WO2019061583A1 - Thermally-driven catalyst and use thereof - Google Patents

Thermally-driven catalyst and use thereof Download PDF

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WO2019061583A1
WO2019061583A1 PCT/CN2017/106475 CN2017106475W WO2019061583A1 WO 2019061583 A1 WO2019061583 A1 WO 2019061583A1 CN 2017106475 W CN2017106475 W CN 2017106475W WO 2019061583 A1 WO2019061583 A1 WO 2019061583A1
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driven catalyst
heat
catalyst
tungsten
thermally driven
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PCT/CN2017/106475
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French (fr)
Chinese (zh)
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罗坚义
黄景诚
梁宝文
莫希伟
廖慧珍
唐秀凤
曾庆光
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五邑大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation

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  • the invention belongs to the technical field of catalyst materials and sewage treatment, and particularly relates to a heat-driven catalyst and an application thereof.
  • the photocatalytic material has an absorption response to the total solar spectrum in terms of the spectral response range, most of the solar energy absorbed by the photocatalyst material becomes heat loss, and only a very small portion of the energy is utilized for photocatalysis. The reaction, thus resulting in the current photocatalytic degradation efficiency is still low.
  • thermally driven catalyst which has the advantages of mild use conditions, continuous driving of a degradation reaction without requiring a specific temperature, high catalytic efficiency, and stable catalytic performance after repeated use.
  • a thermally driven catalyst consisting of a metal oxide nanostructure and a composite structure of the same metal quantum dots attached to the surface of the metal oxide nanostructure.
  • the invention designs a heat-driven catalyst composed of a metal oxide nanostructure and a same metal quantum dot by modifying the structure of the metal and its oxide material.
  • the heat-driven catalyst of the present invention has a special microstructure and can be catalyzed only by the heat in the room temperature environment, and the use condition is mild, the catalytic efficiency is high, and the catalytic performance after repeated use is still It can be kept stable and can be used in the fields of sewage treatment, harmful substance degradation treatment, etc., and has a wide range of applications.
  • the metal oxide nanostructure has a size of 8 to 5000 nm
  • the metal quantum dot has a size of 1 to 10 nm.
  • the metal oxide nanostructure may be specifically one or more of nanowires, nanotubes, nanorods or nanoparticles, and thus the composite structure composed of metal oxide nanostructures and metal quantum dots may also have various forms. .
  • the thermally driven catalyst can exhibit specific quantum size effects, surface effects, and volume effects, ensuring excellent catalytic performance.
  • the metal oxide nanostructure is a tungsten oxide nanowire of the formula W 18 O 49
  • the metal quantum dot is a tungsten (W) quantum dot
  • the catalyst may be referred to as W@W 18 O 49 heat. Drive the catalyst.
  • thermocatalytic degradation reaction of organic matter in the sewage is difficult to achieve only by the heat in the room temperature environment.
  • conventional precious metal thermal catalysts tend to have reduced catalytic efficiency due to excessive use temperatures, and it is difficult to maintain catalytic performance after repeated use, and the service life is short.
  • the price of the conventional precious metal material is high, and the cost of the produced hot catalyst is high, and it is difficult to carry out industrialization and application.
  • the preferred W@W 18 O 49 heat-driven catalyst of the present invention can continuously absorb the heat of the surrounding environment or the heat generated by the infrared radiation in the sunlight, without reaching a specific reaction temperature, in a light-free environment. Continue to absorb heat from the environment, and use the heat to drive the catalytic degradation reaction until the end of the reaction, and also has the characteristics of more heat absorption and higher degradation efficiency.
  • the W@W 18 O 49 heat-driven catalyst can effectively decompose methyl orange at 5 ° C, 25 ° C, 50 ° C, and 75 ° C, so it is more practical and has a longer service life.
  • 10 repeated cycles of the W@W 18 O 49 heat-driven catalyst showed that the catalytic degradation performance remained stable after repeated use.
  • the use of metal tungsten to prepare a thermally driven catalyst is less costly and is advantageous for industrialization and application.
  • the heat-driven catalyst of the invention has the advantages of mild use conditions, continuous driving of degradation reaction without reaching a specific temperature, high catalytic efficiency, no participation in reaction, repeated use and stable catalytic performance, and is expected to be used for sewage treatment. It is widely used in the fields of harmless treatment of various types of flammable and explosive substances, and is expected to be promoted in low-temperature areas such as high-latitude areas and high-altitude areas.
  • the thermally driven catalyst can absorb infrared radiation or absorb external heat by heat transfer, and The absorbed heat is used to drive the degradation reaction of the organic matter in the aqueous solution.
  • the heat-driven catalyst continuously absorbs external heat in a light-free environment to drive degradation reaction of organic substances in the aqueous solution.
  • the thermally driven catalyst is prepared by the following steps: first, synthesizing a metal oxide nanostructure material by a chemical solution method or a physical vapor deposition method; then, in a vacuum environment, an inert gas In a protected anoxic environment or a reducing atmosphere, the metal oxide nanostructured material is heated at a high temperature to cause a decomposition reaction or a reduction reaction on the surface of the metal oxide nanostructure to release oxygen, thereby forming a metal quantum on the surface of the metal oxide nanostructure. At the point, the thermally driven catalyst is obtained.
  • the heat-driven catalyst is specifically prepared by the following steps:
  • the step of preparing the tungsten oxide nanowires is completed by using a vacuum thermal evaporation coating machine, and the preparation efficiency is high, and the vacuum coating cavity does not need to be opened in the middle, and the preparation conditions are easy to adjust, which is favorable for improving the controllability of the operation and the structural stability of the tungsten oxide nanowires. .
  • the prepared tungsten oxide nanowire can ensure high crystallinity and structural stability.
  • high temperature anoxic treatment is used to decompose the surface of the tungsten oxide nanowire, and oxygen is released to form tungsten quantum dots.
  • the step is simple in operation, the processing conditions are easy to realize and adjust, and the size of the tungsten quantum dots is controlled.
  • the structural morphology of the thermally driven catalyst can be effectively controlled to ensure its catalytic performance.
  • the invention also provides the use of the thermally driven catalyst of any of the above, for catalytically degrading organic contaminants.
  • the heat-driven catalyst of the present invention has a catalytic effect on the degradation reaction of organic dyes such as methyl orange and acid chrome K.
  • the application is: adding the heat-driven catalyst to an aqueous solution containing an organic dye, and the heat-driven catalyst catalyzes a degradation reaction of the organic dye in a light-free environment.
  • the application is: adding the heat-driven catalyst to an aqueous solution containing an organic dye, and catalyzing the degradation reaction of the organic dye by the heat-driven catalyst under irradiation of infrared light.
  • FIG. 1 is an SEM image of a W@W 18 O 49 heat-driven catalyst prepared in Example 1; wherein, FIG. 1(a) is a SEM morphology of a W@W 18 O 49 heat-driven catalyst grown on a carbon fiber cloth.
  • Figure 1(b) is a 10x enlarged view of Figure 1(a);
  • FIG. 2 is a TEM image of a W@W 18 O 49 heat-driven catalyst prepared in Example 1; wherein, FIG. 2(a) is a TEM morphology of a W@W 18 O 49 heat-driven catalyst grown on a carbon fiber cloth.
  • Fig. 2(b) is a 4x enlarged view of the boxed area in Fig. 2(a).
  • Example 3 is a characteristic curve showing the concentration of methyl orange solution in the molecular test of catalytically degrading dye under infrared irradiation according to Example 2;
  • Example 4 is a characteristic curve showing the concentration of methyl orange solution in a repeated cycle test of catalytically degrading dye molecules under infrared irradiation according to Example 2;
  • Fig. 5 is a graph showing the comparison of catalytic performance at different temperatures in the repeated cycle test of catalytically degrading dye molecules in the light-free environment of Example 3.
  • the preparation method of the W@W 18 O 49 heat-driven catalyst comprises the following steps:
  • the temperature is lowered at a cooling rate of 100 ° C / min, and the inert gas is continuously introduced into the vacuum chamber.
  • the vacuum coating chamber is opened and taken out. A carbon fiber cloth coated with W 18 O 49 nanowires was used.
  • FIG. 1 is an SEM image of the W@W 18 O 49 heat-driven catalyst prepared in the present example.
  • Fig. 1(a) is a SEM topographical view of a W@W 18 O 49 heat-driven catalyst grown on a carbon fiber cloth. It can be seen that the W 18 O 49 nanorods having a diameter of several micrometers are used as the trunk and the diameter. The W 18 O 49 nanowires of the nanometer size are laterally grown as branches from the trunk surface, and the whole appears as a tree structure.
  • Fig. 1(b) is a 10-fold enlarged view of Fig. 1(a). It can be seen from the analysis and measurement that the diameter of the W 18 O 49 nanowire in the figure is about 50-200 nm.
  • FIG. 2 is a TEM image of the W@W 18 O 49 heat-driven catalyst prepared in the present example.
  • Fig. 2(a) is a TEM topographical view of a W@W 18 O 49 heat-driven catalyst grown on a carbon fiber cloth, in which the W 18 O 49 nanowire is a branch having a smaller diameter in a dendritic structure, the diameter of which is It is about 8 nm, and the surface is uneven, the surface crystal structure is complicated, and the internal structure is regular.
  • Fig. 2(b) is a 4x enlarged view of the boxed area in Fig. 2(a).
  • the W@W 18 O 49 heat-driven catalyst prepared by the above preparation method is a lateral branch of a W 18 O 49 nanorod having a diameter of several micrometers as a trunk.
  • the composite structure consists of a nanometer-sized W 18 O 49 nanowire and a W quantum dot attached to the surface of the W 18 O 49 nanowire with a diameter of several nanometers.
  • the W quantum dot is formed by the high temperature and anoxic treatment of the W 18 O 49 nanowire in a low pressure environment, and a partial decomposition reaction occurs in the surface region.
  • the W 18 O 49 nanowire can be synthesized by a chemical solution method, and then the W 18 O 49 nanowire is subjected to high temperature anoxic treatment in a vacuum environment or a low pressure atmosphere without oxygen.
  • the W@W 18 O 49 heat-driven catalyst is obtained; the obtained W 18 O 49 nanowire can also be placed in a reducing atmosphere such as hydrogen, carbon monoxide or the like for high temperature treatment to obtain a W@W 18 O 49 heat-driven catalyst.
  • Example 2 Experiment of driving catalytic degradation of dye molecules by infrared radiation under infrared irradiation and repeated cycles thereof
  • a carbon fiber cloth (area 1.0 cm 2 ) plated with W@W 18 O 49 heat-driven catalyst prepared in Example 1 was used as a catalyst sample, and added to 10 ml of a methyl orange solution (concentration: 0.12 mmol/L), and then The methyl orange solution was exposed to an infrared oven equipped with a 250 W infrared bulb for 1.5 hours. The UV-visible absorption spectrum of the methyl orange solution was tested every 0.5 hours, and the measured data was used as a characteristic curve of methyl orange concentration with time. . Under the irradiation of infrared light, the temperature of the methyl orange solution was stabilized after rising from room temperature of 30 ° C to 70 ° C.
  • FIG. 3 is a characteristic curve of the concentration of methyl orange solution in the molecular test of catalytic degradation of dye under infrared irradiation according to the embodiment, and the concentration of methyl orange in the infrared radiation is irradiated by the infrared radiation. The time increases and gradually decreases.
  • FIG. 4 is a characteristic curve of the concentration of methyl orange solution in the repeated cycle test of catalytic degradation dye molecules under infrared irradiation according to the embodiment, and the figure shows that W@W in 10 repeated cycles test
  • the catalytic degradation performance of the 18 O 49 heat-driven catalyst was always stable and did not decrease significantly.
  • Example 3 Experiment of using environmental heat to drive catalytic degradation of dye molecules and their repeated cycles in a light-free environment
  • FIG. 5 is a comparative diagram of catalytic performance at different temperatures in a repeated cycle test of catalytically degrading dye molecules in a matte environment of the present embodiment.
  • the W@W 18 O 49 heat-driven catalyst can continuously decompose the methyl orange solution by utilizing the heat in the environment, and the degradation reaction accelerates as the temperature of the environment rises.
  • the W@W 18 O 49 heat-driven catalyst can effectively catalyze degradation even in a low temperature environment of 5 ° C, fully exhibiting the difference from the conventional thermal catalyst, and can be used in a light-free environment without reaching a specific temperature value.
  • the advantages of catalytic degradation are expected to be promoted in perennial low temperature areas such as high latitudes and high altitudes.

Abstract

A thermally-driven catalyst consists of a composite structure, the composite structure being composed of a metal oxide nanostructure and the same metal quantum dots attached to the surface of the metal oxide nanostructure. The metal oxide nanostructure can be a tungsten oxide nanowire having a chemical formula of W18O49 and having a size of 8-5000 nm, and the metal quantum dot can be tungsten quantum dot having a size of 1-10 nm. The thermally-driven catalyst can absorb infrared radiation or absorb external heat by means of heat transfer, and the absorbed heat is used to drive the catalytic degradation reaction of organic materials in an aqueous solution. The thermally-driven catalyst has the advantages of mild use conditions, continuous driving of a degradation reaction without reaching a specific temperature, high catalytic efficiency, and stable catalytic performance being maintained even after repeated use and the like. The thermally-driven catalyst can be used in the fields of sewage treatment, harmless treatment of various types of flammable and explosive materials and the like.

Description

一种热驱动催化剂及其应用Thermally driven catalyst and application thereof 技术领域Technical field
本发明属于催化剂材料和污水治理技术领域，特别涉及一种热驱动催化剂及其应用。The invention belongs to the technical field of catalyst materials and sewage treatment, and particularly relates to a heat-driven catalyst and an application thereof.
背景技术Background technique
随着现代化工业生产技术的飞速发展，人类对于环境的破坏和污染问题也日益明显，特别是生产各类材料与商品过程中所产生的各类污水、有机和剧毒等副产物的污染问题日益突出，如何对这类副产物进行后续无害化处理成为了目前环境保护的重大难题。With the rapid development of modern industrial production technology, human beings are increasingly aware of environmental damage and pollution problems, especially the pollution problems of various types of sewage, organic and highly toxic substances produced in the production of various materials and commodities. It is pointed out that how to carry out the subsequent harmless treatment of such by-products has become a major problem in environmental protection.
基于绿色环保的理念，科学界纷纷提出各种处理化工副产物的手段和方法，主要可分为物理法、化学法、微生物法和光催化法。其中，光催化法被公认为是未来治理污水最环保的方法之一，深受广大学者与产业界人士追捧，这主要是因为它可以直接利用太阳光的能量即可对于有害物质进行有效降解处理，而且催化剂材料本身不参与反应，可重复多次循环使用，符合绿色环保的理念。Based on the concept of green environmental protection, the scientific community has proposed various means and methods for dealing with chemical by-products, which can be mainly divided into physical methods, chemical methods, microbial methods and photocatalytic methods. Among them, photocatalysis is recognized as one of the most environmentally friendly methods for the treatment of sewage in the future. It is highly sought after by scholars and industry professionals. This is mainly because it can directly use the energy of sunlight to effectively degrade harmful substances. Moreover, the catalyst material itself does not participate in the reaction, and can be repeatedly used repeatedly, in line with the concept of green environmental protection.
光催化领域的发展源自于日本科学家对于二氧化钛(TiO2)光催化材料的研究，但二氧化钛只吸收紫外线的能量，而紫外线能量仅占太阳光全能量的5％，能量利用效率低。因此，学者们尝试通过改变材料结构，从而扩展光催化材料的光谱响应范围。目前光催化材料的光谱响应已从紫外线扩展到可见光区域，甚至近年来出现了扩展到红外波段的全太阳光谱响应的光催化材料的相关报道。虽然在光谱响应范围方面，光催化材料已经能对全太阳光谱具有吸收响应，但被光催化剂材料吸收后的大部分太阳能量都会变成热量被损耗掉，只有极小部分能量被利用于光催化反应，因此导致目前光催化剂的降解效率依然较低。The development of photocatalysis originated from the research of titanium dioxide (TiO 2 ) photocatalytic materials by Japanese scientists, but titanium dioxide only absorbs the energy of ultraviolet light, while ultraviolet energy only accounts for 5% of the total energy of sunlight, and the energy utilization efficiency is low. Therefore, scholars have tried to extend the spectral response range of photocatalytic materials by changing the material structure. At present, the spectral response of photocatalytic materials has expanded from ultraviolet light to visible light regions, and even recently, there have been reports on photocatalytic materials that extend the full solar spectrum response to the infrared band. Although the photocatalytic material has an absorption response to the total solar spectrum in terms of the spectral response range, most of the solar energy absorbed by the photocatalyst material becomes heat loss, and only a very small portion of the energy is utilized for photocatalysis. The reaction, thus resulting in the current photocatalytic degradation efficiency is still low.
因此，发展一种能够利用太阳光辐射所产生的热量甚至是利用环境的热量即可降解污水中有机物的热驱动催化剂材料，不仅可大大提高传统光催化剂的光化学转化效率，还可在无光环境下，充分利用环境的热量对污水进行有效的处理，扩展催化降解有机物的应用领域。Therefore, the development of a heat-driven catalyst material capable of utilizing the heat generated by solar radiation or even utilizing the heat of the environment to degrade the organic matter in the sewage can not only greatly improve the photochemical conversion efficiency of the conventional photocatalyst, but also in a matt environment. Under the full use of the environment's heat to effectively treat sewage, expand the application field of catalytic degradation of organic matter.
发明内容Summary of the invention
基于此，本发明的目的在于，提供一种热驱动催化剂，其具有使用条件温和、无需达到特定的温度也能持续驱动降解反应、催化效率高、重复使用后催化性能仍能保持稳定等优点。Based on this, it is an object of the present invention to provide a thermally driven catalyst which has the advantages of mild use conditions, continuous driving of a degradation reaction without requiring a specific temperature, high catalytic efficiency, and stable catalytic performance after repeated use.
本发明采用的技术方案如下：The technical solution adopted by the present invention is as follows:
一种热驱动催化剂，该热驱动催化剂由金属氧化物纳米结构和附着在金属氧化物纳米结构表面的同一金属量子点所构成的复合结构组成。 A thermally driven catalyst consisting of a metal oxide nanostructure and a composite structure of the same metal quantum dots attached to the surface of the metal oxide nanostructure.
本发明通过对金属及其氧化物材料的结构进行改良，设计出一种由金属氧化物纳米结构和同一金属量子点复合而成的热驱动催化剂。相对于传统的热催化剂，本发明所述的热驱动催化剂由于具有特殊的微观结构，仅靠室温环境中的热量即可实现催化作用，其使用条件温和、催化效率高、重复使用后催化性能仍能保持稳定，可用于污水治理、有害物质降解处理等领域，应用范围广。The invention designs a heat-driven catalyst composed of a metal oxide nanostructure and a same metal quantum dot by modifying the structure of the metal and its oxide material. Compared with the conventional thermal catalyst, the heat-driven catalyst of the present invention has a special microstructure and can be catalyzed only by the heat in the room temperature environment, and the use condition is mild, the catalytic efficiency is high, and the catalytic performance after repeated use is still It can be kept stable and can be used in the fields of sewage treatment, harmful substance degradation treatment, etc., and has a wide range of applications.
进一步地，所述金属氧化物纳米结构的尺寸为8-5000nm，所述金属量子点的尺寸为1-10nm。Further, the metal oxide nanostructure has a size of 8 to 5000 nm, and the metal quantum dot has a size of 1 to 10 nm.
所述金属氧化物纳米结构可以具体为纳米线、纳米管、纳米棒或纳米微粒等中的一种或多种，因此由金属氧化物纳米结构和金属量子点所构成的复合结构也有多种形式。通过进一步限定金属氧化物纳米结构和金属量子点的尺寸在适宜范围内，能使所述热驱动催化剂表现出特定的量子尺寸效应、表面效应和体积效应，确保其具备优异的催化性能。The metal oxide nanostructure may be specifically one or more of nanowires, nanotubes, nanorods or nanoparticles, and thus the composite structure composed of metal oxide nanostructures and metal quantum dots may also have various forms. . By further defining the size of the metal oxide nanostructures and metal quantum dots within a suitable range, the thermally driven catalyst can exhibit specific quantum size effects, surface effects, and volume effects, ensuring excellent catalytic performance.
进一步地，所述金属氧化物纳米结构是化学式为W18O49的氧化钨纳米线，所述金属量子点是钨(W)量子点，则所述催化剂可称为W@W18O49热驱动催化剂。Further, the metal oxide nanostructure is a tungsten oxide nanowire of the formula W 18 O 49 , and the metal quantum dot is a tungsten (W) quantum dot, and the catalyst may be referred to as W@W 18 O 49 heat. Drive the catalyst.
国内外有不少以铂(Pt)、钯(Pd)等传统贵金属材料作为热催化剂的研究，其所催化的降解反应需要达到某个较高的特定温度才开始进行，而特定温度值与降解反应所需要的活化能有关，活化能越高，则所需要的温度值就越高，一般而言，污水中有机物的热催化降解反应难以仅靠室温环境中的热量实现。而且，传统贵金属热催化剂往往因为使用温度过高而导致催化效率降低，重复使用后催化性能难以维持，使用寿命较短。另外，传统贵金属材料的价格昂贵，所制成的热催化剂成本高，难以进行产业化推广应用。At home and abroad, there are many researches on the use of traditional precious metal materials such as platinum (Pt) and palladium (Pd) as thermal catalysts. The degradation reaction catalyzed by the catalyst needs to reach a certain higher temperature to start, and the specific temperature value and degradation The activation energy required for the reaction is related. The higher the activation energy, the higher the temperature value required. In general, the thermocatalytic degradation reaction of organic matter in the sewage is difficult to achieve only by the heat in the room temperature environment. Moreover, conventional precious metal thermal catalysts tend to have reduced catalytic efficiency due to excessive use temperatures, and it is difficult to maintain catalytic performance after repeated use, and the service life is short. In addition, the price of the conventional precious metal material is high, and the cost of the produced hot catalyst is high, and it is difficult to carry out industrialization and application.
而经实验验证，本发明优选的W@W18O49热驱动催化剂能够持续吸收周围环境的热量或者太阳光中的红外辐射产生的热量，无需达到特定的反应温度、在无光环境下即可持续从环境中吸收热量，并把热量用于驱动催化降解反应的进行，直至反应结束，而且还具有吸收热量越多，降解效率越高的特点。所述W@W18O49热驱动催化剂在5℃、25℃、50℃、75℃温度下均能对甲基橙进行有效催化降解，因此其实用性更强，使用寿命更长。其次，对W@W18O49热驱动催化剂进行10次重复循环试验发现，在重复使用后其催化降解性能始终能保持稳定。再者，采用金属钨制备热驱动催化剂的成本更低，有利于进行产业化推广应用。It has been experimentally verified that the preferred W@W 18 O 49 heat-driven catalyst of the present invention can continuously absorb the heat of the surrounding environment or the heat generated by the infrared radiation in the sunlight, without reaching a specific reaction temperature, in a light-free environment. Continue to absorb heat from the environment, and use the heat to drive the catalytic degradation reaction until the end of the reaction, and also has the characteristics of more heat absorption and higher degradation efficiency. The W@W 18 O 49 heat-driven catalyst can effectively decompose methyl orange at 5 ° C, 25 ° C, 50 ° C, and 75 ° C, so it is more practical and has a longer service life. Secondly, 10 repeated cycles of the W@W 18 O 49 heat-driven catalyst showed that the catalytic degradation performance remained stable after repeated use. Furthermore, the use of metal tungsten to prepare a thermally driven catalyst is less costly and is advantageous for industrialization and application.
由于本发明的热驱动催化剂具备使用条件温和、无需达到特定的温度也能持续驱动降解反应、催化效率高、不参与反应、可重复多次使用且催化性能稳定等优点，其有望用于污水治理、各类型易燃易爆有害物质的无害化处理等领域，应用广泛，还有望在高纬度区域、高海拔地区等常年低温地区推广使用。The heat-driven catalyst of the invention has the advantages of mild use conditions, continuous driving of degradation reaction without reaching a specific temperature, high catalytic efficiency, no participation in reaction, repeated use and stable catalytic performance, and is expected to be used for sewage treatment. It is widely used in the fields of harmless treatment of various types of flammable and explosive substances, and is expected to be promoted in low-temperature areas such as high-latitude areas and high-altitude areas.
进一步地，所述热驱动催化剂可吸收红外辐射或者以热传递的方式吸收外界热量，并将 所吸收的热量用于驱动催化水溶液中有机物的降解反应。Further, the thermally driven catalyst can absorb infrared radiation or absorb external heat by heat transfer, and The absorbed heat is used to drive the degradation reaction of the organic matter in the aqueous solution.
进一步地，所述热驱动催化剂在无光环境下，可持续吸收外界热量以驱动催化水溶液中有机物的降解反应。Further, the heat-driven catalyst continuously absorbs external heat in a light-free environment to drive degradation reaction of organic substances in the aqueous solution.
进一步地，所述热驱动催化剂由以下步骤制备而成：由以下步骤制备而成：首先，通过化学溶液法或物理蒸镀法合成金属氧化物纳米结构材料；然后，在真空环境、有惰性气体保护的缺氧环境或者还原气氛中，高温加热金属氧化物纳米结构材料，使金属氧化物纳米结构的表面发生分解反应或者还原反应，释放出氧，于是在金属氧化物纳米结构的表面形成金属量子点，得到所述热驱动催化剂。Further, the thermally driven catalyst is prepared by the following steps: first, synthesizing a metal oxide nanostructure material by a chemical solution method or a physical vapor deposition method; then, in a vacuum environment, an inert gas In a protected anoxic environment or a reducing atmosphere, the metal oxide nanostructured material is heated at a high temperature to cause a decomposition reaction or a reduction reaction on the surface of the metal oxide nanostructure to release oxygen, thereby forming a metal quantum on the surface of the metal oxide nanostructure. At the point, the thermally driven catalyst is obtained.
进一步地，所述热驱动催化剂具体由以下步骤制备而成：Further, the heat-driven catalyst is specifically prepared by the following steps:
(1)将钨舟接入真空热蒸发镀膜机的蒸发电极，并往钨舟内加入钨粉，再将衬底放置于距离钨舟2～100毫米处；(1) Connect the tungsten boat to the evaporation electrode of the vacuum thermal evaporation coating machine, add tungsten powder to the tungsten boat, and place the substrate 2 to 100 mm away from the tungsten boat;
(2)开启机械泵对真空镀膜腔体进行抽真空20分钟；(2) Turn on the mechanical pump to evacuate the vacuum coating chamber for 20 minutes;
(3)往真空镀膜腔体内通入氧气和惰性气体，等腔体内压强稳定后，保持20分钟；(3) introducing oxygen and inert gas into the vacuum coating chamber, and maintaining the pressure in the chamber for 20 minutes;
(4)持续往真空镀膜腔体内通入氧气和惰性气体，打开热蒸发电源，加热钨舟至1100℃，然后保温20分钟，使钨粉氧化、升华为气相氧化钨，接着在衬底上生长出化学式为W18O49的固相氧化钨纳米线；(4) Continuously pass oxygen and inert gas into the vacuum coating chamber, turn on the thermal evaporation power source, heat the tungsten boat to 1100 ° C, and then keep it for 20 minutes to oxidize and sublime the tungsten powder into a vapor phase tungsten oxide, and then grow on the substrate. a solid phase tungsten oxide nanowire having a chemical formula of W 18 O 49 ;
(5)进行降温处理，同时持续往真空腔室内通入惰性气体，待氧化钨纳米线冷却至室温后，打开真空镀膜腔体，取出镀有氧化钨纳米线的衬底备用；(5) performing a temperature-lowering treatment while continuously introducing an inert gas into the vacuum chamber. After the tungsten oxide nanowire is cooled to room temperature, the vacuum coating chamber is opened, and the substrate coated with the tungsten oxide nanowire is taken out for use;
(6)将镀有氧化钨纳米线的衬底放置在一真空腔体内的加热台上，真空腔体内为无氧气且有惰性气体保护的环境，加热镀有氧化钨纳米线的衬底至1600℃，保温20分钟后，再进行降温处理，最终得到生长在衬底上的所述热驱动催化剂。(6) placing the substrate coated with the tungsten oxide nanowires on a heating stage in a vacuum chamber, the environment in which the oxygen chamber is protected by an inert gas, heating the substrate coated with the tungsten oxide nanowires to 1600 After the temperature was kept for 20 minutes, the temperature was further lowered to finally obtain the heat-driven catalyst grown on the substrate.
使用真空热蒸发镀膜机完成制备氧化钨纳米线的步骤，制备效率高，中间不需要打开真空镀膜腔体，制备条件易于调整，有利于提高操作的可控性以及氧化钨纳米线的结构稳定性。通过限定衬底与钨舟的距离、腔内压强、通入氧气和惰性气体流量、加热温度、处理时间等工艺参数，能保证制得的氧化钨纳米线结晶度高且结构稳定。另外，采用高温缺氧处理使氧化钨纳米线表面发生分解反应，释放出氧而形成钨量子点，该步骤操作简单，处理条件易于实现和调整，有利于控制形成钨量子点的尺寸大小。通过上述制备方法，能有效控制所述热驱动催化剂的结构形貌，保证其催化性能。The step of preparing the tungsten oxide nanowires is completed by using a vacuum thermal evaporation coating machine, and the preparation efficiency is high, and the vacuum coating cavity does not need to be opened in the middle, and the preparation conditions are easy to adjust, which is favorable for improving the controllability of the operation and the structural stability of the tungsten oxide nanowires. . By defining the distance between the substrate and the tungsten boat, the pressure in the cavity, the flow rate of oxygen and inert gas, the heating temperature, the processing time and the like, the prepared tungsten oxide nanowire can ensure high crystallinity and structural stability. In addition, high temperature anoxic treatment is used to decompose the surface of the tungsten oxide nanowire, and oxygen is released to form tungsten quantum dots. The step is simple in operation, the processing conditions are easy to realize and adjust, and the size of the tungsten quantum dots is controlled. Through the above preparation method, the structural morphology of the thermally driven catalyst can be effectively controlled to ensure its catalytic performance.
本发明还提供上述任一项所述的热驱动催化剂在催化降解有机污染物中的应用。The invention also provides the use of the thermally driven catalyst of any of the above, for catalytically degrading organic contaminants.
经实验验证，本发明的热驱动催化剂对甲基橙、酸性铬兰K等有机染料的降解反应具有催化作用。 It has been experimentally verified that the heat-driven catalyst of the present invention has a catalytic effect on the degradation reaction of organic dyes such as methyl orange and acid chrome K.
进一步地，所述应用为：将所述热驱动催化剂添加到含有有机染料的水溶液中，在无光环境下，使所述热驱动催化剂催化有机染料的降解反应。Further, the application is: adding the heat-driven catalyst to an aqueous solution containing an organic dye, and the heat-driven catalyst catalyzes a degradation reaction of the organic dye in a light-free environment.
进一步地，所述应用为：将所述热驱动催化剂添加到含有有机染料的水溶液中，在红外光照射下，使所述热驱动催化剂催化有机染料的降解反应。Further, the application is: adding the heat-driven catalyst to an aqueous solution containing an organic dye, and catalyzing the degradation reaction of the organic dye by the heat-driven catalyst under irradiation of infrared light.
为了更好地理解和实施，下面结合附图详细说明本发明。For a better understanding and implementation, the invention will be described in detail below with reference to the drawings.
附图说明DRAWINGS
图1为实施例1所制得的W@W18O49热驱动催化剂的SEM图；其中，图1(a)为生长在碳纤维布上的W@W18O49热驱动催化剂的SEM形貌图，图1(b)为图1(a)的10倍放大图；1 is an SEM image of a W@W 18 O 49 heat-driven catalyst prepared in Example 1; wherein, FIG. 1(a) is a SEM morphology of a W@W 18 O 49 heat-driven catalyst grown on a carbon fiber cloth. Figure 1(b) is a 10x enlarged view of Figure 1(a);
图2为实施例1所制得的W@W18O49热驱动催化剂的TEM图；其中，图2(a)为生长在碳纤维布上的W@W18O49热驱动催化剂的TEM形貌图，图2(b)为图2(a)中方框区域的4倍放大图。2 is a TEM image of a W@W 18 O 49 heat-driven catalyst prepared in Example 1; wherein, FIG. 2(a) is a TEM morphology of a W@W 18 O 49 heat-driven catalyst grown on a carbon fiber cloth. Fig. 2(b) is a 4x enlarged view of the boxed area in Fig. 2(a).
图3为实施例2的红外照射下催化降解染料分子试验中甲基橙溶液浓度随时间变化的特性曲线图；3 is a characteristic curve showing the concentration of methyl orange solution in the molecular test of catalytically degrading dye under infrared irradiation according to Example 2;
图4为实施例2的红外照射下催化降解染料分子重复循环试验中甲基橙溶液浓度随时间变化的特性曲线图；4 is a characteristic curve showing the concentration of methyl orange solution in a repeated cycle test of catalytically degrading dye molecules under infrared irradiation according to Example 2;
图5为实施例3的无光环境下催化降解染料分子重复循环试验中不同温度下的催化性能对比图。Fig. 5 is a graph showing the comparison of catalytic performance at different temperatures in the repeated cycle test of catalytically degrading dye molecules in the light-free environment of Example 3.
具体实施方式Detailed ways
实施例1：W@W18O49热驱动催化剂的制备Example 1: Preparation of W@W 18 O 49 heat-driven catalyst
本实施例以W@W18O49热驱动催化剂为例进行详细说明，该W@W18O49热驱动催化剂的制备方法包括以下步骤：This embodiment is described in detail by taking a W@W 18 O 49 heat-driven catalyst as an example. The preparation method of the W@W 18 O 49 heat-driven catalyst comprises the following steps:
(1)将钨舟接入真空热蒸发镀膜机的蒸发电极，并往钨舟内加入0.5g的钨粉(纯度99.95％)，再将碳纤维布放置于钨舟的上方，使碳纤维布与钨舟的距离为2～100毫米。(1) Connect the tungsten boat to the evaporation electrode of the vacuum thermal evaporation coating machine, and add 0.5g of tungsten powder (purity 99.95%) to the tungsten boat, and then place the carbon fiber cloth above the tungsten boat to make the carbon fiber cloth and tungsten. The distance between the boats is 2 to 100 mm.
(2)开启机械泵对真空镀膜腔体进行抽真空20分钟。(2) The mechanical pump was turned on to evacuate the vacuum coating chamber for 20 minutes.
(3)往真空镀膜腔体内通入流量比为1:100的氧气(纯度99.95％)和惰性气体(纯度99.95％)，保持20分钟。(3) An oxygen gas (purity 99.95%) and an inert gas (purity 99.95%) having a flow ratio of 1:100 were introduced into the vacuum coating chamber for 20 minutes.
(4)持续往真空镀膜腔体内通入氧气和惰性气体，打开热蒸发电源，以80℃/分钟的升温速度将钨舟从室温加热至1100℃，然后保温20分钟，使钨粉氧化、升华为气相W18O49， 接着在碳纤维布生长出固相W18O49纳米线。(4) Continuously pass oxygen and inert gas into the vacuum coating chamber, turn on the thermal evaporation power source, heat the tungsten boat from room temperature to 1100 ° C at a heating rate of 80 ° C / min, and then keep it for 20 minutes to oxidize and sublime the tungsten powder. For the gas phase W 18 O 49 , a solid phase W 18 O 49 nanowire is grown on the carbon fiber cloth.
(5)以100℃/分钟的降温速度进行降温处理，同时持续往真空腔室内通入惰性气体，待镀有W18O49纳米线的碳纤维布冷却至室温后，打开真空镀膜腔体，取出镀有W18O49纳米线的碳纤维布备用。(5) The temperature is lowered at a cooling rate of 100 ° C / min, and the inert gas is continuously introduced into the vacuum chamber. After the carbon fiber cloth coated with the W 18 O 49 nanowire is cooled to room temperature, the vacuum coating chamber is opened and taken out. A carbon fiber cloth coated with W 18 O 49 nanowires was used.
(6)把镀有W18O49纳米线的碳纤维布放置在一真空腔体内的加热台上，真空腔体内为无氧气且有氩气保护的低气压环境，加热镀有W18O49纳米线的碳纤维布至1600℃，保温20分钟后，使W18O49纳米线的表面发生分解反应，释放出氧，于是在W18O49纳米线的表面形成W量子点，再进行降温处理，最终得到生长在碳纤维布上的W@W18O49热驱动催化剂。(6) The carbon fiber cloth coated with W 18 O 49 nanowires is placed on a heating table in a vacuum chamber, which is an oxygen-free and argon-protected low-pressure environment, and is heat-plated with W 18 O 49 nm. After the carbon fiber cloth of the wire is heated to 1600 ° C for 20 minutes, the surface of the W 18 O 49 nanowire is decomposed to release oxygen, so that a W quantum dot is formed on the surface of the W 18 O 49 nanowire, and then the temperature is lowered. Finally, a W@W 18 O 49 heat-driven catalyst grown on a carbon fiber cloth was obtained.
请参阅图1，其为本实施例所制得的W@W18O49热驱动催化剂的SEM图。Please refer to FIG. 1 , which is an SEM image of the W@W 18 O 49 heat-driven catalyst prepared in the present example.
图1(a)为生长在碳纤维布上的W@W18O49热驱动催化剂的SEM形貌图，通过该图可见，直径尺寸为几个微米级的W18O49纳米棒作为主干，直径尺寸为纳米级的W18O49纳米线作为分支从主干表面横向生长，整体呈现为树状结构。图1(b)为图1(a)的10倍放大图，通过分析测量可知，图中的W18O49纳米线的直径约为50-200nm。Fig. 1(a) is a SEM topographical view of a W@W 18 O 49 heat-driven catalyst grown on a carbon fiber cloth. It can be seen that the W 18 O 49 nanorods having a diameter of several micrometers are used as the trunk and the diameter. The W 18 O 49 nanowires of the nanometer size are laterally grown as branches from the trunk surface, and the whole appears as a tree structure. Fig. 1(b) is a 10-fold enlarged view of Fig. 1(a). It can be seen from the analysis and measurement that the diameter of the W 18 O 49 nanowire in the figure is about 50-200 nm.
请参阅图2，其为本实施例所制得的W@W18O49热驱动催化剂的TEM图。Please refer to FIG. 2 , which is a TEM image of the W@W 18 O 49 heat-driven catalyst prepared in the present example.
图2(a)为生长在碳纤维布上的W@W18O49热驱动催化剂的TEM形貌图，该图中的W18O49纳米线为树状结构中直径较小的分支，其直径约为8nm，且表面凹凸不平，表面晶体结构复杂，而内部结构规整。图2(b)为图2(a)中方框区域的4倍放大图，通过该图进一步分析测量可知，W18O49纳米线表面存在直径约为2nm的W量子点结构，其晶面间距约为0.228nm，正好符合金属钨单质XRD标准卡片(PDF#04-0806)的(110)面的面间距；W18O49纳米线内部的晶面间距约为0.375nm，也正好符合W18O49的XRD标准卡片(PDF#36-0101)的(010)面的面间距。Fig. 2(a) is a TEM topographical view of a W@W 18 O 49 heat-driven catalyst grown on a carbon fiber cloth, in which the W 18 O 49 nanowire is a branch having a smaller diameter in a dendritic structure, the diameter of which is It is about 8 nm, and the surface is uneven, the surface crystal structure is complicated, and the internal structure is regular. Fig. 2(b) is a 4x enlarged view of the boxed area in Fig. 2(a). Further analysis and measurement by this figure shows that there is a W quantum dot structure with a diameter of about 2 nm on the surface of the W 18 O 49 nanowire, and the interplanar spacing It is about 0.228nm, which is in line with the (110) plane spacing of the metal tungsten XRD standard card (PDF#04-0806); the interplanar spacing of the W 18 O 49 nanowire is about 0.375nm, which is also in line with W 18 The interplanar spacing of the (010) plane of the O 49 XRD standard card (PDF #36-0101).
结合图1与图2可得，上述制备方法制得的W@W18O49热驱动催化剂，是由作为主干的直径尺寸为几个微米的W18O49纳米棒、作为主干的横向分支的直径尺寸为纳米级的W18O49纳米线、以及附着在W18O49纳米线表面的直径为几个纳米的W量子点所构成的复合结构组成。其中，W量子点是W18O49纳米线在低气压环境下经过高温缺氧处理，表面部分区域发生分解反应而形成的。Referring to FIG. 1 and FIG. 2, the W@W 18 O 49 heat-driven catalyst prepared by the above preparation method is a lateral branch of a W 18 O 49 nanorod having a diameter of several micrometers as a trunk. The composite structure consists of a nanometer-sized W 18 O 49 nanowire and a W quantum dot attached to the surface of the W 18 O 49 nanowire with a diameter of several nanometers. Among them, the W quantum dot is formed by the high temperature and anoxic treatment of the W 18 O 49 nanowire in a low pressure environment, and a partial decomposition reaction occurs in the surface region.
除了本实施例所述的制备方法外，还可以先通过化学溶液法合成W18O49纳米线，然后在真空环境或无氧气的低气压环境下对W18O49纳米线进行高温缺氧处理，得到W@W18O49热驱动催化剂；也可以将得到的W18O49纳米线置于还原气氛如氢气、一氧化碳等中，进行高温处理，得到W@W18O49热驱动催化剂。 In addition to the preparation method described in the present embodiment, the W 18 O 49 nanowire can be synthesized by a chemical solution method, and then the W 18 O 49 nanowire is subjected to high temperature anoxic treatment in a vacuum environment or a low pressure atmosphere without oxygen. The W@W 18 O 49 heat-driven catalyst is obtained; the obtained W 18 O 49 nanowire can also be placed in a reducing atmosphere such as hydrogen, carbon monoxide or the like for high temperature treatment to obtain a W@W 18 O 49 heat-driven catalyst.
实施例2：红外照射下利用红外辐射热量驱动催化降解染料分子及其重复循环的试验Example 2: Experiment of driving catalytic degradation of dye molecules by infrared radiation under infrared irradiation and repeated cycles thereof
取实施例1制得的镀有W@W18O49热驱动催化剂的碳纤维布(面积1.0cm2)作为催化剂样品，加入到10ml的甲基橙溶液(浓度0.12mmol/L)中，再将甲基橙溶液置于装有一只250W红外灯泡的红外烤箱中照射1.5小时，每隔0.5小时测试甲基橙溶液的紫外可见吸收光谱，将所测得数据作甲基橙浓度随时间变化特性曲线。在红外光的照射下，甲基橙溶液的温度从室温30℃上升到70℃后达到稳定。A carbon fiber cloth (area 1.0 cm 2 ) plated with W@W 18 O 49 heat-driven catalyst prepared in Example 1 was used as a catalyst sample, and added to 10 ml of a methyl orange solution (concentration: 0.12 mmol/L), and then The methyl orange solution was exposed to an infrared oven equipped with a 250 W infrared bulb for 1.5 hours. The UV-visible absorption spectrum of the methyl orange solution was tested every 0.5 hours, and the measured data was used as a characteristic curve of methyl orange concentration with time. . Under the irradiation of infrared light, the temperature of the methyl orange solution was stabilized after rising from room temperature of 30 ° C to 70 ° C.
请参阅图3，其为本实施例的红外照射下催化降解染料分子试验中甲基橙溶液浓度随时间变化的特性曲线图，通过该图可知，在红外辐射下甲基橙的浓度随着照射时间的增加而逐渐下降。Please refer to FIG. 3 , which is a characteristic curve of the concentration of methyl orange solution in the molecular test of catalytic degradation of dye under infrared irradiation according to the embodiment, and the concentration of methyl orange in the infrared radiation is irradiated by the infrared radiation. The time increases and gradually decreases.
对同一催化剂样品重复上述试验10次，以测试其循环再生的能力。The above test was repeated 10 times for the same catalyst sample to test its ability to recycle.
请参阅图4，其为本实施例的红外照射下催化降解染料分子重复循环试验中甲基橙溶液浓度随时间变化的特性曲线图，通过该图可知，在10次重复循环测试中W@W18O49热驱动催化剂的催化降解性能始终保持稳定，无发生明显下降。Please refer to FIG. 4 , which is a characteristic curve of the concentration of methyl orange solution in the repeated cycle test of catalytic degradation dye molecules under infrared irradiation according to the embodiment, and the figure shows that W@W in 10 repeated cycles test The catalytic degradation performance of the 18 O 49 heat-driven catalyst was always stable and did not decrease significantly.
上述试验结果表明，W@W18O49热驱动催化剂能够有效吸收利用红外辐射产生的热量对有机染料进行催化降解，而且在多次循环使用后仍然能保持其催化性能，展现了其在污水处理等领域的巨大潜能。The above test results show that W@W 18 O 49 heat-driven catalyst can effectively absorb the heat generated by infrared radiation to catalytically degrade organic dyes, and still maintain its catalytic performance after repeated use, showing its treatment in sewage treatment. The huge potential of such fields.
实施例3：无光环境下利用环境热量驱动催化降解染料分子及其重复循环的试验Example 3: Experiment of using environmental heat to drive catalytic degradation of dye molecules and their repeated cycles in a light-free environment
取4块实施例1制得的镀有W@W18O49热驱动催化剂的碳纤维布(面积1.0cm2)作为催化剂样品，分别加入到4瓶10ml的甲基橙溶液(浓度0.12mmol/L)中，再将4瓶甲基橙溶液分别置于5℃、25℃、50℃、75℃的无光环境中20小时，然后分别测试4瓶甲基橙溶液的紫外可见吸收光谱，将所测得数据作甲基橙浓度随温度变化特性曲线。Four carbon fiber cloths (area 1.0 cm 2 ) plated with W@W 18 O 49 heat-driven catalyst prepared in Example 1 were used as catalyst samples, and respectively added to 4 bottles of 10 ml methyl orange solution (concentration 0.12 mmol/L). 4, then placed 4 bottles of methyl orange solution in a light environment of 5 ° C, 25 ° C, 50 ° C, 75 ° C for 20 hours, and then tested the UV-visible absorption spectrum of 4 bottles of methyl orange solution, respectively The measured data was used as a characteristic curve of methyl orange concentration as a function of temperature.
请参阅图5，其为本实施例的无光环境下催化降解染料分子重复循环试验中不同温度下的催化性能对比图。通过该图可知，在无光环境下，W@W18O49热驱动催化剂能够利用环境中的热量，持续对甲基橙溶液进行催化降解，而且随着环境的温度的上升，降解反应加快进行。所述W@W18O49热驱动催化剂即使在5℃的低温环境中也能有效催化降解，充分展现出其与传统热催化剂的区别，具有无需达到特定温度值、在无光环境下也能催化降解反应的优点，有望可在高纬度区域、高海拔地区等常年低温地区推广使用。Please refer to FIG. 5 , which is a comparative diagram of catalytic performance at different temperatures in a repeated cycle test of catalytically degrading dye molecules in a matte environment of the present embodiment. It can be seen from the figure that in the absence of light, the W@W 18 O 49 heat-driven catalyst can continuously decompose the methyl orange solution by utilizing the heat in the environment, and the degradation reaction accelerates as the temperature of the environment rises. . The W@W 18 O 49 heat-driven catalyst can effectively catalyze degradation even in a low temperature environment of 5 ° C, fully exhibiting the difference from the conventional thermal catalyst, and can be used in a light-free environment without reaching a specific temperature value. The advantages of catalytic degradation are expected to be promoted in perennial low temperature areas such as high latitudes and high altitudes.
上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。 The above-described embodiments are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but is not to be construed as limiting the scope of the invention. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention.

Claims (14)

  1. 一种热驱动催化剂，其特征在于：由金属氧化物纳米结构和附着在金属氧化物纳米结构表面的同一金属量子点所构成的复合结构组成。A thermally driven catalyst comprising a composite structure of metal oxide nanostructures and the same metal quantum dots attached to the surface of the metal oxide nanostructures.
  2. 根据权利要求1所述的热驱动催化剂，其特征在于：所述金属氧化物纳米结构的尺寸为8-5000nm，所述金属量子点的尺寸为1-10nm。The thermally driven catalyst according to claim 1, wherein said metal oxide nanostructure has a size of from 8 to 5000 nm, and said metal quantum dots have a size of from 1 to 10 nm.
  3. 根据权利要求2所述的热驱动催化剂，其特征在于：所述金属氧化物纳米结构是化学式为W18O49的氧化钨纳米线，所述金属量子点是钨量子点。The thermally driven catalyst according to claim 2, wherein the metal oxide nanostructure is a tungsten oxide nanowire of the formula W 18 O 49 , and the metal quantum dot is a tungsten quantum dot.
  4. 根据权利要求1～3任一项所述的热驱动催化剂，其特征在于：所述热驱动催化剂可吸收红外辐射或者以热传递的方式吸收外界热量，并将所吸收的热量用于驱动催化水溶液中有机物的降解反应。The thermally driven catalyst according to any one of claims 1 to 3, wherein the thermally driven catalyst absorbs infrared radiation or absorbs external heat by heat transfer, and uses the absorbed heat to drive the catalytic aqueous solution. Degradation reaction of organic matter.
  5. 根据权利要求4所述的热驱动催化剂，其特征在于：所述热驱动催化剂在无光环境下，可持续吸收外界热量以驱动催化水溶液中有机物的降解反应。The thermally driven catalyst according to claim 4, wherein the thermally driven catalyst continuously absorbs external heat in a light-free environment to drive degradation of the organic matter in the catalytic aqueous solution.
  6. 根据权利要求1～3任一项所述的热驱动催化剂，其特征在于：由以下步骤制备而成：首先，通过化学溶液法或物理蒸镀法合成金属氧化物纳米结构材料；然后，在真空环境、有惰性气体保护的缺氧环境或者还原气氛中，高温加热金属氧化物纳米结构材料，使金属氧化物纳米结构的表面发生分解反应或者还原反应，释放出氧，于是在金属氧化物纳米结构的表面形成金属量子点，得到所述热驱动催化剂。The thermally driven catalyst according to any one of claims 1 to 3, which is prepared by the following steps: first, synthesizing a metal oxide nanostructure material by a chemical solution method or a physical vapor deposition method; In the environment, an oxygen-deficient environment protected by an inert gas or a reducing atmosphere, the metal oxide nanostructured material is heated at a high temperature to cause a decomposition reaction or a reduction reaction of the surface of the metal oxide nanostructure to release oxygen, so that the metal oxide nanostructure is The surface forms metal quantum dots to give the thermally driven catalyst.
  7. 根据权利要求6所述的热驱动催化剂，其特征在于：具体由以下步骤制备而成：The thermally driven catalyst according to claim 6, wherein the catalyst is specifically prepared by the following steps:
    (1)将钨舟接入真空热蒸发镀膜机的蒸发电极，并往钨舟内加入钨粉，再将衬底放置于距离钨舟2～100毫米处；(1) Connect the tungsten boat to the evaporation electrode of the vacuum thermal evaporation coating machine, add tungsten powder to the tungsten boat, and place the substrate 2 to 100 mm away from the tungsten boat;
    (2)开启机械泵对真空镀膜腔体进行抽真空20分钟；(2) Turn on the mechanical pump to evacuate the vacuum coating chamber for 20 minutes;
    (3)往真空镀膜腔体内通入氧气和惰性气体，等腔体内压强稳定后，保持20分钟；(3) introducing oxygen and inert gas into the vacuum coating chamber, and maintaining the pressure in the chamber for 20 minutes;
    (4)持续往真空镀膜腔体内通入氧气和惰性气体，打开热蒸发电源，加热钨舟至1100℃，然后保温20分钟，使钨粉氧化、升华为气相氧化钨，接着在衬底上生长出化学式为W18O49的固相氧化钨纳米线；(4) Continuously pass oxygen and inert gas into the vacuum coating chamber, turn on the thermal evaporation power source, heat the tungsten boat to 1100 ° C, and then keep it for 20 minutes to oxidize and sublime the tungsten powder into a vapor phase tungsten oxide, and then grow on the substrate. a solid phase tungsten oxide nanowire having a chemical formula of W 18 O 49 ;
    (5)进行降温处理，同时持续往真空腔室内通入惰性气体，待氧化钨纳米线冷却至室温后，打开真空镀膜腔体，取出镀有氧化钨纳米线的衬底备用；(5) performing a temperature-lowering treatment while continuously introducing an inert gas into the vacuum chamber. After the tungsten oxide nanowire is cooled to room temperature, the vacuum coating chamber is opened, and the substrate coated with the tungsten oxide nanowire is taken out for use;
    (6)将镀有氧化钨纳米线的衬底放置在一真空腔体内的加热台上，真空腔体内为无氧气且有惰性气体保护的环境，加热镀有氧化钨纳米线的衬底至1600℃，保温20分钟后，再进行降温处理，最终得到生长在衬底上的所述热驱动催化剂。 (6) placing the substrate coated with the tungsten oxide nanowires on a heating stage in a vacuum chamber, the environment in which the oxygen chamber is protected by an inert gas, heating the substrate coated with the tungsten oxide nanowires to 1600 After the temperature was kept for 20 minutes, the temperature was further lowered to finally obtain the heat-driven catalyst grown on the substrate.
  8. 权利要求1-3、5或7任一项所述的热驱动催化剂在催化降解有机污染物中的应用。Use of the thermally driven catalyst of any of claims 1-3, 5 or 7 for catalytically degrading organic contaminants.
  9. 权利要求4所述的热驱动催化剂在催化降解有机污染物中的应用。Use of the thermally driven catalyst of claim 4 for catalytically degrading organic contaminants.
  10. 权利要求6所述的热驱动催化剂在催化降解有机污染物中的应用The use of the thermally driven catalyst of claim 6 for catalytically degrading organic pollutants
  11. 根据权利要求8所述的应用，其特征在于：将所述热驱动催化剂添加到含有有机染料的水溶液中，在无光环境下，使所述热驱动催化剂催化有机染料的降解反应。The use according to claim 8, wherein the heat-driven catalyst is added to an aqueous solution containing an organic dye to catalyze the degradation reaction of the organic dye in a light-free environment.
  12. 根据权利要求9或10所述的应用，其特征在于：将所述热驱动催化剂添加到含有有机染料的水溶液中，在无光环境下，使所述热驱动催化剂催化有机染料的降解反应。The use according to claim 9 or 10, characterized in that the heat-driven catalyst is added to an aqueous solution containing an organic dye to catalyze the degradation reaction of the organic dye in a light-free environment.
  13. 根据权利要求8所述的应用，其特征在于：将所述热驱动催化剂添加到含有有机染料的水溶液中，在红外光照射下，使所述热驱动催化剂催化有机染料的降解反应。The use according to claim 8, wherein the heat-driven catalyst is added to an aqueous solution containing an organic dye, and the thermally driven catalyst catalyzes a degradation reaction of the organic dye under irradiation with infrared light.
  14. 根据权利要求9或10所述的应用，其特征在于：将所述热驱动催化剂添加到含有有机染料的水溶液中，在红外光照射下，使所述热驱动催化剂催化有机染料的降解反应。 The use according to claim 9 or 10, characterized in that the heat-driven catalyst is added to an aqueous solution containing an organic dye, and the thermally driven catalyst catalyzes a degradation reaction of the organic dye under irradiation with infrared light.
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