under ultraviolet light. In the solar energy that reaches the ground, the energy in this band is less than 5%, while the proportion of visible light accounts for about 45% of the solar energy. In addition, the photogenerated electrons and holes of Bi 2 O 2 CO 3 photocatalysts are easy to recombine during the photocatalytic process, and the catalytic efficiency is low. Therefore, how to broaden the spectral response range of Bi 2 O 2 CO 3 photocatalysts and improve their photon quantum efficiency has become the focus and difficulty of photocatalysis research. Studies have shown that WO 3 has a bandgap width of 2.77eV and is a photocatalytic material with visible light responsiveness. However, there is no relevant literature report on Bi 2 O 2 CO 3 -WO 3 composite photocatalysts.

发明内容 Contents of the invention

本发明解决的技术问题是提供了一种太阳能利用效率率高且光催化活性好的Bi2O2CO3-WO3复合光催化剂。 The technical problem solved by the invention is to provide a Bi 2 O 2 CO 3 -WO 3 composite photocatalyst with high solar energy utilization efficiency and good photocatalytic activity.

本发明解决的另一个技术问题是提供了一种操作简单且易于实现的Bi2O2CO3-WO3复合光催化剂的制备方法。 Another technical problem solved by the present invention is to provide a preparation method of Bi 2 O 2 CO 3 -WO 3 composite photocatalyst with simple operation and easy realization.

本发明为解决上述技术问题采用如下技术方案，一种Bi2O2CO3-WO3复合光催化剂的制备方法，其特征在于包括以下步骤：（1）将钨酸钠和氯化钠按摩尔比为1:1加入到去离子水中配成钨酸钠与氯化钠的混合溶液，搅拌30min后用盐酸调节混合溶液的pH值为0.5-1，继续搅拌30min后转移至水热反应釜，然后将水热反应釜放入微波消解仪中于180℃微波反应10-30min，待反应结束后经冷却、洗涤、干燥得到WO3粉末；（2）以硝酸铋和去离子水为原料配制硝酸铋水溶液，在搅拌的条件下向硝酸铋水溶液中加入尿素和步骤（1）得到的WO3粉末形成混合溶液，其中所加尿素与硝酸铋的摩尔比为3:1，所加WO3粉末与硝酸铋的摩尔比为0.25-1:1；（3）在室温的条件下将步骤（2）得到的混合溶液搅拌1h后转移至水热反应釜，然后将水热反应釜放入微波消解仪中于180-200℃微波反应10-30min，待反应结束冷却至常温后经离心、洗涤、干燥制得Bi2O2CO3-WO3复合光催化剂。 In order to solve the above-mentioned technical problems, the present invention adopts the following technical scheme, a preparation method of Bi 2 O 2 CO 3 -WO 3 composite photocatalyst, which is characterized in that it includes the following steps: (1) molarally mixing sodium tungstate and sodium chloride Add it into deionized water at a ratio of 1:1 to form a mixed solution of sodium tungstate and sodium chloride. After stirring for 30 minutes, use hydrochloric acid to adjust the pH value of the mixed solution to 0.5-1. After continuing to stir for 30 minutes, transfer it to a hydrothermal reaction kettle. Then put the hydrothermal reaction kettle into the microwave digestion apparatus and react with microwave at 180°C for 10-30min. After the reaction is completed, it is cooled, washed and dried to obtain WO 3 powder; (2) Prepare nitric acid with bismuth nitrate and deionized water as raw materials Bismuth aqueous solution, add urea and WO 3 powder obtained in step (1) to the bismuth nitrate aqueous solution under stirring conditions to form a mixed solution, wherein the molar ratio of added urea to bismuth nitrate is 3:1, and the added WO 3 powder and The molar ratio of bismuth nitrate is 0.25-1:1; (3) Stir the mixed solution obtained in step (2) for 1 hour at room temperature, then transfer it to a hydrothermal reactor, and then put the hydrothermal reactor into a microwave digestion apparatus React in microwave at 180-200°C for 10-30min, after the reaction is finished, cool to normal temperature, centrifuge, wash and dry to prepare Bi 2 O 2 CO 3 -WO 3 composite photocatalyst.

进一步优选，步骤（1）的混合溶液中钨酸钠的摩尔浓度为0.05-0.2mol/L。 Further preferably, the molar concentration of sodium tungstate in the mixed solution in step (1) is 0.05-0.2 mol/L.

进一步优选，步骤（2）的硝酸铋水溶液中硝酸铋的摩尔浓度为0.5-1mol/L。 Further preferably, the molar concentration of bismuth nitrate in the bismuth nitrate aqueous solution in step (2) is 0.5-1 mol/L.

本发明所述的Bi2O2CO3-WO3复合光催化剂，是按照上述方法制备得到的。 The Bi 2 O 2 CO 3 -WO 3 composite photocatalyst of the present invention is prepared according to the above method.

本发明与现有技术相比具有以下有益效果： Compared with the prior art, the present invention has the following beneficial effects:

1、本发明为了拓宽Bi2O2CO3的光谱响范围，将其与具有理想带隙的WO3相复合，利用两种半导体之间的能级差能使光生截流子由一种半导体微粒的能级注入到另一种半导体的能级上，从而提高光生电荷的分离效率； 1. In order to broaden the spectral response range of Bi 2 O 2 CO 3 , the present invention combines it with WO 3 having an ideal band gap, and utilizes the energy level difference between the two semiconductors to make the photo-generated interceptors from a semiconductor particle The energy level is injected into the energy level of another semiconductor, thereby improving the separation efficiency of photogenerated charges;

2、Bi2O2CO3光催化剂的导带电势ECB=0.16eV，价带电势EVB=3.56eV，而WO3光催化剂的导带电势ECB=0.41eV，价带电势EVB=3.18eV，在Bi2O2CO3-WO3复合半导体中，Bi2O2CO3的导带电势更负，光生电子容易从能级低的Bi2O2CO3迁移到能级高的WO3导带上，同时WO3的价带电势更正，光生空穴容易从能级高的WO3价带迁移到能级低的Bi2O2CO3价带上，从而提高光生电荷的分离效率，扩展了Bi2O2CO3的光谱响应范围； 2. The conduction band potential of Bi 2 O 2 CO 3 photocatalyst E CB =0.16eV, the valence band potential E VB =3.56eV, while the conduction band potential of WO 3 photocatalyst E CB =0.41eV, the valence band potential E VB = 3.18eV, in the Bi 2 O 2 CO 3 -WO 3 compound semiconductor, the conduction band potential of Bi 2 O 2 CO 3 is more negative, and the photogenerated electrons can easily migrate from the lower energy level Bi 2 O 2 CO 3 to the higher energy level On the conduction band of WO 3 , while the valence band potential of WO 3 is corrected, the photogenerated holes can easily migrate from the high-energy WO 3 valence band to the low-energy Bi 2 O 2 CO 3 valence band, thereby improving the separation of photo-generated charges Efficiency, extending the spectral response range of Bi 2 O 2 CO 3 ;

3、WO3禁带较窄，能有效拓展Bi2O2CO3-WO3复合光催化剂对可见光的利用率，进而有效提高太阳光的利用率和光催化活性。 3. The narrow bandgap of WO 3 can effectively expand the utilization rate of visible light of the Bi 2 O 2 CO 3 -WO 3 composite photocatalyst, thereby effectively improving the utilization rate of sunlight and photocatalytic activity.

附图说明 Description of drawings

图1为300W的高压汞灯照射下，本发明实施例2制得的Bi2O2CO3-WO3复合光催化剂和纯Bi2O2CO3光催剂对罗丹明B的降解对比曲线图（操作条件：催化剂的量：0.1g；罗丹明B的质量浓度：5mg/L）。 Figure 1 is a comparison curve of the degradation of rhodamine B by the Bi2O2CO3 - WO3 composite photocatalyst prepared in Example 2 of the present invention and the pure Bi2O2CO3 photocatalyst under the irradiation of a 300W high - pressure mercury lamp Figure (operating conditions: amount of catalyst: 0.1 g; mass concentration of rhodamine B: 5 mg/L).

具体实施方式 detailed description

以下通过实施例对本发明的上述内容做进一步详细说明，但不应该将此理解为本发明上述主题的范围仅限于以下的实施例，凡基于本发明上述内容实现的技术均属于本发明的范围。 The above-mentioned contents of the present invention are described in further detail below through the embodiments, but this should not be interpreted as the scope of the above-mentioned themes of the present invention being limited to the following embodiments, and all technologies realized based on the above-mentioned contents of the present invention all belong to the scope of the present invention.

实施例1 Example 1

（1）将0.005mol的钨酸钠和0.005mol的氯化钠加入到去离子水中定容到100mL形成钨酸钠与氯化钠的混合溶液，搅拌30min后用盐酸调节混合溶液的pH值为0.5，继续搅拌30min后转移至水热反应釜，然后将水热反应釜放入微波消解仪中于180℃微波反应10min，待反应结束后经冷却、洗涤、干燥得到WO3粉末； (1) Add 0.005mol of sodium tungstate and 0.005mol of sodium chloride into deionized water and make up to 100mL to form a mixed solution of sodium tungstate and sodium chloride. After stirring for 30 minutes, adjust the pH value of the mixed solution with hydrochloric acid 0.5, continue to stir for 30 minutes, then transfer to a hydrothermal reaction kettle, then put the hydrothermal reaction kettle into a microwave digestion apparatus and react with microwaves at 180°C for 10 minutes, after the reaction is completed, cool, wash and dry to obtain WO 3 powder;

（2）配制摩尔浓度为0.5mol/L的硝酸铋水溶液100mL，在搅拌的条件下向硝酸铋水溶液中加入0.15mol尿素和0.05mol步骤（1）得到的WO3粉体形成混合溶液； (2) Prepare 100 mL of bismuth nitrate aqueous solution with a molar concentration of 0.5 mol/L, add 0.15 mol of urea and 0.05 mol of WO 3 powder obtained in step (1) into the bismuth nitrate aqueous solution under stirring conditions to form a mixed solution;

（3）在室温的条件下将步骤（2）得到的混合溶液搅拌1h后转移至水热反应釜，然后将水热反应釜放入微波消解仪中于180℃微波反应30min，待反应结束冷却至常温后经离心、洗涤、干燥得到具有高催化活性的Bi2O2CO3-WO3复合光催化剂。 (3) Stir the mixed solution obtained in step (2) for 1 hour at room temperature, then transfer it to a hydrothermal reaction kettle, then put the hydrothermal reaction kettle into a microwave digestion apparatus and react with microwaves at 180°C for 30 minutes, and cool down after the reaction is completed After reaching normal temperature, the Bi 2 O 2 CO 3 -WO 3 composite photocatalyst with high catalytic activity is obtained by centrifugation, washing and drying.

实施例2 Example 2

（1）将0.01mol的钨酸钠和0.01mol的氯化钠加入到去离子水中定容到100mL形成钨酸钠和氯化钠的混合溶液，搅拌30min后用盐酸调节混合溶液的pH值为0.5，继续搅拌30min后转移至水热反应釜，然后将水热反应釜放入微波消解仪中于180℃微波反应20min，待反应结束后经冷却、洗涤、干燥得到WO3粉末； (1) Add 0.01mol of sodium tungstate and 0.01mol of sodium chloride into deionized water and make up to 100mL to form a mixed solution of sodium tungstate and sodium chloride. After stirring for 30 minutes, adjust the pH value of the mixed solution with hydrochloric acid 0.5, continue to stir for 30 minutes, then transfer to a hydrothermal reaction kettle, then put the hydrothermal reaction kettle into a microwave digestion apparatus and react with microwaves at 180°C for 20 minutes, after the reaction is completed, cool, wash and dry to obtain WO 3 powder;

（2）配制摩尔浓度为0.75mol/L的硝酸铋水溶液100mL，在搅拌的条件下向硝酸铋水溶液中加入0.225mol尿素和0.0375mol步骤（1）得到的WO3粉体形成混合溶液； (2) Prepare 100 mL of bismuth nitrate aqueous solution with a molar concentration of 0.75 mol/L, add 0.225 mol of urea and 0.0375 mol of WO 3 powder obtained in step (1) into the bismuth nitrate aqueous solution under stirring conditions to form a mixed solution;

（3）在室温的条件下将步骤（2）得到的混合溶液搅拌1h后转移至水热反应釜，然后将水热反应釜放入微波消解仪中于190℃微波反应20min，待反应结束冷却至常温后经离心、洗涤、干燥得到具有高催化活性的Bi2O2CO3-WO3复合光催化剂。 (3) Stir the mixed solution obtained in step (2) for 1 hour at room temperature, then transfer it to a hydrothermal reaction kettle, then put the hydrothermal reaction kettle into a microwave digestion apparatus and react with microwaves at 190°C for 20 minutes, and cool down after the reaction is completed After reaching normal temperature, the Bi 2 O 2 CO 3 -WO 3 composite photocatalyst with high catalytic activity is obtained by centrifugation, washing and drying.

图1是300W的高压汞灯照射下，本实施例制得的Bi2O2CO3-WO3复合光催化剂和纯Bi2O2CO3光催剂对罗丹明B的降解对比曲线图，由图可知，在相同的条件下，光照80min后，纯Bi2O2CO3光催化剂对罗丹明B的降解率为82%左右，而Bi2O2CO3-WO3复合光催化剂对罗丹明B的降解率可达到89%左右，表现出明显增强的光催化活性。 Fig. 1 is under the irradiation of 300W high-pressure mercury lamp, the Bi 2 O 2 CO 3 -WO 3 composite photocatalyst and the pure Bi 2 O 2 CO 3 photocatalyst prepared in this embodiment are compared to the degradation curve of rhodamine B, It can be seen from the figure that under the same conditions, after 80 min of light irradiation, the degradation rate of rhodamine B by pure Bi 2 O 2 CO 3 photocatalyst is about 82%, while the degradation rate of Rhodamine B by Bi 2 O 2 CO 3 -WO 3 composite photocatalyst is The degradation rate of Ming B can reach about 89%, showing a significantly enhanced photocatalytic activity.

实施例3 Example 3

（1）将0.02mol的钨酸钠和0.02mol的氯化钠加入到去离子水中定容到100mL形成钨酸钠和氯化钠的混合溶液，搅拌30min后用盐酸调节混合溶液的pH值为1，继续搅拌30min后转移至水热反应釜，然后将水热反应釜放入微波消解仪中于180℃微波反应30min，待反应结束后经冷却、洗涤、干燥得到WO3粉末； (1) Add 0.02mol of sodium tungstate and 0.02mol of sodium chloride to deionized water and make up to 100mL to form a mixed solution of sodium tungstate and sodium chloride. After stirring for 30 minutes, adjust the pH value of the mixed solution with hydrochloric acid 1. Continue to stir for 30 minutes, then transfer to the hydrothermal reaction kettle, then put the hydrothermal reaction kettle into a microwave digestion apparatus and react with microwave at 180°C for 30 minutes, after the reaction is completed, cool, wash and dry to obtain WO 3 powder;

（2）配制摩尔浓度为1mol/L的硝酸铋水溶液100mL，在搅拌的条件下向硝酸铋水溶液中加入0.3mol尿素和0.025mol步骤（1）得到的WO3粉体形成混合溶液； (2) Prepare 100 mL of bismuth nitrate aqueous solution with a molar concentration of 1 mol/L, add 0.3 mol of urea and 0.025 mol of WO 3 powder obtained in step (1) into the bismuth nitrate aqueous solution under stirring conditions to form a mixed solution;

（3）在室温的条件下将步骤（2）得到的混合溶液搅拌1h后转移至水热反应釜，然后将水热反应釜放入微波消解仪中于200℃微波反应10min，待反应结束冷却至常温后经离心、洗涤、干燥得到具有高催化活性的Bi2O2CO3-WO3复合光催化剂。 (3) Stir the mixed solution obtained in step (2) for 1 hour at room temperature, then transfer it to a hydrothermal reaction kettle, then put the hydrothermal reaction kettle into a microwave digestion apparatus and react with microwaves at 200°C for 10 minutes, and cool down after the reaction is completed After reaching normal temperature, the Bi 2 O 2 CO 3 -WO 3 composite photocatalyst with high catalytic activity is obtained by centrifugation, washing and drying.

以上实施例描述了本发明的基本原理、主要特征及优点，本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明原理的范围下，本发明还会有各种变化和改进，这些变化和改进均落入本发明保护的范围内。 The above embodiments have described the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above embodiments. What are described in the above embodiments and description are only to illustrate the principles of the present invention. Without departing from the scope of the principle of the present invention, there will be various changes and improvements in the present invention, and these changes and improvements all fall within the protection scope of the present invention.

Claims (4)

1.一种Bi2O2CO3-WO3复合光催化剂的制备方法，其特征在于包括以下步骤：（1）将钨酸钠和氯化钠按摩尔比为1:1加入到去离子水中配成钨酸钠与氯化钠的混合溶液，搅拌30min后用盐酸调节混合溶液的pH值为0.5-1，继续搅拌30min后转移至水热反应釜，然后将水热反应釜放入微波消解仪中于180℃微波反应10-30min，待反应结束后经冷却、洗涤、干燥得到WO3粉末；（2）以硝酸铋和去离子水为原料配制硝酸铋水溶液，在搅拌的条件下向硝酸铋水溶液中加入尿素和步骤（1）得到的WO3粉末形成混合溶液，其中所加尿素与硝酸铋的摩尔比为3:1，所加WO3粉末与硝酸铋的摩尔比为0.25-1:1；（3）在室温的条件下将步骤（2）得到的混合溶液搅拌1h后转移至水热反应釜，然后将水热反应釜放入微波消解仪中于180-200℃微波反应10-30min，待反应结束冷却至常温后经离心、洗涤、干燥制得Bi2O2CO3-WO3复合光催化剂。 1. A preparation method of Bi 2 O 2 CO 3 -WO 3 composite photocatalyst, characterized in that it comprises the following steps: (1) adding sodium tungstate and sodium chloride into deionized water at a molar ratio of 1:1 Prepare a mixed solution of sodium tungstate and sodium chloride. After stirring for 30 minutes, adjust the pH value of the mixed solution to 0.5-1 with hydrochloric acid. After continuing to stir for 30 minutes, transfer it to a hydrothermal reaction kettle, and then put the hydrothermal reaction kettle into microwave digestion. Microwave reaction at 180°C for 10-30min in the instrument, after the reaction was completed, it was cooled, washed, and dried to obtain WO 3 powder; Add urea and the WO3 powder obtained in step ( 1 ) to the bismuth aqueous solution to form a mixed solution, wherein the molar ratio of urea to bismuth nitrate is 3 :1, and the molar ratio of WO3 powder to bismuth nitrate is 0.25-1: 1; (3) Stir the mixed solution obtained in step (2) for 1 hour at room temperature and then transfer it to a hydrothermal reaction kettle, then put the hydrothermal reaction kettle into a microwave digestion apparatus and react with microwave at 180-200℃ for 10- After 30 minutes, after the reaction was completed and cooled to room temperature, the Bi 2 O 2 CO 3 -WO 3 composite photocatalyst was obtained by centrifuging, washing and drying. 2.根据权利要求1所述的Bi2O2CO3-WO3复合光催化剂的制备方法，其特征在于：步骤（1）的混合溶液中钨酸钠的摩尔浓度为0.05-0.2mol/L。 2. The preparation method of Bi 2 O 2 CO 3 -WO 3 composite photocatalyst according to claim 1, characterized in that: the molar concentration of sodium tungstate in the mixed solution in step (1) is 0.05-0.2mol/L . 3. 根据权利要求1所述的Bi2O2CO3-WO3复合光催化剂的制备方法，其特征在于：步骤（2）的硝酸铋水溶液中硝酸铋的摩尔浓度为0.5-1mol/L。 3. The preparation method of Bi 2 O 2 CO 3 -WO 3 composite photocatalyst according to claim 1, characterized in that: the molar concentration of bismuth nitrate in the bismuth nitrate aqueous solution in step (2) is 0.5-1mol/L. 4. 一种Bi2O2CO3-WO3复合光催化剂，其特征在于是按照权利要求1-3中任意一项所述的方法制备得到的。 4. A Bi 2 O 2 CO 3 -WO 3 composite photocatalyst, characterized in that it is prepared according to the method described in any one of claims 1-3.
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CN108786872A (en) * 2018-07-05 2018-11-13 河南师范大学 A kind of flower-shaped WS2/Bi2O2CO3The synthetic method of heterojunction photocatalysis material and its application
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