CN115888833B - CdS/Mn-MOF composite photocatalyst and preparation method and application thereof - Google Patents
CdS/Mn-MOF composite photocatalyst and preparation method and application thereof Download PDFInfo
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Abstract
Description
技术领域Technical field
本发明属于光催化技术领域，具体涉及一种CdS/Mn-MOF复合光催化剂及其制备方法、应用。The invention belongs to the field of photocatalysis technology, and specifically relates to a CdS/Mn-MOF composite photocatalyst and its preparation method and application.
背景技术Background technique
现代工业的发展，给人类的生活带来了很多便利，然而环境污染问题也随之而来，其中难降解的有机污染物引起的环境污染问题引起了广泛的关注，并应用了许多工艺来解决这些问题。光催化氧化技术作为一种先进的氧化技术(AOTs)，由于该方法能彻底分解有机污染物以及转化部分重金属污染物，具有处理效率高、无二次污染等优点，而备受青睐。半导体二氧化钛是公认为最重要的光催化剂之一，有着优异的光催化活性，并具有无毒低成本的特点。然而，它的宽带隙决定了它只能吸收占自然光不到5％的高能紫外线(UV)辐射，导致了实际应用的限制，因此，需要开发高效的可见光驱动光催化剂。The development of modern industry has brought a lot of convenience to human life. However, environmental pollution problems have also followed. Among them, environmental pollution problems caused by refractory organic pollutants have attracted widespread attention, and many processes have been applied to solve them. these questions. As an advanced oxidation technology (AOTs), photocatalytic oxidation technology is highly favored because it can completely decompose organic pollutants and convert some heavy metal pollutants. It has the advantages of high treatment efficiency and no secondary pollution. Semiconducting titanium dioxide is recognized as one of the most important photocatalysts. It has excellent photocatalytic activity and is non-toxic and low-cost. However, its wide bandgap determines that it can only absorb high-energy ultraviolet (UV) radiation that accounts for less than 5% of natural light, leading to limitations in practical applications. Therefore, there is a need to develop efficient visible light-driven photocatalysts.
在各种报道的光催化剂中，硫化镉作为一种可见光光催化剂，具有带隙窄(2.2-2.4eV)，制备简单的特点，广泛应用于污染物的降解，析氢和有机转化。然而，光生电子-空穴对的高复合率是限制其应用的一个关键问题。此外，单个硫化镉纳米颗粒容易聚集形成大颗粒，导致表面积减少，重组率增加，从而严重抑制其光催化活性，而导致其在实际应用过程中受限。因此，如何解决硫化镉单体材料带隙宽、光生电子-空穴对的高复合率等问题，制备优异的光催化剂是至关重要的。Among various reported photocatalysts, cadmium sulfide, as a visible light photocatalyst, has the characteristics of narrow band gap (2.2-2.4eV) and simple preparation. It is widely used in the degradation of pollutants, hydrogen evolution and organic transformation. However, the high recombination rate of photogenerated electron-hole pairs is a key issue limiting its application. In addition, individual cadmium sulfide nanoparticles tend to aggregate to form large particles, resulting in a reduction in surface area and an increase in recombination rate, which severely inhibits their photocatalytic activity and limits their practical application. Therefore, it is crucial to solve the problems of wide band gap of cadmium sulfide monomer material and high recombination rate of photogenerated electron-hole pairs, and to prepare excellent photocatalysts.
发明内容Contents of the invention
本发明的目的在于，针对现有存在的上述问题，提供一种CdS/Mn-MOF复合光催化剂及其制备方法、应用，本发明采用水热合成技术制备CdS/Mn-MOF复合光催化剂，该方法操作简单，条件易于控制，成本低，制备的光催化剂性能优异，同时具有良好的稳定性和可重复使用性，能够有效解决硫化镉单体材料带隙宽、光生电子-空穴对的高复合率等问题。The purpose of the present invention is to provide a CdS/Mn-MOF composite photocatalyst and its preparation method and application in view of the above existing problems. The present invention uses hydrothermal synthesis technology to prepare the CdS/Mn-MOF composite photocatalyst. The method is simple to operate, the conditions are easy to control, and the cost is low. The prepared photocatalyst has excellent performance, good stability and reusability, and can effectively solve the problem of wide band gap of cadmium sulfide monomer material and high photogenerated electron-hole pairs. Recombination rate and other issues.
为了实现上述目的，本申请采用的技术方案为：In order to achieve the above objectives, the technical solutions adopted in this application are:
一种CdS/Mn-MOF复合光催化剂的制备方法，包括以下步骤：A preparation method of CdS/Mn-MOF composite photocatalyst, including the following steps:
S1、将5-吡嗪间苯二甲酸和四水氯化锰加入混合溶剂中，搅拌得到悬浊液，然后在145℃下进行水热反应，反应结束后过滤、洗涤和干燥得到Mn-MOF；S1. Add 5-pyrazine isophthalic acid and manganese chloride tetrahydrate into the mixed solvent, stir to obtain a suspension, and then perform a hydrothermal reaction at 145°C. After the reaction is completed, filter, wash and dry to obtain Mn-MOF. ;
S2、将S1得到的Mn-MOF分散在溶剂中，加入二水乙酸镉后在80℃下油浴反应，然后滴加硫代乙酰胺溶液后继续反应，反应结束后离心、洗涤和干燥得到CdS/Mn-MOF复合光催化剂。S2. Disperse the Mn-MOF obtained in S1 in the solvent, add cadmium acetate dihydrate and react in an oil bath at 80°C. Then add thioacetamide solution dropwise and continue the reaction. After the reaction is completed, centrifuge, wash and dry to obtain CdS. /Mn-MOF composite photocatalyst.
进一步的，S1中，所述5-吡嗪间苯二甲酸、四水氯化锰和混合溶剂的质量体积比为3mg:10mg:1mL。Further, in S1, the mass volume ratio of the 5-pyrazine isophthalic acid, manganese chloride tetrahydrate and the mixed solvent is 3mg:10mg:1mL.
进一步的，S1中，所述混合溶剂为乙腈和水，乙腈和水的体积比为1:1。Further, in S1, the mixed solvent is acetonitrile and water, and the volume ratio of acetonitrile and water is 1:1.
进一步的，S1中，所述水热反应的时间为48-72h。Further, in S1, the hydrothermal reaction time is 48-72h.
进一步的，S2中，所述Mn-MOF、溶剂、二水乙酸镉和硫代乙酰胺溶液的质量体积比为50mg:50mL:11-92mg:20mL。Further, in S2, the mass to volume ratio of the Mn-MOF, solvent, cadmium acetate dihydrate and thioacetamide solution is 50mg:50mL:11-92mg:20mL.
进一步的，S2中，所述溶剂为乙醇；所述硫代乙酰胺溶液的浓度为0.15-1.3g/L。Further, in S2, the solvent is ethanol; the concentration of the thioacetamide solution is 0.15-1.3g/L.
进一步的，S2中，所述油浴反应的时间为1h；滴加硫代乙酰胺溶液后继续反应的时间为3h。Further, in S2, the oil bath reaction time is 1 hour; the reaction time after adding the thioacetamide solution dropwise is 3 hours.
进一步的，S1中，所述洗涤和干燥的方式为采用水和乙腈分别洗涤三次，自然晾干；Further, in S1, the washing and drying method is to wash three times with water and acetonitrile respectively, and then dry naturally;
S2中，所述洗涤和干燥的方式为采用水和乙醇分别洗涤三次，干燥12h。In S2, the washing and drying methods include washing three times with water and ethanol respectively, and drying for 12 hours.
此外，本发明还提供了上述制备方法制备的CdS/Mn-MOF复合光催化剂。In addition, the present invention also provides the CdS/Mn-MOF composite photocatalyst prepared by the above preparation method.
本发明还提供了上述CdS/Mn-MOF复合光催化剂在降解有机污染物的应用，将所述CdS/Mn-MOF复合光催化剂与有机污染物混合，在可见光照射下，进行催化降解。The present invention also provides the application of the above-mentioned CdS/Mn-MOF composite photocatalyst in degrading organic pollutants. The CdS/Mn-MOF composite photocatalyst is mixed with organic pollutants and catalytically degraded under visible light irradiation.
与现有技术相比，本发明的有益效果： Compared with the existing technology, the beneficial effects of the present invention are:
(1)本发明采用低成本的水和乙腈为溶剂体系以及原料，采用水热合成技术制备光催化剂CdS/Mn-MOF，将CdS与Mn-MOF复合来构筑异质结获得性能优异的光催化剂，能够有效解决硫化镉单体材料带隙宽、光生电子-空穴对的高复合率等问题。(1) The present invention uses low-cost water and acetonitrile as the solvent system and raw materials, uses hydrothermal synthesis technology to prepare the photocatalyst CdS/Mn-MOF, and combines CdS and Mn-MOF to build a heterojunction to obtain a photocatalyst with excellent performance. , which can effectively solve the problems of wide band gap of cadmium sulfide single material and high recombination rate of photogenerated electron-hole pairs.
(2)本发明制备的光催化剂CdS/Mn-MOF用于有机污染物的降解，具有优异的催化性能，在模拟阳光照射下，在60min时对罗丹明B的降解率为98.3％，此外，该光催化剂具有良好的稳定性和可重复使用性，经过3次运行后罗丹明B降解率仍然可达95.59％，该方法为合理构建MOF/半导体复合催化剂以实现污染物的降解提供了新的思路。(2) The photocatalyst CdS/Mn-MOF prepared by the present invention is used for the degradation of organic pollutants and has excellent catalytic performance. Under simulated sunlight, the degradation rate of rhodamine B in 60 minutes is 98.3%. In addition, The photocatalyst has good stability and reusability, and the rhodamine B degradation rate can still reach 95.59% after three runs. This method provides a new method for rationally constructing MOF/semiconductor composite catalysts to achieve the degradation of pollutants. ideas.
(3)本发明制备工艺简单，只需要调控原料的用量，可操作性强，适合大量生产，水热合成的反应条件温和低于200℃，生产过程安全，具有良好的工业应用前景。(3) The preparation process of the present invention is simple, only the amount of raw materials needs to be controlled, the operability is strong, and it is suitable for mass production. The reaction conditions of hydrothermal synthesis are mild and below 200°C, the production process is safe, and it has good industrial application prospects.
附图说明Description of drawings
图1为本发明制备的CdS/Mn-MOF复合光催化剂的机理图；Figure 1 is a mechanism diagram of the CdS/Mn-MOF composite photocatalyst prepared by the present invention;
图2为本发明实施例1制备CdS/Mn-MOF复合光催化剂的扫描电镜和mapping图；Figure 2 is a scanning electron microscope and mapping diagram of a CdS/Mn-MOF composite photocatalyst prepared in Example 1 of the present invention;
图3为本发明实施例1制备CdS/Mn-MOF复合光催化剂的紫外-可见吸收曲线；Figure 3 is the UV-visible absorption curve of the CdS/Mn-MOF composite photocatalyst prepared in Example 1 of the present invention;
图4为本发明实施例1制备CdS/Mn-MOF复合光催化剂的循环性能图。Figure 4 is a cycle performance diagram of the CdS/Mn-MOF composite photocatalyst prepared in Example 1 of the present invention.
具体实施方式Detailed ways
下面将结合本发明实施例中的数据，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the data in the embodiments of the present invention. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.
需要说明的是，本发明中所使用的专业术语只是为了描述具体实施例的目的，并不是旨在限制本发明的保护范围，除非另有特别说明，本发明以下各实施例中用到的各种原料、试剂、仪器和设备均可通过市场购买得到或者通过现有方法制备得到。It should be noted that the professional terms used in the present invention are only for the purpose of describing specific embodiments and are not intended to limit the protection scope of the present invention. Unless otherwise specified, each term used in the following embodiments of the present invention All raw materials, reagents, instruments and equipment can be purchased in the market or prepared by existing methods.
实施例1Example 1
一种CdS/Mn-MOF复合光催化剂的制备方法，包括以下步骤：A preparation method of CdS/Mn-MOF composite photocatalyst, including the following steps:
S1、将12mg的有机配体5-吡嗪间苯二甲酸和40mg四水氯化锰依次加入2mL水和2mL乙腈的混合溶剂中，搅拌均匀得到悬浊液，然后将悬浊液转移至25mL的聚四氟乙烯反应釜里，反应釜在145℃下进行水热反应48h，反应结束以10℃/h降至室温后，过滤得到淡黄色晶体，用去离子水和乙腈分别洗涤三次，自然晾干得到Mn-MOF；S1. Add 12 mg of the organic ligand 5-pyrazine isophthalic acid and 40 mg of manganese chloride tetrahydrate into a mixed solvent of 2 mL of water and 2 mL of acetonitrile, stir evenly to obtain a suspension, and then transfer the suspension to 25 mL In a polytetrafluoroethylene reaction kettle, the reaction kettle was subjected to a hydrothermal reaction at 145°C for 48 hours. After the reaction was completed and lowered to room temperature at 10°C/h, the light yellow crystals were filtered and washed three times with deionized water and acetonitrile. Naturally Dry to obtain Mn-MOF;
S2、将S1得到的50mg的Mn-MOF分散在50mL的乙醇中，向其加入92mg二水乙酸镉后，在80℃下进行油浴搅拌反应1h，逐渐滴加20mL的硫代乙酰胺溶液后继续反应，硫代乙酰胺溶液为将26mg的硫代乙酰胺溶解在20mL水中得到的硫代乙酰胺溶液，反应结束后冷却，进行离心，用水和乙醇洗涤三次，最后在60℃下真空干燥12h，然后用研钵研磨5min得到CdS/Mn-MOF复合光催化剂。S2. Disperse 50 mg of Mn-MOF obtained in S1 in 50 mL of ethanol, add 92 mg of cadmium acetate dihydrate, and perform an oil bath stirring reaction at 80°C for 1 hour. Gradually add 20 mL of thioacetamide solution dropwise. Continue the reaction. The thioacetamide solution is a thioacetamide solution obtained by dissolving 26 mg of thioacetamide in 20 mL of water. After the reaction is completed, it is cooled, centrifuged, washed three times with water and ethanol, and finally vacuum dried at 60°C for 12 hours. , and then grind it with a mortar for 5 minutes to obtain the CdS/Mn-MOF composite photocatalyst.
实施例2Example 2
一种CdS/Mn-MOF复合光催化剂的制备方法，包括以下步骤：A preparation method of CdS/Mn-MOF composite photocatalyst, including the following steps:
S1、将12mg的有机配体5-吡嗪间苯二甲酸和40mg四水氯化锰依次加入2mL水和2mL乙腈的混合溶剂中，搅拌均匀得到悬浊液，然后将悬浊液转移至25mL的聚四氟乙烯反应釜里，反应釜在145℃下进行水热反应48h，反应结束以10℃/h降至室温后，过滤得到淡黄色晶体，用去离子水和乙腈分别洗涤三次，自然晾干得到Mn-MOF；S1. Add 12 mg of the organic ligand 5-pyrazine isophthalic acid and 40 mg of manganese chloride tetrahydrate into a mixed solvent of 2 mL of water and 2 mL of acetonitrile, stir evenly to obtain a suspension, and then transfer the suspension to 25 mL In a polytetrafluoroethylene reaction kettle, the reaction kettle was subjected to a hydrothermal reaction at 145°C for 48 hours. After the reaction was completed and lowered to room temperature at 10°C/h, the light yellow crystals were filtered and washed three times with deionized water and acetonitrile. Naturally Dry to obtain Mn-MOF;
S2、将S1得到的50mg的Mn-MOF分散在50mL的乙醇中，向其加入11mg二水乙酸镉后，在80℃下进行油浴搅拌反应1h，逐渐滴加20mL的硫代乙酰胺溶液后继续反应，其中，加硫代乙酰胺溶液为将3mg的硫代乙酰胺溶解在20mL水中得到的硫代乙酰胺溶液，反应结束后冷却，进行离心，用水和乙醇洗涤三次，最后在60℃下真空干燥12h，然后用研钵研磨5min得到CdS/Mn-MOF复合光催化剂。S2. Disperse 50 mg of Mn-MOF obtained in S1 in 50 mL of ethanol, add 11 mg of cadmium acetate dihydrate, and perform an oil bath stirring reaction at 80°C for 1 hour. Gradually add 20 mL of thioacetamide solution dropwise. Continue the reaction, where the thioacetamide solution added is a thioacetamide solution obtained by dissolving 3 mg of thioacetamide in 20 mL of water. After the reaction is completed, it is cooled, centrifuged, washed three times with water and ethanol, and finally at 60°C. Vacuum dry for 12 h, and then grind with a mortar for 5 min to obtain the CdS/Mn-MOF composite photocatalyst.
实施例3Example 3
一种CdS/Mn-MOF复合光催化剂的制备方法，包括以下步骤：A preparation method of CdS/Mn-MOF composite photocatalyst, including the following steps:
S1、将12mg的有机配体5-吡嗪间苯二甲酸和40mg四水氯化锰依次加入2mL水和2mL乙腈的混合溶剂中，搅拌均匀得到悬浊液，然后将悬浊液转移至25mL的聚四氟乙烯反应釜里，反应釜在145℃下进行水热反应48h，反应结束以10℃/h降至室温后，过滤得到淡黄色晶体，用去离子水和乙腈分别洗涤三次，自然晾干得到Mn-MOF；S1. Add 12 mg of the organic ligand 5-pyrazine isophthalic acid and 40 mg of manganese chloride tetrahydrate into a mixed solvent of 2 mL of water and 2 mL of acetonitrile, stir evenly to obtain a suspension, and then transfer the suspension to 25 mL In a polytetrafluoroethylene reaction kettle, the reaction kettle was subjected to a hydrothermal reaction at 145°C for 48 hours. After the reaction was completed and lowered to room temperature at 10°C/h, the light yellow crystals were filtered and washed three times with deionized water and acetonitrile. Naturally Dry to obtain Mn-MOF;
S2、将S1得到的50mg的Mn-MOF分散在50mL的乙醇中，向其加入40mg二水乙酸镉后，在80℃下进行油浴搅拌反应1h，逐渐滴加20mL的硫代乙酰胺溶液后继续反应，其中，加硫代乙酰胺溶液为将12mg的硫代乙酰胺溶解在20mL水中得到的硫代乙酰胺溶液，反应结束后冷却，进行离心，用水和乙醇洗涤三次，最后在60℃下真空干燥12h，然后用研钵研磨5min得到CdS/Mn-MOF复合光催化剂。S2. Disperse 50 mg of Mn-MOF obtained in S1 in 50 mL of ethanol, add 40 mg of cadmium acetate dihydrate, and perform an oil bath stirring reaction at 80°C for 1 hour. Gradually add 20 mL of thioacetamide solution dropwise. Continue the reaction, where the thioacetamide solution added is a thioacetamide solution obtained by dissolving 12 mg of thioacetamide in 20 mL of water. After the reaction is completed, it is cooled, centrifuged, washed three times with water and ethanol, and finally at 60°C. Vacuum dry for 12 h, and then grind with a mortar for 5 min to obtain the CdS/Mn-MOF composite photocatalyst.
对比例1Comparative example 1
一种Mn-MOF光催化剂的制备方法，包括以下步骤：A preparation method of Mn-MOF photocatalyst, including the following steps:
将12mg的有机配体5-吡嗪间苯二甲酸和40mg四水氯化锰依次加入2mL水和2mL乙腈的混合溶剂中，搅拌均匀得到悬浊液，然后将悬浊液转移至25mL的聚四氟乙烯反应釜里，反应釜在145℃下进行水热反应48h，反应结束以10℃/h降至室温后，过滤得到淡黄色晶体，用去离子水和乙腈分别洗涤三次，自然晾干得到Mn-MOF。Add 12 mg of the organic ligand 5-pyrazine isophthalic acid and 40 mg of manganese chloride tetrahydrate into a mixed solvent of 2 mL of water and 2 mL of acetonitrile, stir evenly to obtain a suspension, and then transfer the suspension to 25 mL of polyethylene chloride. In the tetrafluoroethylene reaction kettle, the reaction kettle was subjected to a hydrothermal reaction at 145°C for 48 hours. After the reaction was completed and dropped to room temperature at 10°C/h, the light yellow crystals were filtered to obtain light yellow crystals, washed three times with deionized water and acetonitrile, and dried naturally. Obtain Mn-MOF.
对比例2Comparative example 2
单一的CdS催化剂。Single CdS catalyst.
图1为本发明制备的CdS/Mn-MOF复合光催化剂的机理图，从图1可知，CdS(2.08eV)的带隙比Cd-MOF(2.73eV)的带隙窄，在可见光的照射下，异质结构中的硫化镉可以吸收可见光的能量并被激发，之后，硫化镉上的电子将以较低的势能转移到Cd-MOF的导带上，形成电子-空穴对。同时，Mn-MOF的价带上的空穴也将被转移到硫化镉上。在这个过程中，电子的转移产生了一个有效的电荷分离。因此，抑制了电子-空穴复合，提高了硫化镉容易发生光腐蚀的现象，提高了催化剂在光催化过程中的效率。因此，将CdS与Mn-MOF复合来构筑异质结，可以有效解决光生电子-空穴对的高复合率的问题。Figure 1 is a mechanism diagram of the CdS/Mn-MOF composite photocatalyst prepared by the present invention. From Figure 1, it can be seen that the band gap of CdS (2.08eV) is narrower than that of Cd-MOF (2.73eV). Under visible light irradiation , the cadmium sulfide in the heterostructure can absorb the energy of visible light and be excited. After that, the electrons on the cadmium sulfide will be transferred to the conduction band of Cd-MOF at a lower potential energy to form electron-hole pairs. At the same time, the holes in the valence band of Mn-MOF will also be transferred to cadmium sulfide. In this process, the transfer of electrons creates an efficient charge separation. Therefore, the electron-hole recombination is suppressed, the phenomenon that cadmium sulfide is prone to photocorrosion is improved, and the efficiency of the catalyst in the photocatalytic process is improved. Therefore, combining CdS with Mn-MOF to construct a heterojunction can effectively solve the problem of high recombination rate of photogenerated electron-hole pairs.
图2为本发明实施例1制备CdS/Mn-MOF复合光催化剂的扫描电镜和mapping图，其中图2a为CdS，b为Mn-MOF，c为CdS/Mn-MOF；d为CdS/Mn-MOF的mapping图；从图2b可以看出，硫化镉纳米颗粒成功地附着在Mn-MOF表面，图2dmapping图显示C、O、Mn、S和Cd元素分布在CdS/Mn-MOF中，硫化镉纳米颗粒成功地附着在Mn-MOF表面。Figure 2 is a scanning electron microscope and mapping diagram of a CdS/Mn-MOF composite photocatalyst prepared in Example 1 of the present invention, where Figure 2a is CdS, b is Mn-MOF, c is CdS/Mn-MOF; d is CdS/Mn- Mapping diagram of MOF; it can be seen from Figure 2b that cadmium sulfide nanoparticles are successfully attached to the Mn-MOF surface. Figure 2dmapping diagram shows that C, O, Mn, S and Cd elements are distributed in CdS/Mn-MOF. Cadmium sulfide The nanoparticles were successfully attached to the Mn-MOF surface.
分别将实施例1和对比例1-2制备的催化剂15mg分散在100mL的罗丹明B(RhB)水溶液(10mg/mL)烧杯中。辐照前，悬浊液在黑暗中磁搅拌30min，以确保吸附-解吸平衡，然后模拟阳光照射下，采用300WXe灯作为光源，分别照射上述溶液。在降解过程中，光源与烧杯之间的距离固定在10.0cm，保持搅拌状态进而保持混合物悬浮。每10min从烧杯中提取3mL的样品，离心去除分散的粉末。离心后，用紫外-可见分光光度计分析上清液。15 mg of the catalysts prepared in Example 1 and Comparative Examples 1-2 were dispersed in a 100 mL beaker of rhodamine B (RhB) aqueous solution (10 mg/mL). Before irradiation, the suspension was magnetically stirred in the dark for 30 minutes to ensure adsorption-desorption balance. Then, under simulated sunlight, a 300WXe lamp was used as the light source to irradiate the above solutions respectively. During the degradation process, the distance between the light source and the beaker was fixed at 10.0cm, and the stirring state was maintained to keep the mixture suspended. Extract 3 mL of sample from the beaker every 10 min and centrifuge to remove dispersed powder. After centrifugation, the supernatant was analyzed using a UV-visible spectrophotometer.
降解率＝(A0-At)/A0*100％；Degradation rate = (A 0 -A t )/A 0 *100%;
其中A0为罗丹明B的起始浓度，At为罗丹明B在某个时刻的浓度。Where A 0 is the initial concentration of rhodamine B, and A t is the concentration of rhodamine B at a certain moment.
通过紫外-可见分光光度计在某个时刻测定的吸光度值，计算罗丹明B在某个时刻的浓度At。(A＝aC，其中A代表吸光度，C代表浓度，a代表比例系数)The concentration A t of rhodamine B at a certain moment is calculated based on the absorbance value measured by a UV-visible spectrophotometer at a certain moment. (A=aC, where A represents absorbance, C represents concentration, and a represents proportional coefficient)
图3为本发明实施例1及对比例1-2复合光催化剂的紫外-可见吸收曲线，其中图3a为CdS/Mn-MOF，b为Mn-MOF，c为CdS；从图3a可以看出，在模拟阳光照射下，实施例1制备的复合光催化剂在60min时的罗丹明B降解率为98.30％，性能优异，而在模拟阳光照射下，如图3b和c，对比例1和对比例2复合光催化剂在60min时的罗丹明B降解率分别为4.71％和37.84％，实施例1制备的复合光催化剂对罗丹明B降解率显著提高。Figure 3 is the UV-visible absorption curve of the composite photocatalyst of Example 1 and Comparative Examples 1-2 of the present invention, where Figure 3a is CdS/Mn-MOF, b is Mn-MOF, and c is CdS; it can be seen from Figure 3a , under simulated sunlight irradiation, the composite photocatalyst prepared in Example 1 had a rhodamine B degradation rate of 98.30% at 60 minutes, with excellent performance. Under simulated sunlight irradiation, as shown in Figure 3b and c, Comparative Example 1 and Comparative Example 2 The rhodamine B degradation rates of the composite photocatalyst at 60 minutes were 4.71% and 37.84% respectively. The composite photocatalyst prepared in Example 1 significantly improved the rhodamine B degradation rate.
图4为本发明实施例1制备CdS/Mn-MOF复合光催化剂的循环性能图，从图4可以看出，实施例1制备的CdS/Mn-MOF复合光催化剂具有良好的稳定性和可重复使用性，经过3次运行后罗丹明B降解率仍然可达95.59％。Figure 4 is a cycle performance diagram of the CdS/Mn-MOF composite photocatalyst prepared in Example 1 of the present invention. It can be seen from Figure 4 that the CdS/Mn-MOF composite photocatalyst prepared in Example 1 has good stability and repeatability. Usability, the rhodamine B degradation rate can still reach 95.59% after 3 runs.
需要说明的是，本发明中涉及数值范围时，应理解为每个数值范围的两个端点以及两个端点之间任何一个数值均可选用，由于采用的步骤方法与实施例相同，为了防止赘述，本发明描述了优选的实施例。尽管已描述了本发明的优选实施例，但本领域内的技术人员一旦得知了基本创造性概念，则可对这些实施例做出另外的变更和修改。所以，所附权利要求意欲解释为包括优选实施例以及落入本发明范围的所有变更和修改。It should be noted that when the present invention involves a numerical range, it should be understood that the two endpoints of each numerical range and any numerical value between the two endpoints can be selected. Since the steps and methods used are the same as those in the embodiment, in order to avoid redundancy , the present invention describes preferred embodiments. Although the preferred embodiments of the present invention have been described, those skilled in the art will be able to make additional changes and modifications to these embodiments once the basic inventive concepts are apparent. Therefore, it is intended that the appended claims be construed to include the preferred embodiments and all changes and modifications that fall within the scope of the invention.
显然，本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样，倘若本发明的这些修改和变型属于本发明权利要求及其等同技术的范围之内，则本发明也意图包含这些改动和变型在内。Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the invention. In this way, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and equivalent technologies, the present invention is also intended to include these modifications and variations.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103316714A (en) * | 2013-06-28 | 2013-09-25 | 中国石油大学(北京) | Catalyst for photo-catalytically decomposing water to produce hydrogen and preparation method of catalyst |
| CN106513050A (en) * | 2016-09-24 | 2017-03-22 | 上海大学 | Method for preparing CdS/MIL-53(Fe) visible-light-induced photocatalyst |
| CN108499589A (en) * | 2018-03-08 | 2018-09-07 | 成都新柯力化工科技有限公司 | A kind of bismuth sulfide composite photo-catalyst and preparation method for sewage disposal |
| WO2019052167A1 (en) * | 2017-09-15 | 2019-03-21 | 广东工业大学 | Nitrogen-doped mesoporous carbon-wrapped titanium dioxide composite photocatalyst, preparation method therefor and application thereof |
| CN110152737A (en) * | 2019-05-10 | 2019-08-23 | 三峡大学 | Zr-MOF Modified ZnCdS Nano-microsphere Composite Material and Its Application |
| CN112063183A (en) * | 2020-08-14 | 2020-12-11 | 武汉大学 | Three-dimensional ordered structure with semiconductor and MOF framework space complementary, and preparation method and application thereof |
| WO2022083796A1 (en) * | 2020-10-20 | 2022-04-28 | 苏州大学 | Cadmium sulfide/zinc oxide composite material, preparation method therefor and application thereof in piezo/photocatalytic removal of organic pollutants |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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-
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- 2022-10-31 CN CN202211347249.0A patent/CN115888833B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103316714A (en) * | 2013-06-28 | 2013-09-25 | 中国石油大学(北京) | Catalyst for photo-catalytically decomposing water to produce hydrogen and preparation method of catalyst |
| CN106513050A (en) * | 2016-09-24 | 2017-03-22 | 上海大学 | Method for preparing CdS/MIL-53(Fe) visible-light-induced photocatalyst |
| WO2019052167A1 (en) * | 2017-09-15 | 2019-03-21 | 广东工业大学 | Nitrogen-doped mesoporous carbon-wrapped titanium dioxide composite photocatalyst, preparation method therefor and application thereof |
| CN108499589A (en) * | 2018-03-08 | 2018-09-07 | 成都新柯力化工科技有限公司 | A kind of bismuth sulfide composite photo-catalyst and preparation method for sewage disposal |
| CN110152737A (en) * | 2019-05-10 | 2019-08-23 | 三峡大学 | Zr-MOF Modified ZnCdS Nano-microsphere Composite Material and Its Application |
| CN112063183A (en) * | 2020-08-14 | 2020-12-11 | 武汉大学 | Three-dimensional ordered structure with semiconductor and MOF framework space complementary, and preparation method and application thereof |
| WO2022083796A1 (en) * | 2020-10-20 | 2022-04-28 | 苏州大学 | Cadmium sulfide/zinc oxide composite material, preparation method therefor and application thereof in piezo/photocatalytic removal of organic pollutants |
Non-Patent Citations (3)
| Title |
|---|
| In-situ constructing visible light CdS/Cd-MOF photocatalyst withenhanced photodegradation of methylene blue;Cheng Jing;《Particuology》;20211216;第69卷;第111-122页 * |
| Manlu Wang.Ultrasensitive determination and non-chromatographic speciation of inorganic arsenic in foods and water by photochemical vapor generation-ICPMS using CdS/MIL-100(Fe) as adsorbent and photocatalyst.《Food Chemistry》.第375卷全文. * |
| 硫化镉纳米材料对罗丹明B溶液的光催化降解性能;段莉梅;《内蒙古民族大学学报(自然科学版)》;20130531;第28卷(第03期);全文 * |
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