CN116351454A - Bismuth oxychloride photocatalyst anchored by nitrogen-doped carbon quantum dots, and preparation and application thereof - Google Patents

Bismuth oxychloride photocatalyst anchored by nitrogen-doped carbon quantum dots, and preparation and application thereof Download PDF

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CN116351454A
CN116351454A CN202310344341.XA CN202310344341A CN116351454A CN 116351454 A CN116351454 A CN 116351454A CN 202310344341 A CN202310344341 A CN 202310344341A CN 116351454 A CN116351454 A CN 116351454A
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CN116351454B (en
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郭佳茵
孙海波
梁婕
袁兴中
李欢
郭海
赵燕兰
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Hunan University of Technology
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Abstract

The invention discloses a bismuth oxychloride photocatalyst anchored by nitrogen-doped carbon quantum dots, and preparation and application thereof, comprising bismuth oxychloride with a {010} crystal face mainly exposed and nitrogen-doped carbon quantum dots, wherein the nitrogen-doped carbon quantum dots are anchored on the {010} crystal face exposed by bismuth oxychloride. {010} bismuth oxychloride is an ultrathin irregular nano-sheet structure, and the mass percentage of the doped carbon quantum dots is 0.01% -0.08%. The photocatalyst is prepared by mixing bismuth nitrate pentahydrate with nitrogen-doped carbon quantum dot solution, adjusting pH by alkaline solution, and performing hydrothermal reaction, wherein the nitrogen-doped carbon quantum dot solution is prepared by performing hydrothermal reaction on ammonium citrate and ethylenediamine. The catalyst expands the photoresponse range by utilizing the synergistic effect of the high-energy exposed crystal face and the nitrogen doped carbon quantum dots, promotes the migration of photo-generated carriers and accelerates the generation of surface oxidation-reduction reaction, achieves the aim of improving the photocatalytic performance of bismuth oxychloride, has the degradation efficiency of 85.2% in wastewater polluted by antibiotics, and has the advantages of stable photocatalytic performance, strong corrosion resistance and the like.

Description

氮掺杂碳量子点锚定的氯氧化铋光催化剂及其制备与应用Bismuth oxychloride photocatalyst anchored by nitrogen-doped carbon quantum dots and its preparation and application

技术领域technical field

本发明属于光催化技术领域,特别涉及了一种氮掺杂碳量子点锚定的氯氧化铋光催化剂及其制备与应用。The invention belongs to the technical field of photocatalysis, and in particular relates to a bismuth oxychloride photocatalyst anchored by nitrogen-doped carbon quantum dots and its preparation and application.

背景技术Background technique

抗生素是最受欢迎的多功能药物之一,因为它们不仅可以应用于疾病治疗、感染预防还可应用于促进动植物生长等。由此产生的抗生素滥用导致大量抗生素残留物通过水土流失、动物粪便和废水排放进入水生生态系统,严重威胁到生态安全和人类健康。将半导体光催化技术应用于降解水中抗生素等有毒有害持久性污染物对解决水污染问题具有重大意义。然而,光响应能力弱以及光生载流子低利用率仍然是半导体光催化剂的设计瓶颈。因此,积极开发高效可再生的具有可见光响应的光催化剂,充分发挥太阳能的作用,具有重要的意义。Antibiotics are one of the most popular multifunctional drugs because they can be used not only in disease treatment, infection prevention but also in promoting the growth of animals and plants, etc. The resulting abuse of antibiotics has led to a large amount of antibiotic residues entering aquatic ecosystems through soil erosion, animal manure and wastewater discharge, seriously threatening ecological security and human health. The application of semiconductor photocatalysis technology to degrade toxic and harmful persistent pollutants such as antibiotics in water is of great significance to solve the problem of water pollution. However, weak photoresponsiveness and low utilization of photogenerated carriers are still the bottlenecks in the design of semiconductor photocatalysts. Therefore, it is of great significance to actively develop efficient and renewable photocatalysts with visible light response to fully utilize solar energy.

氯氧化铋由于其高化学稳定性,独特的层状结构,耐腐蚀性和良好的光催化性能,被认为是降解污染物的有效光催化剂。然而,有限的光吸收能力、光生电子-空穴对的高复合速率和缓慢的表面反应阻碍了它们的进一步应用。Bismuth oxychloride has been considered as an effective photocatalyst for pollutant degradation due to its high chemical stability, unique layered structure, corrosion resistance, and good photocatalytic performance. However, the limited light absorption ability, high recombination rate of photogenerated electron-hole pairs, and slow surface reactions hinder their further applications.

发明内容Contents of the invention

为克服现有技术的不足,本发明提供一种光响应范围广、光生电子-空穴分离效率高、光催化活性高、稳定性好、耐腐蚀的氯氧化铋基光催化剂及其制备方法和应用。In order to overcome the deficiencies in the prior art, the present invention provides a bismuth oxychloride-based photocatalyst with wide photoresponse range, high photogenerated electron-hole separation efficiency, high photocatalytic activity, good stability and corrosion resistance, and its preparation method and application.

为达到上述目的,本发明首先提出一种氮掺杂碳量子点锚定的氯氧化铋光催化剂,包括氯氧化铋、氮掺杂碳量子点,所述氯氧化铋主要暴露晶面为{010}晶面,所述氮掺杂碳量子点锚定在氯氧化铋暴露的{010}晶面上,所述氮掺杂碳量子点的质量百分含量为0.01%~0.08%,In order to achieve the above object, the present invention first proposes a bismuth oxychloride photocatalyst anchored by nitrogen-doped carbon quantum dots, including bismuth oxychloride and nitrogen-doped carbon quantum dots, and the main exposed crystal plane of the bismuth oxychloride is {010 } crystal plane, the nitrogen-doped carbon quantum dots are anchored on the {010} crystal plane exposed by bismuth oxychloride, and the mass percentage of the nitrogen-doped carbon quantum dots is 0.01% to 0.08%,

作为优选,所述氮掺杂碳量子点的质量百分含量为0.02%。Preferably, the mass percentage content of the nitrogen-doped carbon quantum dots is 0.02%.

作为优选,所述氮掺杂碳量子点的直径<10nm。Preferably, the diameter of the nitrogen-doped carbon quantum dot is <10nm.

作为优选,所述主要暴露晶面为{010}晶面的氯氧化铋为超薄不规整纳米片结构。Preferably, the bismuth oxychloride whose main exposed crystal plane is the {010} crystal plane has an ultra-thin irregular nanosheet structure.

基于一个总的发明构思,本发明还提供了一种氮掺杂碳量子点锚定的氯氧化铋光催化剂的制备方法,包括以下步骤:Based on a general inventive concept, the present invention also provides a method for preparing a bismuth oxychloride photocatalyst anchored by nitrogen-doped carbon quantum dots, comprising the following steps:

S1、将五水合硝酸铋和氮掺杂碳量子点溶液,加至丙三醇-水混合溶剂中,超声搅拌至形成均匀混合液;S1. Add bismuth nitrate pentahydrate and nitrogen-doped carbon quantum dot solution to glycerol-water mixed solvent, and ultrasonically stir until a uniform mixed solution is formed;

S2、向步骤S1得到的混合液中,逐滴加入饱和氯化钠溶液,超声搅拌均匀;S2. Add saturated sodium chloride solution dropwise to the mixed solution obtained in step S1, and stir evenly with ultrasonic;

S3、向步骤S2得到的混合液中滴加一定浓度的碱性溶液调节pH至5~7;S3, adding a certain concentration of alkaline solution dropwise to the mixed solution obtained in step S2 to adjust the pH to 5-7;

S4、将步骤S3得到的混合溶液进行水热处理,得到氮掺杂碳量子点锚定的{010}氯氧化铋。S4. Hydrothermally treating the mixed solution obtained in step S3 to obtain {010} bismuth oxychloride anchored by nitrogen-doped carbon quantum dots.

作为优选,所述S1步骤中五水合硝酸铋和氮掺杂碳量子点溶液的摩尔比为1:0.002~0.008;所述超声分散时间为15min~40min;所述搅拌时间为15min~40min。Preferably, the molar ratio of bismuth nitrate pentahydrate to nitrogen-doped carbon quantum dot solution in the S1 step is 1:0.002-0.008; the ultrasonic dispersion time is 15 min-40 min; the stirring time is 15 min-40 min.

作为优选,所述S2步骤中加入过量饱和氯化钠溶液;所述超声分散时间为15min~40min;所述搅拌时间为15min~40min。Preferably, an excess saturated sodium chloride solution is added in the step S2; the ultrasonic dispersion time is 15 min to 40 min; the stirring time is 15 min to 40 min.

作为优选,所述S3步骤中碱性溶液为氢氧化钠溶液或氢氧化钾溶液中任意一种。Preferably, the alkaline solution in step S3 is any one of sodium hydroxide solution or potassium hydroxide solution.

作为优选,所述S4步骤中水热反应温度120~180℃,反应时间5~10h。Preferably, in the step S4, the hydrothermal reaction temperature is 120-180° C., and the reaction time is 5-10 h.

作为优选,所述氮掺杂碳量子点的制备方法,包括以下步骤:将柠檬酸铵、乙二胺和水混合,得到前驱体溶液;将前驱体溶液进行水热反应,收集反应后的溶液进行透析反应,得到氮掺杂碳量子点溶液。其中,柠檬酸铵、乙二胺的摩尔比为8~15:5~10,水热反应温度为160~200℃;所述的水热反应时间为3~8h;所述透析反应中溶液与超纯水的体积比为1:80~120,透析时间为20~28h。Preferably, the preparation method of nitrogen-doped carbon quantum dots comprises the following steps: mixing ammonium citrate, ethylenediamine and water to obtain a precursor solution; performing a hydrothermal reaction on the precursor solution, and collecting the reacted solution The dialysis reaction is carried out to obtain a nitrogen-doped carbon quantum dot solution. Wherein, the molar ratio of ammonium citrate and ethylenediamine is 8-15:5-10, and the hydrothermal reaction temperature is 160-200°C; the hydrothermal reaction time is 3-8h; in the dialysis reaction, the solution and The volume ratio of ultrapure water is 1:80~120, and the dialysis time is 20~28h.

基于一个总的发明构思,本发明还提供了一种氮掺杂碳量子点锚定的氯氧化铋光催化剂在催化降解废水中抗生素中的应用,包括以下步骤:Based on a general inventive concept, the present invention also provides an application of a nitrogen-doped carbon quantum dot-anchored bismuth oxychloride photocatalyst in the catalytic degradation of antibiotics in wastewater, comprising the following steps:

S1:将氮掺杂碳量子点锚定的{010}氯氧化铋光催化剂与含抗生素污染物废水混合,搅拌;S1: Mix the {010} bismuth oxychloride photocatalyst anchored by nitrogen-doped carbon quantum dots with wastewater containing antibiotic pollutants, and stir;

S2:在光照条件下进行光催化反应,完成对抗生素污染物的降解;S2: Perform photocatalytic reaction under light conditions to complete the degradation of antibiotic pollutants;

作为优选,所述光催化剂在每升含有机污染物废水中的添加量为0.2g~1.0g。Preferably, the photocatalyst is added in an amount of 0.2 g to 1.0 g per liter of wastewater containing organic pollutants.

作为优选,所述有抗生素污染物为环丙沙星。Preferably, the antibiotic pollutant is ciprofloxacin.

作为优选,所述环丙沙星污染物的初始浓度为5mg/L~20mg/L;所述光照条件λ≥420nm;所述光催化反应的时间≥60min。Preferably, the initial concentration of the ciprofloxacin pollutant is 5mg/L-20mg/L; the light condition λ≥420nm; the photocatalytic reaction time ≥60min.

本发明提供的光催化剂主要作用机理为:The main mechanism of action of the photocatalyst provided by the invention is:

晶面效应被认为可以通过调控表面原子配位和排列促进表面氧化还原反应的发生。而氮掺杂碳量子点的上转换效应可以将低能量的入射光转换为高能量光发射,从而有助于提升太阳能的利用率。因此,利用晶面调控和氮掺杂碳量子点锚定的协同作用对于提升氯氧化铋的光催化性能具有重要意义。The crystal facet effect is considered to promote the occurrence of surface redox reactions by regulating the coordination and arrangement of surface atoms. The up-conversion effect of nitrogen-doped carbon quantum dots can convert low-energy incident light into high-energy light emission, which helps to improve the utilization of solar energy. Therefore, utilizing the synergistic effect of facet regulation and anchoring of nitrogen-doped carbon quantum dots is of great significance for improving the photocatalytic performance of bismuth oxychloride.

针对氯氧化铋光响应能力有限、光生电子-空穴对的高复合速率和表面反应缓慢等缺陷,本发明创造性地将氯氧化铋的主要暴露晶面调控为{010}高能晶面,并在该晶面上锚定氮掺杂碳量子点,利用高能暴露晶面和氮掺杂碳量子点的协同作用拓展光响应范围、促进光生载流子迁移、加速表面氧化还原反应的发生,从而达到改善氯氧化铋光催化性能的目的。具体来说,{010}晶面暴露的氯氧化铋具有较大的表面积和开放通道特性可以为氮掺杂碳量子点的负载提供更大的空间。因而,将氮掺杂碳量子点负载于{010}晶面暴露的氯氧化铋表面,可促进氮掺杂碳量子点与氯氧化铋之间有效异质结通道的形成,从而更好地发挥氮掺杂碳量子点的电子传导性能。此外,{010}晶面暴露得更多的末端铋原子可以作为光催化反应的活性位点,氮掺杂碳量子点的上转换性能可有效提升光催化剂的光响应能力。因此,构建的氮掺杂碳量子点锚定的{010}氯氧化铋光催化剂表现出非常优异的可见光吸收能力和光催化性能。另外,本发明中,将氮掺杂碳量子点锚定的{010}氯氧化铋光催化剂应用于模拟可见光(λ≥420nm)条件下降解抗生素污染物时表现出非常优异的降解效果,能够有效降解废水中的抗生素污染物。Aiming at defects such as limited photoresponse ability of bismuth oxychloride, high recombination rate of photogenerated electron-hole pairs, and slow surface reaction, the present invention creatively adjusts the main exposed crystal plane of bismuth oxychloride to {010} high-energy crystal plane, and Nitrogen-doped carbon quantum dots are anchored on the crystal surface, and the synergistic effect of the high-energy exposed crystal surface and nitrogen-doped carbon quantum dots is used to expand the photoresponse range, promote the migration of photogenerated carriers, and accelerate the occurrence of surface redox reactions, thereby achieving The purpose of improving the photocatalytic performance of bismuth oxychloride. Specifically, the bismuth oxychloride exposed on the {010} crystal plane has a large surface area and open channel characteristics, which can provide more space for the loading of nitrogen-doped carbon quantum dots. Therefore, loading nitrogen-doped carbon quantum dots on the surface of bismuth oxychloride exposed to the {010} crystal plane can promote the formation of an effective heterojunction channel between nitrogen-doped carbon quantum dots and bismuth oxychloride, so as to better play Electron conductivity properties of nitrogen-doped carbon quantum dots. In addition, the terminal bismuth atoms with more exposed {010} crystal faces can be used as active sites for photocatalytic reactions, and the upconversion performance of nitrogen-doped carbon quantum dots can effectively improve the photoresponsiveness of photocatalysts. Therefore, the constructed nitrogen-doped carbon quantum dot-anchored {010} bismuth oxychloride photocatalyst exhibits excellent visible light absorption ability and photocatalytic performance. In addition, in the present invention, when the {010} bismuth oxychloride photocatalyst anchored by nitrogen-doped carbon quantum dots is applied to degrade antibiotic pollutants under simulated visible light (λ≥420nm) conditions, it shows a very excellent degradation effect, which can effectively Degradation of antibiotic pollutants in wastewater.

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

(1)本发明提供了一种氮掺杂碳量子点锚定的{010}氯氧化铋光催化剂,首先,将氯氧化铋纳米片的主要暴露晶面调控为{010}晶面,然后再在{010}氯氧化铋纳米片上锚定氮掺杂碳量子点,具有光响应范围广、光生电子-空穴分离效率高、光催化活性高、稳定性好、耐腐蚀等优点,是一种性能优异的新型复合光催化剂,通过将氮掺杂碳量子点锚定的{010}氯氧化铋光催化剂与含抗生素污染物废水混合,经搅拌和光催化反应后,即可实现对废水中抗生素污染物的有效降解,具有光催化性能稳定、耐腐蚀性能强、对污染物降解效率高等优点,具有很好的实际应用前景。(1) The present invention provides a {010} bismuth oxychloride photocatalyst anchored by nitrogen-doped carbon quantum dots. First, the main exposed crystal planes of bismuth oxychloride nanosheets are adjusted to {010} crystal planes, and then Anchoring nitrogen-doped carbon quantum dots on {010} bismuth oxychloride nanosheets has the advantages of wide photoresponse range, high photogenerated electron-hole separation efficiency, high photocatalytic activity, good stability, and corrosion resistance. A new type of composite photocatalyst with excellent performance, by mixing {010} bismuth oxychloride photocatalyst anchored by nitrogen-doped carbon quantum dots with wastewater containing antibiotic pollutants, after stirring and photocatalytic reaction, antibiotic pollution in wastewater can be realized The effective degradation of pollutants has the advantages of stable photocatalytic performance, strong corrosion resistance, and high efficiency of pollutant degradation, and has a good practical application prospect.

(2)本发明氮掺杂碳量子点锚定的{010}氯氧化铋光催化剂中,优化了氯氧化铋的主要暴露晶面为{010}晶面,更有利于氮掺杂碳量子点在氯氧化铋表面的锚定并促进二者之间的充分接触,从而能够获得更加优异的光催化性能,这是因为氮掺杂碳量子点锚定于氯氧化铋{010}晶面时可在异质结界面处形成沿[Bi2O2]2+→N-CQDs→Cl-方向的共价环,从而有利于电子的定向转移从而形成界面电场,从而有利于光生电荷的转移,使所制备的光催化剂具有更加优异的光催化性能。(2) In the {010} bismuth oxychloride photocatalyst anchored by nitrogen-doped carbon quantum dots of the present invention, the main exposed crystal plane of bismuth oxychloride is optimized to be the {010} crystal plane, which is more conducive to nitrogen-doped carbon quantum dots The anchoring on the surface of bismuth oxychloride and the promotion of sufficient contact between the two can obtain more excellent photocatalytic performance, because the nitrogen-doped carbon quantum dots can be anchored on the {010} crystal plane of bismuth oxychloride. A covalent ring along the direction of [Bi2O2]2 + → N-CQDs → Cl- is formed at the heterojunction interface, which is beneficial to the directional transfer of electrons to form an interfacial electric field, which is beneficial to the transfer of photogenerated charges, making the prepared Photocatalysts have more excellent photocatalytic properties.

(3)本发明氮掺杂碳量子点锚定的{010}氯氧化铋光催化剂中,优化了氮掺杂碳量子点的质量百分含量为0.01~0.08%。氮掺杂碳量子点的含量过少时,少量的氮掺杂碳量子点不足以形成有利于电荷转移的界面电场,进而难以实现富铋氯氧化铋纳米片中光生电子空穴的有效分离和迁移,而氮掺杂碳量子点过量时,会破坏有效的异质结截面,从而降低光催化活性。特别的,氮掺杂碳量子点的质量百分含量为0.01%~0.08%时,所得钴氮掺杂碳量子点锚定的{010}氯氧化铋光催化剂具有更加优异的光催化性能。(3) In the {010} bismuth oxychloride photocatalyst anchored by nitrogen-doped carbon quantum dots of the present invention, the mass percentage of nitrogen-doped carbon quantum dots is optimized to be 0.01-0.08%. When the content of nitrogen-doped carbon quantum dots is too small, a small amount of nitrogen-doped carbon quantum dots is not enough to form an interfacial electric field that is conducive to charge transfer, and it is difficult to achieve effective separation and migration of photogenerated electron holes in bismuth-rich bismuth oxychloride nanosheets , and excessive nitrogen-doped carbon quantum dots will destroy the effective heterojunction cross-section, thereby reducing the photocatalytic activity. In particular, when the mass percentage of nitrogen-doped carbon quantum dots is 0.01% to 0.08%, the obtained {010} bismuth oxychloride photocatalyst anchored by cobalt nitrogen-doped carbon quantum dots has more excellent photocatalytic performance.

(4)本发明利用碱性溶液调控氯氧化铋的主要暴露晶面为{010}高能晶面;以柠檬酸铵、乙二胺、水为原料通过采用简单的水热反应制备得到具有吸光范围宽、吸光效率高的氮掺杂碳量子点;具有合成方法简便、原料成本低、耗能少、耗时短、条件易控、制备过程中不产生对环境有污染的副产物等优点,适于连续大规模批量生产,便于工业化利用。(4) The main exposed crystal plane of bismuth oxychloride controlled by alkaline solution is {010} high-energy crystal plane in the present invention; ammonium citrate, ethylenediamine and water are used as raw materials to obtain a crystal with a light-absorbing range by adopting a simple hydrothermal reaction. Nitrogen-doped carbon quantum dots with wide width and high light absorption efficiency; it has the advantages of simple synthesis method, low raw material cost, less energy consumption, short time consumption, easy control of conditions, and no by-products that pollute the environment during the preparation process. It is suitable for continuous large-scale mass production and is convenient for industrialized utilization.

附图说明Description of drawings

为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例中所需要使用的附图作简单的介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the accompanying drawings required in the embodiments. Obviously, the accompanying drawings in the following description are only some of the present invention. Embodiments, for those of ordinary skill in the art, other drawings can also be obtained based on these drawings without any creative effort.

图1为本发明实验例1中{010}氯氧化铋纳米片(BOC-010)、{001}氯氧化铋纳米片(BOC-001)和氮掺杂碳量子点锚定的{010}氯氧化铋纳米片(10NBOC-010)的扫描电镜图,其中图1a为BOC-001,图1b为BOC-010,图1c为10NBOC-010;Fig. 1 is {010} bismuth oxychloride nanosheets (BOC-010), {001} bismuth oxychloride nanosheets (BOC-001) and {010} chlorine anchored by nitrogen-doped carbon quantum dots in Experimental Example 1 of the present invention. Scanning electron microscope images of bismuth oxide nanosheets (10NBOC-010), where Figure 1a is BOC-001, Figure 1b is BOC-010, and Figure 1c is 10NBOC-010;

图2为本发明实验例2中{010}氯氧化铋纳米片(BOC-010)、{001}氯氧化铋纳米片(BOC-001)和氮掺杂碳量子点锚定的{010}氯氧化铋纳米片(10NBOC-010)的TEM图,其中图2a为BOC-001,图2b为BOC-010,图2c为10NBOC-010;Figure 2 shows {010} bismuth oxychloride nanosheets (BOC-010), {001} bismuth oxychloride nanosheets (BOC-001) and {010} chlorine anchored by nitrogen-doped carbon quantum dots in Experimental Example 2 of the present invention. TEM images of bismuth oxide nanosheets (10NBOC-010), where Figure 2a is BOC-001, Figure 2b is BOC-010, and Figure 2c is 10NBOC-010;

图3为本发明实验例3中{010}氯氧化铋纳米片(BOC-010)、{001}氯氧化铋纳米片(BOC-001)、氮掺杂碳量子点锚定的{010}氯氧化铋纳米片(10NBOC-010)和氮掺杂碳量子点锚定的{001}氯氧化铋纳米片(10NBOC-001)的紫外可见漫反射光谱图;Figure 3 shows {010} bismuth oxychloride nanosheets (BOC-010), {001} bismuth oxychloride nanosheets (BOC-001), and {010} chlorine anchored by nitrogen-doped carbon quantum dots in Experimental Example 3 of the present invention. UV-Vis diffuse reflectance spectra of bismuth oxide nanosheets (10NBOC-010) and {001} bismuth oxychloride nanosheets anchored by nitrogen-doped carbon quantum dots (10NBOC-001);

图4为本发明实验例4中{010}氯氧化铋纳米片(BOC-010)、{001}氯氧化铋纳米片(BOC-001)、氮掺杂碳量子点锚定的{010}氯氧化铋纳米片(10NBOC-010)和氮掺杂碳量子点锚定的{001}氯氧化铋纳米片(10NBOC-001)的瞬态光电流图;Figure 4 shows {010} bismuth oxychloride nanosheets (BOC-010), {001} bismuth oxychloride nanosheets (BOC-001), and {010} chlorine anchored by nitrogen-doped carbon quantum dots in Experimental Example 4 of the present invention. Transient photocurrent maps of bismuth oxide nanosheets (10NBOC-010) and {001} bismuth oxychloride nanosheets (10NBOC-001) anchored by nitrogen-doped carbon quantum dots;

图5为本发明实验例5中氮掺杂碳量子点锚定的{010}氯氧化铋纳米片(10NBOC-010)协同效果图,其中图5a为10NBOC-010的三维差分电荷密度图,图5b为10NBOC-010的平面平均差分电荷密度图;Figure 5 is a synergistic effect diagram of {010} bismuth oxychloride nanosheets (10NBOC-010) anchored by nitrogen-doped carbon quantum dots in Experimental Example 5 of the present invention, wherein Figure 5a is a three-dimensional differential charge density diagram of 10NBOC-010, Fig. 5b is the planar average differential charge density map of 10NBOC-010;

图6为本发明实验例6中BOC-010、BOC-001、6NBOC-010、10NBOC-010、14NBOC-010和10NBOC-001降解抗生素污染物的效率结果,其中图6a为{010}氯氧化铋纳米片(BOC-010)、{001}氯氧化铋纳米片(BOC-001)、氮掺杂碳量子点锚定的{010}氯氧化铋纳米片(6NBOC-010、10NBOC-010、14NBOC-010)和氮掺杂碳量子点锚定的{001}氯氧化铋纳米片(10NBOC-001)的在可见光照射条件下光催化降解环丙沙星废水时对应的时间-降解效率的关系图;图6b为不同材料BOC-010、BOC-001、6NBOC-010、10NBOC-010、14NBOC-010和10NBOC-001处理的降解系数。Fig. 6 is the result of the efficiency of BOC-010, BOC-001, 6NBOC-010, 10NBOC-010, 14NBOC-010 and 10NBOC-001 in Experimental Example 6 of the present invention to degrade antibiotic pollutants, wherein Fig. 6a is {010} bismuth oxychloride Nanosheets (BOC-010), {001} bismuth oxychloride nanosheets (BOC-001), {010} bismuth oxychloride nanosheets anchored by nitrogen-doped carbon quantum dots (6NBOC-010, 10NBOC-010, 14NBOC- 010) and nitrogen-doped carbon quantum dot anchored {001} bismuth oxychloride nanosheets (10NBOC-001) photocatalytic degradation of ciprofloxacin wastewater under visible light irradiation conditions corresponding to the time-degradation efficiency relationship diagram; Figure 6b shows the degradation coefficients of different materials BOC-010, BOC-001, 6NBOC-010, 10NBOC-010, 14NBOC-010 and 10NBOC-001.

具体实施方式Detailed ways

为使本发明要解决的技术问题、技术方案和优点更加清楚,下面将结合附图及具体实施例进行详细描述。In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following will describe in detail with reference to the drawings and specific embodiments.

以下实施例用于说明本发明,但不用来限制本发明的范围。在不背离本发明精神和实质的情况下,对本发明方法、步骤或条件所作地修改或替换,均属于本发明的范围。The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention. Without departing from the spirit and essence of the present invention, any modifications or substitutions made to the methods, steps or conditions of the present invention fall within the scope of the present invention.

若未特别指明,实施例中所用的技术手段为本领域技术人员所熟知的常规手段;若未特别指明,实施例中所用试剂均为市售。If not specified, the technical means used in the examples are conventional means well known to those skilled in the art; if not specified, the reagents used in the examples are all commercially available.

实施例1Example 1

氮掺杂碳量子点的制备Preparation of nitrogen-doped carbon quantum dots

具体氮掺杂碳量子点的制备过程:将10mmol柠檬酸铵加至20mL超纯水中,并搅拌至溶解,随后逐滴加入670μL乙二胺。搅拌30min后,将混合溶液密封于不锈钢反应釜中并置于200℃烘箱中反应5h。待反应釜自然冷却至室温后,按体积比溶液:超纯水=1:100的比例透析处理(MWCO 1000)所得溶液24h,最终制得浓度约为0.5M的N-CQDs水溶液。The specific preparation process of nitrogen-doped carbon quantum dots: add 10 mmol ammonium citrate to 20 mL ultrapure water, and stir until dissolved, then add 670 μL ethylenediamine dropwise. After stirring for 30 min, the mixed solution was sealed in a stainless steel reactor and placed in an oven at 200° C. for 5 h. After the reaction kettle was naturally cooled to room temperature, the resulting solution was dialyzed (MWCO 1000) for 24 hours at a volume ratio of solution: ultrapure water = 1:100, and finally an aqueous solution of N-CQDs with a concentration of about 0.5M was obtained.

实施例2Example 2

制备主要暴露晶面为{010}面的氯氧化铋光催化剂Preparation of bismuth oxychloride photocatalyst whose main exposed crystal plane is {010} plane

S1、在搅拌条件下,在25mL丙三醇溶液中依次加入0.486g五水合硝酸铋和25mL超纯水,超声搅拌至形成均一混合溶液;S1. Under stirring conditions, sequentially add 0.486 g of bismuth nitrate pentahydrate and 25 mL of ultrapure water into 25 mL of glycerol solution, and ultrasonically stir until a uniform mixed solution is formed;

S2、将5mL饱和NaCl溶液逐滴加至步骤S1所制备的混合溶液中,超声搅拌至形成均一混合溶液;S2. Add 5 mL of saturated NaCl solution dropwise to the mixed solution prepared in step S1, and ultrasonically stir until a uniform mixed solution is formed;

S3、用氢氧化钠溶液将步骤S2所得的混合溶液pH调节至6;S3. Adjust the pH of the mixed solution obtained in step S2 to 6 with sodium hydroxide solution;

S4、将步骤S3所得pH=6的混合溶液转移到100mL的不锈钢高压釜中,在160℃下水热反应6小时,经冷却、离心、去离子水和乙醇清洗后,干燥,得到主要暴露晶面为{010}面的氯氧化铋光催化剂,命名为BOC-010。S4. Transfer the mixed solution with pH=6 obtained in step S3 to a 100mL stainless steel autoclave, conduct a hydrothermal reaction at 160°C for 6 hours, cool, centrifuge, wash with deionized water and ethanol, and dry to obtain the main exposed crystal planes It is a bismuth oxychloride photocatalyst on the {010} plane, named BOC-010.

对比例1Comparative example 1

制备主要暴露晶面为{001}面的氯氧化铋光催化剂Preparation of bismuth oxychloride photocatalyst whose main exposed crystal plane is {001} plane

S1、在搅拌条件下,在25mL丙三醇溶液中依次加入0.486g五水合硝酸铋和25mL超纯水,超声搅拌至形成均一混合溶液;S1. Under stirring conditions, sequentially add 0.486 g of bismuth nitrate pentahydrate and 25 mL of ultrapure water into 25 mL of glycerol solution, and ultrasonically stir until a uniform mixed solution is formed;

S2、将5mL饱和NaCl溶液逐滴加至步骤S1所制备的混合溶液中,超声搅拌至形成均一混合溶液;S2. Add 5 mL of saturated NaCl solution dropwise to the mixed solution prepared in step S1, and ultrasonically stir until a uniform mixed solution is formed;

S3、将步骤S2所得的混合溶液转移到100mL的不锈钢高压釜中,在160℃下水热反应6小时,经冷却、离心、去离子水和乙醇清洗后,干燥,得到主要暴露晶面为{001}面的氯氧化铋光催化剂,命名为BOC-001。S3. Transfer the mixed solution obtained in step S2 to a 100mL stainless steel autoclave, conduct a hydrothermal reaction at 160°C for 6 hours, cool, centrifuge, wash with deionized water and ethanol, and dry to obtain the main exposed crystal plane as {001 } surface bismuth oxychloride photocatalyst named BOC-001.

实施例3Example 3

制备氮掺杂碳量子点锚定的{010}氯氧化铋光催化剂6NBOC-010Preparation of {010} bismuth oxychloride photocatalyst 6NBOC-010 anchored by nitrogen-doped carbon quantum dots

本实施例中,该氮掺杂碳量子点锚定的{010}氯氧化铋光催化剂中氮掺杂碳量子点的质量百分含量为0.01%,{010}氯氧化铋纳米片的质量百分含量为99.99%。In this embodiment, the mass percentage of nitrogen-doped carbon quantum dots in the {010} bismuth oxychloride photocatalyst anchored by nitrogen-doped carbon quantum dots is 0.01%, and the mass percentage of {010} bismuth oxychloride nanosheets Mineral content is 99.99%.

以主要暴露晶面为{010}面的氯氧化铋纳米片为载体,{010}氯氧化铋纳米片上锚定有氮掺杂碳量子点,制备方法如下:Bismuth oxychloride nanosheets whose main exposed crystal face is the {010} plane are used as the carrier, and nitrogen-doped carbon quantum dots are anchored on the {010} bismuth oxychloride nanosheets. The preparation method is as follows:

S1、在搅拌条件下,在25mL丙三醇溶液中依次加入0.486g五水合硝酸铋、6mL氮掺杂碳量子点溶液和25mL超纯水,超声搅拌至形成均一混合溶液;S1. Under stirring conditions, add 0.486g of bismuth nitrate pentahydrate, 6mL of nitrogen-doped carbon quantum dot solution and 25mL of ultrapure water in sequence in 25mL of glycerol solution, and ultrasonically stir until a uniform mixed solution is formed;

S2、将5mL饱和NaCl溶液逐滴加至步骤S1中所制备的混合溶液中,超声搅拌至形成均一混合溶液;S2. Add 5 mL of saturated NaCl solution dropwise to the mixed solution prepared in step S1, and ultrasonically stir until a uniform mixed solution is formed;

S3、用氢氧化钠溶液将步骤S2所得的混合溶液pH调节至6;S3. Adjust the pH of the mixed solution obtained in step S2 to 6 with sodium hydroxide solution;

S4、将步骤S3所得pH=6的混合溶液转移到100mL的不锈钢高压釜中,在160℃下水热反应6小时,经冷却、离心、去离子水和乙醇清洗后,干燥,得到主要暴露晶面为{010}面的氯氧化铋光催化剂,命名为6NBOC-010。S4. Transfer the mixed solution with pH=6 obtained in step S3 to a 100mL stainless steel autoclave, conduct a hydrothermal reaction at 160°C for 6 hours, cool, centrifuge, wash with deionized water and ethanol, and dry to obtain the main exposed crystal planes It is a bismuth oxychloride photocatalyst on the {010} plane, named 6NBOC-010.

实施例4Example 4

制备氮掺杂碳量子点锚定的{010}氯氧化铋光催化剂10NBOC-010Preparation of {010} bismuth oxychloride photocatalyst 10NBOC-010 anchored by nitrogen-doped carbon quantum dots

本实施例中,该氮掺杂碳量子点锚定的{010}氯氧化铋光催化剂中氮掺杂碳量子点的质量百分含量为0.02%,{010}氯氧化铋纳米片的质量百分含量为99.98%,制备方法如下:In this embodiment, the nitrogen-doped carbon quantum dot anchored {010} bismuth oxychloride photocatalyst has a mass percentage of nitrogen-doped carbon quantum dots of 0.02%, and a mass percentage of {010} bismuth oxychloride nanosheets The component content is 99.98%, and the preparation method is as follows:

S1、在搅拌条件下,在25mL丙三醇溶液中依次加入0.486g五水合硝酸铋、10mL氮掺杂碳量子点溶液和25mL超纯水,超声搅拌至形成均一混合溶液;S1. Under stirring conditions, add 0.486g of bismuth nitrate pentahydrate, 10mL of nitrogen-doped carbon quantum dot solution and 25mL of ultrapure water in sequence in 25mL of glycerol solution, and ultrasonically stir until a uniform mixed solution is formed;

S2、将5mL饱和NaCl溶液逐滴加至步骤S1所制备的混合溶液中,超声搅拌至形成均一混合溶液;S2. Add 5 mL of saturated NaCl solution dropwise to the mixed solution prepared in step S1, and ultrasonically stir until a uniform mixed solution is formed;

S3、用氢氧化钠溶液将步骤S2所得的混合溶液pH调节至6;S3. Adjust the pH of the mixed solution obtained in step S2 to 6 with sodium hydroxide solution;

S4、将步骤S3所得pH=6的混合溶液转移到100mL的不锈钢高压釜中,在160℃下水热反应6小时,经冷却、离心、去离子水和乙醇清洗后,干燥,得到主要暴露晶面为{010}面的氯氧化铋光催化剂,命名为10NBOC-010。S4. Transfer the mixed solution with pH=6 obtained in step S3 to a 100mL stainless steel autoclave, conduct a hydrothermal reaction at 160°C for 6 hours, cool, centrifuge, wash with deionized water and ethanol, and dry to obtain the main exposed crystal planes It is a bismuth oxychloride photocatalyst on the {010} plane, named 10NBOC-010.

实施例5Example 5

制备氮掺杂碳量子点锚定的{010}氯氧化铋光催化剂14NBOC-010Preparation of {010} bismuth oxychloride photocatalyst 14NBOC-010 anchored by nitrogen-doped carbon quantum dots

本实施例中,该氮掺杂碳量子点锚定的{010}氯氧化铋光催化剂中氮掺杂碳量子点的质量百分含量为0.03%,{010}氯氧化铋纳米片的质量百分含量为99.97%,制备方法如下:In this embodiment, the mass percentage of nitrogen-doped carbon quantum dots in the {010} bismuth oxychloride photocatalyst anchored by nitrogen-doped carbon quantum dots is 0.03%, and the mass percentage of {010} bismuth oxychloride nanosheets The component content is 99.97%, and the preparation method is as follows:

S1、在搅拌条件下,在25mL丙三醇溶液中依次加入0.486g五水合硝酸铋、14mL氮掺杂碳量子点溶液和25mL超纯水,超声搅拌至形成均一混合溶液;S1. Under stirring conditions, add 0.486g of bismuth nitrate pentahydrate, 14mL of nitrogen-doped carbon quantum dot solution and 25mL of ultrapure water in sequence in 25mL of glycerol solution, and ultrasonically stir until a uniform mixed solution is formed;

S2、将5mL饱和NaCl溶液逐滴加至步骤S1所制备的混合溶液中,超声搅拌至形成均一混合溶液;S2. Add 5 mL of saturated NaCl solution dropwise to the mixed solution prepared in step S1, and ultrasonically stir until a uniform mixed solution is formed;

S3、用氢氧化钠溶液将步骤S2所得的混合溶液pH调节至6;S3. Adjust the pH of the mixed solution obtained in step S2 to 6 with sodium hydroxide solution;

S4、将步骤(3)所得pH=6的混合溶液转移到100mL的不锈钢高压釜中,在160℃下水热反应6小时,经冷却、离心、去离子水和乙醇清洗后,干燥,得到主要暴露晶面为{010}面的氯氧化铋光催化剂,命名为14NBOC-010。S4. Transfer the mixed solution with pH=6 obtained in step (3) to a 100mL stainless steel autoclave, conduct a hydrothermal reaction at 160°C for 6 hours, cool, centrifuge, wash with deionized water and ethanol, and dry to obtain the main exposure Bismuth oxychloride photocatalyst whose crystal plane is {010} plane is named 14NBOC-010.

对比例2Comparative example 2

制备氮掺杂碳量子点锚定的{001}氯氧化铋光催化剂10NBOC-001Preparation of {001} bismuth oxychloride photocatalyst 10NBOC-001 anchored by nitrogen-doped carbon quantum dots

本对比例中,该氮掺杂碳量子点锚定的{001}氯氧化铋光催化剂中氮掺杂碳量子点的质量百分含量为0.02%,{010}氯氧化铋纳米片的质量百分含量为99.98%。In this comparative example, the mass percent content of nitrogen-doped carbon quantum dots in the {001} bismuth oxychloride photocatalyst anchored by nitrogen-doped carbon quantum dots is 0.02%, and the mass percent of {010} bismuth oxychloride nanosheets Mineral content is 99.98%.

以主要暴露晶面为{001}面的氯氧化铋纳米片为载体,{001}氯氧化铋纳米片上锚定有氮掺杂碳量子点,制备方法如下:Using bismuth oxychloride nanosheets whose main exposed crystal plane is the {001} plane as a carrier, {001} bismuth oxychloride nanosheets are anchored with nitrogen-doped carbon quantum dots. The preparation method is as follows:

S1、在搅拌条件下,在25mL丙三醇溶液中依次加入0.486g五水合硝酸铋、10mL氮掺杂碳量子点溶液和25mL超纯水,超声搅拌至形成均一混合溶液;S1. Under stirring conditions, add 0.486g of bismuth nitrate pentahydrate, 10mL of nitrogen-doped carbon quantum dot solution and 25mL of ultrapure water in sequence in 25mL of glycerol solution, and ultrasonically stir until a uniform mixed solution is formed;

S1、将5mL饱和NaCl溶液逐滴加至步骤S1所制备的混合溶液中,超声搅拌至形成均一混合溶液;S1. Add 5 mL of saturated NaCl solution dropwise to the mixed solution prepared in step S1, and ultrasonically stir until a uniform mixed solution is formed;

S1、将步骤S2所得的混合溶液转移到100mL的不锈钢高压釜中,在160℃下水热反应6小时,经冷却、离心、去离子水和乙醇清洗后,干燥,得到主要暴露晶面为{010}面的氯氧化铋光催化剂,命名为10NBOC-001。S1. Transfer the mixed solution obtained in step S2 to a 100mL stainless steel autoclave, conduct a hydrothermal reaction at 160°C for 6 hours, cool, centrifuge, wash with deionized water and ethanol, and dry to obtain the main exposed crystal plane as {010 } surface bismuth oxychloride photocatalyst, named 10NBOC-001.

实验例1Experimental example 1

考察BOC-001、BOC-010、10NBOC-010的结构特征Investigate the structural characteristics of BOC-001, BOC-010, 10NBOC-010

对{001}氯氧化铋光催化剂(BOC-001)、{010}氯氧化铋光催化剂(BOC-010)、氮掺杂碳量子点锚定于{010}氯氧化铋纳米片(10NBOC-010)进行电镜扫描考察这三种材料的结构特征,结果如图1所示,图1(a)表明了{001}氯氧化铋光催化剂的结构特点为二维片状四方结构,图1(b)表明了{010}氯氧化铋光催化剂的结构特点为超薄不规整纳米片结构,由图1(c)可知,氮掺杂碳量子点锚定于{010}氯氧化铋纳米片的表面,与图1(b)表示的{010}氯氧化铋纳米片结构相比,氮掺杂碳量子点的负载不会改变{010}氯氧化铋纳米片的结构。For {001} bismuth oxychloride photocatalyst (BOC-001), {010} bismuth oxychloride photocatalyst (BOC-010), nitrogen-doped carbon quantum dots anchored on {010} bismuth oxychloride nanosheets (10NBOC-010 ) scanning electron microscope to investigate the structural characteristics of these three materials, the results are shown in Figure 1, Figure 1(a) shows that the structural characteristics of {001} bismuth oxychloride photocatalyst is a two-dimensional sheet-like tetragonal structure, Figure 1(b ) shows that the structure of {010} bismuth oxychloride photocatalyst is an ultrathin irregular nanosheet structure. It can be seen from Fig. 1(c) that nitrogen-doped carbon quantum dots are anchored on the surface of {010} bismuth oxychloride nanosheets , compared with the {010} bismuth oxychloride nanosheet structure shown in Fig. 1(b), the loading of nitrogen-doped carbon quantum dots does not change the structure of {010} bismuth oxychloride nanosheets.

实验例2Experimental example 2

考察BOC-010、BOC-001、10NBOC-010的晶面暴露特征Investigating the exposure characteristics of crystal planes of BOC-010, BOC-001, and 10NBOC-010

利用透射电子显微镜考察{010}氯氧化铋纳米片(BOC-010)、{001}氯氧化铋纳米片(BOC-001)和氮掺杂碳量子点锚定的{010}氯氧化铋纳米片(10NBOC-010)的晶面暴露特征。Inspection of {010} bismuth oxychloride nanosheets (BOC-010), {001} bismuth oxychloride nanosheets (BOC-001) and {010} bismuth oxychloride nanosheets anchored by nitrogen-doped carbon quantum dots by transmission electron microscopy (10NBOC-010) facet exposed features.

结果如图2所示,其中a为BOC-001,b为BOC-010,c为10NBOC-010。由图2a可知,BOC-001晶面间距为0.275nm的清晰晶格条纹对应于与{001}原子平面垂直的{110}原子平面,即BOC-001的主要暴露晶面为{001}晶面;由图2b可知,可以明显观察到晶格间距为0.37nm的(002)原子面,即BOC-010主要被{010}面包围。由图2c可知,{010}氯氧化铋表面分布着直径约为8nm左右的氮掺杂碳量子点。The results are shown in Figure 2, where a is BOC-001, b is BOC-010, and c is 10NBOC-010. It can be seen from Figure 2a that the clear lattice fringes of BOC-001 with a interplanar spacing of 0.275 nm correspond to the {110} atomic plane perpendicular to the {001} atomic plane, that is, the main exposed crystal plane of BOC-001 is the {001} crystal plane ; It can be seen from Figure 2b that the (002) atomic plane with a lattice spacing of 0.37nm can be clearly observed, that is, BOC-010 is mainly surrounded by {010} planes. It can be seen from Fig. 2c that nitrogen-doped carbon quantum dots with a diameter of about 8 nm are distributed on the surface of {010} bismuth oxychloride.

实验例3Experimental example 3

考察BOC-010、BOC-001、10NBOC-010、10NBOC-001的光响应性能Investigate the photoresponse performance of BOC-010, BOC-001, 10NBOC-010, 10NBOC-001

利用紫外可见漫反射光谱对{010}氯氧化铋纳米片(BOC-010)、{001}氯氧化铋纳米片(BOC-001)、氮掺杂碳量子点锚定的{010}氯氧化铋纳米片(10NBOC-010)和氮掺杂碳量子点锚定的{001}氯氧化铋纳米片(10NBOC-001)进行光响应性能检测。{010} bismuth oxychloride nanosheets (BOC-010), {001} bismuth oxychloride nanosheets (BOC-001), and {010} bismuth oxychloride anchored by nitrogen-doped carbon quantum dots by UV-vis diffuse reflectance spectroscopy Nanosheets (10NBOC-010) and {001} bismuth oxychloride nanosheets (10NBOC-001) anchored by nitrogen-doped carbon quantum dots were tested for photoresponse performance.

结果如图3所示。BOC-010和BOC-001的光吸收边缘分别为351nm和375nm。锚定氮掺杂碳量子点后,10NBOC-001的吸收边缘出现轻微的红移(360nm),同时10NBOC-010也有轻微的红移(390nm),氮掺杂碳量子点可以拓宽氯氧化铋的光响应范围但作用有限。然而,关注催化剂对波长280nm至800nm的光响应,可知在负载氮掺杂碳量子点后,10NBOC-010对该范围内的光吸收强度较10NBOC-001明显增强。这主要是因为氮掺杂碳量子点可以作为光敏剂并作为光催化剂的吸光中心,同时氮掺杂碳量子点与氯氧化铋{010}晶面之间的界面电荷转移效应也可以促进光吸收性能的提升。The result is shown in Figure 3. The light absorption edges of BOC-010 and BOC-001 are 351nm and 375nm, respectively. After anchoring nitrogen-doped carbon quantum dots, the absorption edge of 10NBOC-001 has a slight red shift (360nm), and 10NBOC-010 also has a slight red shift (390nm). Nitrogen-doped carbon quantum dots can broaden the absorption edge of bismuth oxychloride Photoresponsive range but limited action. However, focusing on the photoresponse of the catalyst to wavelengths from 280nm to 800nm, it can be seen that after loading nitrogen-doped carbon quantum dots, the light absorption intensity of 10NBOC-010 in this range is significantly stronger than that of 10NBOC-001. This is mainly because nitrogen-doped carbon quantum dots can act as photosensitizers and act as light-absorbing centers of photocatalysts, and the interfacial charge transfer effect between nitrogen-doped carbon quantum dots and bismuth oxychloride {010} crystal planes can also promote light absorption. Performance improvements.

实验例4Experimental example 4

考察BOC-010、BOC-001、10NBOC-010、10NBOC-001的光生载流子迁移性能Investigation of the photogenerated carrier migration performance of BOC-010, BOC-001, 10NBOC-010, 10NBOC-001

利用电化学实验对制得的{010}氯氧化铋纳米片(BOC-010)、{001}氯氧化铋纳米片(BOC-001)、氮掺杂碳量子点锚定的{010}氯氧化铋纳米片(10NBOC-010)和氮掺杂碳量子点锚定的{001}氯氧化铋纳米片(10NBOC-001)进行光生载流子迁移性能检测。The prepared {010} bismuth oxychloride nanosheets (BOC-010), {001} bismuth oxychloride nanosheets (BOC-001), and {010} oxychloride anchored by nitrogen-doped carbon quantum dots were investigated by electrochemical experiments. Bismuth nanosheets (10NBOC-010) and {001} bismuth oxychloride nanosheets (10NBOC-001) anchored by nitrogen-doped carbon quantum dots were used to detect the mobility of photogenerated carriers.

结果如图4所示。BOC-010的载流子分离效率不及BOC-001,然而当负载相同数量的氮掺杂碳量子后10NBOC-010的载流子分离效率优于10NBOC-001。该现象表明氮掺杂碳量子点和氯氧化铋的{010}晶面在促进载流子分离方面具有协同作用。The result is shown in Figure 4. The carrier separation efficiency of BOC-010 is lower than that of BOC-001, but the carrier separation efficiency of 10NBOC-010 is better than that of 10NBOC-001 when the same amount of nitrogen-doped carbon quantum is loaded. This phenomenon indicates that nitrogen-doped carbon quantum dots and {010} crystal planes of bismuth oxychloride have a synergistic effect in promoting carrier separation.

实验例5Experimental example 5

考察氮掺杂碳量子点锚定的{010}氯氧化铋纳米片(10NBOC-010)中氮掺杂碳量子点和氯氧化铋的{010}晶面的协同作用Investigation of the synergistic effect of nitrogen-doped carbon quantum dots and {010} facets of bismuth oxychloride anchored by nitrogen-doped carbon quantum dots in {010} bismuth oxychloride nanosheets (10NBOC-010)

通过计算氮掺杂碳量子点锚定的{010}氯氧化铋纳米片(10NBOC-010)的三维和平面平均差分电荷密度分析氮掺杂碳量子点和氯氧化铋的{010}晶面的协同作用。Analysis of nitrogen-doped carbon quantum dots and {010} crystal planes of bismuth oxychloride nanosheets (10NBOC-010) anchored by nitrogen-doped carbon quantum dots by calculating the three-dimensional and in-plane average differential charge densities synergy.

结果如图5所示,图5a可以观察到沿[Bi2O2]2+→N-CQDs→Cl-方向的共价环,这有利于电子的定向转移从而形成界面电场;由图5b可知,在10NBOC-010复合材料界面中氮掺杂碳量子点的电子转移至氯氧化铋{010}晶面,从而形成了由氮掺杂碳量子点指向氯氧化铋{010}晶面的界面电场,有利于光照条件下10NBOC-010异质界面处光生电荷的转移。The results are shown in Figure 5. In Figure 5a, a covalent ring along the direction of [Bi 2 O 2 ] 2+ →N-CQDs→Cl - can be observed, which is conducive to the directional transfer of electrons and the formation of an interfacial electric field; it can be seen from Figure 5b , the electrons of the nitrogen-doped carbon quantum dots in the 10NBOC-010 composite interface are transferred to the bismuth oxychloride {010} crystal plane, thereby forming an interface electric field pointing from the nitrogen-doped carbon quantum dots to the bismuth oxychloride {010} crystal plane , which is conducive to the transfer of photogenerated charges at the heterointerface of 10NBOC-010 under light conditions.

实验例6Experimental example 6

考察BOC-010、BOC-001、6NBOC-010、10NBOC-010、14NBOC-010和10NBOC-001降解抗生素污染物的效率Investigate the efficiency of BOC-010, BOC-001, 6NBOC-010, 10NBOC-010, 14NBOC-010 and 10NBOC-001 in degrading antibiotic pollutants

利用材料BOC-010、BOC-001、6NBOC-010、10NBOC-010、14NBOC-010和10NBOC-001降解水体中的环丙沙星(CIP),包括以下步骤:Utilize materials BOC-010, BOC-001, 6NBOC-010, 10NBOC-010, 14NBOC-010 and 10NBOC-001 to degrade ciprofloxacin (CIP) in water, including the following steps:

S1、称取{010}氯氧化铋光催化剂(BOC-010)、{001}氯氧化铋光催化剂(BOC-001)、氮掺杂碳量子点锚定的{010}氯氧化铋(6NBOC-010、10NBOC-010、14NBOC-010)和氮掺杂碳量子点锚定的{001}氯氧化铋(10NBOC-001)各0.02g,分别添加到50mL、浓度为10mg/L的环丙沙星(CIP)废水中,在暗处磁力搅拌一个小时,达到吸附平衡S1. Weigh {010} bismuth oxychloride photocatalyst (BOC-010), {001} bismuth oxychloride photocatalyst (BOC-001), {010} bismuth oxychloride anchored by nitrogen-doped carbon quantum dots (6NBOC- 010, 10NBOC-010, 14NBOC-010) and {001} bismuth oxychloride (10NBOC-001) anchored by nitrogen-doped carbon quantum dots (0.02g), were added to 50mL of ciprofloxacin at a concentration of 10mg/L (CIP) wastewater, magnetically stirred for one hour in the dark to reach adsorption equilibrium

S2、打开光源(氙灯),在可见光(λ≥420nm)下照射进行光催化反应60min,完成对废水中CIP的降解。S2. Turn on the light source (xenon lamp), irradiate with visible light (λ≥420nm) to carry out the photocatalytic reaction for 60 minutes, and complete the degradation of CIP in the wastewater.

S3、每隔10min吸取3mL反应容器中的光催化降解液,用0.45μm的滤头过滤,用紫外-可见分光光度计仪器对滤液进行降解效率检测。S3. Take 3 mL of the photocatalytic degradation solution in the reaction vessel every 10 minutes, filter it with a 0.45 μm filter head, and detect the degradation efficiency of the filtrate with an ultraviolet-visible spectrophotometer.

结果如图6所示,图6a为BOC-010、BOC-001、6NBOC-010、10NBOC-010、14NBOC-010和10NBOC-001在可见光照射条件下光催化降解CIP废水时对应的时间-降解效率的关系图。图中Ct代表降解后的CIP的浓度,C表示CIP的初始浓度。The results are shown in Figure 6, and Figure 6a shows the corresponding time-degradation efficiency of BOC-010, BOC-001, 6NBOC-010, 10NBOC-010, 14NBOC-010 and 10NBOC-001 in photocatalytic degradation of CIP wastewater under visible light irradiation conditions relationship diagram. In the figure, Ct represents the concentration of degraded CIP, and C represents the initial concentration of CIP.

从图6中可知:{010}氯氧化铋光催化剂(BOC-010)在光催化反应60min后对CIP的降解效率为33.9%。It can be seen from Fig. 6 that the degradation efficiency of {010} bismuth oxychloride photocatalyst (BOC-010) to CIP is 33.9% after photocatalytic reaction for 60 min.

氮掺杂碳量子点锚定的{010}氯氧化铋光催化剂(6NBOC-010)在光催化反应60min后对CIP的降解效率为76.9%。The nitrogen-doped carbon quantum dot-anchored {010} bismuth oxychloride photocatalyst (6NBOC-010) had a photocatalytic degradation efficiency of 76.9% for CIP after 60 min of photocatalytic reaction.

氮掺杂碳量子点锚定的{010}氯氧化铋光催化剂(10NBOC-010)在光催化反应60min后对CIP的降解效率为85.2%。The nitrogen-doped carbon quantum dot-anchored {010} bismuth oxychloride photocatalyst (10NBOC-010) had a photocatalytic degradation efficiency of 85.2% for CIP after 60 min of photocatalytic reaction.

氮掺杂碳量子点锚定的{010}氯氧化铋光催化剂(14NBOC-010)在光催化反应60min后对CIP的降解效率为80.4%。The nitrogen-doped carbon quantum dot-anchored {010} bismuth oxychloride photocatalyst (14NBOC-010) had a photocatalytic degradation efficiency of 80.4% for CIP after 60 min of photocatalytic reaction.

{001}氯氧化铋光催化剂(BOC-001)在光催化反应60min对CIP的降解效率为9.4%。The degradation efficiency of {001} bismuth oxychloride photocatalyst (BOC-001) to CIP was 9.4% in photocatalytic reaction for 60min.

{001}氯氧化铋光催化剂(10NBOC-001)在光催化反应60min对CIP的降解效率为63.4%。The degradation efficiency of {001} bismuth oxychloride photocatalyst (10NBOC-001) to CIP was 63.4% in photocatalytic reaction for 60min.

由此可知,降解效率由高到低依次为:氮掺杂碳量子点锚定的{010}氯氧化铋光催化剂(10NBOC-010)>氮掺杂碳量子点锚定的{010}氯氧化铋光催化剂(14NBOC-010)>氮掺杂碳量子点锚定的{010}氯氧化铋光催化剂(6NBOC-010)>{001}氯氧化铋光催化剂(10NBOC-001)>{010}氯氧化铋光催化剂(BOC-010)>{001}氯氧化铋光催化剂(BOC-001)。It can be seen that the order of degradation efficiency from high to low is: nitrogen-doped carbon quantum dot anchored {010} bismuth oxychloride photocatalyst (10NBOC-010) > nitrogen-doped carbon quantum dot anchored {010} oxychloride photocatalyst Bismuth photocatalyst (14NBOC-010) > {010} bismuth oxychloride photocatalyst anchored by nitrogen-doped carbon quantum dots (6NBOC-010) > {001} bismuth oxychloride photocatalyst (10NBOC-001) > {010} chlorine Bismuth Oxide Photocatalyst (BOC-010)>{001} Bismuth Oxychloride Photocatalyst (BOC-001).

图6b为BOC-010、BOC-001、6NBOC-010、10NBOC-010、14NBOC-010和10NBOC-001处理的降解系数。Figure 6b shows the degradation coefficients of BOC-010, BOC-001, 6NBOC-010, 10NBOC-010, 14NBOC-010 and 10NBOC-001 treatments.

氮掺杂碳量子点锚定的{010}氯氧化铋光催化剂中氮掺杂碳量子点的质量百分含量为0.02%,{010}氯氧化铋纳米片的质量百分含量为99.98%时的降解效率最高,除此之外,氮掺杂碳量子点的质量百分含量过高或者过低都会显著影响材料的降解效率。When the mass percentage of nitrogen-doped carbon quantum dots in {010} bismuth oxychloride photocatalyst anchored by nitrogen-doped carbon quantum dots is 0.02%, and the mass percentage of {010} bismuth oxychloride nanosheets is 99.98% In addition, the mass percentage of nitrogen-doped carbon quantum dots is too high or too low will significantly affect the degradation efficiency of the material.

以上所述是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明所述原理的前提下,还可以作出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。The above description is a preferred embodiment of the present invention, it should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (10)

1.一种氮掺杂碳量子点锚定的氯氧化铋光催化剂,其特征在于,包括氯氧化铋、氮掺杂碳量子点,所述氯氧化铋主要暴露晶面为{010},所述氮掺杂碳量子点锚定在氯氧化铋暴露的{010}晶面上,所述氮掺杂碳量子点的质量百分含量为0.01~0.08%。1. A bismuth oxychloride photocatalyst anchored by nitrogen-doped carbon quantum dots, characterized in that it comprises bismuth oxychloride and nitrogen-doped carbon quantum dots, and the main exposed crystal face of the bismuth oxychloride is {010}, so The nitrogen-doped carbon quantum dots are anchored on the exposed {010} crystal plane of bismuth oxychloride, and the mass percentage of the nitrogen-doped carbon quantum dots is 0.01-0.08%. 2.根据权利要求1所述的氮掺杂碳量子点锚定氯氧化铋光催化剂,其特征在于,所述氮掺杂碳量子点的直径<10nm。2. The nitrogen-doped carbon quantum dot anchored bismuth oxychloride photocatalyst according to claim 1, characterized in that the diameter of the nitrogen-doped carbon quantum dot is <10nm. 3.根据权利要求1所述的氮掺杂碳量子点锚定氯氧化铋光催化剂,其特征在于,所述氯氧化铋为超薄不规整纳米片结构。3. The nitrogen-doped carbon quantum dot anchored bismuth oxychloride photocatalyst according to claim 1, characterized in that the bismuth oxychloride is an ultra-thin irregular nanosheet structure. 4.一种氮掺杂碳量子点锚定的氯氧化铋光催化剂的制备方法,其特征在于,包括以下步骤:4. A preparation method of a nitrogen-doped carbon quantum dot-anchored bismuth oxychloride photocatalyst, characterized in that, comprising the following steps: S1、将五水合硝酸铋和氮掺杂碳量子点溶液,加至丙三醇和水的混合溶剂中,超声搅拌至形成均匀混合液;S1. Add bismuth nitrate pentahydrate and nitrogen-doped carbon quantum dot solution to a mixed solvent of glycerol and water, and ultrasonically stir until a uniform mixed solution is formed; S2、向步骤S1得到的混合液中,逐滴加入饱和氯化钠溶液,超声搅拌均匀;S2. Add saturated sodium chloride solution dropwise to the mixed solution obtained in step S1, and stir evenly with ultrasonic; S3、向步骤S2得到的混合液中滴加碱性溶液调节pH为5~7;S3, adding an alkaline solution dropwise to the mixed solution obtained in step S2 to adjust the pH to 5-7; S4、将步骤S3得到的混合溶液进行水热反应,经冷却、离心、去离子水和乙醇清洗、干燥,得到氮掺杂碳量子点锚定的{010}氯氧化铋。S4. The mixed solution obtained in step S3 is subjected to hydrothermal reaction, cooled, centrifuged, washed with deionized water and ethanol, and dried to obtain {010} bismuth oxychloride anchored by nitrogen-doped carbon quantum dots. 5.根据权利要求4所述的制备方法,其特征在于,所述S1步骤中五水合硝酸铋和氮掺杂碳量子点溶液的摩尔比为1:0.002~0.008;所述S1步骤中丙三醇与水的体积比为1:0.5~1。5. The preparation method according to claim 4, characterized in that, the molar ratio of bismuth nitrate pentahydrate and nitrogen-doped carbon quantum dot solution in the S1 step is 1:0.002~0.008; The volume ratio of alcohol to water is 1:0.5~1. 6.根据权利要求4所述的制备方法,其特征在于,所述S3步骤中碱性溶液为氢氧化钠溶液或氢氧化钾溶液中任意一种。6. The preparation method according to claim 4, characterized in that, in the step S3, the alkaline solution is any one of sodium hydroxide solution or potassium hydroxide solution. 7.根据权利要求4所述的制备方法,其特征在于,所述S4步骤中水热反应温度120~180℃,反应时间5~10h。7. The preparation method according to claim 4, characterized in that, in the step S4, the hydrothermal reaction temperature is 120-180° C., and the reaction time is 5-10 h. 8.一种如权利要求1~3任一项所述的氮掺杂碳量子点锚定的氯氧化铋光催化剂或如权利要求4~7任一项所述制备方法制得的氮掺杂碳量子点锚定的氯氧化铋光催化剂在催化降解废水中抗生素中的应用。8. A bismuth oxychloride photocatalyst anchored by nitrogen-doped carbon quantum dots as claimed in any one of claims 1 to 3 or a nitrogen-doped photocatalyst prepared by the preparation method according to any one of claims 4 to 7. Application of bismuth oxychloride photocatalyst anchored by carbon quantum dots in the catalytic degradation of antibiotics in wastewater. 9.根据权利要求8所述的应用,其特征在于,所述光催化剂催化降解废水中抗生素包括以下步骤:将所述氮掺杂碳量子点锚定的氯氧化铋光催化剂与含抗生素污染物废水混合,搅拌,在光照条件下进行光催化反应,完成对抗生素污染物的降解;9. application according to claim 8, is characterized in that, described photocatalyst degrades the antibiotic in waste water and comprises the following steps: the bismuth oxychloride photocatalyst anchored by described nitrogen-doped carbon quantum dot and containing antibiotic pollutant Wastewater is mixed, stirred, and photocatalytic reaction is carried out under light conditions to complete the degradation of antibiotic pollutants; 所述光催化剂在每升含有抗生素废水中的添加量为0.2g~1.0g。The photocatalyst is added in an amount of 0.2g-1.0g per liter of antibiotic-containing wastewater. 10.根据权利要求9所述的应用,其特征在于,所述抗生素污染物为环丙沙星,所述环丙沙星污染物的初始浓度为5mg/L~20mg/L;所述光照条件λ≥420nm;所述光催化反应的时间≥60min。10. application according to claim 9, is characterized in that, described antibiotic pollutant is ciprofloxacin, and the initial concentration of described ciprofloxacin pollutant is 5mg/L~20mg/L; λ≥420nm; the photocatalytic reaction time≥60min.
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