CN108295871A - A kind of compound micron bouquet of bismuth tungstate-molybdenum sulfide and its preparation method and application - Google Patents
A kind of compound micron bouquet of bismuth tungstate-molybdenum sulfide and its preparation method and application Download PDFInfo
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Abstract
本发明提供了一种Bi2WO6‑MoS2复合微米花球及其制备方法，所述催化剂包括花球结构的Bi2WO6和分布在Bi2WO6表面的颗粒状MoS2；所述花球结构的Bi2WO6由Bi2WO6组成的片状结构自组装而成。在本发明中，颗粒状MoS2分布于所述Bi2WO6的表面，形成了异质结，促进了电子‑空穴对的有效分离，使得复合材料的光催化活性显著提高。并且花瓣状结构Bi2WO6的存在有助于提高复合材料的比表面积，进而提高对可见光的吸收，为光催化反应体系提供了更大的接触面积和更多的活性位点，本发明将催化剂用于在可见光条件下催化CO2和水反应生成有机物，具有较高的复合材料的光催化效率。
The invention provides a Bi 2 WO 6 ‑MoS 2 composite micron curd and a preparation method thereof, wherein the catalyst comprises Bi 2 WO 6 with a curd structure and granular MoS 2 distributed on the surface of Bi 2 WO 6 ; the The curd structure of Bi 2 WO 6 is self-assembled from the sheet-like structure composed of Bi 2 WO 6 . In the present invention, the granular MoS 2 is distributed on the surface of the Bi 2 WO 6 to form a heterojunction, which promotes the effective separation of electron-hole pairs and significantly improves the photocatalytic activity of the composite material. And the existence of the petal-like structure Bi 2 WO 6 helps to increase the specific surface area of the composite material, thereby improving the absorption of visible light, providing a larger contact area and more active sites for the photocatalytic reaction system, the present invention will The catalyst is used to catalyze the reaction of CO2 and water to generate organic matter under visible light conditions, and has a high photocatalytic efficiency of the composite material.
Description
技术领域technical field
本发明属于光催化材料技术领域，尤其涉及一种Bi2WO6-MoS2复合微米花球及其制备方法和应用。The invention belongs to the technical field of photocatalytic materials, and in particular relates to a Bi 2 WO 6 -MoS 2 composite micron curd and its preparation method and application.
背景技术Background technique
随着工业化的发展，化石燃料的大量使用，排放了大量二氧化碳温室气体。2015年3月的数据显示，大气中的二氧化碳气体已达到400.83ppm，是60万年以来的最高峰，导致了严重的温室效应和全球气候变暖，更带来了海平面上升等诸多问题，解决二氧化碳带来的温室效应问题迫在眉睫。现今科研工作者尝试对二氧化碳进行固化，将其转化为人类可利用的能源。With the development of industrialization and the extensive use of fossil fuels, a large amount of carbon dioxide greenhouse gas is emitted. According to the data in March 2015, the carbon dioxide gas in the atmosphere has reached 400.83ppm, which is the highest peak in 600,000 years, which has caused serious greenhouse effect and global warming, and brought many problems such as sea level rise. It is imminent to solve the problem of greenhouse effect brought by carbon dioxide. Nowadays, scientific researchers try to solidify carbon dioxide and convert it into energy that can be used by human beings.
固定二氧化碳的方法主要涉及这两方面的问题：(1)如何洁净地获得所需能源；(2)如何活化稳定的二氧化碳分子。自从Inoue等在1979年报道了二氧化碳光催化生成有机物的先例，光催化还原二氧化碳的光催化材料成为科研工作者研究的一个焦点。The method of fixing carbon dioxide mainly involves two aspects: (1) how to obtain the required energy cleanly; (2) how to activate stable carbon dioxide molecules. Since Inoue et al. reported the precedent of carbon dioxide photocatalytic generation of organic matter in 1979, photocatalytic materials for photocatalytic reduction of carbon dioxide have become a focus of scientific research.
传统的宽带隙半导体光催化剂，如：TiO2、ZnO等禁带宽带较大，对太阳能的利用率较低，只能吸收太阳能中4％的紫外光，光催化效率较低。为了更为有效地利用太阳能实现对二氧化碳的固化，科研工作者致力于开发新型可见光响应型光催化剂。Bi2WO6是一种具有层状结构的半导体多元氧化物，在可见光下具有一定的响应，以其交替出现的(Bi2O2)2+层和八面体的(WO4)2-堆积而成的结构特征，具有较高的光催化活性，在二氧化碳固化领域受到广泛关注。Traditional wide-bandgap semiconductor photocatalysts, such as TiO 2 and ZnO, have large bandgap bands and low utilization rate of solar energy. They can only absorb 4% of ultraviolet light in solar energy, and their photocatalytic efficiency is low. In order to use solar energy more effectively to solidify carbon dioxide, researchers are committed to developing new visible light-responsive photocatalysts. Bi 2 WO 6 is a semiconductor multi-component oxide with a layered structure. It has a certain response under visible light. Its alternating (Bi 2 O 2 ) 2+ layers and octahedral (WO 4 ) 2 - stacks The resulting structural features have high photocatalytic activity and have received extensive attention in the field of carbon dioxide solidification.
但是，Bi2WO6是一种直接带隙半导体，并且禁带宽度仅为2.75eV左右，光照时产生的光生电子和空穴直接复合几率较高，可见光响应较弱，光量子效率较低，并且Bi2WO6材料的比表面积小，光生电荷迁移距离较长，进而仍存在光催化效率较低，光催化效果仍不理想的问题。However, Bi 2 WO 6 is a direct bandgap semiconductor, and its forbidden band width is only about 2.75eV. The probability of direct recombination of photogenerated electrons and holes generated under illumination is high, the visible light response is weak, and the photon quantum efficiency is low. The Bi 2 WO 6 material has a small specific surface area and a long migration distance of photogenerated charges, which leads to low photocatalytic efficiency and unsatisfactory photocatalytic effect.
发明内容Contents of the invention
有鉴于此，本发明的目的在于提供一种Bi2WO6-MoS2复合微米花球及其制备方法和应用，本发明提供的Bi2WO6-MoS2复合微米花球，具有较高的光催化效率。In view of this, the purpose of the present invention is to provide a Bi 2 WO 6 -MoS 2 composite micron curd and its preparation method and application. The Bi 2 WO 6 -MoS 2 composite micron curd provided by the present invention has a higher Photocatalytic efficiency.
为了实现上述发明目的，本发明提供以下技术方案：In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:
一种Bi2WO6-MoS2复合微米花球，包括花球结构的Bi2WO6和分布在Bi2WO6表面的MoS2；所述花球结构的Bi2WO6由Bi2WO6组成的片状结构自组装而成。A Bi 2 WO 6 -MoS 2 composite micron curd, including Bi 2 WO 6 with a curd structure and MoS 2 distributed on the surface of Bi 2 WO 6 ; the Bi 2 WO 6 with curd structure consists of Bi 2 WO 6 The composed sheet-like structures are self-assembled.
优选的，所述Bi2WO6-MoS2复合微米花球的粒径为2～5μm；Preferably, the particle size of the Bi 2 WO 6 -MoS 2 composite micron curd is 2-5 μm;
所述Bi2WO6-MoS2复合微米花球中MoS2和Bi2WO6的质量比为(0.002～0.005)：1。The mass ratio of MoS 2 to Bi 2 WO 6 in the Bi 2 WO 6 -MoS 2 composite micro-curd is (0.002˜0.005):1.
本发明提供了上述技术方案所述的Bi2WO6-MoS2复合微米花球的制备方法，包括以下步骤：The present invention provides a method for preparing the Bi 2 WO 6 -MoS 2 composite micron curd described in the above technical solution, comprising the following steps:
(1)将仲钼酸铵、硫化氨和氨水混合，进行水浴加热，得到(NH4)2MoS4；(1) Mix ammonium paramolybdate, ammonia sulfide and ammonia water, and heat in a water bath to obtain (NH 4 ) 2 MoS 4 ;
将钨酸钠溶液加入到硝酸铋冰乙酸溶液中，进行加热反应，得到Bi2WO6；Add the sodium tungstate solution into the bismuth nitrate glacial acetic acid solution, and conduct a heating reaction to obtain Bi 2 WO 6 ;
(2)将所述步骤(1)得到的(NH4)2MoS4和Bi2WO6与溶剂混合，进行浸渍，得到预煅烧复合物；(2) mixing (NH 4 ) 2 MoS 4 and Bi 2 WO 6 obtained in the step (1) with a solvent, and impregnating to obtain a pre-calcined composite;
(3)将所述步骤(2)得到的预煅烧复合物进行煅烧，得到Bi2WO6-MoS2复合微米花球。(3) Calcining the pre-calcined composite obtained in the step (2) to obtain Bi 2 WO 6 -MoS 2 composite micron curds.
优选的，所述步骤(1)中仲钼酸铵的质量、硫化氨的体积和氨水的体积比为10～20g:100～200mL:25～50mL；Preferably, the quality of ammonium paramolybdate in the step (1), the volume of ammonia sulfide and the volume ratio of ammonia water are 10～20g:100～200mL:25～50mL;
所述步骤(1)中钨酸钠与硝酸铋的物质的量比为0.5～1:1～2；The substance ratio of sodium tungstate and bismuth nitrate in the step (1) is 0.5～1:1～2;
所述步骤(2)中Bi2WO6的质量、(NH4)2MoS4的质量和溶剂的体积比为1g：(0.0032～0.0081)g：5mL。The volume ratio of the mass of Bi 2 WO 6 , the mass of (NH 4 ) 2 MoS 4 and the solvent in the step (2) is 1 g: (0.0032˜0.0081) g: 5 mL.
优选的，所述步骤(1)中水浴加热的温度为60～70℃，水浴加热的时间为30～40min。Preferably, the temperature of the water bath heating in the step (1) is 60-70° C., and the time of the water bath heating is 30-40 minutes.
优选的，所述步骤(1)中加热反应的温度为180～200℃，加热反应的时间为16～18h。Preferably, the heating reaction temperature in the step (1) is 180-200° C., and the heating reaction time is 16-18 hours.
优选的，所述步骤(2)中的溶剂为乙醇。Preferably, the solvent in the step (2) is ethanol.
优选的，所述步骤(2)中浸渍的时间为10～12h。Preferably, the soaking time in the step (2) is 10-12 hours.
优选的，所述步骤(3)中煅烧的温度为773～823K，所述煅烧的时间为2～3h。Preferably, the calcination temperature in the step (3) is 773-823K, and the calcination time is 2-3 hours.
本发明还提供了上述技术方案所述的Bi2WO6-MoS2复合微米花球作为催化剂在二氧化碳的光催化反应制备有机燃料中的应用。The present invention also provides the application of the Bi 2 WO 6 -MoS 2 composite micron bulbs described in the above technical solution as a catalyst in the photocatalytic reaction of carbon dioxide to prepare organic fuel.
本发明提供了一种Bi2WO6-MoS2复合微米花球，包括花球结构的Bi2WO6和分布在Bi2WO6表面的MoS2；所述花球结构的Bi2WO6由Bi2WO6组成的片状结构自组装而成。The present invention provides a Bi 2 WO 6 -MoS 2 composite micron curd, comprising Bi 2 WO 6 of the curd structure and MoS 2 distributed on the surface of the Bi 2 WO 6 ; the Bi 2 WO 6 of the curd structure is composed of The sheet-like structure composed of Bi 2 WO 6 is self-assembled.
在本发明中，颗粒状MoS2分布于所述Bi2WO6的表面，形成了异质结，促进了电子-空穴对的有效分离，使得复合材料的光催化活性显著提高；并且花瓣状结构Bi2WO6的存在有助于提高复合材料的比表面积，进而提高对可见光的吸收，为光催化反应体系提供了更大的接触面积和更多的活性位点，从而提高复合材料的光催化效率。在本发明中，所述复合微米花球的片状结构，有利于光线在之中不断的反射，充分让入射光和复合材料的相互作用，避免光线仅仅局限在某一部分被光照到的位置，进而提高光催化效率。实施例结果表明，将本发明制备得到的复合材料用于二氧化碳的光催化反应时，甲醇和乙醇的产率较高；经过4h光催化反应，甲醇的产率达27.5μmol/g-Cat，乙醇的产率达37.2μmol/g-Cat。In the present invention, the granular MoS 2 is distributed on the surface of the Bi 2 WO 6 to form a heterojunction, which promotes the effective separation of electron-hole pairs and significantly improves the photocatalytic activity of the composite material; and the petal-shaped The existence of the structure Bi 2 WO 6 helps to increase the specific surface area of the composite material, thereby improving the absorption of visible light, providing a larger contact area and more active sites for the photocatalytic reaction system, thereby improving the light emission of the composite material. catalytic efficiency. In the present invention, the flaky structure of the composite micron curd is conducive to the continuous reflection of light, fully allowing the interaction between the incident light and the composite material, and avoiding that the light is only limited to the position where a certain part is illuminated. Thereby improving the photocatalytic efficiency. The results of the examples show that when the composite material prepared by the present invention is used for the photocatalytic reaction of carbon dioxide, the yields of methanol and ethanol are relatively high; The yield reached 37.2μmol/g-Cat.
附图说明Description of drawings
下面结合附图和具体实施方式对本发明作进一步详细的说明。The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments.
图1为实施例1制备得到的花球状钨酸铋的场发射扫描电镜图；Fig. 1 is the field emission scanning electron micrograph of the spherical bismuth tungstate prepared in embodiment 1;
图2为实施例1制备得到的Bi2WO6-MoS2复合微米花球的场发射扫描电镜图；Fig. 2 is a field emission scanning electron microscope image of the Bi 2 WO 6 -MoS 2 composite micron curd prepared in Example 1;
图3为实施例1制备得到的Bi2WO6-MoS2复合微米花球、以及Bi2WO6、和MoS2的XRD图；Fig. 3 is the XRD pattern of the Bi 2 WO 6 -MoS 2 composite micron curd prepared in Example 1, and Bi 2 WO 6 and MoS 2 ;
图4为实施例1制备得到的Bi2WO6-MoS2复合微米花球的TEM图。FIG. 4 is a TEM image of the Bi 2 WO 6 -MoS 2 composite micron bulbs prepared in Example 1. FIG.
具体实施方式Detailed ways
本发明提供了一种Bi2WO6-MoS2复合微米花球，包括花球结构的Bi2WO6和分布在Bi2WO6表面的MoS2；所述花球结构的Bi2WO6由Bi2WO6组成的片状结构自组装而成。The present invention provides a Bi 2 WO 6 -MoS 2 composite micron curd, comprising Bi 2 WO 6 of the curd structure and MoS 2 distributed on the surface of the Bi 2 WO 6 ; the Bi 2 WO 6 of the curd structure is composed of The sheet-like structure composed of Bi 2 WO 6 is self-assembled.
在本发明中，所述花球状结构的Bi2WO6由Bi2WO6组成的片状结构自组装而成。在本发明中，所述片状结构的厚度优选为50～60nm。在本发明中，所述复合微米花球的片状结构，有利于光线在之中不断的反射，充分让入射光和复合材料的相互作用，避免光线仅仅局限在某一部分被光照到的位置，进而提高光催化效率。In the present invention, the curd-shaped Bi 2 WO 6 is self-assembled from a sheet-like structure composed of Bi 2 WO 6 . In the present invention, the thickness of the sheet-like structure is preferably 50-60 nm. In the present invention, the flaky structure of the composite micron curd is conducive to the continuous reflection of light in it, fully allowing the interaction between incident light and composite materials, and avoiding that the light is only limited to the position where a certain part is illuminated. Thereby improving the photocatalytic efficiency.
在本发明中，所述MoS2为纳米级片状结构，所述MoS2的尺寸优选为25～30nm。在本发明中，所述颗粒状MoS2分布于所述Bi2WO6的表面，形成了异质结，促进了电子-空穴对的有效分离，使得复合材料的光催化活性显著提高。In the present invention, the MoS 2 is a nano-scale sheet structure, and the size of the MoS 2 is preferably 25-30 nm. In the present invention, the granular MoS 2 is distributed on the surface of the Bi 2 WO 6 to form a heterojunction, which promotes the effective separation of electron-hole pairs and significantly improves the photocatalytic activity of the composite material.
在本发明中，所述Bi2WO6-MoS2复合微米花球的粒径优选为2～5μm，进一步优选为2.5～4.5μm，更优选为3～4μm。In the present invention, the particle size of the Bi 2 WO 6 -MoS 2 composite micro-curd is preferably 2-5 μm, more preferably 2.5-4.5 μm, and more preferably 3-4 μm.
在本发明中，所述Bi2WO6-MoS2复合微米花球中MoS2和Bi2WO6的质量比优选为(0.002～0.005):1，进一步优选为(0.003～0.004):1。In the present invention, the mass ratio of MoS 2 to Bi 2 WO 6 in the Bi 2 WO 6 -MoS 2 composite micro-curd is preferably (0.002-0.005):1, more preferably (0.003-0.004):1.
在本发明中，所述Bi2WO6-MoS2复合微米花球中花瓣状结构的存在有助于提高复合材料的比表面积，进而提高对可见光的吸收，为光催化反应体系提供了更大的接触面积和更多的活性位点，从而提高复合材料的光催化效率。In the present invention, the existence of the petal-like structure in the Bi 2 WO 6 -MoS 2 composite micro-curd helps to increase the specific surface area of the composite material, thereby improving the absorption of visible light and providing a larger photocatalytic reaction system. contact area and more active sites, thereby improving the photocatalytic efficiency of the composite.
本发明提供了上述技术方案所述的Bi2WO6-MoS2复合微米花球的制备方法，包括以下步骤：The present invention provides a method for preparing the Bi 2 WO 6 -MoS 2 composite micron curd described in the above technical solution, comprising the following steps:
(1)将仲钼酸铵、硫化氨和氨水混合，进行水浴加热，得到(NH4)2MoS4；将钨酸钠溶液加入到硝酸铋冰乙酸溶液中，进行加热反应，得到Bi2WO6；(1) Mix ammonium paramolybdate, ammonia sulfide and ammonia water, and heat in a water bath to obtain (NH 4 ) 2 MoS 4 ; add sodium tungstate solution to bismuth nitrate glacial acetic acid solution, and conduct a heating reaction to obtain Bi 2 WO 6 ;
(2)将所述步骤(1)得到的(NH4)2MoS4和Bi2WO6与溶剂混合，进行浸渍，得到预煅烧复合物；(2) mixing (NH 4 ) 2 MoS 4 and Bi 2 WO 6 obtained in the step (1) with a solvent, and impregnating to obtain a pre-calcined composite;
(3)将所述步骤(2)得到的预煅烧复合物进行煅烧，得到Bi2WO6-MoS2复合微米花球。(3) Calcining the pre-calcined composite obtained in the step (2) to obtain Bi 2 WO 6 -MoS 2 composite micron curds.
本发明将仲钼酸铵、硫化氨和氨水混合，进行水热反应，得到(NH4)2MoS4。在本发明中，所述仲钼酸铵的质量、硫化氨的体积和氨水的体积比优选为15g:200mL:50mL。在本发明中，所述氨水的质量浓度优选为25％～28％。本发明对所述钼酸铵、硫化氨和氨水的来源没有特殊要求，采用本领域技术人员所熟知的即可。In the invention, ammonium paramolybdate, ammonia sulfide and ammonia water are mixed, and hydrothermal reaction is carried out to obtain (NH 4 ) 2 MoS 4 . In the present invention, the quality of the ammonium paramolybdate, the volume of ammonia sulfide and the volume ratio of ammonia water are preferably 15g:200mL:50mL. In the present invention, the mass concentration of the ammonia water is preferably 25%-28%. The present invention has no special requirements on the sources of the ammonium molybdate, ammonia sulfide and ammonia water, and those familiar to those skilled in the art can be used.
在本发明中，所述仲钼酸铵和硫化氨优选以水溶液的形式提供；本发明对所述钼酸铵和硫化氨的水溶液的浓度没有特殊要求，采用本领域技术人员所熟知的钼酸铵和硫化氨水溶液的浓度即可；在本发明的实施例中，所述钼酸铵溶液的浓度优选为0.3g/mL；所述硫化铵溶液的质量浓度优选为10～20％。本发明对所述混合的方式没有特殊要求，采用本领域技术人员所熟知的溶液混合方式即可；在本发明的实施例中，所述混合具体为将所述钼酸铵与氨水混合后再与硫化铵水溶液混合，便于溶质的充分溶解与均匀混合。In the present invention, described ammonium paramolybdate and ammonia sulfide are preferably provided in the form of aqueous solution; The present invention has no special requirements to the concentration of the aqueous solution of described ammonium molybdate and ammonia sulfide, adopts molybdic acid known to those skilled in the art The concentrations of the ammonium and ammonia sulfide aqueous solutions are sufficient; in an embodiment of the present invention, the concentration of the ammonium molybdate solution is preferably 0.3 g/mL; the mass concentration of the ammonium sulfide solution is preferably 10-20%. The present invention has no special requirements on the mixing method, and the solution mixing method well known to those skilled in the art can be adopted; in the embodiments of the present invention, the mixing is specifically after mixing the ammonium molybdate and ammonia water Mixed with ammonium sulfide aqueous solution to facilitate the full dissolution and uniform mixing of solutes.
在本发明中，所述水浴加热的温度优选为60～70℃，进一步优选为62～68℃，更优选为65℃。在本发明中，所述水热反应的温度优选以水浴加热的形式控制；本发明对所述水浴加热的具体实施方式没有特殊要求，采用本领域技术人员所熟知的水浴加热的实施方式即可。所述水热反应过程中温度的控制，避免温度太高使得合成的(NH4)2MoS4发生分解生成NH3；同时避免温度太低，不能起到促进反应进行的作用。In the present invention, the temperature of the water bath heating is preferably 60-70°C, more preferably 62-68°C, more preferably 65°C. In the present invention, the temperature of the hydrothermal reaction is preferably controlled in the form of water bath heating; the present invention has no special requirements for the specific implementation of the water bath heating, and the implementation of water bath heating well known to those skilled in the art can be used . The temperature control in the hydrothermal reaction process avoids the temperature being too high to decompose the synthesized (NH 4 ) 2 MoS 4 to generate NH 3 ; meanwhile, avoids the temperature being too low to promote the reaction.
在本发明中，所述水浴加热的时间优选为30～40min，进一步优选为32～35min。在本发明中，所述水浴加热优选在搅拌条件下进行；本发明对所述搅拌没有特殊要求，所述搅拌的时间和功率以能实现水热反应过程中溶质的充分接触即可。本发明在所述水浴加热过程中，仲钼酸铵和硫化氨在氨水溶剂中，反应生成(NH4)2MoS4。In the present invention, the heating time in the water bath is preferably 30-40 minutes, more preferably 32-35 minutes. In the present invention, the heating in the water bath is preferably carried out under stirring conditions; the present invention has no special requirements for the stirring, and the time and power of the stirring can be sufficient to realize sufficient contact of the solute during the hydrothermal reaction. In the present invention, during the heating process in the water bath, the ammonium paramolybdate and the ammonia sulfide react in the ammonia solvent to generate (NH 4 ) 2 MoS 4 .
在本发明中，所述氨水发挥溶剂的作用，使得仲钼酸铵和硫化氨在溶液状态下混合均匀，便于水热反应高效进行；并且以氨水为溶剂，与仲钼酸铵和硫化氨中所含有的NH4 +协调配合，不仅能够防止仲钼酸铵和硫化铵的水解，还能防止引入其他的离子生成其他的化合物。In the present invention, the ammonia water plays the role of solvent, so that the ammonium paramolybdate and the ammonia sulfide are mixed evenly in the solution state, which is convenient for the hydrothermal reaction to be carried out efficiently; The coordinated coordination of the contained NH 4 + can not only prevent the hydrolysis of ammonium paramolybdate and ammonium sulfide, but also prevent the introduction of other ions to form other compounds.
所述水浴加热后，本发明优选将所述水浴加热后的溶液进行冷却结晶。本发明对所述冷却结晶的方式没有特殊要求，采用本领域技术人员所熟知的冷却结晶方式以能实现溶质的充分析出。After the water bath is heated, in the present invention, the solution heated in the water bath is preferably cooled and crystallized. The present invention has no special requirements on the cooling crystallization method, and the cooling crystallization method well known to those skilled in the art is adopted to achieve sufficient separation of the solute.
本发明将钨酸钠溶液加入到硝酸铋冰乙酸溶液中，进行加热反应，得到Bi2WO6。在本发明中，所述Bi2WO6为花瓣状结构，由Bi2WO6组成的片状结构自组装而成。在本发明中，所述片状结构的厚度优选为50～60nm；在本发明中，所述片状结构的长度优选为2～5μm。In the present invention, the sodium tungstate solution is added to the bismuth nitrate glacial acetic acid solution, and the heating reaction is carried out to obtain Bi 2 WO 6 . In the present invention, the Bi 2 WO 6 is a petal-like structure, and the sheet-like structure composed of Bi 2 WO 6 is self-assembled. In the present invention, the thickness of the sheet-like structure is preferably 50-60 nm; in the present invention, the length of the sheet-like structure is preferably 2-5 μm.
在本发明中，所述钨酸钠与硝酸铋的物质的量比优选为0.5～1:1～2，进一步优选为0.5～0.8:1.5。在本发明中，所述钨酸钠溶液中溶剂优选为去离子水；钨酸钠溶液中硝酸钠的物质的量和溶剂体积比为1mmol：20～50mL，进一步优选为1mmol：30mL。在本发明中，所述硝酸铋冰乙酸溶液中溶质硝酸铋的物质的量和溶剂冰乙酸的体积比优选为2～4mmol：5～10mL，进一步优选为3mmol：9mL。在本发明中，所述冰乙酸为加热反应提供了酸性条件，有效防止了硝酸铋的水解，对Bi2WO6的形成具有导向作用，有助于花瓣状结构的Bi2WO6的生成。In the present invention, the molar ratio of sodium tungstate to bismuth nitrate is preferably 0.5-1:1-2, more preferably 0.5-0.8:1.5. In the present invention, the solvent in the sodium tungstate solution is preferably deionized water; the volume ratio of the amount of sodium nitrate in the sodium tungstate solution to the solvent volume is 1mmol: 20-50mL, more preferably 1mmol: 30mL. In the present invention, the volume ratio of the solute bismuth nitrate in the bismuth nitrate glacial acetic acid solution to the solvent glacial acetic acid is preferably 2-4 mmol: 5-10 mL, more preferably 3 mmol: 9 mL. In the present invention, the glacial acetic acid provides acidic conditions for the heating reaction, effectively prevents the hydrolysis of bismuth nitrate, guides the formation of Bi 2 WO 6 , and contributes to the formation of petal-shaped Bi 2 WO 6 .
本发明将所述钨酸钠溶液加入到硝酸铋冰乙酸溶液中，避免硝酸铋在水溶液中发生水解生成氢氧化铋沉淀。在本发明中，所述钨酸钠溶液加入到硝酸铋冰乙酸溶液中的方式优选为滴加。本发明对所述滴加的方式没有特殊要求，采用本领域技术人员所熟知的滴加方式即可。在本发明中，所述滴加能够有效防止钨酸钠溶液与硝酸铋冰乙酸溶液混合过程产物的团聚。In the present invention, the sodium tungstate solution is added to the bismuth nitrate glacial acetic acid solution to prevent bismuth nitrate from being hydrolyzed in the aqueous solution to form bismuth hydroxide precipitates. In the present invention, the sodium tungstate solution is preferably added dropwise to the bismuth nitrate glacial acetic acid solution. The present invention has no special requirements on the dripping method, and the dripping method well known to those skilled in the art can be used. In the present invention, the dropping can effectively prevent the agglomeration of the product in the mixing process of the sodium tungstate solution and the bismuth nitrate glacial acetic acid solution.
所述混合后，本发明对混合溶液进行加热反应。在本发明中，加热反应的温度优选为180～200℃，进一步优选为185～190℃；加热反应的时间优选为16～18h。After the mixing, the present invention heats the mixed solution for reaction. In the present invention, the temperature of the heating reaction is preferably 180-200° C., more preferably 185-190° C.; the time of the heating reaction is preferably 16-18 hours.
在本发明中，所述加热反应优选在反应釜中进行；本发明对所述反应釜的型号没有特殊要求，采用本领域技术人员所熟知的反应釜即可。在本发明中，所述加热反应优选在反应釜的密封条件下进行，进而有助于水热反应过程产生的水蒸气的积累，进而有助于促进晶体的形成。In the present invention, the heating reaction is preferably carried out in a reactor; the present invention has no special requirements on the model of the reactor, and a reactor well known to those skilled in the art can be used. In the present invention, the heating reaction is preferably carried out under the sealed condition of the reaction vessel, which is helpful to the accumulation of water vapor generated during the hydrothermal reaction process, and further helps to promote the formation of crystals.
所述加热反应后，本发明优选将所述加热反应产物进行后处理，得到Bi2WO6。在本发明中，所述后处理优选包括：将所述加热反应产物依次洗涤、离心和干燥。在本发明中，所述洗涤优选依次采用乙醇和蒸馏水对所述加热反应产物进行洗涤。本发明对所述洗涤的方式没有特殊要求，采用本领域技术人员所熟知的洗涤方式即可。在本发明的实施例中，所述洗涤具体为采用乙醇洗涤3次、采用蒸馏水洗涤3次。After the heating reaction, the present invention preferably processes the heating reaction product to obtain Bi 2 WO 6 . In the present invention, the post-treatment preferably includes: sequentially washing, centrifuging and drying the heated reaction product. In the present invention, the washing preferably uses ethanol and distilled water to wash the heated reaction product in sequence. The present invention has no special requirements on the washing method, and the washing method known to those skilled in the art can be used. In an embodiment of the present invention, the washing specifically includes washing with ethanol for 3 times and washing with distilled water for 3 times.
完成所述洗涤后，本发明优选对所述洗涤产物进行离心。本发明对所述离心的具体实施方式没有特殊要求，采用本领域技术人员所熟知的离心方式即可；在本发明中，所述离心优选在离心机中进行，本发明对所述离心机的型号没有特殊要求。After the washing is completed, the present invention preferably centrifuges the washed product. The present invention has no special requirements on the specific implementation of the centrifuge, and the centrifugation method well known to those skilled in the art can be adopted; There are no special requirements for the model.
完成所述离心后，本发明优选对所述洗涤产物进行干燥。在本发明中，所述干燥的温度优选为60～80℃；在本发明中，所述干燥的时间优选为10～12h。本发明对所述干燥的方式没有特殊要求，采用本领域技术人员所熟知的干燥方式即可。After the centrifugation is completed, the present invention preferably dries the washed product. In the present invention, the drying temperature is preferably 60-80° C.; in the present invention, the drying time is preferably 10-12 hours. The present invention has no special requirements on the drying method, and the drying method known to those skilled in the art can be used.
得到所述(NH4)2MoS4和Bi2WO6后，本发明将得到的(NH4)2MoS4和Bi2WO6与溶剂混合，进行浸渍，得到预煅烧复合物。在本发明中，所述Bi2WO6的质量、(NH4)2MoS4的质量和溶剂的体积比优选为1g：(0.0032～0.0081)g：5mL，进一步优选为1g：(0.004～0.006)g：5mL。在本发明中，所述(NH4)2MoS4和Bi2WO6与溶剂的混合过程实现(NH4)2MoS4在Bi2WO6表面的浸渍；所述溶剂的存在，有助于(NH4)2MoS4的分散均匀，进而便于(NH4)2MoS4在Bi2WO6表面的分布。在本发明中，所述浸渍的时间优选为10～12h，进一步优选为10.5～11h。在本发明中，所述混合优选在搅拌条件下进行；本发明对所述搅拌的具体实施方式没有特殊要求，采用本领域技术人员所熟知的搅拌方式即可。本发明在所述搅拌过程中，实现溶剂的蒸发，得到预煅烧复合物。After the (NH 4 ) 2 MoS 4 and Bi 2 WO 6 are obtained, the present invention mixes the obtained (NH 4 ) 2 MoS 4 and Bi 2 WO 6 with a solvent and impregnates to obtain a pre-calcined composite. In the present invention, the volume ratio of the mass of Bi 2 WO 6 , the mass of (NH 4 ) 2 MoS 4 and the solvent is preferably 1g:(0.0032-0.0081)g:5mL, more preferably 1g:(0.004-0.006 ) g: 5 mL. In the present invention, the mixing process of (NH 4 ) 2 MoS 4 and Bi 2 WO 6 with solvent realizes the impregnation of (NH 4 ) 2 MoS 4 on the surface of Bi 2 WO 6 ; the presence of the solvent helps The uniform dispersion of (NH 4 ) 2 MoS 4 facilitates the distribution of (NH 4 ) 2 MoS 4 on the surface of Bi 2 WO 6 . In the present invention, the soaking time is preferably 10-12 hours, more preferably 10.5-11 hours. In the present invention, the mixing is preferably carried out under stirring conditions; the present invention has no special requirements for the specific implementation of the stirring, and a stirring method well known to those skilled in the art can be used. In the present invention, during the stirring process, the solvent is evaporated to obtain the precalcined compound.
在本发明中，所述溶剂优选为乙醇；所述溶剂能够溶解四硫代钼酸铵，并且易于挥发，避免对后续煅烧过程的影响。In the present invention, the solvent is preferably ethanol; the solvent can dissolve ammonium tetrathiomolybdate, and is easy to volatilize, so as to avoid influence on the subsequent calcination process.
得到所述预煅烧复合物后，本发明将所述预煅烧复合物进行煅烧，得到Bi2WO6-MoS2复合微米花球。在本发明中，所述煅烧的温度优选为773～825K，进一步优选为780～800K；所述煅烧的时间优选为2～3h。在本发明中，所述煅烧优选在保护气氛下进行，所述保护气氛优选为氮气、氩气或氦气；所述保护气氛的控制，能够充分排除氧气，避免在煅烧过程发生氧化反应，产生杂质产物。After the pre-calcined composite is obtained, the present invention calcines the pre-calcined composite to obtain Bi 2 WO 6 -MoS 2 composite micron curds. In the present invention, the calcination temperature is preferably 773-825K, more preferably 780-800K; the calcination time is preferably 2-3 hours. In the present invention, the calcination is preferably carried out under a protective atmosphere, and the protective atmosphere is preferably nitrogen, argon or helium; the control of the protective atmosphere can fully exclude oxygen and avoid oxidation reactions during the calcination process, resulting in impurity products.
在本发明中，所述煅烧过程，浸渍于Bi2WO6表面的四硫代钼酸铵发生反应生成MoS2，得到Bi2WO6-MoS2复合微米花球。In the present invention, in the calcination process, the ammonium tetrathiomolybdate impregnated on the surface of Bi 2 WO 6 reacts to form MoS 2 , and obtains Bi 2 WO 6 -MoS 2 composite micron curds.
本发明还提供了上述技术方案Bi2WO6-MoS2复合微米花球作为催化剂在二氧化碳的光催化反应制备有机燃料中的应用。在本发明中，所述应用优选具体为：将所述Bi2WO6-MoS2复合微米花球作为催化剂用于二氧化碳的光催化反应，得到甲醇和乙醇。The present invention also provides the application of the Bi 2 WO 6 -MoS 2 composite micron curd as a catalyst in the photocatalytic reaction of carbon dioxide to prepare organic fuel. In the present invention, the application is preferably specifically: using the Bi 2 WO 6 -MoS 2 composite micron curd as a catalyst for the photocatalytic reaction of carbon dioxide to obtain methanol and ethanol.
在本发明中，所述应用进一步优选包括：将所述Bi2WO6-MoS2复合微米花球与水混合，得到Bi2WO6-MoS2复合微米花球的水分散液；去除所述Bi2WO6-MoS2复合微米花球的水分散液中的气体后，通入CO2气体，在无光照条件下静置，然后在光照条件下进行催化反应。在本发明中，所述Bi2WO6-MoS2复合微米花球的水溶液中Bi2WO6-MoS2复合微米花球的质量和水的体积比优选为20～50mg：50～100mL，进一步优选为50mg：50mL；所述气体的去除方式优选为真空除气，本发明对所述真空除气的方式没有特殊要求，采用本领域技术人员所熟知的真空除气方式即可。在本发明中，所述CO2气体自所述SnS2-Bi2WO6复合微米花球的水分散液中的气体去除后起至提供光照条件前持续通入。在本发明中，所述CO2气体的通入速率优选为50～100mL/min。In the present invention, the application further preferably includes: mixing the Bi 2 WO 6 -MoS 2 composite micron curds with water to obtain an aqueous dispersion of Bi 2 WO 6 -MoS 2 composite micron curds; removing the After the gas in the aqueous dispersion of Bi 2 WO 6 -MoS 2 composite micron curds was injected, CO 2 gas was introduced, and the catalyst was left standing in the absence of light, and then the catalytic reaction was carried out in the light. In the present invention, the volume ratio of the mass of Bi 2 WO 6 -MoS 2 composite micron curds to water in the aqueous solution of Bi 2 WO 6 -MoS 2 composite micron curds is preferably 20-50 mg: 50-100 mL, further The preferred ratio is 50mg: 50mL; the removal method of the gas is preferably vacuum degassing. The present invention has no special requirements on the method of vacuum degassing, and the vacuum degassing method well known to those skilled in the art can be used. In the present invention, the CO 2 gas is fed continuously from the time when the gas in the water dispersion of the SnS 2 -Bi 2 WO 6 composite micron bulbs is removed to before the light conditions are provided. In the present invention, the feeding rate of the CO 2 gas is preferably 50-100 mL/min.
在本发明中，所述无光照条件下的静置的时间优选为0.5～1h；所述无光照条件下的静置使得CO2充分吸附在催化剂表面，达到吸附平衡，同时CO2在水中的溶解度也达到饱和。在本发明中，所述光照条件优选为波长≥420nm范围内的光照条件，所述光照条件的波长进一步优选为450～700nm；所述光照条件下的催化反应时间优选为4～6h。In the present invention, the time of standing under the condition of no light is preferably 0.5～1h; the standing under the condition of no light makes CO fully adsorbed on the surface of the catalyst to reach the adsorption equilibrium, while CO in water Solubility is also saturated. In the present invention, the illumination conditions are preferably illumination conditions with a wavelength ≥ 420 nm, and the wavelength of the illumination conditions is more preferably 450-700 nm; the catalytic reaction time under the illumination conditions is preferably 4-6 hours.
在本发明的实施例中，所述光催化反应的温度优选为4℃；所述光催化反应优选在密闭的石英反应器中进行。所述光催化反应具体为：(1)将50mL超纯水和50mg Bi2WO6-MoS2复合微米花球混合；(2)在磁力搅拌条件下采用抽真空的方式去除水中的气体后，以50mL/min的速率通入高纯CO2气体半小时后在波长≥420nm的300W氙灯光照下进行光反应4h后，测定产物中甲醇和乙醇的含量。In the embodiment of the present invention, the temperature of the photocatalytic reaction is preferably 4°C; the photocatalytic reaction is preferably carried out in a closed quartz reactor. The photocatalytic reaction is specifically: (1) mixing 50mL ultrapure water and 50mg Bi 2 WO 6 -MoS 2 composite micron curds; (2) removing the gas in the water by vacuuming under the condition of magnetic stirring, After feeding high-purity CO2 gas at a rate of 50mL/min for half an hour, the photoreaction was carried out under the illumination of a 300W xenon lamp with a wavelength ≥ 420nm for 4h, and then the content of methanol and ethanol in the product was measured.
下面结合实施例对本发明提供的一种Bi2WO6-MoS2复合微米花球及其制备方法和应用进行详细的说明，但是不能把它们理解为对本发明保护范围的限定。A Bi 2 WO 6 -MoS 2 composite micron curd provided by the present invention and its preparation method and application will be described in detail below in conjunction with the examples, but they should not be construed as limiting the protection scope of the present invention.
实施例1Example 1
(1)(NH4)2MoS4的合成：将15g仲钼酸铵溶于50mL温热的氨水中,然后加入200mL硫化铵溶液,水浴加热到60-70℃，搅拌使其反应30min,将反应体系冷却至0℃，结晶60min，抽滤(乙醇和水洗)，晾干。(1) Synthesis of (NH 4 ) 2 MoS 4 : Dissolve 15g of ammonium paramolybdate in 50mL of warm ammonia water, then add 200mL of ammonium sulfide solution, heat in a water bath to 60-70°C, stir for 30min to react, and The reaction system was cooled to 0°C, crystallized for 60 min, filtered with suction (washed with ethanol and water), and dried in the air.
(2)花球状结构的Bi2WO6的合成：称取0.97g五水合硝酸铋溶于5mL冰乙酸中，将0.41g二水合钨酸钠溶解于30mL的去离子水中搅拌至溶解，并将其逐滴加入硝酸铋溶液中，搅拌2h，转移到100mL的反应釜中，在180℃下反应16h，反应结束后自然冷却至室温。产物分别用乙醇和蒸馏水洗涤三次，离心分离，在60℃的烘箱干燥12h。(2) Synthesis of Bi 2 WO 6 with flower spherical structure: Weigh 0.97g bismuth nitrate pentahydrate and dissolve it in 5mL glacial acetic acid, dissolve 0.41g sodium tungstate dihydrate in 30mL deionized water and stir until dissolved, and It was added dropwise into the bismuth nitrate solution, stirred for 2 hours, transferred to a 100 mL reactor, and reacted at 180° C. for 16 hours, and naturally cooled to room temperature after the reaction. The product was washed three times with ethanol and distilled water, separated by centrifugation, and dried in an oven at 60° C. for 12 hours.
(3)Bi2WO6-MoS2的合成:按照Bi2WO6和MoS2质量比为1:0.002，分别称取1g Bi2WO6和0.0032g的四硫代钼酸铵溶于5mL的乙醇中，搅拌至蒸发干，然后将混合物移至瓷舟中，在Ar的保护下，在773K下煅烧2h。反应结束后冷却至室温，研磨得到Bi2WO6-MoS2，产物用2BM来表示。(3) Synthesis of Bi 2 WO 6 -MoS 2 : According to the mass ratio of Bi 2 WO 6 and MoS 2 of 1:0.002, weigh 1g of Bi 2 WO 6 and 0.0032g of ammonium tetrathiomolybdate and dissolve them in 5mL of Ethanol, stirred until evaporated to dryness, and then the mixture was moved to a porcelain boat, under the protection of Ar, calcined at 773K for 2h. After the reaction, cool to room temperature and grind to obtain Bi 2 WO 6 -MoS 2 , which is represented by 2BM.
图3可通过XRD图定性分析出纯的Bi2WO6、MoS2及Bi2WO6/MoS2纳米复合材料，复合材料中没有显示出MoS2的峰，本身MoS2的晶型并不是很好，纯样的峰都为较宽的馒头峰，并且又因为MoS2的负载量较小，在Bi2WO6上又较分散。Figure 3 can qualitatively analyze pure Bi 2 WO 6 , MoS 2 and Bi 2 WO 6 /MoS 2 nanocomposites through the XRD pattern. There is no peak of MoS 2 in the composite material, and the crystal form of MoS 2 itself is not very good. Well, the peaks of the pure sample are broad steamed bread peaks, and because of the small loading of MoS 2 , they are more dispersed on Bi 2 WO 6 .
对制备得到的花瓣状钨酸铋以及Bi2WO6-MoS2复合微米花球进行场发射扫描电镜分析，结果分别如图1和图2所示。由图1和图2可知，制备得到的钨酸铋具有花瓣状结构，并且复合材料同样为花球结构；The prepared petal-shaped bismuth tungstate and Bi 2 WO 6 -MoS 2 composite micron curds were analyzed by field emission scanning electron microscopy, and the results are shown in Figure 1 and Figure 2, respectively. It can be seen from Figure 1 and Figure 2 that the prepared bismuth tungstate has a petal-like structure, and the composite material is also a flower ball structure;
并对得到的复合微米花球进行XRD分析，结果如图3所示。由图3可知，单一相Bi2WO6的衍射峰与标准卡片PDF#39-0256相吻合，几个特征峰的衍射角2θ为28.3o、32.8o、47.0o、55.9o、58.5o、68.7o分别对应(131)、(200)、(260)、(133)、(262)、(400)晶面，并且没有发现其他的杂峰，可证实材料属于纯的斜方晶系Bi2WO6材料。纯相MoS2主要有到四个较强的衍射峰，与标准卡片PDF#37-1492的(002)、(100)、(103)、(110)相匹配。当MoS2与Bi2WO6复合时，MoS2/Bi2WO6复合材料并没有检测到明显的MoS2的特征峰，MoS2高度分散在复合物中，制备得到的复合材料为Bi2WO6-MoS2，组成微球主体的片状结构部分的成分为Bi2WO6。And XRD analysis was carried out on the obtained composite micron bulbs, and the results are shown in FIG. 3 . It can be seen from Figure 3 that the diffraction peaks of the single phase Bi 2 WO 6 coincide with the standard card PDF#39-0256, and the diffraction angles 2θ of several characteristic peaks are 28.3 o , 32.8 o , 47.0 o , 55.9 o , 58.5 o , 68.7 oCorresponding to (131), (200), (260), (133), (262), (400) crystal planes respectively, and no other miscellaneous peaks were found, it can be confirmed that the material belongs to the pure orthorhombic Bi 2 WO 6 materials. Pure-phase MoS 2 mainly has four strong diffraction peaks, which match (002), (100), (103), and (110) of the standard card PDF#37-1492. When MoS 2 is combined with Bi 2 WO 6 , the MoS 2/ Bi 2 WO 6 composite does not detect the obvious characteristic peak of MoS 2 , and MoS 2 is highly dispersed in the composite, and the prepared composite is Bi 2 WO 6 -MoS 2 , the composition of the flake structure part of the main body of the microsphere is Bi 2 WO 6 .
为了进一步确定复合材料的组分，对制备得到的复合微米花球的TEM图，结果如图4所示，由图4可知，微小片状的MoS2分散于在片状Bi2WO6表面。In order to further confirm the composition of the composite material, the TEM images of the prepared composite micro-curdlings are shown in Figure 4. From Figure 4, it can be seen that the tiny flake-like MoS 2 is dispersed on the surface of the flake-like Bi 2 WO 6 .
实施例2Example 2
按照实施例1的方式制备复合微米花球，区别在于，按照Bi2WO6和MoS2质量比为1:0.003，称取1gBi2WO6和0.0049g的四硫代钼酸铵溶于5mL的乙醇中，得到Bi2WO6-MoS2，用3BM来表示。Composite micron curds were prepared according to the method of Example 1, the difference was that, according to the mass ratio of Bi 2 WO 6 and MoS 2 was 1:0.003, 1gBi 2 WO 6 and 0.0049g of ammonium tetrathiomolybdate were weighed and dissolved in 5mL of In ethanol, Bi 2 WO 6 -MoS 2 is obtained, represented by 3BM.
实施例3Example 3
按照实施例1的方式制备复合微米花球，区别在于，按照Bi2WO6和MoS2质量比为1:0.004，称取1g Bi2WO6和0.0065g的四硫代钼酸铵溶于5mL的乙醇中，得到Bi2WO6-MoS2，用4BM来表示。Composite micron curds were prepared according to the method of Example 1, with the difference that, according to the mass ratio of Bi 2 WO 6 and MoS 2 of 1:0.004, 1g of Bi 2 WO 6 and 0.0065g of ammonium tetrathiomolybdate were weighed and dissolved in 5mL In ethanol, Bi 2 WO 6 -MoS 2 is obtained, represented by 4BM.
实施例4Example 4
按照实施例1的方式制备复合微米花球，区别在于，按照Bi2WO6和MoS2质量比为1:0.005，称取1gBi2WO6和0.0081g的四硫代钼酸铵溶于5mL的乙醇中，得到Bi2WO6-MoS2，用5BM来表示。Composite micron curds were prepared according to the method of Example 1, the difference was that, according to the mass ratio of Bi 2 WO 6 and MoS 2 was 1:0.005, 1gBi 2 WO 6 and 0.0081g of ammonium tetrathiomolybdate were weighed and dissolved in 5mL of In ethanol, Bi 2 WO 6 -MoS 2 is obtained, represented by 5BM.
分别对实施例2～4制备得到的花球状Bi2WO6以及Bi2WO6-MoS2复合微米花球进行场发射扫描电镜分析，能够明确制备得到的Bi2WO6具有花瓣球状结构，并且复合材料同样为花球结构；MoS2颗粒分散于在片状Bi2WO6表面。Field emission scanning electron microscope analysis was carried out on the curd-shaped Bi 2 WO 6 and Bi 2 WO 6 -MoS 2 composite micron curds prepared in Examples 2-4, and it was clear that the prepared Bi 2 WO 6 had a petal-like spherical structure, and The composite material also has a curd structure; MoS 2 particles are dispersed on the surface of sheet-like Bi 2 WO 6 .
实施例5：Example 5:
将实施例1～4制备得到的Bi2WO6-MoS2复合微米花球以及纯Bi2WO6，分别作为光催化剂用于二氧化碳的光催化反应。The Bi 2 WO 6 -MoS 2 composite micron bulbs and pure Bi 2 WO 6 prepared in Examples 1-4 were respectively used as photocatalysts for the photocatalytic reaction of carbon dioxide.
光催化反应在密闭的石英反应器中进行，温度控制在4℃以维持反应温度。在反应器中加入50mL超纯水和50mg光催化剂，磁力搅拌条件下抽真空除去水中的气体后，连续通入高纯CO2气体(流量为50mL/min)，半小时后在波长≥420nm的300W氙灯光照下进行光反应4h后，测定产物中甲醇和乙醇的含量，不同催化剂的甲醇和乙醇产率如表1所示：The photocatalytic reaction was carried out in a closed quartz reactor, and the temperature was controlled at 4 °C to maintain the reaction temperature. Add 50mL of ultrapure water and 50mg of photocatalyst into the reactor, vacuumize and remove the gas in the water under the condition of magnetic stirring, and then continuously feed high-purity CO2 gas (the flow rate is 50mL/min), half an hour later, at wavelength ≥ 420nm After photoreaction under 300W xenon lamp illumination for 4h, measure the content of methanol and ethanol in the product, the methanol and ethanol productivity of different catalysts are as shown in table 1:
表1不同光催化剂条件下，二氧化碳光催化反应的甲醇和乙醇的产率Table 1 The yields of methanol and ethanol in the photocatalytic reaction of carbon dioxide under different photocatalyst conditions
由表1可知，本发明制备得到的Bi2WO6-MoS2复合微米花球用于二氧化碳光催化反应，甲醇产率均远高于20μmol/g-Cat，乙醇产率均高于20μmol/g-Cat；远高于纯MoS2、纯Bi2WO6以及Bi2WO6和MoS2的物理混合物作为二氧化碳光催化反应中催化剂时甲醇和乙醇的产率。其中，甲醇和乙醇的产率的测定方式为：首先测定光反应后水中甲醇和乙醇的含量，再根据催化剂的用量来计算每克催化剂理论催化产生的甲醇和乙醇的含量。It can be seen from Table 1 that the Bi 2 WO 6 -MoS 2 composite micron bulbs prepared by the present invention are used in the photocatalytic reaction of carbon dioxide, and the yield of methanol is much higher than 20 μmol/g-Cat, and the yield of ethanol is higher than 20 μmol/g -Cat; much higher than the methanol and ethanol yields when pure MoS 2 , pure Bi 2 WO 6 , and physical mixtures of Bi 2 WO 6 and MoS 2 are used as catalysts in carbon dioxide photocatalytic reactions. Among them, the method of measuring the yield of methanol and ethanol is: firstly measure the content of methanol and ethanol in water after the photoreaction, and then calculate the content of methanol and ethanol theoretically catalyzed by each gram of catalyst according to the amount of catalyst used.
以上所述仅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，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, and it should be pointed out that for those of ordinary skill in the art, some improvements and modifications can be made without departing from the principle of the present invention. It should be regarded as the protection scope of the present invention.
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Application publication date: 20180720 |