WO2022048262A1 - Metal type molybdenum disulfide quantum dot-modified tin nanotube array composite material and preparation method therefor - Google Patents

Metal type molybdenum disulfide quantum dot-modified tin nanotube array composite material and preparation method therefor Download PDF

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WO2022048262A1
WO2022048262A1 PCT/CN2021/102617 CN2021102617W WO2022048262A1 WO 2022048262 A1 WO2022048262 A1 WO 2022048262A1 CN 2021102617 W CN2021102617 W CN 2021102617W WO 2022048262 A1 WO2022048262 A1 WO 2022048262A1
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mos
type mos
quantum dots
nanotube array
composite material
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王玮
康琪
刘天宇
汪敏
柏寄荣
邓瑶瑶
许�鹏
孙潇楠
张金涛
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常州工学院
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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

Definitions

  • the invention belongs to the technical field of nanomaterial preparation, and in particular relates to a TiN nanotube array composite material decorated with metallic molybdenum disulfide quantum dots and a preparation method thereof.
  • MoS2 has excellent physical and chemical properties, and has important application prospects in the fields of electrocatalysis and biosensing.
  • MoS quantum dots are concerned, due to their small size, large specific surface area, and many active sites at the exposed edges, they exhibit excellent electrocatalytic properties, which can be applied to electrocatalytic hydrogen evolution reactions and highly sensitive sensors.
  • thermodynamically stable MoS 2 is a semiconducting type, and the electrocatalytic performance of semiconducting MoS 2 needs to be further improved because of its weak electron transport ability, while the metal type MoS 2 has good electron transport ability, so the metal type MoS 2 Quantum dots have broader application prospects in the field of electrocatalysis.
  • MoS2 QDs are prone to agglomeration in the dispersed phase medium, which reduces their electrocatalytic performance, thereby limiting their applications.
  • Titanium nitride nanomaterials are materials with good physical and chemical properties, exhibiting thermodynamic stability, good electrical conductivity, and good biocompatibility.
  • the purpose of the present invention is to provide a TiN nanotube array decorated with metallic molybdenum disulfide quantum dots
  • the composite material and the preparation method thereof are simple in process and convenient for industrial production.
  • a preparation method of a TiN nanotube array composite material decorated with metallic MoS2 quantum dots specifically comprising the following steps:
  • step (3) (4) placing the TiN nanotube array in the solution of metallic MoS 2 quantum dots described in step (3), and then performing ultrasonic treatment, soaking and drying in sequence to obtain a composite of TiN nanotube arrays decorated with metallic MoS 2 quantum dots Material.
  • the manual grinding method in step (1) is specifically: placing the semiconductor - type MoS block in ethanol or isopropanol to obtain a mixed solution, and then placing the mixed solution in an agate mortar , manually grind for 60 min, and after ethanol or isopropanol evaporates, and after natural drying, semiconductor-type MoS 2 powder is obtained.
  • the size of the semiconductor-type MoS 2 bulk is 6 ⁇ m, and the size of the semiconductor-type MoS 2 powder is ⁇ 1 ⁇ m;
  • the addition amount of the ethanol or isopropanol is based on the mass concentration of the semiconductor-type MoS 2 block in the mixed solution being 100 mg/mL.
  • the water content and oxygen content in the glove box of the anhydrous and oxygen-free environment in step (2) are both less than 1 ppm, and the inert gas is one or more of nitrogen, argon and helium, and the inert gas The purity is 99.99%.
  • the butyllithium solution in step (2) is a n-hexane solution of butyllithium, the molar concentration of the butyllithium in the butyllithium solution is 2.5 mol/L, and the butyllithium solution is The amount of butyllithium used is based on the volume of butyllithium, and the volume-to-mass ratio of the butyllithium to the semiconducting MoS 2 powder is 500 ⁇ L: 20 mg.
  • the solvent in step (3) is deionized water or ethanol
  • the mass-volume ratio of the semiconductor-type MoS 2 powder to the solvent is (10-30) mg:20 mL
  • the ultrasonic treatment time is 30 min.
  • the number of times of centrifugation described in step (3) is 3 times, and the specific operations are: firstly centrifuge at 600rpm for 10min, take a supernatant; then carry out the first supernatant at 10000rpm Centrifugal separation to take the secondary supernatant; finally, the secondary supernatant is further purified and centrifuged at a rotational speed of 15000 rpm, and the obtained supernatant is a metallic MoS 2 quantum dot solution.
  • the size of the metal-type MoS 2 quantum dots is 3-10 nm.
  • the mass concentration of the metal-type MoS 2 quantum dots in the metal-type MoS 2 quantum dot solution is 0.5-1.5 mg/mL
  • the ultrasonic treatment time is 10s
  • the soaking time is 2min
  • the drying is 60min in an oven with a temperature of 60°C.
  • Another object of the present invention is to provide a TiN nanotube array composite material decorated with metallic MoS 2 quantum dots prepared by the method.
  • the quantum dots are loaded on the outer and inner surfaces of TiN nanotubes, and the TiN nanotubes have an outer diameter of 60-90 nm and an inner diameter of 20-30 nm.
  • the semiconductor-type MoS 2 powder is first processed into metal-type MoS 2 quantum dots by lithium intercalation treatment, and then ultrasonic treatment, soaking and drying are performed to obtain the TiN nanotube array composite modified by the metal-type MoS 2 quantum dots
  • the material and the preparation process are simple and feasible, and have wide practical application value and industrial production prospect.
  • the semiconductor-type MoS 2 is processed into metal-type MoS 2 quantum dots, which improves the electron transport capability, thereby improving the electrocatalytic performance; on the other hand, the metal-type MoS 2 quantum dots are compounded in TiN nanotubes On the outer and inner surfaces of the array, nanocomposites with stable structure and excellent performance are obtained, which have both the electrocatalytic properties of metal - type MoS2 quantum dots and the thermodynamic stability and good electrical conductivity of titanium nitride nanotube arrays.
  • the problem of easy agglomeration of MoS 2 quantum dots makes the TiN nanotube array composites decorated with metallic MoS 2 quantum dots expected to be used in enzyme-free hydrogen peroxide electrochemical sensors.
  • FIG. 1 is a schematic structural diagram of the TiN nanotube array composite material decorated with metallic MoS 2 quantum dots of the present invention.
  • a preparation method of a TiN nanotube array composite material decorated with metallic MoS2 quantum dots specifically comprising the following steps:
  • the manual grinding method is used to grind, and the semiconductor-type MoS 2 block with a size of 6 ⁇ m is placed in ethanol or isopropanol to obtain a mixed solution with a mass concentration of 100 mg/mL, Then the mixed solution is placed in an agate mortar, manually ground for 60 min, and after ethanol or isopropanol is evaporated and naturally dried, a semiconductor - type MoS powder with a size of less than 1 ⁇ m is obtained;
  • TiN nanotube array material is placed in the metal-type MoS 2 quantum dot solution described in step (3), and then ultrasonically treated for 10s at room temperature, soaked for 2min, and dried in an oven at 60°C for 60min to obtain metal-type MoS2 quantum dots.
  • the TiN nanotube array composite material decorated with metallic MoS 2 quantum dots prepared in this example wherein the TiN nanotubes are vertically grown on the Ti sheet substrate, and the metallic MoS 2 quantum dots are supported on TiN
  • the outer surface and inner surface of the nanotube are described, the outer diameter of the TiN nanotube is 60-90 nm, and the inner diameter is 20-30 nm.
  • a preparation method of a TiN nanotube array composite material decorated with metallic MoS2 quantum dots specifically comprising the following steps:
  • the manual grinding method is used to grind, and the semiconductor-type MoS 2 block with a size of 6 ⁇ m is placed in ethanol or isopropanol to obtain a mixed solution with a mass concentration of 100 mg/mL, Then the mixed solution is placed in an agate mortar, manually ground for 60 min, and after ethanol or isopropanol is evaporated and naturally dried, a semiconductor - type MoS powder with a size of less than 1 ⁇ m is obtained;
  • TiN nanotube array material is placed in the metal-type MoS 2 quantum dot solution described in step (3), and then ultrasonically treated for 10s at room temperature, soaked for 2min, and dried in an oven at 60°C for 60min to obtain metal-type MoS2 quantum dots.
  • the TiN nanotube array composite material decorated with metallic MoS 2 quantum dots prepared in this example wherein the TiN nanotubes are vertically grown on the Ti sheet substrate, and the metallic MoS 2 quantum dots are supported on TiN
  • the outer surface and inner surface of the nanotube are described, the outer diameter of the TiN nanotube is 60-90 nm, and the inner diameter is 20-30 nm.
  • a preparation method of a TiN nanotube array composite material decorated with metallic MoS2 quantum dots specifically comprising the following steps:
  • the manual grinding method is used to grind, and the semiconductor-type MoS 2 block with a size of 6 ⁇ m is placed in ethanol or isopropanol to obtain a mixed solution with a mass concentration of 100 mg/mL, Then the mixed solution is placed in an agate mortar, manually ground for 60 min, and after ethanol or isopropanol is evaporated and naturally dried, a semiconductor - type MoS powder with a size of less than 1 ⁇ m is obtained;
  • TiN nanotube array material is placed in the metal-type MoS 2 quantum dot solution described in step (3), and then ultrasonically treated for 10s at room temperature, soaked for 2min, and dried in an oven at 60°C for 60min to obtain metal-type MoS2 quantum dots.
  • the TiN nanotube array composite material decorated with metallic MoS 2 quantum dots prepared in this example wherein the TiN nanotubes are vertically grown on the Ti sheet substrate, and the metallic MoS 2 quantum dots are supported on TiN
  • the outer surface and inner surface of the nanotube are described, the outer diameter of the TiN nanotube is 60-90 nm, and the inner diameter is 20-30 nm.

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Abstract

The present invention relates to the technical field of preparation of nanomaterials, and in particular, to a metal type molybdenum disulfide quantum dot-modified TiN nanotube array composite material and a preparation method therefor. The preparation method comprises: (1) using a manual grinding method to grind a large-size semiconductor MoS2 block to obtain the semiconductor MoS2 powder; (2) performing lithium intercalation treatment on the semiconductor MoS2 powder; (3) dispersing the semiconductor MoS2 powder subjected to the lithium intercalation treatment into a solvent, performing ultrasonic treatment, and performing centrifugal separation to obtain a metal type MoS2 quantum dot solution; (4) placing a TiN nanotube array into the metal type MoS2 quantum dot solution, and then sequentially performing ultrasonic treatment, immersing same, and drying same to obtain the metal type MoS2 quantum dot-modified TiN nanotube array composite material. The metal type MoS2 quantum dot-modified TiN nanotube array composite material of the present invention has excellent electrocatalytic performance and stability.

Description

一种金属型二硫化钼量子点修饰的TiN纳米管阵列复合材料及其制备方法A metallic molybdenum disulfide quantum dot-modified TiN nanotube array composite material and preparation method thereof 技术领域technical field
本发明属于纳米材料制备的技术领域，具体涉及一种金属型二硫化钼量子点修饰的TiN纳米管阵列复合材料及其制备方法。The invention belongs to the technical field of nanomaterial preparation, and in particular relates to a TiN nanotube array composite material decorated with metallic molybdenum disulfide quantum dots and a preparation method thereof.
背景技术Background technique
MoS 2具有优良的物理化学性能，在电催化以及生物传感等领域具有重要的应用前景。MoS 2的尺寸和形貌调控以及相应的物理化学性质，近年来成为材料科学以及相关领域的研究热点。就MoS 2量子点而言，因其具有尺寸小、比表面积大、暴露边缘活动位点多等特点，从而表现出优异的电催化性能，可以应用于电催化析氢反应以及高灵敏性传感器。然而，热力学稳定的MoS 2为半导体型，而半导体型MoS 2因为其电子传输能力较弱，其电催化性能还有待进一步提升，而金属型MoS 2具有良好的电子传输能力，因此金属型MoS 2量子点在电催化领域具有更为广阔的应用前景。另一方面，MoS 2量子点在分散相介质中很容易发生团聚而使其电催化性能降低，进而使其应用受限。氮化钛纳米材料是一种具有良好的物理化学特性的材料，表现出热力学稳定性、良好的导电性以及良好的生物相容性等。 MoS2 has excellent physical and chemical properties, and has important application prospects in the fields of electrocatalysis and biosensing. The regulation of size and morphology of MoS2, as well as the corresponding physical and chemical properties, has become a research hotspot in materials science and related fields in recent years. As far as MoS quantum dots are concerned, due to their small size, large specific surface area, and many active sites at the exposed edges, they exhibit excellent electrocatalytic properties, which can be applied to electrocatalytic hydrogen evolution reactions and highly sensitive sensors. However, thermodynamically stable MoS 2 is a semiconducting type, and the electrocatalytic performance of semiconducting MoS 2 needs to be further improved because of its weak electron transport ability, while the metal type MoS 2 has good electron transport ability, so the metal type MoS 2 Quantum dots have broader application prospects in the field of electrocatalysis. On the other hand, MoS2 QDs are prone to agglomeration in the dispersed phase medium, which reduces their electrocatalytic performance, thereby limiting their applications. Titanium nitride nanomaterials are materials with good physical and chemical properties, exhibiting thermodynamic stability, good electrical conductivity, and good biocompatibility.
发明内容SUMMARY OF THE INVENTION
为了解决现有技术存在MoS 2量子点在分散相介质中很容易发生团聚而使其电催化性能降低的缺陷，本发明的目的在于提供一种金属 型二硫化钼量子点修饰的TiN纳米管阵列复合材料及其工艺简单、便于工业生产的制备方法。 In order to solve the defect in the prior art that MoS 2 quantum dots are easily agglomerated in a dispersed phase medium and their electrocatalytic performance is reduced, the purpose of the present invention is to provide a TiN nanotube array decorated with metallic molybdenum disulfide quantum dots The composite material and the preparation method thereof are simple in process and convenient for industrial production.
本发明是通过如下技术方案实现的：The present invention is achieved through the following technical solutions:
一种金属型MoS 2量子点修饰的TiN纳米管阵列复合材料的制备方法，具体包括如下步骤： A preparation method of a TiN nanotube array composite material decorated with metallic MoS2 quantum dots, specifically comprising the following steps:
(1)以半导体型MoS 2块体为原料，采用手动研磨法研磨，得到半导体型MoS 2粉末； (1) take semiconductor type MoS 2 block as raw material, adopt manual grinding method to grind, obtain semiconductor type MoS 2 powder;
(2)在无水无氧环境的手套箱中，以惰性气体为保护气体，采用丁基锂溶液对所述半导体型MoS 2粉末进行锂插层处理； (2) in a glove box in an anhydrous and oxygen-free environment, using an inert gas as a protective gas, a butyllithium solution is used to carry out lithium intercalation treatment on the semiconductor - type MoS powder;
(3)将锂插层处理后的半导体型MoS 2粉末分散在溶剂中，随后进行超声处理，得到剥离后的MoS 2-溶剂混合物，然后进行离心分离，得到金属型MoS 2量子点溶液； (3) dispersing the semiconductor-type MoS 2 powder after lithium intercalation treatment in a solvent, and then performing ultrasonic treatment to obtain a peeled MoS 2 -solvent mixture, and then performing centrifugal separation to obtain a metal-type MoS 2 quantum dot solution;
(4)将TiN纳米管阵列置于步骤(3)中所述金属型MoS 2量子点溶液中，然后依次进行超声处理、浸泡、干燥，得金属型MoS 2量子点修饰的TiN纳米管阵列复合材料。 (4) placing the TiN nanotube array in the solution of metallic MoS 2 quantum dots described in step (3), and then performing ultrasonic treatment, soaking and drying in sequence to obtain a composite of TiN nanotube arrays decorated with metallic MoS 2 quantum dots Material.
优选地，步骤(1)中所述手动研磨法具体为：将所述半导体型MoS 2块体置于乙醇或异丙醇中，得到混合液，然后将所述混合液置于玛瑙研钵中，手动研磨60min，待乙醇或异丙醇蒸发，自然干燥后，得到半导体型MoS 2粉末。 Preferably, the manual grinding method in step (1) is specifically: placing the semiconductor - type MoS block in ethanol or isopropanol to obtain a mixed solution, and then placing the mixed solution in an agate mortar , manually grind for 60 min, and after ethanol or isopropanol evaporates, and after natural drying, semiconductor-type MoS 2 powder is obtained.
优选地，所述半导体型MoS 2块体的尺寸为6μm，所述半导体型MoS 2粉末的尺寸为＜1μm； Preferably, the size of the semiconductor-type MoS 2 bulk is 6 μm, and the size of the semiconductor-type MoS 2 powder is <1 μm;
所述乙醇或异丙醇的加入量以所述半导体型MoS 2块体在混合液中的质量浓度为100mg/mL为准。 The addition amount of the ethanol or isopropanol is based on the mass concentration of the semiconductor-type MoS 2 block in the mixed solution being 100 mg/mL.
优选地，步骤(2)中所述无水无氧环境的手套箱中水含量和氧含量均小于1ppm，所述惰性气体为氮气、氩气和氦气中的一种或多种，惰性气体的纯度为99.99％。Preferably, the water content and oxygen content in the glove box of the anhydrous and oxygen-free environment in step (2) are both less than 1 ppm, and the inert gas is one or more of nitrogen, argon and helium, and the inert gas The purity is 99.99%.
优选地，步骤(2)中所述丁基锂溶液为丁基锂的正己烷溶液，所述丁基锂溶液中所述丁基锂的摩尔浓度为2.5mol/L，所述丁基锂溶液的用量以丁基锂的体积计，所述丁基锂与半导体型MoS 2粉末的体积质量比为500μL:20mg。 Preferably, the butyllithium solution in step (2) is a n-hexane solution of butyllithium, the molar concentration of the butyllithium in the butyllithium solution is 2.5 mol/L, and the butyllithium solution is The amount of butyllithium used is based on the volume of butyllithium, and the volume-to-mass ratio of the butyllithium to the semiconducting MoS 2 powder is 500 μL: 20 mg.
优选地，步骤(3)中所述溶剂为去离子水或乙醇，所述半导体型MoS 2粉末与溶剂的质量体积比为(10-30)mg:20mL，所述超声处理的时间为30min。 Preferably, the solvent in step (3) is deionized water or ethanol, the mass-volume ratio of the semiconductor-type MoS 2 powder to the solvent is (10-30) mg:20 mL, and the ultrasonic treatment time is 30 min.
优选地，步骤(3)中所述离心分离的次数为3此，具体操作为：首先采用600rpm的转速进行离心10min，取一次上清液；然后将所述一次上清液在10000rpm转速下进行离心分离，取二次上清液；最后将所述二次上清液在15000rpm转速下进行进一步纯化离心分离，得到的上清液为金属型MoS 2量子点溶液。 Preferably, the number of times of centrifugation described in step (3) is 3 times, and the specific operations are: firstly centrifuge at 600rpm for 10min, take a supernatant; then carry out the first supernatant at 10000rpm Centrifugal separation to take the secondary supernatant; finally, the secondary supernatant is further purified and centrifuged at a rotational speed of 15000 rpm, and the obtained supernatant is a metallic MoS 2 quantum dot solution.
优选地，所述金属型MoS 2量子点的尺寸为3-10nm。 Preferably, the size of the metal-type MoS 2 quantum dots is 3-10 nm.
优选地，步骤(4)中所述金属型MoS 2量子点溶液中金属型MoS 2量子点的质量浓度为0.5-1.5mg/mL，所述超声处理的时间为10s，所述浸泡的时间为2min，所述干燥为在温度60℃的烘箱中干燥60min。 Preferably, in the step (4), the mass concentration of the metal-type MoS 2 quantum dots in the metal-type MoS 2 quantum dot solution is 0.5-1.5 mg/mL, the ultrasonic treatment time is 10s, and the soaking time is 2min, and the drying is 60min in an oven with a temperature of 60°C.
本发明的目的还在于提供一种所述的方法制备的金属型MoS 2量子点修饰的TiN纳米管阵列复合材料，具体地，TiN纳米管垂直生长在Ti片基底上，所述金属型MoS 2量子点负载在TiN纳米管的外表面和内表面所述，所述TiN纳米管的外直径为60-90nm，内直径为20-30nm。 Another object of the present invention is to provide a TiN nanotube array composite material decorated with metallic MoS 2 quantum dots prepared by the method. The quantum dots are loaded on the outer and inner surfaces of TiN nanotubes, and the TiN nanotubes have an outer diameter of 60-90 nm and an inner diameter of 20-30 nm.
与现有技术相比，本发明的有益效果是：Compared with the prior art, the beneficial effects of the present invention are:
(1)本发明首先通过锂插层处理，将半导体型MoS 2粉末处理成金属型MoS 2量子点，然后通过超声处理、浸泡、干燥，得到金属型MoS 2量子点修饰的TiN纳米管阵列复合材料，制备工艺简单可行，具有广泛的实际应用价值与工业生产前景。 (1) In the present invention, the semiconductor-type MoS 2 powder is first processed into metal-type MoS 2 quantum dots by lithium intercalation treatment, and then ultrasonic treatment, soaking and drying are performed to obtain the TiN nanotube array composite modified by the metal-type MoS 2 quantum dots The material and the preparation process are simple and feasible, and have wide practical application value and industrial production prospect.
(2)本发明将半导体型MoS 2处理成金属型MoS 2量子点，提高了电其子传输能力，进而提升了电催化性能；另一方面，将金属型MoS 2量子点复合在TiN纳米管阵列的外表面和内表面，得到结构稳定和性能优良的纳米复合材料，兼备金属型MoS 2量子点的电催化性能和氮化钛纳米管阵列的热力学稳定和良好的导电性能，且解决了单一MoS 2量子点的易团聚的问题，使得金属型MoS 2量子点修饰的TiN纳米管阵列复合材料有望应用于无酶过氧化氢电化学传感器中。 (2) In the present invention, the semiconductor-type MoS 2 is processed into metal-type MoS 2 quantum dots, which improves the electron transport capability, thereby improving the electrocatalytic performance; on the other hand, the metal-type MoS 2 quantum dots are compounded in TiN nanotubes On the outer and inner surfaces of the array, nanocomposites with stable structure and excellent performance are obtained, which have both the electrocatalytic properties of metal - type MoS2 quantum dots and the thermodynamic stability and good electrical conductivity of titanium nitride nanotube arrays. The problem of easy agglomeration of MoS 2 quantum dots makes the TiN nanotube array composites decorated with metallic MoS 2 quantum dots expected to be used in enzyme-free hydrogen peroxide electrochemical sensors.
附图说明Description of drawings
图1为本发明的金属型MoS 2量子点修饰的TiN纳米管阵列复合材料的结构示意图。 FIG. 1 is a schematic structural diagram of the TiN nanotube array composite material decorated with metallic MoS 2 quantum dots of the present invention.
具体实施方式detailed description
下面将结合本发明实施例中的附图，对本发明实施例中的技术方 案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。以下对至少一个示例性实施例的描述实际上仅仅是说明性的，决不作为对本发明及其应用或使用的任何限制。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
除非另外具体说明，否则在这些实施例中阐述的数值不限制本发明的范围。对于相关领域普通技术人员已知的技术、方法可能不作详细讨论，但在适当情况下，所述技术、方法应当被视为说明书的一部分。在这里示出和讨论的所有示例中，任何具体值应被解释为仅仅是示例性的，而不是作为限制。因此，示例性实施例的其它示例可以具有不同的值。Unless specifically stated otherwise, the numerical values set forth in these examples do not limit the scope of the invention. Techniques and methods known to those of ordinary skill in the relevant art may not be discussed in detail, but where appropriate, the techniques and methods should be considered as part of the specification. In all examples shown and discussed herein, any specific value should be construed as illustrative only and not as limiting. Accordingly, other examples of exemplary embodiments may have different values.
实施例1Example 1
一种金属型MoS 2量子点修饰的TiN纳米管阵列复合材料的制备方法，具体包括如下步骤： A preparation method of a TiN nanotube array composite material decorated with metallic MoS2 quantum dots, specifically comprising the following steps:
(1)以半导体型MoS 2块体为原料，采用手动研磨法研磨，将尺寸为6μm的半导体型MoS 2块体置于乙醇或异丙醇中，得到质量浓度为100mg/mL的混合液，然后将所述混合液置于玛瑙研钵中，手动研磨60min，待乙醇或异丙醇蒸发，自然干燥后，得到尺寸为小于1μm的半导体型MoS 2粉末； (1) Using the semiconductor-type MoS 2 block as a raw material, the manual grinding method is used to grind, and the semiconductor-type MoS 2 block with a size of 6 μm is placed in ethanol or isopropanol to obtain a mixed solution with a mass concentration of 100 mg/mL, Then the mixed solution is placed in an agate mortar, manually ground for 60 min, and after ethanol or isopropanol is evaporated and naturally dried, a semiconductor - type MoS powder with a size of less than 1 μm is obtained;
(2)在水含量和氧含量均小于1ppm的无水无氧环境的手套箱中，以惰性气体(纯度为99.99％的氮气)为保护气体，采用丁基锂摩尔浓度为2.5mol/L的丁基锂溶液对所述半导体型MoS 2粉末在室温 环境下浸泡进行锂插层处理，所述丁基锂与半导体型MoS 2粉末的体积质量比为500μL:20mg； (2) In the glove box of anhydrous and oxygen-free environment with water content and oxygen content less than 1ppm, use inert gas (nitrogen with a purity of 99.99%) as protective gas, and use butyllithium molar concentration of 2.5mol/L. The semiconductor-type MoS 2 powder is immersed in a butyllithium solution to perform lithium intercalation treatment at room temperature, and the volume-to-mass ratio of the butyllithium to the semiconductor-type MoS 2 powder is 500 μL: 20 mg;
(3)将锂插层处理后的半导体型MoS 2粉末20mg分散在20mL去离子水中，随后进行超声处理30min，得到剥离后的MoS 2-溶剂混合物，然后对剥离后的MoS 2-溶剂混合物进行离心分离：首先采用600rpm的转速进行离心10min，取一次上清液；然后将所述一次上清液在10000rpm转速下进行离心分离，取二次上清液；最后将所述二次上清液在15000rpm转速下进行进一步纯化离心分离，得到的上清液为质量浓度1mg/mL的金属型MoS 2量子点溶液，所述金属型MoS 2量子点的尺寸为3-10nm； (3) Disperse 20 mg of the semiconductor-type MoS 2 powder after lithium intercalation treatment in 20 mL of deionized water, and then perform ultrasonic treatment for 30 min to obtain the exfoliated MoS 2 -solvent mixture, and then the exfoliated MoS 2 -solvent mixture was subjected to Centrifugation: firstly centrifuge at 600rpm for 10min, and take a supernatant; then centrifuge the first supernatant at 10,000rpm, and take a secondary supernatant; finally, use the secondary supernatant Carry out further purification and centrifugal separation at 15000rpm rotating speed, and the obtained supernatant is a metal-type MoS 2 quantum dot solution with a mass concentration of 1 mg/mL, and the size of the metal-type MoS 2 quantum dots is 3-10nm;
(4)TiN纳米管阵列材料置于步骤(3)中所述金属型MoS 2量子点溶液中，然后室温环境下依次进行超声处理10s、浸泡2min、60℃的烘箱中干燥60min，得金属型MoS 2量子点修饰的TiN纳米管阵列复合材料。 (4) The TiN nanotube array material is placed in the metal-type MoS 2 quantum dot solution described in step (3), and then ultrasonically treated for 10s at room temperature, soaked for 2min, and dried in an oven at 60°C for 60min to obtain metal-type MoS2 quantum dots. TiN nanotube array composites decorated with MoS quantum dots.
如图1所示，本实施例制备的金属型MoS 2量子点修饰的TiN纳米管阵列复合材料，其中，TiN纳米管垂直生长在Ti片基底上，所述金属型MoS 2量子点负载在TiN纳米管的外表面和内表面所述，所述TiN纳米管的外直径为60-90nm，内直径为20-30nm。 As shown in FIG. 1 , the TiN nanotube array composite material decorated with metallic MoS 2 quantum dots prepared in this example, wherein the TiN nanotubes are vertically grown on the Ti sheet substrate, and the metallic MoS 2 quantum dots are supported on TiN The outer surface and inner surface of the nanotube are described, the outer diameter of the TiN nanotube is 60-90 nm, and the inner diameter is 20-30 nm.
实施例2Example 2
一种金属型MoS 2量子点修饰的TiN纳米管阵列复合材料的制备方法，具体包括如下步骤： A preparation method of a TiN nanotube array composite material decorated with metallic MoS2 quantum dots, specifically comprising the following steps:
(1)以半导体型MoS 2块体为原料，采用手动研磨法研磨，将尺寸为6μm的半导体型MoS 2块体置于乙醇或异丙醇中，得到质量浓度为100mg/mL的混合液，然后将所述混合液置于玛瑙研钵中，手动研磨60min，待乙醇或异丙醇蒸发，自然干燥后，得到尺寸为小于1μm的半导体型MoS 2粉末； (1) Using the semiconductor-type MoS 2 block as a raw material, the manual grinding method is used to grind, and the semiconductor-type MoS 2 block with a size of 6 μm is placed in ethanol or isopropanol to obtain a mixed solution with a mass concentration of 100 mg/mL, Then the mixed solution is placed in an agate mortar, manually ground for 60 min, and after ethanol or isopropanol is evaporated and naturally dried, a semiconductor - type MoS powder with a size of less than 1 μm is obtained;
(2)在水含量和氧含量均小于1ppm的无水无氧环境的手套箱中，以惰性气体(纯度为99.99％的氩气)为保护气体，采用丁基锂摩尔浓度为2.5mol/L的丁基锂溶液对所述半导体型MoS 2粉末在室温环境下浸泡进行锂插层处理，所述丁基锂与半导体型MoS 2粉末的体积质量比为500μL:20mg； (2) In a glove box in an anhydrous and oxygen-free environment with both water content and oxygen content less than 1 ppm, use an inert gas (argon with a purity of 99.99%) as the protective gas, and the molar concentration of butyllithium is 2.5 mol/L. The semiconducting MoS 2 powder is immersed in a room temperature environment to perform lithium intercalation treatment, and the volume-to-mass ratio of the butyl lithium and the semiconducting MoS 2 powder is 500 μL: 20 mg;
(3)将锂插层处理后的半导体型MoS 2粉末10mg分散在20mL去离子水中，随后进行超声处理30min，得到剥离后的MoS 2-溶剂混合物，然后对剥离后的MoS 2-溶剂混合物进行离心分离：首先采用600rpm的转速进行离心10min，取一次上清液；然后将所述一次上清液在10000rpm转速下进行离心分离，取二次上清液；最后将所述二次上清液在15000rpm转速下进行进一步纯化离心分离，得到的上清液为质量浓度0.5mg/mL的金属型MoS 2量子点溶液，所述金属型MoS 2量子点的尺寸为3-10nm； (3) Disperse 10 mg of the semiconductor-type MoS 2 powder after lithium intercalation treatment in 20 mL of deionized water, and then perform ultrasonic treatment for 30 min to obtain the exfoliated MoS 2 -solvent mixture, and then the exfoliated MoS 2 -solvent mixture was subjected to Centrifugation: firstly centrifuge at 600rpm for 10min, and take a supernatant; then centrifuge the first supernatant at 10,000rpm, and take a secondary supernatant; finally, use the secondary supernatant Carry out further purification and centrifugal separation at 15000rpm rotating speed, and the obtained supernatant is a solution of metallic MoS 2 quantum dots with a mass concentration of 0.5 mg/mL, and the size of the metallic MoS 2 quantum dots is 3-10 nm;
(4)TiN纳米管阵列材料置于步骤(3)中所述金属型MoS 2量子点溶液中，然后室温环境下依次进行超声处理10s、浸泡2min、60℃的烘箱中干燥60min，得金属型MoS 2量子点修饰的TiN纳米管阵列复合材料。 (4) The TiN nanotube array material is placed in the metal-type MoS 2 quantum dot solution described in step (3), and then ultrasonically treated for 10s at room temperature, soaked for 2min, and dried in an oven at 60°C for 60min to obtain metal-type MoS2 quantum dots. TiN nanotube array composites decorated with MoS quantum dots.
如图1所示，本实施例制备的金属型MoS 2量子点修饰的TiN纳米管阵列复合材料，其中，TiN纳米管垂直生长在Ti片基底上，所述金属型MoS 2量子点负载在TiN纳米管的外表面和内表面所述，所述TiN纳米管的外直径为60-90nm，内直径为20-30nm。 As shown in FIG. 1 , the TiN nanotube array composite material decorated with metallic MoS 2 quantum dots prepared in this example, wherein the TiN nanotubes are vertically grown on the Ti sheet substrate, and the metallic MoS 2 quantum dots are supported on TiN The outer surface and inner surface of the nanotube are described, the outer diameter of the TiN nanotube is 60-90 nm, and the inner diameter is 20-30 nm.
实施例3Example 3
一种金属型MoS 2量子点修饰的TiN纳米管阵列复合材料的制备方法，具体包括如下步骤： A preparation method of a TiN nanotube array composite material decorated with metallic MoS2 quantum dots, specifically comprising the following steps:
(1)以半导体型MoS 2块体为原料，采用手动研磨法研磨，将尺寸为6μm的半导体型MoS 2块体置于乙醇或异丙醇中，得到质量浓度为100mg/mL的混合液，然后将所述混合液置于玛瑙研钵中，手动研磨60min，待乙醇或异丙醇蒸发，自然干燥后，得到尺寸为小于1μm的半导体型MoS 2粉末； (1) Using the semiconductor-type MoS 2 block as a raw material, the manual grinding method is used to grind, and the semiconductor-type MoS 2 block with a size of 6 μm is placed in ethanol or isopropanol to obtain a mixed solution with a mass concentration of 100 mg/mL, Then the mixed solution is placed in an agate mortar, manually ground for 60 min, and after ethanol or isopropanol is evaporated and naturally dried, a semiconductor - type MoS powder with a size of less than 1 μm is obtained;
(2)在水含量和氧含量均小于1ppm的无水无氧环境的手套箱中，以惰性气体(纯度为99.99％的氮气)为保护气体，采用丁基锂摩尔浓度为2.5mol/L的丁基锂溶液对所述半导体型MoS 2粉末在室温环境下浸泡进行锂插层处理，所述丁基锂与半导体型MoS 2粉末的体积质量比为500μL:20mg； (2) In the glove box of anhydrous and oxygen-free environment with water content and oxygen content less than 1ppm, use inert gas (nitrogen with a purity of 99.99%) as protective gas, and use butyllithium molar concentration of 2.5mol/L. The semiconductor-type MoS 2 powder is immersed in a butyllithium solution to perform lithium intercalation treatment at room temperature, and the volume-to-mass ratio of the butyllithium to the semiconductor-type MoS 2 powder is 500 μL: 20 mg;
(3)将锂插层处理后的半导体型MoS 2粉末30mg分散在20mL去离子水中，随后进行超声处理30min，得到剥离后的MoS 2-溶剂混合物，然后对剥离后的MoS 2-溶剂混合物进行离心分离：首先采用600rpm的转速进行离心10min，取一次上清液；然后将所述一次上清液在10000rpm转速下进行离心分离，取二次上清液；最后将所述 二次上清液在15000rpm转速下进行进一步纯化离心分离，得到的上清液为质量浓度1.5mg/mL的金属型MoS 2量子点溶液，所述金属型MoS 2量子点的尺寸为3-10nm； (3) Disperse 30 mg of the semiconductor-type MoS 2 powder after lithium intercalation treatment in 20 mL of deionized water, and then perform ultrasonic treatment for 30 min to obtain the exfoliated MoS 2 -solvent mixture, and then the exfoliated MoS 2 -solvent mixture was subjected to Centrifugation: firstly centrifuge at 600rpm for 10min, and take a supernatant; then centrifuge the first supernatant at 10,000rpm, and take a secondary supernatant; finally, use the secondary supernatant Carry out further purification and centrifugal separation at 15000rpm rotating speed, and the obtained supernatant is a metal-type MoS 2 quantum dot solution with a mass concentration of 1.5 mg/mL, and the size of the metal-type MoS 2 quantum dots is 3-10nm;
(4)TiN纳米管阵列材料置于步骤(3)中所述金属型MoS 2量子点溶液中，然后室温环境下依次进行超声处理10s、浸泡2min、60℃的烘箱中干燥60min，得金属型MoS 2量子点修饰的TiN纳米管阵列复合材料。 (4) The TiN nanotube array material is placed in the metal-type MoS 2 quantum dot solution described in step (3), and then ultrasonically treated for 10s at room temperature, soaked for 2min, and dried in an oven at 60°C for 60min to obtain metal-type MoS2 quantum dots. TiN nanotube array composites decorated with MoS quantum dots.
如图1所示，本实施例制备的金属型MoS 2量子点修饰的TiN纳米管阵列复合材料，其中，TiN纳米管垂直生长在Ti片基底上，所述金属型MoS 2量子点负载在TiN纳米管的外表面和内表面所述，所述TiN纳米管的外直径为60-90nm，内直径为20-30nm。 As shown in FIG. 1 , the TiN nanotube array composite material decorated with metallic MoS 2 quantum dots prepared in this example, wherein the TiN nanotubes are vertically grown on the Ti sheet substrate, and the metallic MoS 2 quantum dots are supported on TiN The outer surface and inner surface of the nanotube are described, the outer diameter of the TiN nanotube is 60-90 nm, and the inner diameter is 20-30 nm.
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。The above description is only a preferred embodiment of the present invention, but the protection scope of the present invention is not limited to this. The equivalent replacement or change of the inventive concept thereof shall be included within the protection scope of the present invention.

Claims (10)

  1. 一种金属型MoS 2量子点修饰的TiN纳米管阵列复合材料的制备方法，其特征在于，包括如下步骤： A preparation method of a TiN nanotube array composite material decorated with metallic MoS2 quantum dots is characterized in that, comprising the following steps:
    (1)以半导体型MoS 2块体为原料，采用手动研磨法研磨，得到半导体型MoS 2粉末； (1) take semiconductor type MoS 2 block as raw material, adopt manual grinding method to grind, obtain semiconductor type MoS 2 powder;
    (2)在无水无氧环境的手套箱中，以惰性气体为保护气体，采用丁基锂溶液对所述半导体型MoS 2粉末进行锂插层处理； (2) in a glove box in an anhydrous and oxygen-free environment, using an inert gas as a protective gas, a butyllithium solution is used to carry out lithium intercalation treatment on the semiconductor - type MoS powder;
    (3)将锂插层处理后的半导体型MoS 2粉末分散在溶剂中，随后进行超声处理，得到剥离后的MoS 2-溶剂混合物，然后进行离心分离，得到金属型MoS 2量子点溶液； (3) dispersing the semiconductor-type MoS 2 powder after lithium intercalation treatment in a solvent, and then performing ultrasonic treatment to obtain a peeled MoS 2 -solvent mixture, and then performing centrifugal separation to obtain a metal-type MoS 2 quantum dot solution;
    (4)将TiN纳米管阵列置于步骤(3)中所述金属型MoS 2量子点溶液中，然后依次进行超声处理、浸泡、干燥，得金属型MoS 2量子点修饰的TiN纳米管阵列复合材料。 (4) placing the TiN nanotube array in the solution of metallic MoS 2 quantum dots described in step (3), and then performing ultrasonic treatment, soaking and drying in sequence to obtain a composite of TiN nanotube arrays decorated with metallic MoS 2 quantum dots Material.
  2. 根据权利要求1所述的一种金属型MoS 2量子点修饰的TiN纳米管阵列复合材料的制备方法，其特征在于，步骤(1)中所述手动研磨法具体为：将所述半导体型MoS 2块体置于乙醇或异丙醇中，得到混合液，然后将所述混合液置于玛瑙研钵中，手动研磨60min，待乙醇或异丙醇蒸发，自然干燥后，得到半导体型MoS 2粉末。 The method for preparing a TiN nanotube array composite material decorated with metal-type MoS quantum dots according to claim 1 , wherein the manual grinding method in step (1) is specifically: the semiconductor-type MoS 2 blocks are placed in ethanol or isopropanol to obtain a mixed solution, then the mixed solution is placed in an agate mortar, manually ground for 60 min, and after the ethanol or isopropanol is evaporated and naturally dried, semiconductor - type MoS is obtained. powder.
  3. 根据权利要求2所述的一种金属型MoS 2量子点修饰的TiN纳米管阵列复合材料的制备方法，其特征在于，所述半导体型MoS 2块体的尺寸为6μm，所述半导体型MoS 2粉末的尺寸为＜1μm； The method for preparing a TiN nanotube array composite material modified by metal-type MoS 2 quantum dots according to claim 2, wherein the size of the semiconductor-type MoS 2 block is 6 μm, and the semiconductor-type MoS 2 The size of the powder is <1 μm;
    所述乙醇或异丙醇的加入量以所述半导体型MoS 2块体在混合液中的质量浓度为100mg/mL为准。 The addition amount of the ethanol or isopropanol is based on the mass concentration of the semiconductor-type MoS 2 block in the mixed solution being 100 mg/mL.
  4. 根据权利要求1所述的一种金属型MoS 2量子点修饰的TiN纳米管阵列复合材料的制备方法，其特征在于，步骤(2)中所述无水无氧环境的手套箱中水含量和氧含量均小于1ppm，所述惰性气体为氮气、氩气和氦气中的一种或多种，惰性气体的纯度为99.99％。 The method for preparing a TiN nanotube array composite material decorated with metallic MoS2 quantum dots according to claim 1 , wherein the water content in the glove box of the anhydrous and oxygen-free environment described in step (2) and the The oxygen content is all less than 1 ppm, the inert gas is one or more of nitrogen, argon and helium, and the purity of the inert gas is 99.99%.
  5. 根据权利要求1所述的一种金属型MoS 2量子点修饰的TiN纳米管阵列复合材料的制备方法，其特征在于，步骤(2)中所述丁基锂溶液为丁基锂的正己烷溶液，所述丁基锂溶液中所述丁基锂的摩尔浓度为2.5mol/L，所述丁基锂溶液的用量以丁基锂的体积计，所述丁基锂与半导体型MoS 2粉末的体积质量比为500μL:20mg。 The method for preparing a TiN nanotube array composite material decorated with metallic MoS quantum dots according to claim 1 , wherein the butyllithium solution in step (2) is a n-hexane solution of butyllithium , the molar concentration of the butyllithium in the butyllithium solution is 2.5 mol/L, the consumption of the butyllithium solution is based on the volume of butyllithium, and the difference between the butyllithium and the semiconducting MoS powder The volume-to-mass ratio was 500 μL:20 mg.
  6. 根据权利要求1所述的一种金属型MoS 2量子点修饰的TiN纳米管阵列复合材料的制备方法，其特征在于，步骤(3)中所述溶剂为去离子水或乙醇，所述半导体型MoS 2粉末与溶剂的质量体积比为(10-30)mg:20mL，所述超声处理的时间为30min。 The method for preparing a TiN nanotube array composite material modified by metal-type MoS2 quantum dots according to claim 1 , wherein the solvent in step (3) is deionized water or ethanol, and the semiconductor-type The mass volume ratio of the MoS 2 powder to the solvent was (10-30) mg:20 mL, and the ultrasonic treatment time was 30 min.
  7. 根据权利要求1所述的一种金属型MoS 2量子点修饰的TiN纳米管阵列复合材料的制备方法，其特征在于，步骤(3)中所述离心分离的次数为3此，具体操作为：首先采用600rpm的转速进行离心10min，取一次上清液；然后将所述一次上清液在10000rpm转速下进行离心分离，取二次上清液；最后将所述二次上清液在15000rpm转速下进行进一步纯化离心分离，得到的上清液为金属型MoS 2量子点溶液。 The method for preparing a TiN nanotube array composite material decorated with metallic MoS2 quantum dots according to claim 1 , wherein the number of times of centrifugal separation in step (3) is 3 times, and the specific operations are: First, centrifuge at 600 rpm for 10 min, and take the primary supernatant; then centrifuge the primary supernatant at 10,000 rpm, and take the secondary supernatant; finally, spin the secondary supernatant at 15,000 rpm Further purification and centrifugation were carried out under the following conditions, and the obtained supernatant was a solution of metallic MoS 2 quantum dots.
  8. 根据权利要求1所述的一种金属型MoS 2量子点修饰的TiN纳米管阵列复合材料的制备方法，其特征在于，所述金属型MoS 2量子点的尺寸为3-10nm。 The method for preparing a TiN nanotube array composite material decorated with metallic MoS 2 quantum dots according to claim 1, wherein the size of the metallic MoS 2 quantum dots is 3-10 nm.
  9. 根据权利要求1所述的一种金属型MoS 2量子点修饰的TiN纳米管阵列复合材料的制备方法，其特征在于，步骤(4)中所述金属型MoS 2量子点溶液中金属型MoS 2量子点的质量浓度为0.5-1.5mg/mL，所述超声处理的时间为10s，所述浸泡的时间为2min，所述干燥为在温度60℃的烘箱中干燥60min。 The method for preparing a TiN nanotube array composite material decorated with metal-type MoS 2 quantum dots according to claim 1, wherein the metal-type MoS 2 in the metal-type MoS 2 quantum dot solution in step (4) The mass concentration of the quantum dots is 0.5-1.5 mg/mL, the ultrasonic treatment time is 10s, the soaking time is 2min, and the drying is drying in an oven at a temperature of 60° C. for 60min.
  10. 一种权利要求1-9任一项所述的方法制备的金属型MoS 2量子点修饰的TiN纳米管阵列复合材料，其特征在于，TiN纳米管垂直生长在Ti片基底上，所述金属型MoS 2量子点负载在TiN纳米管的外表面和内表面所述，所述TiN纳米管的外直径为60-90nm，内直径为20-30nm。 A metal - type MoS quantum dot-modified TiN nanotube array composite material prepared by the method of any one of claims 1-9, wherein the TiN nanotubes are vertically grown on a Ti sheet substrate, and the metal-type MoS MoS 2 quantum dots are loaded on the outer and inner surfaces of TiN nanotubes, and the TiN nanotubes have an outer diameter of 60-90 nm and an inner diameter of 20-30 nm.
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