WO2019061584A1 - Metal tungsten quantum dot preparation method - Google Patents

Metal tungsten quantum dot preparation method Download PDF

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WO2019061584A1
WO2019061584A1 PCT/CN2017/106477 CN2017106477W WO2019061584A1 WO 2019061584 A1 WO2019061584 A1 WO 2019061584A1 CN 2017106477 W CN2017106477 W CN 2017106477W WO 2019061584 A1 WO2019061584 A1 WO 2019061584A1
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tungsten
metal
quantum dot
quantum dots
metal tungsten
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French (fr)
Chinese (zh)
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罗坚义
唐秀凤
黄景诚
廖慧珍
胡晓燕
郑国祥
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五邑大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
    • C09K11/68—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5846—Reactive treatment

Definitions

  • the invention belongs to the technical field of nanometer powder preparation of high temperature metal materials, and particularly relates to a preparation method of metal tungsten quantum dots.
  • Nano-powder materials due to their small particle size and large specific surface area, exhibit different "size effects", “surface and interface effects” and “quantum size effects” from bulk materials, and thus can be widely used.
  • Surfactants single-electron devices, lithium battery electrode materials, electron field emission materials, sensors, and the like.
  • the smaller the particle size of the nano-powder the more obvious the quantum size effect and the superior performance, but the smaller the particle size of the particle, the easier it is to re-agglomerate during the preparation process, so that the particle size of the powder becomes larger. . Therefore, the preparation of nano-powder materials with good dispersibility and small particle size has become an important research direction in this field.
  • Metal tungsten has excellent properties such as high melting point (3410 ° C), high density, high strength, low thermal expansion coefficient, good corrosion resistance and thermal electron emission capability in many fields such as aerospace, military industry and electronics industry. Has been widely used. Since the 1960s, researchers have begun to conduct in-depth research on the preparation of tungsten and its compound nanopowders. Tungsten particles have evolved from the initial micron scale to the current nanoscale. Even some scholars have prepared ultrafine ⁇ -W nanoparticles by liquid ablation in liquid nitrogen, with an average particle size as small as 3 nm.
  • the commonly used preparation methods include thermal plasma technology and tungsten salt degradation method: the hot plasma technology is to re-form the tungsten powder after being melted in an argon, hydrogen or nitrogen atmosphere, and is usually used for preparing submicron spherical tungsten powder.
  • the technology is also recognized as the most effective way to prepare spherical tungsten nano-powders in the metallurgical industry, but the technology is complicated, the cost is high, and the particle size of the powder is difficult to do.
  • the tungsten salt degradation method is to chemically treat the tungsten salt (W(CO) 6 , WCl 6 , etc.) under the action of sodium salt or other reducing aids (Mg, Fe, NaN 3 , NaBH 4 , etc.) Degradation, nano-scale tungsten particles are obtained, but the method has the disadvantages of cumbersome process steps, various reagents used, strong acid and alkali, and environmental friendliness.
  • an object of the present invention is to provide a method for preparing a metal tungsten quantum dot, which has the advantages of simple process steps, single raw materials, easy preparation conditions, and controllable particle size of the obtained tungsten tungsten quantum dots.
  • a method for preparing a metal tungsten quantum dot comprises the steps of: placing a tungsten oxide nanostructure in an oxygen-deficient environment protected by an inert gas or a high-temperature annealing treatment in a reducing atmosphere, and adjusting the time of the high-temperature annealing treatment to make the tungsten oxide
  • Metal tungsten tungsten dots are grown on the surface of the nanostructure, and then the tungsten oxide nanostructures and the tungsten tungsten quantum dots are separated to obtain metal tungsten quantum dots.
  • the tungsten oxide nanostructure is used as a raw material, and the surface of the tungsten oxide nanostructure is subjected to a decomposition reaction or a reduction reaction by high-temperature annealing treatment, thereby depositing metal tungsten particles.
  • the degree of the decomposition reaction or the reduction reaction can be controlled, thereby effectively regulating the particle size of the metal tungsten particles.
  • the size of the tungsten oxide nanostructure is sufficiently small and the specific surface area is large, the particle size of the metal tungsten particles can reach the quantum dot level.
  • the metal tungsten quantum dots are formed on the surface of the tungsten oxide nanostructures, agglomeration is less likely to occur, resulting in a larger particle size, and the size thereof can be kept stable.
  • the process steps of the invention are simple, the raw materials are single, do not need to use a plurality of reagents, are environmentally friendly, and the preparation conditions are easy to realize and control, and the preparation is simple. low cost.
  • the temperature of the high temperature annealing treatment is 1200 ° C or more, and the time is 10-30 minutes.
  • the high temperature annealing treatment needs to reach a suitable temperature to promote decomposition or reduction of the surface of the tungsten oxide nanostructure. If the time of the high temperature annealing treatment is too short, the metal tungsten quantum dots cannot be fully analyzed. If the time is too long, the particle size of the precipitated metal tungsten particles will be too large and exceed the quantum dot level, so the time control of the high temperature annealing treatment is required. Within the appropriate range.
  • the tungsten oxide nanostructure is prepared by a vacuum thermal evaporation method.
  • the tungsten oxide nanostructure is obtained by heating and evaporating a tungsten source in an oxygen-containing atmosphere, followed by deposition on a substrate, the tungsten source being bulk tungsten.
  • the preparation method of the invention adopts the vacuum thermal evaporation method to prepare the tungsten oxide nanostructure, the process steps are simple, the raw materials are single, the preparation cost is low, the preparation conditions are easy to control, the obtained tungsten oxide nanostructure has controllable morphology, high crystallinity and stable structure.
  • the tungsten oxide nanostructure is a W 18 O 49 nanowire.
  • the tungsten oxide nanostructure has a size of 50-500 nm, and the obtained metal tungsten quantum dot has a particle size of 1-20 nm.
  • the step of separating the tungsten oxide nanostructures and the metal tungsten quantum dots is: putting tungsten tungsten nanostructures with metal tungsten quantum dots on the surface into a solvent, and separating the tungsten tungsten quantum dots and the tungsten oxide nanostructures by ultrasonic vibration. Then, the tungsten oxide nanostructure is removed by filtration to obtain a solution containing metal tungsten quantum dots, and then the solvent in the solution containing the metal tungsten quantum dots is dried to obtain a metal tungsten quantum dot powder.
  • preparation method specifically includes the following steps:
  • the vacuum thermal evaporation coating machine is used to complete the steps of preparing W 18 O 49 nanowires by vacuum thermal evaporation and preparing tungsten tungsten quantum dots by high temperature annealing. No other equipment is needed in the middle, the preparation efficiency is high, the preparation conditions are easy to adjust, and the operation is improved. The controllability and the reduction of the preparation cost make it convenient to adjust the time of the high temperature annealing treatment to realize the regulation of the particle size of the metal tungsten quantum dots.
  • the substrate was heated from room temperature to 1600 ° C at a temperature increase rate of 80 ° C / minute, and the substrate was cooled to room temperature at a temperature decreasing rate of 100 ° C / minute.
  • the present invention also provides a metal tungsten quantum dot obtained by the above preparation method.
  • FIG. 1 is a TEM image of the W 18 O 49 nanowire obtained in the step (1); wherein, FIG. 1(a) is a low-power TEM image of a single W 18 O 49 nanowire, and FIG. 1(b) is a graph 1 ( a) An enlarged TEM image of the boxed area, and Figure 1(c) is a HRTEM image of the boxed area in Figure 1(b).
  • FIG. 3 is a TEM image of the W 18 O 49 nanowire obtained in the step (2); wherein, FIG. 3(a) is a low-power TEM image of the W 18 O 49 nanowire, and FIG. 3(b) is a FIG. 3(a). A partial enlarged TEM image, and Fig. 3(c) is a HRTEM image of the boxed area in Fig. 3(b).
  • FIG. 5 is a TEM image of the W 18 O 49 nanowire before and after the ultrasonic vibration in step (3); wherein, FIG. 5( a ) is a TEM image of the W 18 O 49 nanowire before ultrasonic vibration, and FIG. 5( b ) is TEM image of W 18 O 49 nanowire after ultrasonic vibration.
  • a W 18 O 49 nanowire is used as a raw material, and a tungsten tungsten quantum dot is prepared by high temperature annealing in an oxygen-deficient environment protected by an inert gas, and specifically includes the following steps:
  • step (1) Growth of tungsten metal quantum dots of the present embodiment in step (1) obtained is grown W on the CFRP 18 O 49 nanowires, and the step (2) resulting surface W 18 O 49 nanowires are a TEM and XRD measurement , to characterize its surface morphology and phase structure.
  • FIG. 1 is a TEM image of the W 18 O 49 nanowire obtained in the step (1); wherein FIG. 1( a ) is a low-power TEM image of a single W 18 O 49 nanowire, FIG. 1( b ) It is an enlarged TEM image of the boxed area in Fig. 1(a), and Fig. 1(c) is an HRTEM image of the boxed area in Fig. 1(b).
  • the W 18 O 49 nanowire obtained in the step (1) has a smooth surface and a diameter of about 360 nm.
  • the interplanar spacing of the nanowires is 0.372 nm, which is in accordance with the interplanar spacing of the (010) crystal planes of the cubic system W 18 O 49 .
  • FIG. 2 is an XRD pattern of the W 18 O 49 nanowire obtained in the step (1).
  • the diffraction peak position of the (010) crystal orientation corresponds to the monoclinic system W 18 O 49 (JCPDS card: No. PDF-36-0101) except that the carbon fiber cloth has a width at 20-30 degrees.
  • step (1) vacuum thermal evaporation method produces pure W 18 O 49 nanowires without the presence of metal tungsten.
  • FIG. 3 is a TEM image of the W 18 O 49 nanowire obtained in the step (2); wherein, FIG. 3( a ) is a low-power TEM image of the W 18 O 49 nanowire, and FIG. 3( b ) is a diagram. 3(a) is a partially enlarged TEM image, and FIG. 3(c) is a HRTEM image of the boxed area in FIG. 3(b).
  • the surface of the W 18 O 49 nanowire obtained in the step (2) is rough, and the surface thereof is full of quantum dots having a particle diameter of about 10 nm.
  • the interplanar spacing of these quantum dots is 0.224 nm, which is in accordance with the interplanar spacing of the (110) crystal faces of the cubic metal tungsten.
  • FIG. 4 is an XRD pattern of the W 18 O 49 nanowire obtained in the step (2).
  • the diffraction peak position of the (010) crystal orientation corresponds to the monoclinic system W 18 O 49 (JCPDS card: No. PDF-36-0101), and other than this, it is more obvious that (110), The diffraction peak positions of the (200) and (211) crystal directions correspond to the cubic metal tungsten (JCPDS card: No. PDF-04-0806), indicating high temperature annealing treatment in an oxygen-deficient environment protected by an inert gas. After the W 18 O 49 nanowire, metal tungsten appears on the surface.
  • FIG. 5 is a TEM image of the W 18 O 49 nanowire before and after the ultrasonic vibration in step (3); wherein, FIG. 5( a ) is a TEM image of the W 18 O 49 nanowire before ultrasonic vibration, and FIG. 5( b ) is TEM image of W 18 O 49 nanowire after ultrasonic vibration.
  • the preparation method of the present invention has various embodiments, for example, in addition to the method for preparing a metal tungsten quantum dot in a high temperature annealing treatment in an oxygen-deficient environment protected by an inert gas, as described in the above embodiments, it is also possible to carry out a high temperature in a reducing atmosphere.
  • Annealing, step (2) can be changed to: open the vacuum coating chamber, uniformly distribute the toner around the W 18 O 49 nanowire, then close the vacuum coating chamber, vacuum the chamber to 6.5Pa, then turn on the heat Evaporate the power supply, heat the carbon fiber cloth from room temperature to 1400 ° C at a heating rate of 80 ° C / min, perform high temperature annealing at 1400 ° C for 10 minutes, then turn off the thermal evaporation power supply at a cooling rate of 100 ° C / min.
  • the carbon fiber cloth is cooled to room temperature, and the surface of the W 18 O 49 nanowire is subjected to a reduction reaction, thereby obtaining a metal tungsten quantum dot grown on the surface of the W 18 O 49 nanowire; the operation of placing the carbon powder can also be changed to the introduction of carbon monoxide or hydrogen.
  • the W 18 O 49 nanowires can be prepared by a chemical solution method or the like in addition to being prepared by a vacuum thermal evaporation method.

Abstract

A metal tungsten quantum dot preparation method. The preparation method comprises the following steps: putting a tungsten oxide nano structure in an oxygen deficient environment protected by inert gas or a reduction atmosphere to perform high temperature annealing treatment, enabling metal tungsten quantum dots to grow on the surface of the tungsten oxide nano structure by adjusting time of the high temperature annealing treatment, and then separating the tungsten oxide nano structure from the metal tungsten quantum dots to obtain the metal tungsten quantum dots. The preparation method has the advantages that process steps are simple and easy, few raw materials may be involved, preparation conditions are easy to achieve, and the prepared tungsten quantum dots have a controllable particle size.

Description

一种金属钨量子点的制备方法Method for preparing metal tungsten quantum dots 技术领域Technical field
本发明属于高温金属材料的纳米粉体制备技术领域，特别涉及一种金属钨量子点的制备方法。The invention belongs to the technical field of nanometer powder preparation of high temperature metal materials, and particularly relates to a preparation method of metal tungsten quantum dots.
背景技术Background technique
纳米粉体材料，由于具有小的粒径尺寸和大的比表面积，表现出不同于块体材料的“尺寸效应”、“表面与界面效应”及“量子尺寸效应”，从而可被广泛应用于表面活性剂、单电子器件、锂电池电极材料、电子场发射材料、传感器等领域。一般来说，纳米粉体的粒径越小，量子尺寸效应就越明显，性能也更加优越，但颗粒的粒径越小，容易在制备过程中发生再团聚从而使得粉体的粒径变大。因此，制备分散性好、且粒径尺寸小的纳米粉体材料成为了该领域的重要研究方向。Nano-powder materials, due to their small particle size and large specific surface area, exhibit different "size effects", "surface and interface effects" and "quantum size effects" from bulk materials, and thus can be widely used. Surfactants, single-electron devices, lithium battery electrode materials, electron field emission materials, sensors, and the like. In general, the smaller the particle size of the nano-powder, the more obvious the quantum size effect and the superior performance, but the smaller the particle size of the particle, the easier it is to re-agglomerate during the preparation process, so that the particle size of the powder becomes larger. . Therefore, the preparation of nano-powder materials with good dispersibility and small particle size has become an important research direction in this field.
金属钨由于具有极高的熔点(3410℃)、高密度、高强度、低热膨胀系数、良好的抗腐蚀性能和热电子发射能力等优良性能，在航空航天、军事工业和电子工业等诸多领域都得到了广泛应用。从20世纪60年代开始，学者们就开始对钨及其化合物纳米粉体的制备进行了深入的研究。钨颗粒从起初的微米级发展到现在的纳米级，甚至有学者于液氮中通过激光消融技术制备得到了超细β-W纳米颗粒，其平均粒径小至3nm。目前，常用的制备方法还有热等离子技术和钨盐降解法：热等离子技术是将钨粉处于氩气、氢气或氮气气氛中熔融后再次成型，通常用来制备亚微米级的球形钨粉，以提高粉体的流动性和烧结后的孔隙均匀性，该技术也被冶金业内公认为制备球形钨纳米粉体的最有效途径，但是该技术工艺复杂，成本高昂、粉体的粒径难做到纳米级；钨盐降解法是在钠盐或其它还原辅助剂(Mg、Fe、NaN3、NaBH4等)的作用下，以化学法将钨盐(W(CO)6、WCl6等)降解，得到纳米级钨颗粒，但是该方法存在着工艺步骤繁琐、使用的试剂繁多、使用了强酸和强碱、对环境不友好等缺点。Metal tungsten has excellent properties such as high melting point (3410 ° C), high density, high strength, low thermal expansion coefficient, good corrosion resistance and thermal electron emission capability in many fields such as aerospace, military industry and electronics industry. Has been widely used. Since the 1960s, scholars have begun to conduct in-depth research on the preparation of tungsten and its compound nanopowders. Tungsten particles have evolved from the initial micron scale to the current nanoscale. Even some scholars have prepared ultrafine β-W nanoparticles by liquid ablation in liquid nitrogen, with an average particle size as small as 3 nm. At present, the commonly used preparation methods include thermal plasma technology and tungsten salt degradation method: the hot plasma technology is to re-form the tungsten powder after being melted in an argon, hydrogen or nitrogen atmosphere, and is usually used for preparing submicron spherical tungsten powder. In order to improve the fluidity of the powder and the uniformity of the pores after sintering, the technology is also recognized as the most effective way to prepare spherical tungsten nano-powders in the metallurgical industry, but the technology is complicated, the cost is high, and the particle size of the powder is difficult to do. To the nanometer scale; the tungsten salt degradation method is to chemically treat the tungsten salt (W(CO) 6 , WCl 6 , etc.) under the action of sodium salt or other reducing aids (Mg, Fe, NaN 3 , NaBH 4 , etc.) Degradation, nano-scale tungsten particles are obtained, but the method has the disadvantages of cumbersome process steps, various reagents used, strong acid and alkali, and environmental friendliness.
因此，发展一种工艺简单、制备成本低、对环境友好的金属钨纳米粉体的制备方法显得尤为重要。Therefore, it is particularly important to develop a preparation method of metal tungsten nano-powder which is simple in process, low in preparation cost and environmentally friendly.
发明内容Summary of the invention
基于此，本发明的目的在于，提供一种金属钨量子点的制备方法，其具有工艺步骤简易，原料单一，制备条件易于实现，制得的金属钨量子点的粒径可控等优点。Based on this, an object of the present invention is to provide a method for preparing a metal tungsten quantum dot, which has the advantages of simple process steps, single raw materials, easy preparation conditions, and controllable particle size of the obtained tungsten tungsten quantum dots.
本发明采用的技术方案为： The technical solution adopted by the invention is:
一种金属钨量子点的制备方法，包括以下步骤：将氧化钨纳米结构置于有惰性气体保护的缺氧环境中或者还原气氛中进行高温退火处理，通过调节高温退火处理的时间，使氧化钨纳米结构表面生长出金属钨量子点，然后分离氧化钨纳米结构与金属钨量子点，得到金属钨量子点。A method for preparing a metal tungsten quantum dot comprises the steps of: placing a tungsten oxide nanostructure in an oxygen-deficient environment protected by an inert gas or a high-temperature annealing treatment in a reducing atmosphere, and adjusting the time of the high-temperature annealing treatment to make the tungsten oxide Metal tungsten tungsten dots are grown on the surface of the nanostructure, and then the tungsten oxide nanostructures and the tungsten tungsten quantum dots are separated to obtain metal tungsten quantum dots.
本发明的制备方法以氧化钨纳米结构为原料，通过高温退火处理使氧化钨纳米结构表面发生分解反应或还原反应，从而析出金属钨颗粒。其次，通过调节高温退火处理的时间，可以控制分解反应或还原反应的程度，进而有效调控金属钨颗粒的粒径尺寸。再者，由于氧化钨纳米结构的尺寸足够小、比表面积大，因此金属钨颗粒的粒径能够达到量子点级别。而且，因为金属钨量子点是在氧化钨纳米结构表面生长形成的，所以不容易发生团聚而导致粒径变大，其尺寸能够保持稳定。In the preparation method of the present invention, the tungsten oxide nanostructure is used as a raw material, and the surface of the tungsten oxide nanostructure is subjected to a decomposition reaction or a reduction reaction by high-temperature annealing treatment, thereby depositing metal tungsten particles. Secondly, by adjusting the time of the high temperature annealing treatment, the degree of the decomposition reaction or the reduction reaction can be controlled, thereby effectively regulating the particle size of the metal tungsten particles. Furthermore, since the size of the tungsten oxide nanostructure is sufficiently small and the specific surface area is large, the particle size of the metal tungsten particles can reach the quantum dot level. Moreover, since the metal tungsten quantum dots are formed on the surface of the tungsten oxide nanostructures, agglomeration is less likely to occur, resulting in a larger particle size, and the size thereof can be kept stable.
相对于现有的激光消融技术、热等离子技术和钨盐热解法，本发明的工艺步骤简易，原料单一，不需要用到多种试剂，对环境友好，而且制备条件易于实现和控制，制备成本低。Compared with the existing laser ablation technology, thermal plasma technology and tungsten salt pyrolysis method, the process steps of the invention are simple, the raw materials are single, do not need to use a plurality of reagents, are environmentally friendly, and the preparation conditions are easy to realize and control, and the preparation is simple. low cost.
进一步地，所述高温退火处理的温度为1200℃或以上，时间为10-30分钟。Further, the temperature of the high temperature annealing treatment is 1200 ° C or more, and the time is 10-30 minutes.
高温退火处理需要达到合适的温度，才能促使氧化钨纳米结构表面发生分解反应或还原反应。如果高温退火处理的时间过短，不能充分析出金属钨量子点，如果时间过长，所析出的金属钨颗粒的粒径则会过大而超过量子点级别，因此需要将高温退火处理的时间控制在适宜范围内。The high temperature annealing treatment needs to reach a suitable temperature to promote decomposition or reduction of the surface of the tungsten oxide nanostructure. If the time of the high temperature annealing treatment is too short, the metal tungsten quantum dots cannot be fully analyzed. If the time is too long, the particle size of the precipitated metal tungsten particles will be too large and exceed the quantum dot level, so the time control of the high temperature annealing treatment is required. Within the appropriate range.
进一步地，所述氧化钨纳米结构通过真空热蒸发法制备而成。Further, the tungsten oxide nanostructure is prepared by a vacuum thermal evaporation method.
进一步地，所述氧化钨纳米结构通过在含氧气氛中加热并蒸发钨源，继而在衬底上沉积所得，所述钨源为块材钨。Further, the tungsten oxide nanostructure is obtained by heating and evaporating a tungsten source in an oxygen-containing atmosphere, followed by deposition on a substrate, the tungsten source being bulk tungsten.
本发明的制备方法采用真空热蒸发法制备氧化钨纳米结构，工艺步骤简易，原料单一，制备成本低廉，制备条件容易控制，所得氧化钨纳米结构形貌可控、结晶度高、结构稳定。The preparation method of the invention adopts the vacuum thermal evaporation method to prepare the tungsten oxide nanostructure, the process steps are simple, the raw materials are single, the preparation cost is low, the preparation conditions are easy to control, the obtained tungsten oxide nanostructure has controllable morphology, high crystallinity and stable structure.
进一步地，所述的氧化钨纳米结构为W18O49纳米线。Further, the tungsten oxide nanostructure is a W 18 O 49 nanowire.
进一步地，所述氧化钨纳米结构的尺寸为50-500nm，制得的金属钨量子点的粒径尺寸为1-20nm。通过限制氧化钨纳米结构的尺寸在合适范围内，保证其表面形成的金属钨颗粒达到量子点级别。Further, the tungsten oxide nanostructure has a size of 50-500 nm, and the obtained metal tungsten quantum dot has a particle size of 1-20 nm. By limiting the size of the tungsten oxide nanostructure within a suitable range, it is ensured that the metal tungsten particles formed on the surface thereof reach the quantum dot level.
进一步地，分离氧化钨纳米结构与金属钨量子点的步骤为：将表面生长有金属钨量子点的氧化钨纳米结构投入到溶剂中，再采用超声震荡法分离金属钨量子点与氧化钨纳米结构，然后过滤除去氧化钨纳米结构，得到含有金属钨量子点的溶液，接着烘干除去含有金属钨量子点的溶液中的溶剂，得到金属钨量子点粉体。Further, the step of separating the tungsten oxide nanostructures and the metal tungsten quantum dots is: putting tungsten tungsten nanostructures with metal tungsten quantum dots on the surface into a solvent, and separating the tungsten tungsten quantum dots and the tungsten oxide nanostructures by ultrasonic vibration. Then, the tungsten oxide nanostructure is removed by filtration to obtain a solution containing metal tungsten quantum dots, and then the solvent in the solution containing the metal tungsten quantum dots is dried to obtain a metal tungsten quantum dot powder.
进一步地，所述制备方法具体包括以下步骤： Further, the preparation method specifically includes the following steps:
(1)W18O49纳米线的制备：将钨源接入真空热蒸发镀膜机的蒸发电极，再将衬底放置于距离钨源2-100毫米处，然后对真空镀膜腔内抽真空，接着通入流量比为1:100的氧气和惰性气体，再打开热蒸发电源，将钨源从室温加热至1400℃，保温20分钟后，关闭热蒸发电源，使衬底冷却至室温，得到生长在衬底上的W18O49纳米线；(1) Preparation of W 18 O 49 nanowire: the tungsten source is connected to the evaporation electrode of the vacuum thermal evaporation coating machine, and then the substrate is placed at a distance of 2-100 mm from the tungsten source, and then the vacuum coating chamber is evacuated. Then, oxygen and inert gas with a flow ratio of 1:100 were introduced, and then the thermal evaporation power was turned on. The tungsten source was heated from room temperature to 1400 ° C, and after being kept for 20 minutes, the thermal evaporation power was turned off, and the substrate was cooled to room temperature to obtain growth. W 18 O 49 nanowires on a substrate;
(2)金属钨量子点的制备：中断氧气供给，再对真空镀膜腔内抽真空，然后通入惰性气体，再打开热蒸发电源，将衬底从室温加热至1600℃，在1600℃下进行高温退火处理，处理时间为20分钟，然后关闭热蒸发电源，使衬底冷却至室温，得到生长于W18O49纳米线表面的金属钨量子点；(2) Preparation of metal tungsten quantum dots: interrupt the supply of oxygen, vacuum the vacuum coating chamber, then pass an inert gas, then open the thermal evaporation power source, and heat the substrate from room temperature to 1600 ° C at 1600 ° C. High temperature annealing treatment, the treatment time is 20 minutes, then the thermal evaporation power supply is turned off, and the substrate is cooled to room temperature to obtain metal tungsten quantum dots grown on the surface of the W 18 O 49 nanowire;
(3)W18O49纳米线与金属钨量子点的分离：将表面生长有金属钨量子点的W18O49纳米线投入到去离子水中，然后利用超声波清洗机进行超声震荡，接着用筛网将W18O49纳米线过滤除去，得到含有金属钨量子点的去离子水；(3) W 18 O 49 nanowires and tungsten quantum dots separated: the input surface of the grown tungsten quantum dots W 18 O 49 nanowires deionized water, and then with an ultrasonic cleaner for ultrasonic vibration, followed by a sieve The mesh removes the W 18 O 49 nanowires to obtain deionized water containing metal tungsten quantum dots;
(4)金属钨量子点的提取：将含有金属钨量子点的去离子水置于90℃的干燥箱中烘干，待去离子水完全挥发后，得到金属钨量子点粉体。(4) Extraction of metal tungsten quantum dots: Deionized water containing metal tungsten quantum dots is dried in a drying oven at 90 ° C, and after the deionized water is completely evaporated, a metal tungsten quantum dot powder is obtained.
使用真空热蒸发镀膜机完成真空热蒸发制备W18O49纳米线、以及高温退火处理制备金属钨量子点的步骤，中间不需要使用其他设备，制备效率高，制备条件易于调整，有利于提高操作的可控性以及降低制备成本，方便调节高温退火处理的时间，实现对金属钨量子点的粒径尺寸的调控。The vacuum thermal evaporation coating machine is used to complete the steps of preparing W 18 O 49 nanowires by vacuum thermal evaporation and preparing tungsten tungsten quantum dots by high temperature annealing. No other equipment is needed in the middle, the preparation efficiency is high, the preparation conditions are easy to adjust, and the operation is improved. The controllability and the reduction of the preparation cost make it convenient to adjust the time of the high temperature annealing treatment to realize the regulation of the particle size of the metal tungsten quantum dots.
进一步地，在步骤(2)中，以80℃/分钟的升温速率将衬底从室温加热至1600℃，以100℃/分钟的降温速率使衬底冷却至室温。通过限定升温、降温速率，有利于维持高温退火处理前W18O49纳米线的结构稳定，以及维持高温退火处理后金属钨量子点的结构稳定。Further, in the step (2), the substrate was heated from room temperature to 1600 ° C at a temperature increase rate of 80 ° C / minute, and the substrate was cooled to room temperature at a temperature decreasing rate of 100 ° C / minute. By limiting the temperature rise and temperature drop rates, it is beneficial to maintain the structural stability of the W 18 O 49 nanowire before the high temperature annealing treatment and to maintain the structural stability of the metal tungsten quantum dots after the high temperature annealing treatment.
本发明还提供上述任一项制备方法制得的金属钨量子点。The present invention also provides a metal tungsten quantum dot obtained by the above preparation method.
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为步骤(1)所得的W18O49纳米线的TEM图；其中，图1(a)为单根W18O49纳米线的低倍TEM图，图1(b)为图1(a)中方框区域的放大TEM图，图1(c)为图1(b)中方框区域的HRTEM图。1 is a TEM image of the W 18 O 49 nanowire obtained in the step (1); wherein, FIG. 1(a) is a low-power TEM image of a single W 18 O 49 nanowire, and FIG. 1(b) is a graph 1 ( a) An enlarged TEM image of the boxed area, and Figure 1(c) is a HRTEM image of the boxed area in Figure 1(b).
图2为步骤(1)所得的W18O49纳米线的XRD图。2 is an XRD pattern of the W 18 O 49 nanowire obtained in the step (1).
图3为步骤(2)所得的W18O49纳米线的TEM图；其中，图3(a)为W18O49纳米线的低倍TEM图，图3(b)为图3(a)的局部放大TEM图，图3(c)为图3(b)中方框区域的HRTEM图。 3 is a TEM image of the W 18 O 49 nanowire obtained in the step (2); wherein, FIG. 3(a) is a low-power TEM image of the W 18 O 49 nanowire, and FIG. 3(b) is a FIG. 3(a). A partial enlarged TEM image, and Fig. 3(c) is a HRTEM image of the boxed area in Fig. 3(b).
图4为步骤(2)所得的W18O49纳米线的XRD图。4 is an XRD pattern of the W 18 O 49 nanowire obtained in the step (2).
图5为步骤(3)超声震荡前、后的W18O49纳米线的TEM图；其中，图5(a)为超声震荡前W18O49纳米线的TEM图，图5(b)为超声震荡后W18O49纳米线的TEM图。5 is a TEM image of the W 18 O 49 nanowire before and after the ultrasonic vibration in step (3); wherein, FIG. 5( a ) is a TEM image of the W 18 O 49 nanowire before ultrasonic vibration, and FIG. 5( b ) is TEM image of W 18 O 49 nanowire after ultrasonic vibration.
具体实施方式Detailed ways
本实施例以W18O49纳米线为原材料，在有惰性气体保护的缺氧环境中高温退火处理制备金属钨量子点，具体包括以下步骤：In this embodiment, a W 18 O 49 nanowire is used as a raw material, and a tungsten tungsten quantum dot is prepared by high temperature annealing in an oxygen-deficient environment protected by an inert gas, and specifically includes the following steps:
(1)W18O49纳米线的制备：将钨舟接入真空热蒸发镀膜机的蒸发电极，再将碳纤维布放置于距离钨舟2毫米处，然后对真空镀膜腔内抽真空至6.5Pa，接着通入流量比为1:100的氧气和氩气，再打开热蒸发电源，以80℃/分钟的升温速率将钨舟从室温加热至1400℃，保温20分钟后，关闭热蒸发电源，以100℃/分钟的降温速率使碳纤维布冷却至室温，得到生长在碳纤维布上的W18O49纳米线。(1) Preparation of W 18 O 49 nanowire: Connect the tungsten boat to the evaporation electrode of the vacuum thermal evaporation coating machine, then place the carbon fiber cloth at 2 mm away from the tungsten boat, and then evacuate the vacuum coating chamber to 6.5 Pa. Then, oxygen and argon gas having a flow ratio of 1:100 were introduced, and then the thermal evaporation power source was turned on, and the tungsten boat was heated from room temperature to 1400 ° C at a heating rate of 80 ° C / min. After the heat preservation for 20 minutes, the thermal evaporation power was turned off. The carbon fiber cloth was cooled to room temperature at a cooling rate of 100 ° C / min to obtain W 18 O 49 nanowires grown on carbon fiber cloth.
(2)金属钨量子点的制备：关闭氧气阀，中断氧气供给，再对真空镀膜腔内抽真空至6.5Pa，然后通入氩气，再打开热蒸发电源，以80℃/分钟的升温速率将镀有W18O49纳米线的碳纤维布从室温加热至1600℃，在1600℃下进行高温退火处理，处理时间为20分钟，然后关闭热蒸发电源，以100℃/分钟的降温速率使碳纤维布冷却至室温，W18O49纳米线表面发生了分解反应，于是得到生长于W18O49纳米线表面的金属钨量子点。(2) Preparation of metal tungsten quantum dots: the oxygen valve is closed, the oxygen supply is interrupted, and the vacuum coating chamber is evacuated to 6.5 Pa, then argon gas is introduced, and then the thermal evaporation power source is turned on at a heating rate of 80 ° C / minute. The carbon fiber cloth coated with W 18 O 49 nanowires was heated from room temperature to 1600 ° C, and subjected to high temperature annealing treatment at 1600 ° C for 20 minutes, then the thermal evaporation power was turned off, and the carbon fiber was cooled at a cooling rate of 100 ° C / minute. The cloth was cooled to room temperature, and a decomposition reaction occurred on the surface of the W 18 O 49 nanowire, thereby obtaining a metal tungsten quantum dot grown on the surface of the W 18 O 49 nanowire.
(3)W18O49纳米线与金属钨量子点的分离：将表面生长有金属钨量子点的W18O49纳米线投入到去离子水中，然后利用超声波清洗机进行超声震荡，震荡功率为240W，频率为40kHz，震荡时间为5-20分钟，接着用能够阻挡W18O49纳米线但允许金属钨量子点通过的筛网将W18O49纳米线过滤除去，得到含有金属钨量子点的去离子水。(3) separating the W 18 O 49 nanowires and tungsten quantum dots: surface growth of tungsten quantum dots W 18 O 49 nanowires into deionized water, and then with an ultrasonic cleaner for ultrasonic vibration, shock power 240W, frequency is 40kHz, oscillation time is 5-20 minutes, then W 18 O 49 nanowires are removed by filtration with a screen capable of blocking W 18 O 49 nanowires but allowing metal tungsten quantum dots to pass, to obtain metal tungsten quantum dots. Deionized water.
(4)金属钨量子点的提取：将含有金属钨量子点的去离子水置于90℃的干燥箱中烘干，待去离子水完全挥发后，得到金属钨量子点粉体。(4) Extraction of metal tungsten quantum dots: Deionized water containing metal tungsten quantum dots is dried in a drying oven at 90 ° C, and after the deionized water is completely evaporated, a metal tungsten quantum dot powder is obtained.
对本实施例中步骤(1)所得的生长在碳纤维布上的W18O49纳米线、以及步骤(2)所得的表面生长有金属钨量子点的W18O49纳米线分别进行TEM和XRD测试，表征其表面形貌及物相结构。Growth of tungsten metal quantum dots of the present embodiment in step (1) obtained is grown W on the CFRP 18 O 49 nanowires, and the step (2) resulting surface W 18 O 49 nanowires are a TEM and XRD measurement , to characterize its surface morphology and phase structure.
请参阅图1，其为步骤(1)所得的W18O49纳米线的TEM图；其中，图1(a)为单根W18O49纳米线的低倍TEM图，图1(b)为图1(a)中方框区域的放大TEM图，图1(c)为图1(b)中方框区域的HRTEM图。Please refer to FIG. 1 , which is a TEM image of the W 18 O 49 nanowire obtained in the step (1); wherein FIG. 1( a ) is a low-power TEM image of a single W 18 O 49 nanowire, FIG. 1( b ) It is an enlarged TEM image of the boxed area in Fig. 1(a), and Fig. 1(c) is an HRTEM image of the boxed area in Fig. 1(b).
通过该图可见，步骤(1)所得的W18O49纳米线表面光滑，其直径约为360nm。经HRTEM分析可得，该纳米线的面间距为0.372nm，符合立方晶系的W18O49的(010)晶面的面间距。 It can be seen from the figure that the W 18 O 49 nanowire obtained in the step (1) has a smooth surface and a diameter of about 360 nm. According to HRTEM analysis, the interplanar spacing of the nanowires is 0.372 nm, which is in accordance with the interplanar spacing of the (010) crystal planes of the cubic system W 18 O 49 .
请参阅图2，其为步骤(1)所得的W18O49纳米线的XRD图。Please refer to FIG. 2 , which is an XRD pattern of the W 18 O 49 nanowire obtained in the step (1).
通过该图可见，(010)晶向的衍射峰位对应于单斜晶系的W18O49(JCPDS card:No.PDF-36-0101)，除了碳纤维布具有位于20-30度处的宽峰和杂散峰以外，没有其它明显的衍射峰，说明步骤(1)真空热蒸发法制得的是纯W18O49纳米线，并没有金属钨的存在。As can be seen from the figure, the diffraction peak position of the (010) crystal orientation corresponds to the monoclinic system W 18 O 49 (JCPDS card: No. PDF-36-0101) except that the carbon fiber cloth has a width at 20-30 degrees. There are no other obvious diffraction peaks other than peaks and stray peaks, indicating that step (1) vacuum thermal evaporation method produces pure W 18 O 49 nanowires without the presence of metal tungsten.
请参阅图3，其为步骤(2)所得的W18O49纳米线的TEM图；其中，图3(a)为W18O49纳米线的低倍TEM图，图3(b)为图3(a)的局部放大TEM图，图3(c)为图3(b)中方框区域的HRTEM图。Please refer to FIG. 3 , which is a TEM image of the W 18 O 49 nanowire obtained in the step (2); wherein, FIG. 3( a ) is a low-power TEM image of the W 18 O 49 nanowire, and FIG. 3( b ) is a diagram. 3(a) is a partially enlarged TEM image, and FIG. 3(c) is a HRTEM image of the boxed area in FIG. 3(b).
通过该图可见，步骤(2)所得的W18O49纳米线表面粗糙，其表面长满了粒径在10nm左右的量子点。经HRTEM分析可得，这些量子点的面间距为0.224nm，符合立方晶系的金属钨的(110)晶面的面间距。It can be seen from the figure that the surface of the W 18 O 49 nanowire obtained in the step (2) is rough, and the surface thereof is full of quantum dots having a particle diameter of about 10 nm. According to HRTEM analysis, the interplanar spacing of these quantum dots is 0.224 nm, which is in accordance with the interplanar spacing of the (110) crystal faces of the cubic metal tungsten.
请参阅图4，其为步骤(2)所得的W18O49纳米线的XRD图。Please refer to FIG. 4 , which is an XRD pattern of the W 18 O 49 nanowire obtained in the step (2).
通过该图可见，(010)晶向的衍射峰位对应于单斜晶系的W18O49(JCPDS card:No.PDF-36-0101)，除此以外，较为明显的是(110)、(200)、(211)晶向的衍射峰位，对应于立方晶系的金属钨(JCPDS card:No.PDF-04-0806)，说明经过在有惰性气体保护的缺氧环境中高温退火处理后的W18O49纳米线，其表面出现金属钨。As can be seen from the figure, the diffraction peak position of the (010) crystal orientation corresponds to the monoclinic system W 18 O 49 (JCPDS card: No. PDF-36-0101), and other than this, it is more obvious that (110), The diffraction peak positions of the (200) and (211) crystal directions correspond to the cubic metal tungsten (JCPDS card: No. PDF-04-0806), indicating high temperature annealing treatment in an oxygen-deficient environment protected by an inert gas. After the W 18 O 49 nanowire, metal tungsten appears on the surface.
图5为步骤(3)超声震荡前、后的W18O49纳米线的TEM图；其中，图5(a)为超声震荡前W18O49纳米线的TEM图，图5(b)为超声震荡后W18O49纳米线的TEM图。5 is a TEM image of the W 18 O 49 nanowire before and after the ultrasonic vibration in step (3); wherein, FIG. 5( a ) is a TEM image of the W 18 O 49 nanowire before ultrasonic vibration, and FIG. 5( b ) is TEM image of W 18 O 49 nanowire after ultrasonic vibration.
通过对比图5(a)和图5(b)可知，在超声震荡前，W18O49纳米线表面附着有颗粒状的量子点，但是在超声震荡后，W18O49纳米线表面的颗粒状的量子点消失。该结果表明，超声震荡可以有效地将W18O49纳米线与金属钨量子点进行分离。By comparing Fig. 5(a) and Fig. 5(b), before the ultrasonic vibration, the surface of the W 18 O 49 nanowire is attached with granular quantum dots, but after ultrasonic vibration, the particles on the surface of the W 18 O 49 nanowire The quantum dots disappear. The results show that ultrasonic oscillation can effectively separate W 18 O 49 nanowires from metal tungsten quantum dots.
本发明的制备方法具有多种实施方式，例如，除了上述实施例所述的在有惰性气体保护的缺氧环境中高温退火处理制备金属钨量子点的方法外，还可以在还原气氛中进行高温退火处理，则步骤(2)可改为：打开真空镀膜腔，在W18O49纳米线四周均匀撒放碳粉，再关闭真空镀膜腔，并对腔内抽真空至6.5Pa，然后打开热蒸发电源，以80℃/分钟的升温速率将碳纤维布从室温加热至1400℃，在1400℃下进行高温退火处理，处理时间为10分钟，然后关闭热蒸发电源，以100℃/分钟的降温速率使碳纤维布冷却至室温，W18O49纳米线表面发生了还原反应，于是得到生长于W18O49纳米线表面的金属钨量子点；放置碳粉的操作也可改为通入一氧化碳或氢气；此外，W18O49纳米线除了通过真空热蒸发法制备外，还可以通过化学溶液法制备等等。The preparation method of the present invention has various embodiments, for example, in addition to the method for preparing a metal tungsten quantum dot in a high temperature annealing treatment in an oxygen-deficient environment protected by an inert gas, as described in the above embodiments, it is also possible to carry out a high temperature in a reducing atmosphere. Annealing, step (2) can be changed to: open the vacuum coating chamber, uniformly distribute the toner around the W 18 O 49 nanowire, then close the vacuum coating chamber, vacuum the chamber to 6.5Pa, then turn on the heat Evaporate the power supply, heat the carbon fiber cloth from room temperature to 1400 ° C at a heating rate of 80 ° C / min, perform high temperature annealing at 1400 ° C for 10 minutes, then turn off the thermal evaporation power supply at a cooling rate of 100 ° C / min. The carbon fiber cloth is cooled to room temperature, and the surface of the W 18 O 49 nanowire is subjected to a reduction reaction, thereby obtaining a metal tungsten quantum dot grown on the surface of the W 18 O 49 nanowire; the operation of placing the carbon powder can also be changed to the introduction of carbon monoxide or hydrogen. In addition, the W 18 O 49 nanowires can be prepared by a chemical solution method or the like in addition to being prepared by a vacuum thermal evaporation method.
以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 for those of ordinary skill in the art, Many modifications and improvements can be made without departing from the spirit and scope of the invention.

Claims (11)

  1. 一种金属钨量子点的制备方法，其特征在于：包括以下步骤：将氧化钨纳米结构置于有惰性气体保护的缺氧环境中或者还原气氛中进行高温退火处理，通过调节高温退火处理的时间，使氧化钨纳米结构表面生长出金属钨量子点，然后分离氧化钨纳米结构与金属钨量子点，得到金属钨量子点。A method for preparing a tungsten metal quantum dot, comprising the steps of: placing a tungsten oxide nanostructure in an oxygen-deficient environment protected by an inert gas or a high-temperature annealing treatment in a reducing atmosphere, and adjusting a time of high-temperature annealing treatment; The tungsten tungsten quantum dots are grown on the surface of the tungsten oxide nanostructure, and then the tungsten oxide nanostructures and the tungsten metal quantum dots are separated to obtain metal tungsten quantum dots.
  2. 根据权利要求1所述的金属钨量子点的制备方法，其特征在于：所述高温退火处理的温度为1200℃或以上，时间为10-30分钟。The method for preparing a metal tungsten quantum dot according to claim 1, wherein the high temperature annealing treatment has a temperature of 1200 ° C or more and a time of 10-30 minutes.
  3. 根据权利要求1所述的金属钨量子点的制备方法，其特征在于：所述氧化钨纳米结构通过真空热蒸发法制备而成。The method for preparing a metal tungsten quantum dot according to claim 1, wherein the tungsten oxide nanostructure is prepared by a vacuum thermal evaporation method.
  4. 根据权利要求3所述的金属钨量子点的制备方法，其特征在于：所述氧化钨纳米结构通过在含氧气氛中加热并蒸发钨源，继而在衬底上沉积所得，所述钨源为块材钨。The method for preparing a tungsten metal quantum dot according to claim 3, wherein the tungsten oxide nanostructure is obtained by heating and evaporating a tungsten source in an oxygen-containing atmosphere, followed by deposition on a substrate, wherein the tungsten source is Block tungsten.
  5. 根据权利要求4所述的金属钨量子点的制备方法，其特征在于：所述的氧化钨纳米结构为W18O49纳米线。The method for preparing a metal tungsten quantum dot according to claim 4, wherein the tungsten oxide nanostructure is a W 18 O 49 nanowire.
  6. 根据权利要求1所述的金属钨量子点的制备方法，其特征在于：所述氧化钨纳米结构的尺寸为50-500nm，制得的金属钨量子点的粒径尺寸为1-20nm。The method for preparing a metal tungsten quantum dot according to claim 1, wherein the tungsten oxide nanostructure has a size of 50 to 500 nm, and the obtained metal tungsten quantum dot has a particle size of 1 to 20 nm.
  7. 根据权利要求1所述的金属钨量子点的制备方法，其特征在于：分离氧化钨纳米结构与金属钨量子点的步骤为：将表面生长有金属钨量子点的氧化钨纳米结构投入到溶剂中，再采用超声震荡法分离金属钨量子点与氧化钨纳米结构，然后过滤除去氧化钨纳米结构，得到含有金属钨量子点的溶液，接着烘干除去含有金属钨量子点的溶液中的溶剂，得到金属钨量子点粉体。The method for preparing a tungsten metal quantum dot according to claim 1, wherein the step of separating the tungsten oxide nanostructure and the metal tungsten quantum dot comprises: introducing a tungsten oxide nanostructure having a surface of a tungsten tungsten quantum dot into a solvent. The metal tungsten tungsten quantum dots and the tungsten oxide nanostructures are separated by ultrasonic vibration, and then the tungsten oxide nanostructures are removed by filtration to obtain a solution containing metal tungsten quantum dots, followed by drying to remove the solvent in the solution containing the metal tungsten quantum dots. Metal tungsten quantum dot powder.
  8. 根据权利要求1-7任一项所述的金属钨量子点的制备方法，其特征在于：具体包括以下步骤：The method for preparing a metal tungsten quantum dot according to any one of claims 1 to 7, which comprises the following steps:
    (1)W18O49纳米线的制备：将钨源接入真空热蒸发镀膜机的蒸发电极，再将衬底放置于距离钨源2-100毫米处，然后对真空镀膜腔内抽真空，接着通入流量比为1:100的氧气和惰性气体，再打开热蒸发电源，将钨源从室温加热至1400℃，保温20分钟后，关闭热蒸发电源，使衬底冷却至室温，得到生长在衬底上的W18O49纳米线；(1) Preparation of W 18 O 49 nanowire: the tungsten source is connected to the evaporation electrode of the vacuum thermal evaporation coating machine, and then the substrate is placed at a distance of 2-100 mm from the tungsten source, and then the vacuum coating chamber is evacuated. Then, oxygen and inert gas with a flow ratio of 1:100 were introduced, and then the thermal evaporation power was turned on. The tungsten source was heated from room temperature to 1400 ° C, and after being kept for 20 minutes, the thermal evaporation power was turned off, and the substrate was cooled to room temperature to obtain growth. W 18 O 49 nanowires on a substrate;
    (2)金属钨量子点的制备：中断氧气供给，再对真空镀膜腔内抽真空，然后通入惰性气体，再打开热蒸发电源，将衬底从室温加热至1600℃，在1600℃下进行高温退火处理，处理时间为20分钟，然后关闭热蒸发电源，使衬底冷却至室温，得到生长于W18O49纳米线表面的金属钨量子点； (2) Preparation of metal tungsten quantum dots: interrupt the supply of oxygen, vacuum the vacuum coating chamber, then pass an inert gas, then open the thermal evaporation power source, and heat the substrate from room temperature to 1600 ° C at 1600 ° C. High temperature annealing treatment, the treatment time is 20 minutes, then the thermal evaporation power supply is turned off, and the substrate is cooled to room temperature to obtain metal tungsten quantum dots grown on the surface of the W 18 O 49 nanowire;
    (3)W18O49纳米线与金属钨量子点的分离：将表面生长有金属钨量子点的W18O49纳米线投入到去离子水中，然后利用超声波清洗机进行超声震荡，接着用筛网将W18O49纳米线过滤除去，得到含有金属钨量子点的去离子水；(3) W 18 O 49 nanowires and tungsten quantum dots separated: the input surface of the grown tungsten quantum dots W 18 O 49 nanowires deionized water, and then with an ultrasonic cleaner for ultrasonic vibration, followed by a sieve The mesh removes the W 18 O 49 nanowires to obtain deionized water containing metal tungsten quantum dots;
    (4)金属钨量子点的提取：将含有金属钨量子点的去离子水置于90℃的干燥箱中烘干，待去离子水完全挥发后，得到金属钨量子点粉体。(4) Extraction of metal tungsten quantum dots: Deionized water containing metal tungsten quantum dots is dried in a drying oven at 90 ° C, and after the deionized water is completely evaporated, a metal tungsten quantum dot powder is obtained.
  9. 根据权利要求8所述的金属钨量子点的制备方法，其特征在于：在步骤(2)中，以80℃/分钟的升温速率将衬底从室温加热至1600℃，以100℃/分钟的降温速率使衬底冷却至室温。The method for preparing a metal tungsten quantum dot according to claim 8, wherein in the step (2), the substrate is heated from room temperature to 1600 ° C at a temperature increase rate of 80 ° C / minute, at 100 ° C / min. The rate of cooling cools the substrate to room temperature.
  10. 权利要求1-7或9任一项所述制备方法制得的金属钨量子点。A metal tungsten quantum dot obtained by the production method according to any one of claims 1 to 7.
  11. 权利要求8所述制备方法制得的金属钨量子点。 The metal tungsten quantum dot produced by the preparation method of claim 8.
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