CN106944074B - A kind of visible-light response type composite photo-catalyst and its preparation method and application - Google Patents

A kind of visible-light response type composite photo-catalyst and its preparation method and application Download PDF

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CN106944074B
CN106944074B CN201710160064.1A CN201710160064A CN106944074B CN 106944074 B CN106944074 B CN 106944074B CN 201710160064 A CN201710160064 A CN 201710160064A CN 106944074 B CN106944074 B CN 106944074B
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陈晓娟
徐颂
王海龙
陈忻
陈美纶
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Abstract

本发明的一种可见光响应型复合光催化剂及其制备方法和应用，所述可见光响应型复合光催化剂为CuBi2O4/β‑Bi2O3，所述可见光响应型复合光催化剂中CuBi2O4为空心微米球，β‑Bi2O3为不规则纳米颗粒，且CuBi2O4与β‑Bi2O3之间紧密接触。本发明所制备的可见光响应型复合光催化剂在整个可见光谱范围内均有较强吸收，且相较纯β‑Bi2O3具有更好的光催化性能和更高的循环利用率。将0.4 g的CuBi2O4/β‑Bi2O3（1:2.25，wt%）用于处理双氯芬酸难降解有机废水，可见光照射3 h，对1 L 5 mg/L双氯芬酸溶液的去除率为89.02%，重复利用第七次，对双氯芬酸溶液去除率为78.43%。

A visible light responsive composite photocatalyst, a preparation method and application thereof of the present invention, the visible light responsive composite photocatalyst is CuBi 2 O 4 / β- Bi 2 O 3 , and the visible light responsive composite photocatalyst is CuBi 2 O 4 is a hollow microsphere, β- Bi 2 O 3 is irregular nanoparticles, and CuBi 2 O 4 and β- Bi 2 O 3 are in close contact. The visible light-responsive composite photocatalyst prepared by the invention has strong absorption in the entire visible spectrum range, and has better photocatalytic performance and higher recycling rate than pure β- Bi 2 O 3 . 0.4 g of CuBi 2 O 4 / β- Bi 2 O 3 (1:2.25, wt%) was used to treat diclofenac refractory organic wastewater, irradiated with visible light for 3 h, and the removal rate of 1 L of 5 mg/L diclofenac solution was 89.02%, reused for the seventh time, and the removal rate of diclofenac solution was 78.43%.

Description

一种可见光响应型复合光催化剂及其制备方法和应用A kind of visible light responsive composite photocatalyst and preparation method and application thereof

技术领域technical field

本发明涉及光催化技术领域，尤其涉及一种可见光响应型复合光催化剂及其制备方法和应用。The invention relates to the technical field of photocatalysis, in particular to a visible light-responsive composite photocatalyst and a preparation method and application thereof.

背景技术Background technique

近年来，经济社会的不断发展以及工业化进程的不断深入，导致了大量新兴有机污染物废水的排放，但目前市政污水处理***难以将其完全去除，从而导致这些新兴有机污染物在地表水、地下水、甚至饮用水***中被检测出。而这些新兴有机污染物，如双氯酚酸等，即使在痕量浓度下，如若人类及动植物长期暴露其中也会受到严重的危害。因此，废水中新兴有机污染物的去除仍是目前环境保护领域的重点和难点。In recent years, the continuous development of the economy and society and the deepening of the industrialization process have led to the discharge of a large number of emerging organic pollutants in wastewater. However, it is difficult for the municipal sewage treatment system to completely remove them, resulting in these emerging organic pollutants in surface water and groundwater. , even detected in drinking water systems. And these emerging organic pollutants, such as diclofenac, even at trace concentrations, if humans, animals and plants are exposed to them for a long time, they will be seriously harmed. Therefore, the removal of emerging organic pollutants in wastewater is still the focus and difficulty in the field of environmental protection.

光催化氧化技术具有反应条件温和、反应速度快、矿化率高、二次污染少等优势。美国环保局将其列为最有前景的环保高新技术。TiO2基半导体光催化材料是当前国内外研究最为广泛的光催化剂，但该材料的带隙较宽（3.2 eV），而且只有在紫外光（仅占太阳辐射总量4%）照射下产生光催化活性，这大大限制了它的应用。因此，可高效利用廉价太阳光的可见光响应型光催化剂研制成为目前光催化氧化技术领域的热点。Photocatalytic oxidation technology has the advantages of mild reaction conditions, fast reaction speed, high mineralization rate, and less secondary pollution. The United States Environmental Protection Agency listed it as the most promising environmental protection technology. TiO2 -based semiconductor photocatalytic materials are the most widely studied photocatalysts at home and abroad, but the material has a wide band gap (3.2 eV), and only generates light under the irradiation of ultraviolet light (only 4% of the total solar radiation). catalytic activity, which greatly limits its application. Therefore, the development of visible light-responsive photocatalysts that can efficiently utilize cheap sunlight has become a hot spot in the field of photocatalytic oxidation technology.

氧化铋（Bi2O3）是一种可见光响应型半导体材料，由于其独特的光学及电学性能，已在气体传感器、光伏电池、光学涂层、燃料电池、超级电容等方面有广泛研究。此外，Bi2O3结构中的Bi 6s轨道孤对电子诱导的内部极化场有助于光生电子-空穴对的分离及载流子的传递，从而使Bi2O3具有一定的光催化作用。Bi2O3主要存在α、β、γ、δ四种晶型结构，其中α-Bi2O3常温下稳定，禁带宽度约为2.8 eV（导带0.33 eV，价带3.13 eV），将其作为可见光响应型光催化剂已有大量研究。然而，虽然β-Bi2O3的禁带宽度为2.4 eV，具有比α-Bi2O3更强的可见光吸收能力，但是β-Bi2O3作为光催化剂的研究仍然存在三方面问题：（1）β-Bi2O3在光催化过程中易转变成α-Bi2O3，并与CO2反应生成碳酸盐，导致光催化活性下降；（2）β-Bi2O3光催化体系的量子效率低，导致其光催化活性较差；（3）β-Bi2O3的导带低于H+/H2的还原电位，导致光生电子极易与光生空穴复合，从而影响光催化效率。Bismuth oxide (Bi 2 O 3 ) is a visible light-responsive semiconductor material. Due to its unique optical and electrical properties, it has been widely studied in gas sensors, photovoltaic cells, optical coatings, fuel cells, and supercapacitors. In addition, the internal polarization field induced by the Bi 6s orbital lone pair electrons in the Bi 2 O 3 structure contributes to the separation of photogenerated electron-hole pairs and the transfer of carriers, so that Bi 2 O 3 has certain photocatalytic properties. effect. Bi 2 O 3 mainly has four crystal structures, α, β, γ, and δ . Among them, α -Bi 2 O 3 is stable at room temperature and has a forbidden band width of about 2.8 eV (conduction band 0.33 eV, valence band 3.13 eV). It has been extensively studied as a visible light-responsive photocatalyst. However, although β- Bi2O3 has a forbidden band width of 2.4 eV and has stronger visible light absorption ability than α - Bi2O3 , there are still three problems in the research of β- Bi2O3 as a photocatalyst: (1) β- Bi 2 O 3 is easily converted into α -Bi 2 O 3 during the photocatalytic process, and reacts with CO 2 to form carbonate, resulting in a decrease in photocatalytic activity; (2) β- Bi 2 O 3 photocatalytic The low quantum efficiency of the catalytic system leads to its poor photocatalytic activity; (3) the conduction band of β- Bi 2 O 3 is lower than the reduction potential of H + /H 2 , which leads to the recombination of photo-generated electrons with photo-generated holes, thereby affect the photocatalytic efficiency.

因此，现有技术还有待于改进和发展。Therefore, the existing technology still needs to be improved and developed.

发明内容SUMMARY OF THE INVENTION

鉴于上述现有技术的不足，本发明的目的在于提供一种可见光响应型复合光催化剂及其制备方法和应用，旨在解决现有β-Bi2O3作为光催化剂的研究中存在上述技术缺陷的问题。In view of the above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a visible light-responsive composite photocatalyst and a preparation method and application thereof, aiming to solve the above-mentioned technical defects in the research of the existing β- Bi 2 O 3 as a photocatalyst The problem.

本发明的技术方案如下：The technical scheme of the present invention is as follows:

一种可见光响应型复合光催化剂，其中，所述可见光响应型复合光催化剂为CuBi2O4/β-Bi2O3，所述可见光响应型复合光催化剂中CuBi2O4为空心微米球，β-Bi2O3为不规则纳米颗粒，且CuBi2O4与β-Bi2O3之间紧密接触。A visible light responsive composite photocatalyst, wherein the visible light responsive composite photocatalyst is CuBi 2 O 4 / β- Bi 2 O 3 , and the visible light responsive composite photocatalyst CuBi 2 O 4 is a hollow microsphere, β- Bi 2 O 3 is irregular nanoparticles, and CuBi 2 O 4 and β- Bi 2 O 3 are in close contact.

所述的可见光响应型复合光催化剂，其中，CuBi2O4/β-Bi2O3中，CuBi2O4与β-Bi2O3的质量比为1：（0.5-20）。In the visible light-responsive composite photocatalyst, in CuBi 2 O 4 / β- Bi 2 O 3 , the mass ratio of CuBi 2 O 4 to β- Bi 2 O 3 is 1:(0.5-20).

一种如上任一所述的可见光响应型复合光催化剂的制备方法，其中，包括以下步骤：A method for preparing a visible light-responsive composite photocatalyst as described above, comprising the following steps:

（1）CuBi2O4的制备：将Bi(NO3)3·5H2O溶解在浓HNO3中，搅拌至完全溶解，再加入Cu(NO3)2·3H2O，搅拌至混合均匀，而后逐滴滴加0.5-2 mol/L的碱性沉淀剂溶液，并将滴加后溶液稀释，继续搅拌0.5-2 h后，将该溶液转移至反应釜中，升高温度至80-150 ℃，反应18-30 h，待反应釜冷却至室温后，将反应得到的沉淀物洗涤，并通过离心分离，然后真空干燥，研磨、过筛，即得CuBi2O4；(1) Preparation of CuBi 2 O 4 : Dissolve Bi(NO 3 ) 3 ·5H 2 O in concentrated HNO 3 , stir until completely dissolved, then add Cu(NO 3 ) 2 ·3H 2 O, and stir until the mixture is uniform , then dropwise add 0.5-2 mol/L alkaline precipitant solution, dilute the solution after dropwise addition, continue stirring for 0.5-2 h, transfer the solution to the reaction kettle, raise the temperature to 80- 150 ℃, react for 18-30 h, after the reaction kettle is cooled to room temperature, wash the precipitate obtained by the reaction, and separate by centrifugation, then vacuum dry, grind and sieve to obtain CuBi 2 O 4 ;

（2）CuBi2O4@C的制备：将步骤（1）中所制备的CuBi2O4分散于葡萄糖酸溶液中，超声10-50 min后，将混合液移至反应釜中，升高温度至150-250 ℃，待反应釜自然冷却至室温后，通过离心分离回收反应得到的沉淀物，并将沉淀物洗涤，然后真空干燥，研磨、过筛，即得CuBi2O4@C；(2) Preparation of CuBi 2 O 4 @C: Disperse the CuBi 2 O 4 prepared in step (1) in a gluconic acid solution, and after sonicating for 10-50 min, transfer the mixture to the The temperature reaches 150-250 °C, after the reaction kettle is naturally cooled to room temperature, the precipitate obtained by the reaction is recovered by centrifugal separation, and the precipitate is washed, then vacuum-dried, ground and sieved to obtain CuBi 2 O 4 @C;

（3）CuBi2O4/β-Bi2O3的制备：将步骤（2）中所制备的CuBi2O4@C分散于HNO3溶液中，超声10-50 min，得到溶液A；将Bi(NO3)3·5H2O溶解于HNO3溶液中，室温下剧烈搅拌30-120min，得到溶液B；将碱式碳酸盐溶解于超纯水中，搅拌10-50 min，得到溶液C；先将溶液A和溶液B混合后磁力搅拌10-50 min，再向其中逐滴滴加溶液C，继续搅拌10-50 min，将反应产生的沉淀物洗涤，并通过离心分离收集沉淀物；将洗涤后的沉淀物放入程序升温炉，设置程序升温炉在10-60 min内升温至300-800 ℃，并在程序升温炉中反应2-10 h，待程序升温炉自然冷却至室温后，收集固体沉淀物，即可得到CuBi2O4/β-Bi2O3。(3) Preparation of CuBi 2 O 4 / β- Bi 2 O 3 : Disperse the CuBi 2 O 4 @C prepared in step (2) in HNO 3 solution, and ultrasonicate for 10-50 min to obtain solution A; Dissolve Bi(NO 3 ) 3 ·5H 2 O in HNO 3 solution, stir vigorously for 30-120 min at room temperature to obtain solution B; dissolve basic carbonate in ultrapure water, stir for 10-50 min to obtain solution C; first mix solution A and solution B, then magnetically stir for 10-50 min, then add solution C dropwise to it, continue stirring for 10-50 min, wash the precipitate produced by the reaction, and collect the precipitate by centrifugation ; Put the washed precipitate into the programmed heating furnace, set the programmed heating furnace to heat up to 300-800 °C within 10-60 min, and react in the programmed heating furnace for 2-10 h, and let the programmed heating furnace cool down to room temperature naturally Then, collect the solid precipitate to obtain CuBi 2 O 4 / β- Bi 2 O 3 .

所述的可见光响应型复合光催化剂的制备方法，其中，步骤（1）中，所述碱性沉淀剂溶液中的碱性沉淀剂为氢氧化钠、氢氧化钾和氨水中的一种或多种。The preparation method of the visible light responsive composite photocatalyst, wherein, in step (1), the alkaline precipitating agent in the alkaline precipitating agent solution is one or more of sodium hydroxide, potassium hydroxide and ammonia water. kind.

所述的可见光响应型复合光催化剂的制备方法，其中，步骤（2）中，所述葡萄糖酸溶液中葡萄糖酸的体积为0.04-0.8 mL。In the preparation method of the visible light responsive composite photocatalyst, in step (2), the volume of gluconic acid in the gluconic acid solution is 0.04-0.8 mL.

所述的可见光响应型复合光催化剂的制备方法，其中，步骤（3）中，所述Bi(NO3)3·5H2O加入的摩尔量为0.1-3.6 mmol。In the preparation method of the visible light-responsive composite photocatalyst, in step (3), the molar amount of Bi(NO 3 ) 3 ·5H 2 O added is 0.1-3.6 mmol.

所述的可见光响应型复合光催化剂的制备方法，其中，步骤（3）中，所述碱式碳酸盐与Bi(NO3)3·5H2O的摩尔量之比为（1-10）:1。The preparation method of the visible light-responsive composite photocatalyst, wherein, in step (3), the molar ratio of the basic carbonate to Bi(NO 3 ) 3 ·5H 2 O is (1-10) :1.

所述的可见光响应型复合光催化剂的制备方法，其中，步骤（3）中，所述程序升温炉的温度升高至300-800 ℃。In the preparation method of the visible light-responsive composite photocatalyst, in step (3), the temperature of the temperature-programmed furnace is increased to 300-800°C.

所述的可见光响应型复合光催化剂的制备方法，其中，步骤（3）中，所述程序升温炉的反应时间为2-10 h。In the preparation method of the visible light-responsive composite photocatalyst, in step (3), the reaction time of the temperature-programmed furnace is 2-10 h.

一种可见光响应型复合光催化剂的应用，其中，将如上任一所述的可见光响应型复合光催化剂应用于处理含有非甾体类抗炎药的废水。An application of a visible-light-responsive composite photocatalyst, wherein the visible-light-responsive composite photocatalyst described in any of the above is applied to the treatment of wastewater containing non-steroidal anti-inflammatory drugs.

有益效果：相较纯β-Bi2O3，本发明所制备的可见光响应型复合光催化剂具有可见光吸收强度更高、光催化性能更好、循环利用率更高等优点。Beneficial effects: Compared with pure β- Bi 2 O 3 , the visible light responsive composite photocatalyst prepared in the present invention has the advantages of higher visible light absorption intensity, better photocatalytic performance, higher recycling rate and the like.

附图说明Description of drawings

图1为本发明实施例1中CuBi2O4/β-Bi2O3的扫描电子显微镜图。FIG. 1 is a scanning electron microscope image of CuBi 2 O 4 / β- Bi 2 O 3 in Example 1 of the present invention.

图2为本发明实施例1中CuBi2O4/β-Bi2O3的X射线衍射图谱。FIG. 2 is an X-ray diffraction pattern of CuBi 2 O 4 / β- Bi 2 O 3 in Example 1 of the present invention.

图3为本发明实施例1中CuBi2O4/β-Bi2O3的紫外-可见漫反射光谱图。FIG. 3 is an ultraviolet-visible diffuse reflection spectrum diagram of CuBi 2 O 4 / β- Bi 2 O 3 in Example 1 of the present invention.

图4为本发明实施例1中CuBi2O4/β-Bi2O3的光催化性能示意图。4 is a schematic diagram of the photocatalytic performance of CuBi 2 O 4 / β- Bi 2 O 3 in Example 1 of the present invention.

图5为本发明实施例9中CuBi2O4/β-Bi2O3重复利用性能示意图。FIG. 5 is a schematic diagram of the reuse performance of CuBi 2 O 4 / β- Bi 2 O 3 in Example 9 of the present invention.

具体实施方式Detailed ways

本发明提供一种可见光响应型复合光催化剂及其制备方法和应用，为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。The present invention provides a visible light-responsive composite photocatalyst and a preparation method and application thereof. In order to make the purpose, technical solution and effect of the present invention clearer and clearer, the present invention is further described below in detail. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.

为提高β-Bi2O3的光催化活性，将其与其它具有合适能带结构的半导体复合构筑复合光催化剂是一种有效的技术手段。一方面，可利用两种半导体不同的能带结构差异所形成的新的能带结构特征，改善复合光催化体系中光生电子-空穴的迁移规律，从而减小光生电子-空穴的复合率，提高β-Bi2O3的光催化活性；另一方面，还可借助其它半导体的化学稳定性来改善β-Bi2O3的结构稳定性。CuBi2O4半导体具有可见光响应强、化学稳定性好等优势，并且其导带位置较高，其光生电子具有较强的还原能力。此外，相较β-Bi2O3，CuBi2O4的导带和价带势能均较负，这两种半导体复合势必会改变整个反应体系的光催化性能。因此，本发明通过将CuBi2O4与β-Bi2O3复合构筑复合型光催化剂来提高β-Bi2O3的光催化活性和结构稳定性。In order to improve the photocatalytic activity of β- Bi 2 O 3 , it is an effective technique to combine it with other semiconductors with suitable energy band structure to construct a composite photocatalyst. On the one hand, the new energy band structure features formed by the different energy band structures of the two semiconductors can be used to improve the migration law of photogenerated electrons and holes in the composite photocatalytic system, thereby reducing the recombination rate of photogenerated electrons and holes. , to improve the photocatalytic activity of β- Bi 2 O 3 ; on the other hand, the structural stability of β- Bi 2 O 3 can also be improved by means of the chemical stability of other semiconductors. CuBi 2 O 4 semiconductor has the advantages of strong visible light response and good chemical stability, and its conduction band position is high, and its photogenerated electrons have strong reducing ability. In addition, compared with β- Bi 2 O 3 , the conduction band and valence band potential of CuBi 2 O 4 are both negative, and the recombination of these two semiconductors is bound to change the photocatalytic performance of the whole reaction system. Therefore, the present invention improves the photocatalytic activity and structural stability of β -Bi 2 O 3 by compounding CuBi 2 O 4 and β- Bi 2 O 3 to construct a composite photocatalyst.

具体地，本发明提供一种可见光响应型复合光催化剂，其中，所述可见光响应型复合光催化剂为CuBi2O4/β-Bi2O3，所述可见光响应型复合光催化剂中CuBi2O4为空心微米球，β-Bi2O3为不规则纳米颗粒，且CuBi2O4与β-Bi2O3之间紧密接触。即本发明所述可见光响应型复合光催化剂为CuBi2O4/β-Bi2O3，所述CuBi2O4/β-Bi2O3是由空心微米球CuBi2O4与不规则纳米颗粒β-Bi2O3紧密接触而形成的复合光催化剂。Specifically, the present invention provides a visible light responsive composite photocatalyst, wherein the visible light responsive composite photocatalyst is CuBi 2 O 4 / β- Bi 2 O 3 , and the visible light responsive composite photocatalyst is CuBi 2 O 4 is a hollow microsphere, β- Bi 2 O 3 is an irregular nanoparticle, and CuBi 2 O 4 and β- Bi 2 O 3 are in close contact. That is, the visible light-responsive composite photocatalyst of the present invention is CuBi 2 O 4 / β- Bi 2 O 3 , and the CuBi 2 O 4 / β- Bi 2 O 3 is composed of hollow microspheres CuBi 2 O 4 and irregular nanometers The composite photocatalyst formed by the close contact of particles β- Bi 2 O 3 .

本发明CuBi2O4/β-Bi2O3中，CuBi2O4与β-Bi2O3的质量比为1：（0.5-20）。优选地，CuBi2O4与β-Bi2O3的质量比为1:（1-15）。更优选地，CuBi2O4与β-Bi2O3的质量比为1:（1.5-10）。再优选地，CuBi2O4与β-Bi2O3的质量比为1：（1.8-5）。再进一步优选地，CuBi2O4与β-Bi2O3的质量比为1：（2-3），例如，CuBi2O4与β-Bi2O3的质量比为1:2.25。In the CuBi 2 O 4 / β- Bi 2 O 3 of the present invention, the mass ratio of CuBi 2 O 4 to β- Bi 2 O 3 is 1:(0.5-20). Preferably, the mass ratio of CuBi 2 O 4 to β- Bi 2 O 3 is 1:(1-15). More preferably, the mass ratio of CuBi 2 O 4 to β- Bi 2 O 3 is 1:(1.5-10). More preferably, the mass ratio of CuBi 2 O 4 to β- Bi 2 O 3 is 1:(1.8-5). Still further preferably, the mass ratio of CuBi 2 O 4 to β- Bi 2 O 3 is 1:(2-3), for example, the mass ratio of CuBi 2 O 4 to β- Bi 2 O 3 is 1:2.25.

本发明还提供一种如上任一所述的可见光响应型复合光催化剂的制备方法，其包括以下步骤：The present invention also provides a preparation method of the visible light-responsive composite photocatalyst as described above, which comprises the following steps:

（1）CuBi2O4的制备：将Bi(NO3)3·5H2O溶解在浓HNO3中，搅拌至完全溶解，再加入Cu(NO3)2·3H2O，搅拌至混合均匀，而后逐滴滴加0.5-2 mol/L的碱性沉淀剂溶液，并将滴加后溶液稀释，继续搅拌0.5-2 h后，将该溶液转移至反应釜中，升高温度至80-150 ℃，反应18-30 h，待反应釜冷却至室温后，将反应得到的沉淀物洗涤，并通过离心分离，然后真空干燥，研磨、过筛，即得CuBi2O4。(1) Preparation of CuBi 2 O 4 : Dissolve Bi(NO 3 ) 3 ·5H 2 O in concentrated HNO 3 , stir until completely dissolved, then add Cu(NO 3 ) 2 ·3H 2 O, and stir until the mixture is uniform , then dropwise add 0.5-2 mol/L alkaline precipitant solution, dilute the solution after dropwise addition, continue stirring for 0.5-2 h, transfer the solution to the reaction kettle, raise the temperature to 80- 150 ℃, react for 18-30 h, after the reaction kettle is cooled to room temperature, wash the precipitate obtained by the reaction, and separate by centrifugation, then vacuum dry, grind and sieve to obtain CuBi 2 O 4 .

上述步骤（1）中，所述碱性沉淀剂溶液中的碱性沉淀剂可以为氢氧化钠、氢氧化钾和氨水中的一种或几种。In the above step (1), the alkaline precipitating agent in the alkaline precipitating agent solution may be one or more of sodium hydroxide, potassium hydroxide and ammonia water.

本发明上述步骤（1）采用水热法制备形貌结构均匀的CuBi2O4。上述步骤（1）具体为，将0.04摩尔份的Bi(NO3)3·5H2O溶解在2-6 mL浓HNO3中，优选2-5 mL，进一步优选2.5-4mL（如3 mL），搅拌使其完全溶解，再加入20 mL 0.02摩尔份的Cu(NO3)2·3H2O，搅拌使其混合均匀，而后逐滴滴加0.5-2 mol/L的碱性沉淀剂溶液，优选0.8-1.5 mol/L的碱性沉淀剂溶液，进一步优选1-1.4 mol/L（如1.2 mol/L）的碱性沉淀剂溶液，并将滴加后溶液稀释至50-100 mL，优选60-80 mL（如70 mL），继续搅拌0.5-2 h，优选搅拌0.8-1.5 h后，将该溶液转移至高压反应釜中，升高温度至80-150 ℃，优选90-110 ℃（如100 ℃），反应18-30 h，优选22-26 h（如24 h），待反应釜自然冷却至室温后，将反应得到的沉淀物洗涤（优选采用超纯水反复超声洗涤），并通过离心分离（转速优选用5000-7000 r/min），然后真空干燥（优选在40-80 ℃真空干燥箱中干燥6-18 h，如12 h），研磨、过筛（优选过60-120目筛，如80目筛），即得CuBi2O4。The above-mentioned step (1) of the present invention adopts a hydrothermal method to prepare CuBi 2 O 4 with uniform morphology and structure. The above-mentioned step (1) is specifically, dissolving 0.04 molar portion of Bi(NO 3 ) 3 ·5H 2 O in 2-6 mL of concentrated HNO 3 , preferably 2-5 mL, more preferably 2.5-4 mL (such as 3 mL) , stir to make it completely dissolved, then add 20 mL of 0.02 mol of Cu(NO 3 ) 2 ·3H 2 O, stir to mix evenly, and then dropwise add 0.5-2 mol/L of alkaline precipitant solution, Preferably 0.8-1.5 mol/L alkaline precipitant solution, more preferably 1-1.4 mol/L (such as 1.2 mol/L) alkaline precipitating agent solution, and the solution after dropping is diluted to 50-100 mL, preferably 60-80 mL (such as 70 mL), continue to stir for 0.5-2 h, preferably after 0.8-1.5 h, transfer the solution to an autoclave, raise the temperature to 80-150 °C, preferably 90-110 °C ( Such as 100 ℃), react for 18-30 h, preferably 22-26 h (such as 24 h), after the reaction kettle is naturally cooled to room temperature, wash the precipitate obtained by the reaction (preferably with ultrapure water for repeated ultrasonic washing), and Centrifugal separation (the rotation speed is preferably 5000-7000 r/min), then vacuum drying (preferably drying in a vacuum drying oven at 40-80 °C for 6-18 h, such as 12 h), grinding, sieving (preferably 60-120 mesh sieve, such as 80 mesh sieve) to obtain CuBi 2 O 4 .

（2）CuBi2O4/β-Bi2O3的制备：将步骤（1）中所制备的CuBi2O4分散于葡萄糖酸溶液中，超声10-50 min后，将混合液移至反应釜中，升高温度至150-250 ℃，待反应釜自然冷却至室温后，通过离心分离回收反应得到的沉淀物，并将沉淀物洗涤，然后真空干燥，研磨、过筛，即得CuBi2O4@C。(2) Preparation of CuBi 2 O 4 / β- Bi 2 O 3 : Disperse the CuBi 2 O 4 prepared in step (1) in a gluconic acid solution, and after sonicating for 10-50 min, move the mixture to the reaction In the kettle, the temperature is raised to 150-250 °C, and after the reaction kettle is naturally cooled to room temperature, the precipitate obtained by the reaction is recovered by centrifugal separation, and the precipitate is washed, then vacuum-dried, ground and sieved to obtain CuBi 2 O 4 @C.

步骤（2）中，所述葡萄糖酸溶液中葡萄糖酸的体积为0.04-0.8 mL，优选0.1-0.6mL，进一步优选0.2-0.4 mL。In step (2), the volume of gluconic acid in the gluconic acid solution is 0.04-0.8 mL, preferably 0.1-0.6 mL, more preferably 0.2-0.4 mL.

本发明上述步骤（2）采用水热法制备CuBi2O4@C。上述步骤（2）具体为，将步骤（1）中所制备的CuBi2O4分散于70 mL葡萄糖酸溶液中（含葡萄糖酸的体积为0.04-0.8 mL，优选0.1-0.6 mL，进一步优选0.2-0.4 mL，如0.3 mL），超声10-50 min，优选20-40 min（如30min），将混合液移至100 mL高压反应釜中，升高温度至150-250 ℃，优选160-200 ℃（如180℃），反应2-10 h，优选2.5-6 h，再进一步优选3-5 h（如4 h），待反应釜自然冷却至室温后，通过转速为4000-10000 r/min，优选5000-7000 r/min（如6000 r/min）的离心机离心分离回收反应得到的固体沉淀物，并将固体沉淀物洗涤（优选用超纯水反复超声洗涤），然后真空干燥（优选在40-80 ℃真空干燥箱中干燥6-18 h，如在60 ℃真空干燥箱中干燥12 h），研磨、过筛（优选过60-120目筛，如过80目筛），即得CuBi2O4@C。The above-mentioned step (2) of the present invention adopts a hydrothermal method to prepare CuBi 2 O 4 @C. The above step (2) is specifically, the CuBi 2 O 4 prepared in the step (1) is dispersed in 70 mL of gluconic acid solution (the volume containing gluconic acid is 0.04-0.8 mL, preferably 0.1-0.6 mL, more preferably 0.2 mL). -0.4 mL, such as 0.3 mL), ultrasonicate for 10-50 min, preferably 20-40 min (such as 30 min), transfer the mixture to a 100 mL autoclave, raise the temperature to 150-250 ℃, preferably 160-200 ℃ (such as 180 ℃), the reaction is 2-10 h, preferably 2.5-6 h, and more preferably 3-5 h (such as 4 h), after the reaction kettle is naturally cooled to room temperature, the passing speed is 4000-10000 r/min , preferably 5000-7000 r/min (such as 6000 r/min) centrifuge centrifugation to recover the solid precipitate obtained by the reaction, wash the solid precipitate (preferably with repeated ultrasonic washing with ultrapure water), and then vacuum dry (preferably Dry in a vacuum drying oven at 40-80 °C for 6-18 h, such as drying in a vacuum drying oven at 60 °C for 12 h), grind and sieve (preferably through a 60-120 mesh sieve, such as through an 80 mesh sieve) to obtain CuBi 2 O 4 @C.

（3）CuBi2O4/β-Bi2O3的制备：将步骤（2）中所制备的CuBi2O4@C分散于HNO3溶液中，超声10-50 min，得到溶液A；将Bi(NO3)3·5H2O溶解于HNO3溶液中，室温下剧烈搅拌30-120min，得到溶液B；将碱式碳酸盐溶解于超纯水中，搅拌10-50 min，得到溶液C；先将溶液A和溶液B混合后磁力搅拌10-50 min，再向其中逐滴滴加溶液C，继续搅拌10-50 min，将反应产生的沉淀物洗涤，并通过离心分离收集沉淀物；将洗涤后的沉淀物放入程序升温炉，设置程序升温炉在10-60 min内升温至300-800 ℃，并在程序升温炉中反应2-10 h，待程序升温炉自然冷却至室温后，收集固体沉淀物，即可得到CuBi2O4/β-Bi2O3。 (3) Preparation of CuBi 2 O 4 / β- Bi 2 O 3 : Disperse the CuBi 2 O 4 @C prepared in step (2) in HNO 3 solution, and ultrasonicate for 10-50 min to obtain solution A; Dissolve Bi(NO 3 ) 3 ·5H 2 O in HNO 3 solution, stir vigorously for 30-120 min at room temperature to obtain solution B; dissolve basic carbonate in ultrapure water, stir for 10-50 min to obtain solution C; first mix solution A and solution B, then magnetically stir for 10-50 min, then add solution C dropwise to it, continue stirring for 10-50 min, wash the precipitate produced by the reaction, and collect the precipitate by centrifugation ; Put the washed precipitate into the programmed heating furnace, set the programmed heating furnace to heat up to 300-800 °C within 10-60 min, and react in the programmed heating furnace for 2-10 h, and let the programmed heating furnace cool down to room temperature naturally Then, collect the solid precipitate to obtain CuBi 2 O 4 / β- Bi 2 O 3 .

步骤（3）中，所述Bi(NO3)3·5H2O加入的摩尔量为0.1-3.6 mmol，优选0.2-2.5mmol，进一步优选0.25-1.5 mmol，再优选0.3-1.0 mmol，更优选0.35-0.5 mmol。In step (3), the molar amount of Bi(NO 3 ) 3 ·5H 2 O added is 0.1-3.6 mmol, preferably 0.2-2.5 mmol, more preferably 0.25-1.5 mmol, more preferably 0.3-1.0 mmol, more preferably 0.35-0.5 mmol.

步骤（3）中，所述碱式碳酸盐为碳酸钠、碳酸钾和碳酸铵中的一种或几种。In step (3), the basic carbonate is one or more of sodium carbonate, potassium carbonate and ammonium carbonate.

步骤（3）中，所述碱式碳酸盐与Bi(NO3)3·5H2O的摩尔量之比为（1-10）:1，优选（3-8）:1，进一步优选（5-7）:1。In step (3), the molar ratio of the basic carbonate to Bi(NO 3 ) 3 .5H 2 O is (1-10): 1, preferably (3-8): 1, more preferably ( 5-7): 1.

步骤（3）中，所述程序升温炉的温度升高至300-800 ℃，优选400-700 ℃，进一步优选500-650 ℃。In step (3), the temperature of the temperature-programmed furnace is increased to 300-800 °C, preferably 400-700 °C, more preferably 500-650 °C.

步骤（3）中，所述程序升温炉的反应时间为2-10 h，优选3-7 h，进一步优选4-6 h。In step (3), the reaction time of the temperature-programmed furnace is 2-10 h, preferably 3-7 h, more preferably 4-6 h.

本发明上述步骤（3）采用液相合成-煅烧相结合的技术制备CuBi2O4/β-Bi2O3。上述步骤（3）具体为，将步骤（2）中所制备的CuBi2O4@C分散于20 mL HNO3溶液（其中HNO3的浓度为0.5-4 mol/L，优选0.6-2 mol/L，进一步优选0.8-1.5 mol/L，如1.0 mol/L）中，超声10-50 min，优选20-40 min（如30 min），得到溶液A；将0.1-3.6 mmol，优选0.2-2.5 mmol，进一步优选0.25-1.5 mmol，再优选0.3-1.0 mmol，更优选0.35-0.5 mmol（如0.39 mmol）Bi(NO3)3·5H2O加入到20 mL HNO3溶液（其中HNO3的浓度为0.5-4 mol/L，优选0.6-2 mol/L，进一步优选0.8-1.5 mol/L，如1.0 mol/L）中，室温下剧烈搅拌30-120 min，优选40-90 min（如60 min），得到溶液B；将一定摩尔量的碱式碳酸盐（碱式碳酸盐与Bi(NO3)3·5H2O的摩尔量之比为（1-10）:1，优选（3-8）:1，进一步优选（5-7）:1，如6:1）加入到40 mL超纯水中，搅拌10-50 min，优选20-40 min（如30 min），得到溶液C。先将溶液A和溶液B混合后磁力搅拌10-50 min，优选20-40 min（如30 min），再向其中逐滴滴加溶液C，此时会产生大量白色沉淀，继续搅拌10-50 min，优选20-40 min（如30 min），通过转速为4000-10000 r/min，优选5000-7000 r/min（如6000 r/min）的离心机离心分离回收反应得到的固体沉淀物，并将固体沉淀物洗涤（优选用无水乙醇和超纯水反复超声洗涤）。将洗涤后的沉淀物放入程序升温炉，设置程序升温炉在10-60 min，优选20-40 min（如30 min）内升温至300-800 ℃，优选400-700 ℃，进一步优选500-650 ℃（如600 ℃），并在程序升温炉中反应2-10 h，优选3-7h，进一步优选4-6 h（如5 h），待程序升温炉自然冷却至室温后，收集固体沉淀物，即可得到CuBi2O4/β-Bi2O3。In the above-mentioned step (3) of the present invention, CuBi 2 O 4 / β- Bi 2 O 3 is prepared by the combined technique of liquid phase synthesis and calcination. The above step (3) is specifically, the CuBi 2 O 4 @C prepared in step (2) is dispersed in 20 mL of HNO 3 solution (wherein the concentration of HNO 3 is 0.5-4 mol/L, preferably 0.6-2 mol/ L, more preferably 0.8-1.5 mol/L, such as 1.0 mol/L), ultrasonication for 10-50 min, preferably 20-40 min (such as 30 min), to obtain solution A; 0.1-3.6 mmol, preferably 0.2-2.5 mmol, more preferably 0.25-1.5 mmol, more preferably 0.3-1.0 mmol, more preferably 0.35-0.5 mmol (such as 0.39 mmol) Bi(NO 3 ) 3 5H 2 O was added to 20 mL of HNO 3 solution (wherein the concentration of HNO 3 0.5-4 mol/L, preferably 0.6-2 mol/L, more preferably 0.8-1.5 mol/L, such as 1.0 mol/L), vigorously stir at room temperature for 30-120 min, preferably 40-90 min (such as 60 min) to obtain solution B; a certain molar amount of basic carbonate (the molar ratio of basic carbonate to Bi(NO 3 ) 3 5H 2 O is (1-10): 1, preferably ( 3-8): 1, more preferably (5-7): 1, such as 6: 1) is added to 40 mL of ultrapure water, stirred for 10-50 min, preferably 20-40 min (such as 30 min), to obtain a solution C. First mix solution A and solution B, stir magnetically for 10-50 min, preferably 20-40 min (such as 30 min), and then add solution C dropwise to it. At this time, a large amount of white precipitate will be produced, continue stirring for 10-50 min. min, preferably 20-40 min (such as 30 min), the solid precipitate obtained by the reaction is recovered by centrifugation with a centrifuge with a rotating speed of 4000-10000 r/min, preferably 5000-7000 r/min (such as 6000 r/min), And the solid precipitate is washed (preferably with repeated ultrasonic washing with absolute ethanol and ultrapure water). Put the washed precipitate into a programmed heating furnace, set the programmed heating furnace to heat up to 300-800 °C, preferably 400-700 °C, more preferably 500-500 °C within 10-60 min, preferably 20-40 min (such as 30 min). 650 ℃ (such as 600 ℃), and react in a temperature-programmed furnace for 2-10 h, preferably 3-7 h, more preferably 4-6 h (such as 5 h), after the temperature-programmed furnace is naturally cooled to room temperature, collect the solid precipitate Then, CuBi 2 O 4 / β- Bi 2 O 3 can be obtained.

本发明还提供一种可见光响应型复合光催化剂的应用，其中，将如上任一所述的可见光响应型复合光催化剂应用于处理含有非甾体类抗炎药（如双氯芬酸）的废水。The present invention also provides an application of a visible light responsive composite photocatalyst, wherein the visible light responsive composite photocatalyst as described above is applied to the treatment of wastewater containing non-steroidal anti-inflammatory drugs (such as diclofenac).

本发明的可见光响应型复合光催化剂的应用方法是向含有非甾体类抗炎药的模拟废水（如双氯芬酸水溶液）中加入可见光响应型复合光催化剂，即CuBi2O4/β-Bi2O3，先进行暗吸附反应，待达到平衡后进行可见光光照。在应用过程中按一定时间间隔取样测定废水中非甾体类抗炎药（如双氯芬酸）的浓度。The application method of the visible light responsive composite photocatalyst of the present invention is to add the visible light responsive composite photocatalyst, namely CuBi 2 O 4 / β- Bi 2 O, to the simulated wastewater (such as diclofenac aqueous solution) containing non-steroidal anti-inflammatory drugs 3. The dark adsorption reaction is carried out first, and the visible light irradiation is carried out after the equilibrium is reached. The concentration of non-steroidal anti-inflammatory drugs (such as diclofenac) in wastewater was determined by sampling at certain time intervals during the application process.

优选地，在应用中，CuBi2O4/β-Bi2O3的用量是：废水中所含的非甾体类抗炎药（如双氯芬酸）与CuBi2O4/β-Bi2O3的质量之比为1:（10-150），优选1:（50-120），进一步优选1:（70-100），如1:80。Preferably, in application, the dosage of CuBi 2 O 4 / β- Bi 2 O 3 is: the non-steroidal anti-inflammatory drugs (such as diclofenac) contained in the wastewater and CuBi 2 O 4 / β- Bi 2 O 3 The mass ratio is 1:(10-150), preferably 1:(50-120), more preferably 1:(70-100), such as 1:80.

本发明首先利用水热合成法制备形貌结构均匀、化学性质稳定的可见光响应型半导体CuBi2O4和核壳结构CuBi2O4@C，在此基础上，通过液相合成-煅烧相结合的技术在程序升温的条件下得到CuBi2O4/β-Bi2O3。相较纯β-Bi2O3，本发明所制备的可见光响应型复合光催化剂具有可见光吸收强度更高、光催化性能更好、循环利用率更高等优点。In the present invention, the visible light responsive semiconductor CuBi 2 O 4 and the core-shell structure CuBi 2 O 4 @C with uniform morphology and stable chemical properties are prepared by hydrothermal synthesis method. The technology obtained CuBi 2 O 4 / β- Bi 2 O 3 under temperature-programmed conditions. Compared with pure β- Bi 2 O 3 , the visible light-responsive composite photocatalyst prepared in the present invention has the advantages of higher visible light absorption intensity, better photocatalytic performance, higher recycling rate and the like.

下面通过实施例对本发明进行详细说明。The present invention will be described in detail below through examples.

实施例1Example 1

可见光响应型复合光催化剂的制备：Preparation of visible light-responsive composite photocatalysts:

（1）、首先采用水热法制备形貌结构均匀的CuBi2O4，即将0.04摩尔份的Bi(NO3)3·5H2O溶解在3 mL浓HNO3中，搅拌使其完全溶解，再加入20 mL 0.02摩尔份的Cu(NO3)2·3H2O，搅拌使其混合均匀，而后逐滴滴加20 mL 1.2 mol/L的NaOH，并将滴加后的混合液稀释至70mL，继续搅拌1 h后，将该混合液转移至高压反应釜中，升高温度至100 ℃，反应24 h，待反应釜自然冷却至室温后，将反应得到的沉淀物用超纯水反复超声洗涤，并在6000 r/min的转速下离心分离，然后在60 ℃真空干燥箱中干燥12 h，研磨、过80目筛，即得CuBi2O4。(1) First, CuBi 2 O 4 with uniform morphology and structure was prepared by hydrothermal method, that is, 0.04 mol of Bi(NO 3 ) 3 ·5H 2 O was dissolved in 3 mL of concentrated HNO 3 , and stirred to make it completely dissolved, Then add 20 mL of 0.02 mol portion of Cu(NO 3 ) 2 ·3H 2 O, stir to mix evenly, then dropwise add 20 mL of 1.2 mol/L NaOH, and dilute the dropwise mixture to 70 mL , after stirring for 1 h, the mixture was transferred to an autoclave, the temperature was raised to 100 °C, and the reaction was carried out for 24 h. After the reaction kettle was naturally cooled to room temperature, the precipitate obtained by the reaction was repeatedly sonicated with ultrapure water. Washed and centrifuged at 6000 r/min, then dried in a vacuum drying oven at 60 °C for 12 h, ground and passed through an 80-mesh sieve to obtain CuBi 2 O 4 .

（2）、再进一步采用水热法制备CuBi2O4@C。即准确称取0.1 g步骤（1）中所制备的CuBi2O4分散于70 mL葡萄糖酸溶液中（含有0.3 mL葡萄糖酸），超声30 min后，将混合液移至100 mL高压反应釜中，升高温度至180 ℃，反应4 h，待反应釜自然冷却至室温后，将沉淀物用超纯水反复超声洗涤，并在6000 r/min的转速下离心分离，然后在60 ℃真空干燥箱中干燥12 h，研磨、过80目筛，即得质量比为1:1.4的CuBi2O4@C。(2), and further adopt the hydrothermal method to prepare CuBi 2 O 4 @C. That is, 0.1 g of CuBi 2 O 4 prepared in step (1) was accurately weighed and dispersed in 70 mL of gluconic acid solution (containing 0.3 mL of gluconic acid), and after sonicating for 30 min, the mixture was transferred to a 100 mL autoclave. , raise the temperature to 180 °C, and react for 4 h. After the reactor was naturally cooled to room temperature, the precipitate was repeatedly ultrasonically washed with ultrapure water, centrifuged at 6000 r/min, and then vacuum-dried at 60 °C. Dry in an oven for 12 h, grind and pass through an 80-mesh sieve to obtain CuBi 2 O 4 @C with a mass ratio of 1:1.4.

（3）、最后采用液相合成-煅烧相结合的技术制备CuBi2O4/β-Bi2O3。准确称取0.1 g步骤（2）中所制备的CuBi2O4@C分散于20 mL HNO3溶液（1 mol/L）中，超声30 min使其充分分散，得到溶液A；将0.39 mmol Bi(NO3)3·5H2O加入到20 mL HNO3溶液（1 mol/L）中，室温下剧烈搅拌1 h使其完全溶解，得到溶液B；将2.34 mmol Na2CO3加入到40 mL超纯水中，搅拌30min，得到溶液C。先将溶液A和溶液B混合后磁力搅拌30 min，使其混合均匀，再向其中逐滴滴加溶液C，此时会产生大量白色沉淀，继续搅拌30 min后，用无水乙醇和去离子水洗涤沉淀物。而后将洗涤后的沉淀物放入程序升温炉，设置程序升温炉在30 min内升温至600 ℃，并在600 ℃反应5 h，待程序升温炉自然冷却至室温后，即可得到质量比为1:2.25的CuBi2O4/β-Bi2O3。所制得CuBi2O4/β-Bi2O3的SEM（扫描电子显微镜图）、XRD（X射线衍射图谱）、UV-Vis（紫外-可见漫反射光谱）表征结果分别见图1至图3。由SEM可看到，可见光响应型复合光催化剂中CuBi2O4为空心微米球，β-Bi2O3为不规则纳米颗粒，并经XRD分析证明了可见光响应型复合光催化剂的成分主要是CuBi2O4和β-Bi2O3，UV-Vis图谱则可以看到，CuBi2O4/β-Bi2O3在整个可见光谱范围内均有较高的光吸收强度。(3) Finally, CuBi 2 O 4 / β- Bi 2 O 3 was prepared by the combination of liquid phase synthesis and calcination. Accurately weigh 0.1 g of CuBi 2 O 4 @C prepared in step (2) and disperse it in 20 mL of HNO 3 solution (1 mol/L), and ultrasonicate for 30 min to fully disperse to obtain solution A; 0.39 mmol Bi (NO 3 ) 3 ·5H 2 O was added to 20 mL of HNO 3 solution (1 mol/L), stirred vigorously for 1 h at room temperature to completely dissolve to obtain solution B; 2.34 mmol of Na 2 CO 3 was added to 40 mL of In ultrapure water, stir for 30 min to obtain solution C. First mix solution A and solution B, and then magnetically stir for 30 min to make it evenly mixed, and then add solution C dropwise to it. At this time, a large amount of white precipitate will be formed. After stirring for 30 min, use absolute ethanol and deionized The precipitate was washed with water. Then, the washed precipitate was put into a programmed heating furnace, and the programmed heating furnace was set to heat up to 600 °C within 30 min, and reacted at 600 °C for 5 h. After the programmed heating furnace was naturally cooled to room temperature, the mass ratio was obtained as 1:2.25 of CuBi 2 O 4 / β- Bi 2 O 3 . The characterization results of SEM (scanning electron microscope), XRD (X-ray diffraction pattern) and UV-Vis (ultraviolet-visible diffuse reflectance spectrum) of the prepared CuBi 2 O 4 / β- Bi 2 O 3 are shown in Fig. 1 to Fig. 3. It can be seen from SEM that CuBi 2 O 4 in the visible light responsive composite photocatalyst is a hollow microsphere, and β- Bi 2 O 3 is an irregular nanoparticle. The XRD analysis proves that the visible light responsive composite photocatalyst is mainly composed of CuBi 2 O 4 and β -Bi 2 O 3 , the UV-Vis spectrum shows that CuBi 2 O 4 / β -Bi 2 O 3 has higher light absorption intensity in the entire visible spectral range.

可见光响应型复合光催化剂应用于去除水中双氯芬酸的性能测试：在1 L 5 mg/L双氯芬酸溶液中，投加0.4 g上述可见光响应型复合光催化剂，先进行暗吸附反应30 min达到吸附平衡后，再在300 W氙灯照射条件下光催化反应3 h，实验结束后通过离心使固液分离，并测定上清液中双氯芬酸残余浓度，该可见光响应型复合光催化剂的光催化性能如图4。由测试结果可知，可见光响应型复合光催化剂对双氯芬酸的去除效率为89.02%，远远高于纯β-Bi2O3对双氯芬酸的去除效率（60.19%）。The performance test of the visible light responsive composite photocatalyst applied to the removal of diclofenac in water: in 1 L 5 mg/L diclofenac solution, 0.4 g of the above visible light responsive composite photocatalyst was added, and the dark adsorption reaction was carried out for 30 min to reach the adsorption equilibrium. The photocatalytic reaction was carried out under 300 W xenon lamp irradiation for 3 h. After the experiment, the solid-liquid was separated by centrifugation, and the residual concentration of diclofenac in the supernatant was measured. The photocatalytic performance of the visible light-responsive composite photocatalyst is shown in Figure 4. It can be seen from the test results that the removal efficiency of diclofenac by the visible light-responsive composite photocatalyst is 89.02%, which is much higher than that of pure β- Bi 2 O 3 (60.19%).

实施例2Example 2

可见光响应型复合光催化剂的制备与实施例1相同。The preparation of the visible light-responsive composite photocatalyst is the same as that in Example 1.

可见光响应型复合光催化剂应用于去除水中双氯芬酸的性能测试：在1 L 5 mg/L双氯芬酸溶液中，投加0.2 g上述可见光响应型复合光催化剂，先进行暗吸附反应30 min达到吸附平衡后，再在300 W氙灯照射条件下光催化反应3 h，实验结束后通过离心使固液分离，并测定上清液中双氯芬酸残余浓度。由测试结果可知，可见光响应型复合光催化剂对双氯芬酸的去除效率为80.49%。The performance test of the visible light responsive composite photocatalyst applied to the removal of diclofenac in water: 0.2 g of the above visible light responsive composite photocatalyst was added to 1 L 5 mg/L diclofenac solution, and the dark adsorption reaction was carried out for 30 min to reach the adsorption equilibrium. The photocatalytic reaction was carried out under 300 W xenon lamp irradiation for 3 h. After the experiment, the solid-liquid was separated by centrifugation, and the residual concentration of diclofenac in the supernatant was determined. It can be seen from the test results that the removal efficiency of diclofenac by the visible light-responsive composite photocatalyst is 80.49%.

实施例3Example 3

可见光响应型复合光催化剂的制备与实施例1相同，只是葡萄糖酸溶液中葡萄糖酸的体积为0.6 mL。The preparation of the visible light-responsive composite photocatalyst is the same as that in Example 1, except that the volume of gluconic acid in the gluconic acid solution is 0.6 mL.

可见光响应型复合光催化剂应用于去除水中双氯芬酸的性能测试：在1 L 5 mg/L双氯芬酸溶液中，投加0.4 g上述可见光响应型复合光催化剂，先进行暗吸附反应30 min达到吸附平衡后，再在300 W氙灯照射条件下光催化反应3 h，实验结束后通过离心使固液分离，并测定上清液中双氯芬酸残余浓度。由测试结果可知，可见光响应型复合光催化剂对双氯芬酸的去除效率为78.62%。The performance test of the visible light responsive composite photocatalyst applied to the removal of diclofenac in water: in 1 L 5 mg/L diclofenac solution, 0.4 g of the above visible light responsive composite photocatalyst was added, and the dark adsorption reaction was carried out for 30 min to reach the adsorption equilibrium. The photocatalytic reaction was carried out under 300 W xenon lamp irradiation for 3 h. After the experiment, the solid-liquid was separated by centrifugation, and the residual concentration of diclofenac in the supernatant was determined. It can be seen from the test results that the removal efficiency of visible light responsive composite photocatalyst on diclofenac is 78.62%.

实施例4Example 4

可见光响应型复合光催化剂的制备：Preparation of visible light-responsive composite photocatalysts:

（1）、CuBi2O4的制备与实施例1相同。(1) The preparation of CuBi 2 O 4 is the same as that of Example 1.

（2）、CuBi2O4@C的制备与实施例1相同。(2) The preparation of CuBi 2 O 4 @C is the same as in Example 1.

（3）、最后，采用液相合成-煅烧相结合的技术制备CuBi2O4/β-Bi2O3。准确称取0.1g步骤（2）中所制备的CuBi2O4@C分散于20 mL HNO3溶液（1 mol/L）中，超声30 min使其充分分散，得到溶液A；将1.29 mmol Bi(NO3)3·5H2O加入到20 mL HNO3溶液（1 mol/L）中，室温下剧烈搅拌1 h使其完全溶解，得到溶液B；将7.74 mmol Na2CO3加入到40 mL超纯水中，搅拌30 min，得到溶液C。先将溶液A和溶液B混合后磁力搅拌30 min，使其混合均匀，再向其中逐滴滴加溶液C，此时会产生大量白色沉淀，继续搅拌30 min后，用无水乙醇和去离子水洗涤沉淀物。而后将洗涤后的沉淀物放入程序升温炉，设置程序升温炉在30 min内升温至600℃，并在600 ℃反应5 h，待程序升温炉自然冷却至室温后，即可得到质量比为1:6的CuBi2O4/β-Bi2O3。(3) Finally, CuBi 2 O 4 / β- Bi 2 O 3 was prepared by the combined technique of liquid phase synthesis and calcination. Accurately weigh 0.1 g of CuBi 2 O 4 @C prepared in step (2) and disperse it in 20 mL of HNO 3 solution (1 mol/L), and ultrasonicate for 30 min to fully disperse to obtain solution A; (NO 3 ) 3 ·5H 2 O was added to 20 mL of HNO 3 solution (1 mol/L), and stirred vigorously for 1 h at room temperature to completely dissolve to obtain solution B; 7.74 mmol of Na 2 CO 3 was added to 40 mL of The solution C was obtained by stirring for 30 min in ultrapure water. First mix solution A and solution B, and then magnetically stir for 30 min to make it evenly mixed, and then add solution C dropwise to it. At this time, a large amount of white precipitate will be formed. After stirring for 30 min, use absolute ethanol and deionized The precipitate was washed with water. Then, the washed precipitate was put into a programmed heating furnace, and the programmed heating furnace was set to heat up to 600 °C within 30 min, and reacted at 600 °C for 5 h. After the programmed heating furnace was naturally cooled to room temperature, the mass ratio was obtained as 1:6 CuBi 2 O 4 / β- Bi 2 O 3 .

可见光响应型复合光催化剂应用于去除水中双氯芬酸的性能测试：在1 L 5 mg/L双氯芬酸溶液中，投加0.4 g上述可见光响应型复合光催化剂，先进行暗吸附反应30 min达到吸附平衡后，再在300 W氙灯照射条件下光催化反应3 h，实验结束后通过离心使固液分离，并测定上清液中双氯芬酸残余浓度。由测试结果可知，可见光响应型复合光催化剂对双氯芬酸的去除效率为81.36%。The performance test of the visible light responsive composite photocatalyst applied to the removal of diclofenac in water: in 1 L 5 mg/L diclofenac solution, 0.4 g of the above visible light responsive composite photocatalyst was added, and the dark adsorption reaction was carried out for 30 min to reach the adsorption equilibrium. The photocatalytic reaction was carried out under 300 W xenon lamp irradiation for 3 h. After the experiment, the solid-liquid was separated by centrifugation, and the residual concentration of diclofenac in the supernatant was determined. It can be seen from the test results that the removal efficiency of diclofenac by the visible light-responsive composite photocatalyst is 81.36%.

实施例5Example 5

可见光响应型复合光催化剂的制备与实施例1相同，只是程序升温炉的反应温度为500 ℃。The preparation of the visible light-responsive composite photocatalyst was the same as that in Example 1, except that the reaction temperature of the temperature-programmed furnace was 500°C.

可见光响应型复合光催化剂应用于去除水中双氯芬酸的性能测试：在1 L 5 mg/L双氯芬酸溶液中，投加0.4 g上述可见光响应型复合光催化剂，先进行暗吸附反应30 min达到吸附平衡后，再在300 W氙灯照射条件下光催化反应3 h，实验结束后通过离心使固液分离，并测定上清液中双氯芬酸残余浓度。由测试结果可知，可见光响应型复合光催化剂对双氯芬酸的去除效率为85.27%。The performance test of the visible light responsive composite photocatalyst applied to the removal of diclofenac in water: in 1 L 5 mg/L diclofenac solution, 0.4 g of the above visible light responsive composite photocatalyst was added, and the dark adsorption reaction was carried out for 30 min to reach the adsorption equilibrium. The photocatalytic reaction was carried out under 300 W xenon lamp irradiation for 3 h. After the experiment, the solid-liquid was separated by centrifugation, and the residual concentration of diclofenac in the supernatant was determined. It can be seen from the test results that the removal efficiency of diclofenac by the visible light-responsive composite photocatalyst is 85.27%.

实施例6Example 6

可见光响应型复合光催化剂的制备与实施例3相同，只是程序升温炉的反应温度为700 ℃。The preparation of the visible light-responsive composite photocatalyst was the same as that in Example 3, except that the reaction temperature of the temperature-programmed furnace was 700°C.

可见光响应型复合光催化剂应用于去除水中双氯芬酸的性能测试：在1 L 5 mg/L双氯芬酸溶液中，投加0.4 g上述可见光响应型复合光催化剂，先进行暗吸附反应30 min达到吸附平衡后，再在300 W氙灯照射条件下光催化反应3 h，实验结束后通过离心使固液分离，并测定上清液中双氯芬酸残余浓度。由测试结果可知，可见光响应型复合光催化剂对双氯芬酸的去除效率为83.78%。The performance test of the visible light responsive composite photocatalyst applied to the removal of diclofenac in water: in 1 L 5 mg/L diclofenac solution, 0.4 g of the above visible light responsive composite photocatalyst was added, and the dark adsorption reaction was carried out for 30 min to reach the adsorption equilibrium. The photocatalytic reaction was carried out under 300 W xenon lamp irradiation for 3 h. After the experiment, the solid-liquid was separated by centrifugation, and the residual concentration of diclofenac in the supernatant was determined. It can be seen from the test results that the removal efficiency of diclofenac by the visible light-responsive composite photocatalyst is 83.78%.

实施例7Example 7

可见光响应型复合光催化剂的制备与实施例1相同，只是程序升温炉的反应时间为3 h。The preparation of the visible light-responsive composite photocatalyst was the same as that in Example 1, except that the reaction time of the temperature-programmed furnace was 3 h.

可见光响应型复合光催化剂应用于去除水中双氯芬酸的性能测试：在1 L 5 mg/L双氯芬酸溶液中，投加0.4 g上述可见光响应型复合光催化剂，先进行暗吸附反应30 min达到吸附平衡后，再在300 W氙灯照射条件下光催化反应3 h，实验结束后通过离心使固液分离，并测定上清液中双氯芬酸残余浓度。由测试结果可知，可见光响应型复合光催化剂对双氯芬酸的去除效率为75.92%。The performance test of the visible light responsive composite photocatalyst applied to the removal of diclofenac in water: in 1 L 5 mg/L diclofenac solution, 0.4 g of the above visible light responsive composite photocatalyst was added, and the dark adsorption reaction was carried out for 30 min to reach the adsorption equilibrium. The photocatalytic reaction was carried out under 300 W xenon lamp irradiation for 3 h. After the experiment, the solid-liquid was separated by centrifugation, and the residual concentration of diclofenac in the supernatant was determined. It can be seen from the test results that the removal efficiency of diclofenac by the visible light-responsive composite photocatalyst is 75.92%.

实施例8Example 8

可见光响应型复合光催化剂的制备与实施例1相同。The preparation of the visible light-responsive composite photocatalyst is the same as that in Example 1.

可见光响应型复合光催化剂应用于去除水中双氯芬酸的性能测试：在1 L 20 mg/L双氯芬酸溶液中，投加0.4 g上述可见光响应型复合光催化剂，先进行暗吸附反应30 min达到吸附平衡后，再在300 W氙灯照射条件下光催化反应3 h，实验结束后通过离心使固液分离，并测定上清液中双氯芬酸残余浓度，由测试结果可知，可见光响应型复合光催化剂对双氯芬酸的去除效率为72.46%。The performance test of the visible light responsive composite photocatalyst applied to the removal of diclofenac in water: in 1 L 20 mg/L diclofenac solution, 0.4 g of the above visible light responsive composite photocatalyst was added, and the dark adsorption reaction was carried out for 30 min to reach the adsorption equilibrium. Then, the photocatalytic reaction was carried out under the condition of 300 W xenon lamp irradiation for 3 h. After the experiment, the solid-liquid separation was carried out by centrifugation, and the residual concentration of diclofenac in the supernatant was measured. From the test results, it can be seen that the visible light-responsive composite photocatalyst has a removal efficiency of diclofenac. was 72.46%.

实施例9：Example 9:

可见光响应型复合光催化剂的制备与实施例1相同。The preparation of the visible light-responsive composite photocatalyst is the same as that in Example 1.

可见光响应型复合光催化剂重复应用于去除水中有机物的性能测试：在1 L 5mg/L双氯芬酸溶液中，投加0.4 g上述可见光响应型复合光催化剂，先进行暗吸附反应30min达到吸附平衡后，再在300 W氙灯照射条件下光催化反应3 h，实验结束后通过离心使固液分离，并测定上清液中双氯芬酸残余浓度。回收的可见光响应型复合光催化剂经超纯水洗涤数次、在60 ℃真空干燥箱中干燥后，研磨，过80目筛，再次应用于双氯芬酸废水处理，处理过程同上，其重复利用效率如图5所示，由测试结果可知，可见光响应型复合光催化剂重复利用第七次时，其对双氯芬酸的降解效率为78.43%。The performance test of the visible-light-responsive composite photocatalyst repeatedly applied to the removal of organic matter in water: add 0.4 g of the above-mentioned visible-light-responsive composite photocatalyst to 1 L of 5mg/L diclofenac solution, first perform a dark adsorption reaction for 30 min to reach the adsorption equilibrium, and then add 0.4 g of the above-mentioned visible light-responsive composite photocatalyst. The photocatalytic reaction was carried out under 300 W xenon lamp irradiation for 3 h. After the experiment, the solid-liquid was separated by centrifugation, and the residual concentration of diclofenac in the supernatant was determined. The recovered visible light-responsive composite photocatalyst was washed several times with ultrapure water, dried in a vacuum drying oven at 60 °C, ground, passed through an 80-mesh sieve, and used again in the treatment of diclofenac wastewater. The treatment process is the same as above, and its reuse efficiency is shown in the figure 5, it can be seen from the test results that when the visible light-responsive composite photocatalyst is reused for the seventh time, its degradation efficiency to diclofenac is 78.43%.

综上所述，本发明提供的一种可见光响应型复合光催化剂及其制备方法和应用，本发明首先利用水热合成法制备形貌结构均匀、化学性质稳定的可见光响应型半导体CuBi2O4和核壳结构CuBi2O4@C，在此基础上，通过液相合成-煅烧相结合的技术在程序升温的条件下得到CuBi2O4/β-Bi2O3。本发明所制备的可见光响应型复合光催化剂在整个可见光谱范围内均有较强吸收，且相较纯β-Bi2O3具有更好的光催化性能和更高的循环利用率。将0.4 g的CuBi2O4/β-Bi2O3（1:2.25，wt%）用于处理双氯芬酸难降解有机废水，可见光照射3h，对1 L 5 mg/L双氯芬酸溶液的去除率为89.02%，重复利用第七次，对双氯芬酸溶液去除率为78.43%。To sum up, the present invention provides a visible light responsive composite photocatalyst and its preparation method and application. The present invention firstly utilizes a hydrothermal synthesis method to prepare a visible light responsive semiconductor CuBi 2 O 4 with uniform morphology and structure and stable chemical properties and core-shell structure CuBi 2 O 4 @C, on this basis, CuBi 2 O 4 / β- Bi 2 O 3 was obtained by a combination of liquid phase synthesis and calcination under temperature-programmed conditions. The visible light-responsive composite photocatalyst prepared by the invention has strong absorption in the entire visible spectrum range, and has better photocatalytic performance and higher recycling rate than pure β- Bi 2 O 3 . 0.4 g of CuBi 2 O 4 / β- Bi 2 O 3 (1:2.25, wt%) was used to treat diclofenac refractory organic wastewater, irradiated with visible light for 3 h, the removal rate of 1 L 5 mg/L diclofenac solution was 89.02 %, reused for the seventh time, the removal rate of diclofenac solution was 78.43%.

应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。It should be understood that the application of the present invention is not limited to the above examples. For those of ordinary skill in the art, improvements or transformations can be made according to the above descriptions, and all these improvements and transformations should belong to the protection scope of the appended claims of the present invention.

Claims (8)

1. a kind of preparation method of visible-light response type composite photo-catalyst, which is characterized in that the visible-light response type is compound Photochemical catalyst is CuBi2O4/β-Bi2O3, CuBi in the visible-light response type composite photo-catalyst2O4For hollow sub-microsphere,β- Bi2O3For irregular nano particle, and CuBi2O4Withβ-Bi2O3Between be in close contact, CuBi2O4/β-Bi2O3In, CuBi2O4Withβ-Bi2O3Mass ratio be 1:(0.5-20)；The preparation method comprises the following steps:
(1) CuBi2O4Preparation: by Bi (NO3)3·5H2O is dissolved in dense HNO3In, it stirs to being completely dissolved, adds Cu (NO3)2·3H2The alkaline sedimentation agent solution of 0.5-2 mol/L is then added dropwise to being uniformly mixed in O, stirring dropwise, and will be after dropwise addition Solution dilution continues after stirring 0.5-2 h, solution is transferred in reaction kettle, increases temperature to 80-150 DEG C, reacts 18-30 H, after reaction kettle is cooled to room temperature, the sediment that reaction is obtained is washed, and by centrifuge separation, is then dried in vacuo, is ground Mill is sieved to get CuBi2O4；
(2) CuBi2O4The preparation of@C: by CuBi prepared in step (1)2O4It is scattered in gluconic acid solution, ultrasonic 10-50 After min, mixed liquor is moved in reaction kettle, temperature is increased to 150-250 DEG C, after reaction kettle cooled to room temperature, passes through The obtained sediment of centrifuge separation recycling reaction, and sediment is washed, is then dried in vacuo, be ground up, sieved to get CuBi2O4@C；
(3) CuBi2O4/β-Bi2O3Preparation: by CuBi prepared in step (2)2O4@C is scattered in HNO3In solution, ultrasound 10-50 min, obtains solution A；By Bi (NO3)3·5H2O is dissolved in HNO3In solution, it is vigorously stirred 30-120 min at room temperature, Obtain solution B；Subcarbonate is dissolved in ultrapure water, 10-50 min is stirred, obtains solution C；First by solution A and solution B Magnetic agitation 10-50 min after mixing, then solution C is added dropwise dropwise thereto, continue to stir 10-50 min, reaction is generated Sediment washing, and sediment is collected by centrifuge separation；Sediment after washing is put into temperature programming furnace, program liter is set Warm furnace is warming up to 300-800 DEG C in 10-60 min, and 2-10 h is reacted in temperature programming furnace, natural to temperature programming furnace After being cooled to room temperature, solid sediment is collected, CuBi can be obtained2O4/β-Bi2O3。
2. the preparation method of visible-light response type composite photo-catalyst according to claim 1, which is characterized in that step (1) in, the alkaline precipitating agent in the alkaline sedimentation agent solution is one of sodium hydroxide, potassium hydroxide and ammonium hydroxide or more Kind.
3. the preparation method of visible-light response type composite photo-catalyst according to claim 1, which is characterized in that step (2) in, the volume of gluconic acid is 0.04-0.8 mL in the gluconic acid solution.
4. the preparation method of visible-light response type composite photo-catalyst according to claim 1, which is characterized in that step (3) in, the Bi (NO3)3·5H2The mole that O is added is 0.1-3.6 mmol.
5. the preparation method of visible-light response type composite photo-catalyst according to claim 1, which is characterized in that step (3) in, the subcarbonate and Bi (NO3)3·5H2The ratio between mole of O is (1-10): 1.
6. the preparation method of visible-light response type composite photo-catalyst according to claim 1, which is characterized in that step (3) in, the temperature of described program heating furnace is increased to 300-800 DEG C.
7. the preparation method of visible-light response type composite photo-catalyst according to claim 1, which is characterized in that step (3) in, the reaction time of described program heating furnace is 2-10 h.
8. a kind of application of visible-light response type composite photo-catalyst, which is characterized in that will be as claimed in claim 1 The visible-light response type composite photo-catalyst that preparation method is prepared is applied to waste water of the processing containing non-steroid anti-inflammatory drug.
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