CN110102317B

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Info

Publication number: CN110102317B
Application number: CN201910295377.7A
Authority: CN
Inventors: 徐方方; 陈玲艳; 杨靖霞
Original assignee: Shanghai University of Engineering Science
Current assignee: Shanghai University of Engineering Science
Priority date: 2019-04-12
Filing date: 2019-04-12
Publication date: 2022-05-20
Anticipated expiration: 2039-04-12
Also published as: CN110102317A

Abstract

The invention relates to a MoS₂‑CeO₂The compound and the preparation method thereof comprise the following steps: (1) taking Ce (NO)₃)₃·6H₂Dissolving O and PVP in glycol, and stirring until the solution is clear to obtain a solution A; (2) dissolving urea and PVP in ethylene glycol, and stirring until the solution is clear to obtain a solution B; (3) mixing the solution A and the solution B for reaction, washing and drying to obtain CeO₂(ii) a (4) The CeO obtained in the step (3) is added₂Dissolving sodium molybdate and thiourea in ethylene glycol, performing ultrasonic post-reaction, washing, performing ultrasonic treatment, centrifuging and drying after the reaction is finished to obtain MoS₂‑CeO₂And (c) a complex. Compared with the prior art, the method can easily prepare different compounds by adjusting the proportion of each substance, has particularly obvious catalytic effect on imine reaction, has simple and convenient whole process route and low energy consumption, and obtains MoS₂‑CeO₂The compound yield is high, and the compound condition is better.

Description

Translated fromChinese

MoS2-CeO2复合物及其制备方法MoS2-CeO2 composite and preparation method thereof

技术领域technical field

本发明涉及一种复合物及其制备方法，尤其是涉及一种MoS₂-CeO₂复合物及其制备方法。The invention relates to a compound and a preparation method thereof, in particular to a MoS₂ -CeO₂ compound and a preparation method thereof.

背景技术Background technique

近年来，CeO₂被广泛的用作载体，和一些其他材料复合成新型的具有独特性质的复合物，其独特而优异的储氧能力已经成为研究热点。CeO₂作为一种重要的稀土氧化物，已被广泛地应用于催化、光学、电化学和环境化学等技术领域。CeO₂表面的缺陷主要是由氧空位造成的，在少氧环境中，CeO₂可形成大量的氧空位,向环境中释放出氧；在富氧环境中，CeO₂又可以通过氧空位达到存储氧的目的，所以CeO₂具有优异的释放、存储氧的能力。由于单一的CeO₂催化效果较低，性质单一，有必要与其它一些材料合成某些复合物，使其多方面、高效率的发挥作用。 MoS₂是典型的层状过渡金属化合物，MoS₂表现出良好的催化以及电性能，越来越受到关注与应用。此外，二硫化钼纳米片本身具有较大的比表面积，表现出良好的吸附性，然而对于二硫化钼与其他材料复合方面鲜少研究，尤其是与CeO₂的复合。本文采用水热法合成CeO₂，因为它不仅操作简单，而且可以产生具有优异性能的产品。In recent years, CeO₂ has been widely used as a carrier, and composited with some other materials to form a new type of composite with unique properties, and its unique and excellent oxygen storage capacity has become a research hotspot. As an important rare earth oxide, CeO₂ has been widely used in the fields of catalysis, optics, electrochemistry and environmental chemistry. The defects on the surface of CeO₂ are mainly caused by oxygen vacancies. In a low-oxygen environment, CeO₂ can form a large number of oxygen vacancies and release oxygen to the environment; in an oxygen-rich environment, CeO₂ can be stored through oxygen vacancies. The purpose of oxygen, so CeO₂ has an excellent ability to release and store oxygen. Since a single CeO₂ has a low catalytic effect and a single property, it is necessary to synthesize some complexes with other materials to make it play a multi-faceted and efficient role. MoS₂ is a typical layered transition metal compound. MoS₂ exhibits good catalytic and electrical properties, and has attracted more and more attention and applications. In addition, molybdenum disulfide nanosheets themselves have a large specific surface area and show good adsorption properties, however, there is little research on the composite of molybdenum disulfide with other materials, especially the composite with CeO₂ . In this paper, the hydrothermal method was used to synthesize CeO₂ , because it is not only simple to operate, but also yields products with excellent properties.

到目前为止，有关CeO₂纳米薄片的报道很少，而且大多数都是一些大尺寸或者与其他一些金属材料复合而成，合成一些复合物燃料电池或者一些光催化剂， CeO₂纳米薄片大尺寸和薄层仍在等待开发。So far, there are few reports on CeO₂ nanosheets, and most of them are made of some large size or composite with some other metal materials to synthesize some composite fuel cells or some photocatalysts, CeO₂ nanosheets with large size and Thin layers are still waiting to be developed.

中国专利CN106636824A公开了一种CeO₂+MoS₂复合催化的燃料电池用高容量贮氢合金及其制备方法，但并没有涉及CeO₂+MoS₂的制备方法。Chinese patent CN106636824A discloses a CeO₂ +MoS₂ composite catalyzed high-capacity hydrogen storage alloy for fuel cells and a preparation method thereof, but does not involve the preparation method of CeO₂ +MoS₂ .

发明内容SUMMARY OF THE INVENTION

本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种MoS₂-CeO₂复合物及其制备方法。The purpose of the present invention is to provide a MoS₂ -CeO₂ composite and a preparation method thereof in order to overcome the above-mentioned defects of the prior art.

本发明的目的可以通过以下技术方案来实现：The object of the present invention can be realized through the following technical solutions:

一种MoS₂-CeO₂复合物及其制备方法，具体步骤如下：A MoS₂ -CeO₂ composite and a preparation method thereof, the specific steps are as follows:

(1)取Ce(NO₃)₃·6H₂O和PVP，溶于乙二醇中，搅拌至澄清，得到溶液A；(1) Take Ce(NO₃ )₃ ·6H₂ O and PVP, dissolve them in ethylene glycol, and stir until clear to obtain solution A;

(2)取尿素和PVP，溶于乙二醇中，搅拌至澄清，得到溶液B；(2) get urea and PVP, dissolve in ethylene glycol, stir until clear, obtain solution B;

(3)将溶液A和溶液B混合反应后，洗涤、干燥后，得到CeO₂；(3) after the mixed reaction of solution A and solution B, after washing and drying, CeO₂ is obtained;

(4)将步骤(3)中得到的CeO₂与钼酸钠和硫脲溶于乙二醇中，超声后反应，反应结束后，洗涤、超声、离心、干燥，得到MoS₂-CeO₂复合物。(4) CeO₂ obtained in step (3), sodium molybdate and thiourea are dissolved in ethylene glycol, and the reaction is performed after ultrasonication. After the reaction is completed, washing, ultrasonication, centrifugation and drying are performed to obtain a MoS₂ -CeO₂ composite thing.

优选的，步骤(1)中：Ce(NO₃)₃·6H₂O、PVP和乙二醇的配比为 (1-30)g:(1-10)g:(20-200)ml。Preferably, in step (1): the ratio of Ce(NO₃ )₃ ·6H₂ O, PVP and ethylene glycol is (1-30) g: (1-10) g: (20-200) ml.

优选的，步骤(2)中：尿素、PVP和乙二醇的配比为(1-20)g:(10-80)g:(2-200)mL。Preferably, in step (2): the ratio of urea, PVP and ethylene glycol is (1-20) g: (10-80) g: (2-200) mL.

优选的，步骤(3)中反应的工艺条件为：反应温度160-220℃，反应时间为 2-8h。Preferably, the process conditions for the reaction in step (3) are: the reaction temperature is 160-220°C, and the reaction time is 2-8h.

优选的，步骤(3)中洗涤的步骤为：依次用去离子水、乙醇超声、离心，各清洗3遍，超声时间为10-40min，离心时间为2-10min，转速为5000-10000rpm。Preferably, the washing step in step (3) is as follows: deionized water, ethanol, ultrasonication, and centrifugation are used in sequence, and each cleaning is performed 3 times, the ultrasonic time is 10-40min, the centrifugation time is 2-10min, and the rotating speed is 5000-10000rpm.

优选的，步骤(3)中对得到的CeO₂进行煅烧，煅烧的工艺条件为：空气中 400-800℃煅烧1-3h。煅烧后得到的CeO₂比不进行煅烧的CeO₂，性能好，无溶剂等其他杂质，煅烧后的CeO₂的储氧和释放性能较强，其与MoS₂材料进行复合后，储氧和释放性能增强。Preferably, in step (3), the obtained CeO₂ is calcined, and the calcining process conditions are: calcining in air at 400-800° C. for 1-3 hours. The CeO₂ obtained after calcination has better performance than the CeO₂ without calcination, and has no other impurities such as solvents. The calcined CeO₂ has stronger oxygen storage and release properties. After it is compounded with MoS₂ materials, oxygen storage and release Performance enhancements.

优选的，步骤(3)中：干燥采用真空干燥箱，干燥温度为50-80℃，干燥时间为12-24h。Preferably, in step (3): a vacuum drying oven is used for drying, the drying temperature is 50-80° C., and the drying time is 12-24 h.

优选的，步骤(4)中：加入的CeO₂的量，以Na₂MoO₄-CeO₂的不同摩尔比，计算各物质用量，以此可得到不同配比的复合物。Preferably, in step (4): the amount of the added CeO₂ is calculated according to the different molar ratios of Na₂ MoO₄ -CeO₂ , so as to obtain complexes with different ratios.

优选的，步骤(4)中：钼酸钠和硫脲的摩尔比为(0.5-3):(1-10)。Preferably, in step (4): the molar ratio of sodium molybdate and thiourea is (0.5-3): (1-10).

优选的，步骤(4)中：反应前超声时间为10-40min，反应温度为160-220℃，反应时间为12-24h。Preferably, in step (4): the ultrasonic time before the reaction is 10-40min, the reaction temperature is 160-220°C, and the reaction time is 12-24h.

优选的，步骤(4)中：依次用去离子水、乙醇超声、离心，各清洗3遍，超声时间为10-40min，离心时间为2-10min，转速为5000-10000rpm。Preferably, in step (4): deionized water, ethanol, ultrasonication, and centrifugation are used in sequence, and each cleaning is performed 3 times, the ultrasonic time is 10-40min, the centrifugation time is 2-10min, and the rotating speed is 5000-10000rpm.

在制备过程中，如果材料添加量过多或者过少，形成的材料的纯度、产率均会受到影响。温度过低或者过高、时间过长或者过短，均会造成形成的材料性能降低或者不能合成目标材料。In the preparation process, if the amount of material added is too much or too little, the purity and yield of the formed material will be affected. If the temperature is too low or too high, or the time is too long or too short, the properties of the formed material will be reduced or the target material cannot be synthesized.

本发明利用CeO₂特殊的性质，将其作为基底，与一定量的MoS₂复合，形成一种新型的催化剂，其催化效率远远高于单一材料的催化效率。采用水热法，制备不同比例的MoS₂/CeO₂新型复合物，催化效果显著，高于一般复合物，以 CeO₂-MoS₂-ca(1:2)复合物为催化剂的体系出现最佳亚胺转化率为 106.109mmol·g-¹h-¹，高于参考文献(H.Ding,J.Yang,S.Ma,N.Yigit,J.Xu,G. Rupprechter,J.Wang,Large Dimensional CeO₂Nanoflakes byMicrowave-Assisted Synthesis:Lamellar Nano-Channels and Surface OxygenVacancies Promote Catalytic Activity,ChemCatChem,10(2018)4100-4108.)中的50℃时的9.52mmol·g^-1h^-1样品，和参考文献(J.Zhang,J.Yang,J.Wang,H.Ding,Q.Liu,U.Schubert,Y.Rui,J.Xu, Surface oxygen vacancies dominated CeO₂as efficientcatalyst for imine synthesis: Influences of different cerium precursors,Molecular Catalysis,443(2017)131-138.)中 50℃时的4.9mmol·g^-1h^-1样品。The invention utilizes the special properties of CeO₂ and uses it as a substrate to be compounded with a certain amount of MoS₂ to form a new type of catalyst whose catalytic efficiency is much higher than that of a single material._The new MoS₂ /CeO₂ composites with different ratios_were prepared by hydrothermal method, and the catalytic effect was remarkable, which was higher than that of ordinary composites. The conversion rate of imine is 106.109 mmol·g-¹ h-¹ , which is higher than the reference (H.Ding, J. Yang, S. Ma, N. Yigit, J. Xu, G. Rupprechter, J. Wang, Large Dimensional CeO₂ Nanoflakes by Microwave-Assisted Synthesis: Lamellar Nano-Channels and Surface OxygenVacancies Promote Catalytic Activity, ChemCatChem, 10 (2018) 4100-4108. 9.52 mmol·g⁻¹ h⁻¹ sample at 50 °C, and ref. (J.Zhang,J.Yang,J.Wang,H.Ding,Q.Liu,U.Schubert,Y.Rui,J.Xu, Surface oxygen vacancies dominated CeO₂ as efficientcatalyst for imine synthesis: Influences of different cerium precursors , Molecular Catalysis, 443 (2017) 131-138.) 4.9 mmol·g^-1 h^-1 sample at 50 °C.

本文以CeO₂为基底，与一定量MoS₂复合成具有强氧化性的新型的复合物，它在高温(120℃)条件下，打破常规的低温催化，反应时间短，催化效率却是以往报道的最高的亚胺催化转化率的10倍(106.109mmol·g^-1h^-1)。In this paper, CeO₂ is used as the substrate and combined with a certain amount of MoS₂ to form a new type of composite with strong oxidizing property. It breaks the conventional low-temperature catalysis under high temperature (120 °C) conditions, and the reaction time is short, but the catalytic efficiency is the highest in previous reports. The highest catalytic conversion of imine was 10 times (106.109 mmol·g^-1 h^-1 ).

本发明制备得到的MoS₂-CeO₂复合物化学性质稳定并具有较强的催化活性，高于一般同类型复合物10倍以上，因此作为一种低成本，高催化性能的催化剂，代替一些高成本、低催化性能的复合物。The MoS₂ -CeO₂ compound prepared by the present invention has stable chemical properties and strong catalytic activity, which is more than 10 times higher than that of the general compound of the same type. Therefore, as a catalyst with low cost and high catalytic performance, it can replace some high Low-cost, low-catalytic composites.

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)MoS₂-CeO₂复合物提供了一种催化性能较高的复合物催化剂，打破传统低温催化，催化效率低的情况；(1) The MoS₂ -CeO₂ composite provides a composite catalyst with high catalytic performance, breaking the traditional low-temperature catalysis and low catalytic efficiency;

(2)MoS₂-CeO₂复合物制备方法工艺路线简单，原料成本低；(2) The preparation method of MoS₂ -CeO₂ complex has a simple process route and low cost of raw materials;

(3)MoS₂-CeO₂复合物在亚胺催化中，发挥了重大作用，可取代一般的催化剂，应用于反应，使其反应速率大大提升。(3) The MoS₂ -CeO₂ complex plays an important role in the catalysis of imines, and can replace the general catalyst and be used in the reaction to greatly improve the reaction rate.

附图说明Description of drawings

图1为制备得到的MoS₂-CeO₂复合物的XRD谱图；Fig. 1 is the XRD pattern of the prepared MoS₂ -CeO₂ composite;

图2为实施例7中制备得到的CeO₂-MoS₂-ca(2:1)复合物场发射扫描电镜图；2 is a field emission scanning electron microscope image of the CeO₂ -MoS₂ -ca (2:1) composite prepared in Example 7;

图3为实施例8中制备得到的CeO₂-MoS₂-ca(1:1)复合物场发射扫描电镜图；3 is a field emission scanning electron microscope image of the CeO₂ -MoS₂ -ca (1:1) composite prepared in Example 8;

图4为实施例10中制备得到的CeO₂-MoS₂-ca(1:5)复合物场发射扫描电镜图；4 is a field emission scanning electron microscope image of the CeO₂ -MoS₂ -ca (1:5) composite prepared in Example 10;

图5为不同MoS₂-CeO₂复合物催化亚胺反应的转化率的结果图；Fig. 5 is the result graph of the conversion rate of the imine reaction catalyzed by different MoS₂ -CeO₂ complexes;

图6为实施例1-4中制备的MoS₂-CeO₂复合物催化亚胺反应的转化率与反应时间的关系曲线图；6 is a graph showing the relationship between the conversion rate and the reaction time of the MoS₂ -CeO₂ composite catalyzed imine reaction prepared in Examples 1-4;

图7为实施例4、8、11中制备的MoS₂-CeO₂复合物催化亚胺反应和单独的 MoS₂、CeO₂催化亚胺反应的转化率与反应时间的关系曲线图。7 is a graph showing the relationship between the conversion rate and the reaction time of the MoS₂ -CeO₂ composite catalyzed imine reaction prepared in Examples 4, 8 and 11 and the MoS₂ and CeO₂ catalyzed imine reaction alone.

具体实施方式Detailed ways

下面结合附图和具体实施例对本发明进行详细说明。The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

实施例中：aa中的第一个a表示合成的复合物，合成时所用的CeO₂是未经过煅烧的，第二个a表示所合成的CeO₂-MoS₂(x:y)复合物，未经过煅烧处理；In the embodiment: the first a in aa represents the synthesized complex, the CeO₂ used in the synthesis is not calcined, and the second a represents the synthesized CeO₂ -MoS₂ (x:y) complex, Not calcined;

ca中的第一个a表示合成的复合物，合成时所用的CeO₂是经过高温(500℃) 煅烧的，第二个a表示所合成的CeO₂-MoS₂(x:y)复合物，未经过煅烧处理；The first a in ca represents the synthesized composite, the CeO₂ used in the synthesis is calcined at high temperature (500°C), the second a represents the synthesized CeO₂ -MoS₂ (x:y) composite, Not calcined;

ac中的a表示合成的复合物，合成时所用的CeO₂是未经过煅烧的，c表示所合成的CeO₂-MoS₂(x:y)复合物，在540℃下，煅烧1小时得到。a in ac represents the synthesized composite, the CeO₂ used in the synthesis is not calcined, and c represents the synthesized CeO₂ -MoS₂ (x:y) composite, obtained by calcining at 540°C for 1 hour.

实施例1Example 1

MoS₂-CeO₂复合物的制备方法如下：_The preparation method of MoS2_- CeO2 composite is as follows:

(1)取Ce(NO₃)₃·6H₂O(2.17g)和PVP(0.5g)，溶于20mL的EG(乙二醇)，搅拌至澄清。同时称取尿素(0.45g)和PVP(0.5g)，溶于15mL EG中，搅拌至澄清。然后将两溶液充分混合，转移至反应釜，在190℃下，反应6h后，用乙醇洗三遍，然后放置在真空干燥箱中，60℃干燥12h，得到CeO₂；(1) Take Ce(NO₃ )₃ ·6H₂ O (2.17 g) and PVP (0.5 g), dissolve them in 20 mL of EG (ethylene glycol), and stir until clear. At the same time, urea (0.45 g) and PVP (0.5 g) were weighed, dissolved in 15 mL of EG, and stirred until clear. Then the two solutions were fully mixed, transferred to a reaction kettle, and after reacting at 190°C for 6 hours, washed three times with ethanol, then placed in a vacuum drying box, and dried at 60°C for 12 hours to obtain CeO₂ ;

(2)取步骤(1)中获得的CeO₂(0.516g)，与钼酸钠(0.036g)、硫脲(0.057g)充分混匀，用50mL的EG溶解，超声30分钟后，转移至反应釜中，反应控制在200℃下，反应24h；(2) Take CeO₂ (0.516g) obtained in step (1), mix well with sodium molybdate (0.036g) and thiourea (0.057g), dissolve with 50mL of EG, sonicate for 30 minutes, transfer to In the reaction kettle, the reaction is controlled at 200°C for 24h;

(3)待反应结束后，用去离子水和乙醇各反复洗涤三遍，利用超声和离心，达到较好的洗涤效果，最后放入真空干燥箱中，60℃干燥12h，即得 MoS₂-CeO₂-aa(20:1)复合物。(3) After the reaction is completed, wash with deionized water and ethanol three times, and use ultrasonic wave and centrifugation to achieve better washing effect. Finally, put it in a vacuum drying box and dry at 60 ° C for 12 hours to obtain MoS₂ - CeO2_- aa(20:1) complex.

实施例2Example 2

(1)取Ce(NO₃)₃·6H₂O(2.17g)和PVP(0.5g)，溶于20mL的EG，搅拌至澄清。同时称取尿素(0.45g)和PVP(0.5g)，溶于15mL EG中，搅拌至澄清。然后将两溶液充分混合，转移至反应釜，在190℃下，反应6h后,用乙醇洗三遍，然后放置在真空干燥箱中，60℃干燥12h，得到CeO₂；(1) Take Ce(NO₃ )₃ ·6H₂ O (2.17 g) and PVP (0.5 g), dissolve in 20 mL of EG, and stir until clear. At the same time, urea (0.45 g) and PVP (0.5 g) were weighed, dissolved in 15 mL of EG, and stirred until clear. Then the two solutions were fully mixed, transferred to the reaction kettle, washed three times with ethanol after reacting at 190° C. for 6 hours, and then placed in a vacuum drying oven, and dried at 60° C. for 12 hours to obtain CeO₂ ;

(2)取步骤(1)中获得的CeO₂(0.516g)，与钼酸钠(0.145g)、硫脲(0.228g)充分混匀，用50mL的EG溶解，超声30分钟后，转移至反应釜中，反应控制在200℃下，反应24h；(2) Take the CeO₂ (0.516g) obtained in step (1), mix well with sodium molybdate (0.145g) and thiourea (0.228g), dissolve with 50mL of EG, sonicate for 30 minutes, transfer to In the reaction kettle, the reaction is controlled at 200°C for 24h;

(3)待反应结束后，用去离子水和乙醇各反复洗涤三遍，利用超声和离心，达到较好的洗涤效果，最后放入真空干燥箱中，60℃干燥12h，即得 MoS₂-CeO₂-aa(5:1)复合物(3) After the reaction is completed, wash with deionized water and ethanol three times, and use ultrasonic wave and centrifugation to achieve better washing effect. Finally, put it in a vacuum drying box and dry at 60 ° C for 12 hours to obtain MoS₂ - CeO₂ -aa(5:1) complex

实施例3Example 3

(1)取Ce(NO₃)₃·6H₂O(2.17g)和PVP(0.5g)，溶于20mL的EG，搅拌至澄清。同时称取尿素(0.45g)和PVP(0.5g)，溶于15mL EG中，搅拌至澄清。然后将两溶液充分混合，转移至反应釜，在190℃下，反应6h后，用乙醇洗三遍，然后放置在真空干燥箱中，60℃干燥12h，得到CeO₂；(1) Take Ce(NO₃ )₃ ·6H₂ O (2.17 g) and PVP (0.5 g), dissolve in 20 mL of EG, and stir until clear. At the same time, urea (0.45 g) and PVP (0.5 g) were weighed, dissolved in 15 mL of EG, and stirred until clear. Then the two solutions were fully mixed, transferred to a reaction kettle, and after reacting at 190°C for 6 hours, washed three times with ethanol, then placed in a vacuum drying box, and dried at 60°C for 12 hours to obtain CeO₂ ;

(2)取步骤(1)中获得的CeO₂(0.516g)，与钼酸钠(0.363g)、硫脲(0.570g)充分混匀，用50mL的EG溶解，超声30分钟后，转移至反应釜中，反应控制在200℃下，反应24h；(2) Take CeO₂ (0.516g) obtained in step (1), mix well with sodium molybdate (0.363g) and thiourea (0.570g), dissolve with 50mL of EG, ultrasonicate for 30 minutes, transfer to In the reaction kettle, the reaction is controlled at 200°C for 24h;

(3)待反应结束后，用去离子水和乙醇各反复洗涤三遍，利用超声和离心，达到较好的洗涤效果，最后放入真空干燥箱中，60℃干燥12h，即得 MoS₂-CeO₂-aa(2:1)复合物。(3) After the reaction is completed, wash with deionized water and ethanol three times, and use ultrasonic wave and centrifugation to achieve better washing effect. Finally, put it in a vacuum drying box and dry at 60 ° C for 12 hours to obtain MoS₂ - CeO2-aa(₂ :1) complex.

实施例4Example 4

(2)取步骤(1)中获得的CeO₂(0.516g)，与钼酸钠(0.725g)、硫脲(1.141g)充分混匀，用50mL的EG溶解，超声30分钟后，转移至反应釜中，反应控制在200℃下，反应24h；(2) Take the CeO₂ (0.516g) obtained in step (1), mix well with sodium molybdate (0.725g) and thiourea (1.141g), dissolve with 50mL of EG, ultrasonicate for 30 minutes, transfer to In the reaction kettle, the reaction is controlled at 200°C for 24h;

(3)待反应结束后，用去离子水和乙醇各反复洗涤三遍，利用超声和离心，达到较好的洗涤效果，最后放入真空干燥箱中，60℃干燥12h，即得 MoS₂-CeO₂-aa(1:1)复合物.(3) After the reaction is completed, wash with deionized water and ethanol three times, and use ultrasonic wave and centrifugation to achieve better washing effect. Finally, put it in a vacuum drying box and dry at 60 ° C for 12 hours to obtain MoS₂ - CeO₂ -aa(1:1) complex.

实施例5Example 5

(1)取Ce(NO₃)₃·6H₂O(2.17g)和PVP(0.5g)，溶于20mL的EG，搅拌至澄清。同时称取尿素(0.45g)和PVP(0.5g)，溶于15mL EG中，搅拌至澄清。然后将两溶液充分混合，转移至反应釜，在190℃下，反应6h后，用乙醇洗三遍，然后放置在真空干燥箱中，60℃干燥12h，得到CeO₂，然后放置马弗炉中，高温500℃下煅烧1h，得到c-CeO₂；(1) Take Ce(NO₃ )₃ ·6H₂ O (2.17 g) and PVP (0.5 g), dissolve in 20 mL of EG, and stir until clear. At the same time, urea (0.45 g) and PVP (0.5 g) were weighed, dissolved in 15 mL of EG, and stirred until clear. Then the two solutions were thoroughly mixed, transferred to the reaction kettle, washed three times with ethanol after reacting at 190 °C for 6 hours, then placed in a vacuum drying oven, dried at 60 °C for 12 hours to obtain CeO₂ , and then placed in a muffle furnace , calcined at a high temperature of 500 °C for 1 h to obtain c-CeO₂ ;

(2)取步骤(1)中获得的CeO₂(0.516g)，与钼酸钠(0.036mg)、硫脲(0.057g) 充分混匀，用50mL的EG溶解，超声30分钟后，转移至反应釜中，反应控制在 200℃下，反应24h；(2) Take CeO₂ (0.516g) obtained in step (1), mix well with sodium molybdate (0.036mg) and thiourea (0.057g), dissolve with 50mL of EG, sonicate for 30 minutes, transfer to In the reaction kettle, the reaction is controlled at 200°C for 24h;

(3)待反应结束后，用去离子水和乙醇各反复洗涤三遍，利用超声和离心，达到较好的洗涤效果，最后放入真空干燥箱中，60℃干燥12h，即得 MoS₂-CeO₂-ca(20:1)复合物。(3) After the reaction is completed, wash with deionized water and ethanol three times, and use ultrasonic wave and centrifugation to achieve better washing effect. Finally, put it in a vacuum drying box and dry at 60 ° C for 12 hours to obtain MoS₂ - CeO2_- ca(20:1) complex.

实施例6Example 6

(1)取Ce(NO₃)₃·6H₂O(2.17g)和PVP(0.5g)，溶于20mL的EG，搅拌至澄清。同时称取尿素(0.45g)和PVP(0.5g)，溶于15ml EG中，搅拌至澄清。然后将两溶液充分混合，转移至反应釜，在190℃下，反应6h后，用乙醇洗三遍，然后放置在真空干燥箱中，60℃干燥12h，得到CeO₂，然后放置马弗炉中，高温500℃下煅烧1h，得到c-CeO₂；(1) Take Ce(NO₃ )₃ ·6H₂ O (2.17 g) and PVP (0.5 g), dissolve in 20 mL of EG, and stir until clear. At the same time, urea (0.45 g) and PVP (0.5 g) were weighed, dissolved in 15 ml of EG, and stirred until clear. Then the two solutions were fully mixed, transferred to the reaction kettle, washed three times with ethanol after reacting at 190 °C for 6 hours, then placed in a vacuum drying box, dried at 60 °C for 12 hours to obtain CeO₂ , and then placed in a muffle furnace , calcined at a high temperature of 500 °C for 1 h to obtain c-CeO₂ ;

(3)待反应结束后，用去离子水和乙醇各反复洗涤三遍，利用超声和离心，达到较好的洗涤效果，最后放入真空干燥箱中，60℃干燥12h，即得 MoS₂-CeO₂-ca(5:1)复合物。(3) After the reaction is completed, wash with deionized water and ethanol three times, and use ultrasonic wave and centrifugation to achieve better washing effect. Finally, put it in a vacuum drying box and dry at 60 ° C for 12 hours to obtain MoS₂ - CeO₂ -ca (5:1) complex.

实施例7Example 7

(1)取Ce(NO₃)₃·6H₂O(2.17g)和PVP(0.5g)，溶于20mL的EG，搅拌至澄清。同时称取尿素(0.45g)和PVP(0.5g)，溶于15mL EG中，搅拌至澄清。然后将两溶液充分混合，转移至反应釜，在190℃下，反应6h后,用乙醇洗三遍，然后放置在真空干燥箱中，60℃干燥12h，得到CeO₂，然后放置马弗炉中，高温500℃下煅烧 1h，得到c-CeO₂；(1) Take Ce(NO₃ )₃ ·6H₂ O (2.17 g) and PVP (0.5 g), dissolve in 20 mL of EG, and stir until clear. At the same time, urea (0.45 g) and PVP (0.5 g) were weighed, dissolved in 15 mL of EG, and stirred until clear. Then the two solutions were fully mixed, transferred to the reaction kettle, washed three times with ethanol after reacting at 190°C for 6 hours, then placed in a vacuum drying oven, dried at 60°C for 12 hours to obtain CeO₂ , and then placed in a muffle furnace , calcined at a high temperature of 500 °C for 1 h to obtain c-CeO₂ ;

(3)待反应结束后，用去离子水和乙醇各反复洗涤三遍，利用超声和离心，达到较好的洗涤效果，最后放入真空干燥箱中，60℃干燥12h，即得 MoS₂-CeO₂-ca(2:1)复合物。(3) After the reaction is completed, wash with deionized water and ethanol three times, and use ultrasonic wave and centrifugation to achieve better washing effect. Finally, put it in a vacuum drying box and dry at 60 ° C for 12 hours to obtain MoS₂ - CeO2-ca(₂ :1) complex.

实施例8Example 8

(3)待反应结束后，用去离子水和乙醇各反复洗涤三遍，利用超声和离心，达到较好的洗涤效果，最后放入真空干燥箱中，60℃干燥12h，即得 MoS₂-CeO₂-ca(1:1)复合物。(3) After the reaction is completed, wash with deionized water and ethanol three times, and use ultrasonic wave and centrifugation to achieve better washing effect. Finally, put it in a vacuum drying box and dry at 60 ° C for 12 hours to obtain MoS₂ - CeO₂ -ca (1:1) complex.

实施例9Example 9

(1)取Ce(NO₃)₃·6H₂O(2.17g)和PVP(0.5g)，溶于20mL的EG，搅拌至澄清。同时称取尿素(0.45g)和PVP(0.5g)，溶于15mL EG中，搅拌至澄清。然后将两溶液充分混合，转移至反应釜，在190℃下，反应6h后,用乙醇洗三遍，然后放置在真空干燥箱中，60℃干燥12h，得到CeO₂.然后放置马弗炉中，高温500℃下煅烧 1h，得到c-CeO₂；(1) Take Ce(NO₃ )₃ ·6H₂ O (2.17 g) and PVP (0.5 g), dissolve in 20 mL of EG, and stir until clear. At the same time, urea (0.45 g) and PVP (0.5 g) were weighed, dissolved in 15 mL of EG, and stirred until clear. Then the two solutions were fully mixed, transferred to the reaction kettle, washed three times with ethanol after reacting at 190°C for 6 hours, then placed in a vacuum drying oven, dried at 60°C for 12 hours to obtain CeO₂ . Then placed in a muffle furnace , calcined at a high temperature of 500 °C for 1 h to obtain c-CeO₂ ;

(2)取步骤(1)中获得的CeO₂(0.516g)，与钼酸钠(1.451g)、硫脲(2.28g)充分混匀，用50mL的EG溶解，超声30分钟后，转移至反应釜中，反应控制在200℃下，反应24h；(2) Take CeO₂ (0.516g) obtained in step (1), mix well with sodium molybdate (1.451g) and thiourea (2.28g), dissolve with 50mL of EG, sonicate for 30 minutes, transfer to In the reaction kettle, the reaction is controlled at 200°C for 24h;

(3)待反应结束后，用去离子水和乙醇各反复洗涤三遍，利用超声和离心，达到较好的洗涤效果，最后放入真空干燥箱中，60℃干燥12h，即得 MoS₂-CeO₂-ca(1:2)复合物。(3) After the reaction is completed, wash with deionized water and ethanol three times, and use ultrasonic wave and centrifugation to achieve better washing effect. Finally, put it in a vacuum drying box and dry at 60 ° C for 12 hours to obtain MoS₂ - CeO2_- ca(1:2) complex.

实施例10Example 10

(1)取Ce(NO₃)₃·6H₂O(2.17g)和PVP(0.5g)，溶于20mL的EG，搅拌至澄清。同时称取尿素(0.45g)和PVP(0.5g)，溶于15mL EG中，搅拌至澄清。然后将两溶液充分混合，转移至反应釜，在190℃下，反应6h后，用乙醇洗三遍，然后放置在真空干燥箱中，60℃干燥12h,得到CeO₂，然后放置马弗炉中，高温500℃下煅烧1h，得到c-CeO₂；(1) Take Ce(NO₃ )₃ ·6H₂ O (2.17 g) and PVP (0.5 g), dissolve in 20 mL of EG, and stir until clear. At the same time, urea (0.45 g) and PVP (0.5 g) were weighed, dissolved in 15 mL of EG, and stirred until clear. Then the two solutions were fully mixed, transferred to the reaction kettle, washed three times with ethanol after reacting at 190 °C for 6 hours, then placed in a vacuum drying oven, dried at 60 °C for 12 hours to obtain CeO₂ , and then placed in a muffle furnace , calcined at a high temperature of 500 °C for 1 h to obtain c-CeO₂ ;

(2)取步骤(1)中获得的CeO₂(0.516g)，与钼酸钠(3.629g)、硫脲(5.079mg) 充分混匀，用50mL的EG溶解，超声30分钟后，转移至反应釜中，反应控制在 200℃下，反应24h；(2) Take CeO₂ (0.516g) obtained in step (1), mix well with sodium molybdate (3.629g) and thiourea (5.079mg), dissolve with 50mL of EG, ultrasonicate for 30 minutes, transfer to In the reaction kettle, the reaction is controlled at 200°C for 24h;

(3)待反应结束后，用去离子水和乙醇各反复洗涤三遍，利用超声和离心，达到较好的洗涤效果，最后放入真空干燥箱中，60℃干燥12h，即得 MoS₂-CeO₂-ca(1:5)复合物。(3) After the reaction is completed, wash with deionized water and ethanol three times, and use ultrasonic wave and centrifugation to achieve better washing effect. Finally, put it in a vacuum drying box and dry at 60 ° C for 12 hours to obtain MoS₂ - CeO₂ -ca (1:5) complex.

实施例11Example 11

(2)取步骤(1)中获得的CeO₂(0.516g)，与钼酸钠(0.725g)、硫脲(1.141mg) 充分混匀，用50mL的EG溶解，超声30分钟后，转移至反应釜中，反应控制在 200℃下，反应24h；(2) Take CeO₂ (0.516g) obtained in step (1), mix well with sodium molybdate (0.725g) and thiourea (1.141mg), dissolve with 50mL of EG, ultrasonicate for 30 minutes, transfer to In the reaction kettle, the reaction is controlled at 200°C for 24h;

(3)待反应结束后，用去离子水和乙醇各反复洗涤三遍，利用超声和离心，达到较好的洗涤效果，最后放入真空干燥箱中，60℃干燥12h，然后放置马弗炉中，在氩气的保护下，高温500℃下煅烧1h，即得MoS₂-CeO₂-cc(1:1)复合物。(3) After the reaction is over, wash three times with deionized water and ethanol each, and use ultrasonic and centrifugation to achieve a better washing effect. Finally, put it in a vacuum drying box, dry at 60 °C for 12 hours, and then place it in a muffle furnace. , under the protection of argon gas, calcined at a high temperature of 500 ° C for 1 h to obtain MoS₂ -CeO₂ -cc (1:1) composite.

实施例12Example 12

(2)取步骤(1)中获得的CeO₂(0.516g),与钼酸钠(0.725g)、硫脲(1.141g)充分混匀，用50mL的EG溶解，超声30分钟后，转移至反应釜中，反应控制在200℃下，反应24h；(2) Take CeO₂ (0.516g) obtained in step (1), mix well with sodium molybdate (0.725g) and thiourea (1.141g), dissolve with 50mL of EG, sonicate for 30 minutes, transfer to In the reaction kettle, the reaction is controlled at 200°C for 24h;

(3)待反应结束后，用去离子水和乙醇各反复洗涤三遍，利用超声和离心，达到较好的洗涤效果，最后放入真空干燥箱中，60℃干燥12h，然后放置马弗炉中，高温500℃下煅烧1h，即得MoS₂-CeO₂-ac(1:1)复合物。(3) After the reaction is over, wash three times with deionized water and ethanol each, and use ultrasonic and centrifugation to achieve a better washing effect. Finally, put it in a vacuum drying box, dry at 60 °C for 12 hours, and then place it in a muffle furnace. , and calcined at a high temperature of 500 °C for 1 h to obtain a MoS₂ -CeO₂ -ac (1:1) composite.

实施例13Example 13

(1)取Ce(NO₃)₃·6H₂O(3g)和PVP(1g)，溶于20mL的EG，搅拌至澄清。同时称取尿素(2g)和PVP(8g)，溶于20mL EG中，搅拌至澄清。然后将两溶液充分混合，转移至反应釜，在160℃下，反应8h后，用乙醇洗三遍，然后放置在真空干燥箱中，50℃干燥24h，得到CeO₂；(1) Take Ce(NO₃ )₃ ·6H₂ O (3 g) and PVP (1 g), dissolve in 20 mL of EG, and stir until clear. At the same time, urea (2 g) and PVP (8 g) were weighed, dissolved in 20 mL of EG, and stirred until clear. Then the two solutions were fully mixed, transferred to the reaction kettle, washed three times with ethanol after reacting at 160° C. for 8 hours, and then placed in a vacuum drying oven, and dried at 50° C. for 24 hours to obtain CeO₂ ;

(2)取步骤(1)中获得的CeO₂(0.516g),与钼酸钠(0.618g)、硫脲(0.761g)充分混匀，用50mL的EG溶解，超声30分钟后，转移至反应釜中，反应控制在220℃下，反应12h；(2) Take CeO₂ (0.516g) obtained in step (1), mix well with sodium molybdate (0.618g) and thiourea (0.761g), dissolve with 50mL of EG, sonicate for 30 minutes, transfer to In the reaction kettle, the reaction was controlled at 220°C for 12h;

(3)待反应结束后，用去离子水和乙醇各反复洗涤三遍，利用超声和离心，达到较好的洗涤效果，最后放入真空干燥箱中，60℃干燥12h，即得MoS₂-CeO₂复合物。(3) After the reaction is completed, wash with deionized water and ethanol three times, and use ultrasonic wave and centrifugation to achieve better washing effect. Finally, put it in a vacuum drying box and dry at 60 ° C for 12 hours to obtain MoS₂ -_CeO2 complex.

实施例14Example 14

(1)取Ce(NO₃)₃·6H₂O(1g)和PVP(5g)，溶于20mL的EG，搅拌至澄清。同时称取尿素(0.1g)和PVP(1g)，溶于0.2mL EG中，搅拌至澄清。然后将两溶液充分混合，转移至反应釜，在220℃下，反应2h后，用乙醇洗三遍，然后放置在真空干燥箱中，80℃干燥18h，得到CeO₂；(1) Take Ce(NO₃ )₃ ·6H₂ O (1 g) and PVP (5 g), dissolve in 20 mL of EG, and stir until clear. At the same time, urea (0.1 g) and PVP (1 g) were weighed, dissolved in 0.2 mL of EG, and stirred until clear. Then, the two solutions were fully mixed, transferred to a reaction kettle, reacted at 220° C. for 2 hours, washed three times with ethanol, and then placed in a vacuum drying oven, and dried at 80° C. for 18 hours to obtain CeO₂ ;

(2)取步骤(1)中获得的CeO₂(0.516g)，与钼酸钠(0.103g)、硫脲(0.076g)充分混匀，用50mL的EG溶解，超声30分钟后，转移至反应釜中，反应控制在160℃下，反应18h；(2) Take the CeO₂ (0.516g) obtained in step (1), mix well with sodium molybdate (0.103g) and thiourea (0.076g), dissolve with 50mL of EG, sonicate for 30 minutes, transfer to In the reaction kettle, the reaction was controlled at 160°C for 18h;

将制备得到的MoS₂-CeO₂复合物用于亚胺合成反应，方程式如下：The prepared MoS₂ -CeO₂ complex was used in the imine synthesis reaction with the following equation:

具体步骤为：取苯甲醇(10mmol)与苯胺(20mmol)，加入CeO₂-MoS₂复合的催化剂(50mg)，混合后，在120℃油浴下搅拌，每两个小时取一次样，共取5 次(最后一个取样，与前一次取样，间隔4小时)，通过HPLC，检测反应情况，计算反应速率、转化率和选择性，以比较那种复合材料催化性能较好。The specific steps are: take benzyl alcohol (10 mmol) and aniline (20 mmol), add a CeO₂ -MoS₂ composite catalyst (50 mg), after mixing, stir in an oil bath at 120 ° C, take a sample every two hours, and take a total of 5 times (the last sampling, and the previous sampling, with an interval of 4 hours), the reaction conditions were detected by HPLC, and the reaction rate, conversion rate and selectivity were calculated to compare the better catalytic performance of the composite material.

图1为制备得到的CeO₂-MoS₂复合物的XRD谱图，所制备的MoS₂(MoS₂-a) 纳米薄片显示出几乎无定形的结构，表明MoS₂-a的结晶度低。煅烧的CeO₂-c纳米薄片显示出典型的CeO₂结晶相(JCPDF No：34-0394)。CeO₂-MoS₂-ca(1:2)的复合物显示出与纯CeO₂-c几乎相同的XRD图案。不同比例的CeO₂-MoS₂-ca复合材料表现出相似的结果，但由于表面MoS₂较多，CeO₂相的(111)峰强度降低。Figure 1 is the XRD pattern of the prepared CeO₂ -MoS₂ composite. The prepared MoS₂ (MoS₂ -a) nanoflakes show an almost amorphous structure, indicating that MoS₂ -a has low crystallinity. The calcined CeO₂ -c nanoflakes showed a typical CeO₂ crystalline phase (JCPDF No: 34-0394). The composite of CeO₂ -MoS₂ -ca (1:2) shows almost the same XRD pattern as pure CeO₂ -c. The CeO₂ -MoS₂ -ca composites with different ratios showed similar results, but the (111) peak intensity of the CeO₂ phase decreased due to more surface MoS₂ .

图2-4分别为实施例7、8、10的SEM数据，如图MoS₂-a和CeO₂-c均表现出纳米薄片结构，当CeO₂-c纳米薄片与MoS₂-a以一定的比例结合时，片材结构仍然可以用更厚层结构保存，其他比例的CeO₂-MoS₂-ca具有相似的形态，当CeO₂所占比例适当较大时，材料复合的较好，类似于球形，片层较少，催化性能也较好。Figures 2-4 are the SEM data of Examples 7, 8, and 10, respectively. As shown in the figure, both MoS₂ -a and CeO₂ -c exhibit nanoflake structures. When CeO₂ -c nanoflakes and MoS₂ -a have a certain relationship When the proportion is combined, the sheet structure can still be preserved with a thicker layer structure, and other proportions of CeO₂_-MoS₂ -ca have similar morphologies. Spherical, less lamellae, and better catalytic performance.

图5为不同温度下，对于不同条件下合成的复合物(25mmol)催化亚胺合成反应(12h)所得转化率。由图可知，在60℃下，复合物的催化效果远低于在120℃条件下复合物的催化效果，CeO₂-MoS₂-ac(2:1)(Ar)指在氩气保护下， CeO₂-MoS₂-ac(2:1)在540℃下，煅烧1小时。CeO₂-MoS₂-ac(2:1)(Air)指在空气中， CeO₂-MoS₂-ac(2:1)在540℃下，煅烧1小时。CeO₂-MoS₂-aa(2:1)指未煅烧处理的复合物，最后发现CeO₂-MoS₂-aa(2:1)复合物的催化效果最好。Figure 5 shows the conversion ratios obtained by catalyzing the imine synthesis reaction (12h) for the complex (25mmol) synthesized under different conditions at different temperatures. It can be seen from the figure that at 60 °C, the catalytic effect of the composite is much lower than that of the composite at 120 °C. CeO₂ -MoS₂ -ac(2:1)(Ar) means that under the protection of argon, CeO₂ -MoS₂ -ac (2:1) was calcined at 540°C for 1 hour. CeO₂ -MoS₂ -ac(2:1)(Air) means CeO₂ -MoS₂ -ac(2:1) was calcined at 540°C for 1 hour in air. CeO₂ -MoS₂ -aa(2:1) refers to the uncalcined composite, and finally the CeO₂ -MoS₂ -aa(2:1) composite was found to have the best catalytic effect.

图6为不同比例的复合物(25mmol)，在120℃下，催化亚胺合成反应(12h) 所得转化率。通过比较4种不同比例合成的复合物，发现CeO₂-MoS₂-aa(1:1)复合物催化反应的转化率最高，说明其催化效果最好，CeO₂-MoS₂-aa(20:1)复合物催化反应的转化率最低，说明合成的复合物中CeO₂含量过多，会影响催化效果。Figure 6 shows the conversion ratios obtained by catalyzing the synthesis reaction of imines (12h) at 120°C with different ratios of complexes (25mmol). By comparing four kinds of composites synthesized in different ratios, it was found that the CeO₂ -MoS₂ -aa(1:1) composite had the highest conversion rate of the catalytic reaction, indicating that its catalytic effect was the best. CeO₂ -MoS₂ -aa(20:1)₁ ) The conversion rate of the composite catalyzed reaction is the lowest, indicating that the content of CeO2 in the synthesized composite is too much, which will affect the catalytic effect.

图7为不同状态下合成的复合物(25mmol)，在120℃下，催化亚胺合成反应 (12h)所得转化率，通过比较3种不同条件下合成的复合物，发现CeO₂-MoS₂-ca(1:1) 复合物催化反应的转化率最高，其催化效果最好，说明合成的复合物中用高温煅烧后的CeO₂，会加强催化剂的催化能力，促进CeO₂中的Ce³⁺转移到Ce⁴⁺并促进在环境中从O₂产生活性氧原子(O*)，使其催化效果更好。Figure 7 shows the composites (25 mmol) synthesized in different states. At 120 °C, the conversion rate obtained by catalyzing the imine synthesis reaction (12 h) was compared. By comparing the composites synthesized under three different conditions, it was found that CeO₂ -MoS₂ - The ca(1:1) complex has the highest conversion rate and the best catalytic effect, which indicates that CeO₂ calcined at high temperature in the synthesized complex will strengthen the catalytic ability of the catalyst and promote the Ce³⁺ in CeO₂ transfer to Ce⁴⁺ and facilitate the generation of reactive oxygen atoms (O*) from O₂ in the environment, making it more catalytically effective.

上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于上述实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。The foregoing description of the embodiments is provided to facilitate understanding and use of the invention by those of ordinary skill in the art. It will be apparent to those skilled in the art that various modifications to these embodiments can be readily made, and the generic principles described herein can be applied to other embodiments without inventive step. Therefore, the present invention is not limited to the above-mentioned embodiments, and improvements and modifications made by those skilled in the art according to the disclosure of the present invention without departing from the scope of the present invention should all fall within the protection scope of the present invention.

Claims

Translated fromChinese

1.一种MoS₂-CeO₂复合物在苯甲醇与苯胺反应制备亚胺中的应用，其特征在于，具体步骤为：取苯甲醇与苯胺，加入CeO₂-MoS₂复合的催化剂，混合后，在120℃油浴下搅拌，每两个小时取一次样，共取5次，通过HPLC，检测反应情况；1. the application of a MoS₂ -CeO_compound in the reaction of benzyl alcohol and aniline to prepare imine, is characterized in that, concrete steps are: get benzyl alcohol and aniline, add CeO₂ -MoS₂ composite catalyst, after mixing , stir in an oil bath at 120 °C, take a sample every two hours, a total of 5 times, and detect the reaction by HPLC;

所述MoS₂-CeO₂复合物的制备方法为：The preparation method of the MoS₂ -CeO₂ composite is:

（1）取Ce(NO₃)₃•6H₂O和PVP，溶于乙二醇中，搅拌至澄清，得到溶液A；(1) Take Ce(NO₃ )₃ •6H₂ O and PVP, dissolve them in ethylene glycol, stir until clear, and obtain solution A;

（2）取尿素和PVP，溶于乙二醇中，搅拌至澄清，得到溶液B；(2) Take urea and PVP, dissolve in ethylene glycol, and stir until clear to obtain solution B;

（3）将溶液A和溶液B混合反应后，洗涤、干燥后，得到CeO₂；(3) After the solution A and the solution B are mixed and reacted, washed and dried, CeO₂ is obtained;

（4）将步骤（3）中得到的CeO₂与钼酸钠和硫脲溶于乙二醇中，超声后反应，反应结束后，洗涤、超声、离心、干燥，得到MoS₂-CeO₂复合物；(4) Dissolve the CeO₂ obtained in step (3) with sodium molybdate and thiourea in ethylene glycol, and react after ultrasonication. After the reaction is completed, wash, ultrasonicate, centrifuge, and dry to obtain a MoS₂ -CeO₂ composite thing;

步骤（1）中：Ce(NO₃)₃•6H₂O、PVP和乙二醇的配比为(1-30)g:(1-10)g:(20-200)ml；In step (1): the ratio of Ce(NO₃ )₃ 6H₂ O, PVP and ethylene glycol is (1-30)g:(1-10)g:(20-200)ml;

步骤（2）中：尿素、PVP和乙二醇的配比为(1-20)g:(10-80)g:(2-200)ml；In step (2): the proportioning of urea, PVP and ethylene glycol is (1-20) g: (10-80) g: (2-200) ml;

步骤（3）中反应的工艺条件为：反应温度160-220℃，反应时间为2-8h。The technological conditions of the reaction in step (3) are: the reaction temperature is 160-220° C., and the reaction time is 2-8h.

2.根据权利要求1所述的一种MoS₂-CeO₂复合物在苯甲醇与苯胺反应制备亚胺中的应用，其特征在于，步骤（3）中洗涤的步骤为：依次用去离子水、乙醇超声、离心，各清洗3遍，超声时间为10-40min，离心时间为2-10min，转速为5000-10000rpm。2. the application of a kind of MoS₂ -CeO₂ complex in the reaction of benzyl alcohol and aniline to prepare imine according to claim 1, is characterized in that, the step of washing in step (3) is: sequentially use deionized water , ethanol ultrasonication, centrifugation, each washing 3 times, the ultrasonic time is 10-40min, the centrifugation time is 2-10min, and the rotating speed is 5000-10000rpm.

3.根据权利要求1所述的一种MoS₂-CeO₂复合物在苯甲醇与苯胺反应制备亚胺中的应用，其特征在于，步骤（3）中对得到的CeO₂进行煅烧，煅烧的工艺条件为：空气中400-800℃煅烧1-3h。3. the application of a kind of MoS₂ -CeO₂ composite in the reaction of benzyl alcohol and aniline to prepare imine according to claim 1, is characterized in that, in step (3), the CeO obtained is calcined, and the calcined CeO₂ is calcined. The process conditions are: calcination in air at 400-800℃ for 1-3h.

4.根据权利要求1所述的一种MoS₂-CeO₂复合物在苯甲醇与苯胺反应制备亚胺中的应用，其特征在于，步骤（3）中：干燥采用真空干燥箱，干燥温度为50-80℃，干燥时间为12-24h。4. the application of a kind of MoS₂ -CeO₂ compound in the reaction of benzyl alcohol and aniline to prepare imine according to claim 1, is characterized in that, in step (3): drying adopts vacuum drying oven, and drying temperature is 50-80℃, drying time is 12-24h.

5.根据权利要求1所述的一种MoS₂-CeO₂复合物在苯甲醇与苯胺反应制备亚胺中的应用，其特征在于，步骤（4）中：钼酸钠和硫脲的摩尔比为(0.5-3):(1-10)。5. the application of a kind of MoS₂ -CeO₂ complex in the reaction of benzyl alcohol and aniline to prepare imine according to claim 1, is characterized in that, in step (4): the mol ratio of sodium molybdate and thiourea is (0.5-3):(1-10).

6.根据权利要求1所述的一种MoS₂-CeO₂复合物在苯甲醇与苯胺反应制备亚胺中的应用，其特征在于，步骤（4）中：反应前超声时间为10-40min，反应温度为160-220℃，反应时间为12-24h。6. the application of a kind of MoS₂ -CeO₂ complex in the reaction of benzyl alcohol and aniline to prepare imine according to claim 1, is characterized in that, in step (4): ultrasonic time before reaction is 10-40min, The reaction temperature is 160-220°C, and the reaction time is 12-24h.

7.根据权利要求1所述的一种MoS₂-CeO₂复合物在苯甲醇与苯胺反应制备亚胺中的应用，其特征在于，步骤（4）中：依次用去离子水、乙醇超声、离心，各清洗3遍，超声时间为10-40min，离心时间为2-10min，转速为5000-10000rpm。7. The application of a MoS₂ -CeO₂ complex in the reaction of benzyl alcohol and aniline to prepare imine according to claim 1, wherein in step (4): deionized water, ethanol ultrasound, Centrifuge, wash 3 times each, ultrasonic time is 10-40min, centrifugation time is 2-10min, rotating speed is 5000-10000rpm.