阅读说明：本技术 一种氧缺陷型氧化vib族元素量子点的制备方法及其制备的量子点和应用 (Preparation method of oxygen-deficient oxidized VIB group element quantum dot, quantum dot prepared by preparation method and application of quantum dot ) 是由 沈艳飞 杨二利 潘登 于 2020-06-03 设计创作，主要内容包括：本发明提供了一种氧缺陷型氧化VIB族元素量子点的制备方法及其制备的量子点和应用,包括以下步骤：将VIB族元素硫化物粉末与二甲基甲酰胺混合,形成混合溶液；将混合溶液超声,得黑色溶液；将黑色溶液搅拌回流得回流溶液；将回流溶液离心取上清液,将上清液加热,洗涤沉淀；将沉淀干燥得到氧缺陷型氧化VIB族元素量子点固体；将固体分散在超纯水中得到氧缺陷型氧化VIB族元素量子点溶液。本发明的氧缺陷型氧化VIB族元素量子点的制备方法,其具有制备过程简易,可大量制备的优点,制备出的氧缺陷型氧化VIB族元素量子点是一种新型纳米材料,可应用在光催化、超级电容器、锂电池信息储存材料和生物医药中。(The invention provides a preparation method of oxygen-deficient oxidized VIB group element quantum dots, the prepared quantum dots and application thereof, comprising the following steps: mixing VIB group element sulfide powder with dimethyl formamide to form a mixed solution; carrying out ultrasonic treatment on the mixed solution to obtain a black solution; stirring and refluxing the black solution to obtain a reflux solution; centrifuging the reflux solution to obtain supernatant, heating the supernatant, and washing the precipitate; drying the precipitate to obtain oxygen-deficient oxidized VIB group element quantum dot solid; and dispersing the solid in ultrapure water to obtain an oxygen-deficient oxidized VIB group element quantum dot solution. The preparation method of the oxygen-deficient oxidized VIB group element quantum dot has the advantages of simple preparation process and large-scale preparation, and the prepared oxygen-deficient oxidized VIB group element quantum dot is a novel nano material and can be applied to photocatalysis, supercapacitors, lithium battery information storage materials and biomedicine.)

1. A preparation method of oxygen-deficient oxidized VIB element quantum dots is characterized by comprising the following steps:

(1) mixing VIB group element sulfide powder with dimethyl formamide to form a mixed solution;

(2) carrying out ultrasonic treatment on the mixed solution to obtain a black solution;

(3) stirring and refluxing the black solution to obtain a reflux solution;

(4) centrifuging the reflux solution to obtain supernatant, heating the supernatant, and washing the precipitate;

(5) drying the precipitate to obtain oxygen-deficient oxidized VIB group element quantum dot solid;

(6) and dispersing the solid in ultrapure water to obtain an oxygen-deficient oxidized VIB group element quantum dot solution.

2. The method for preparing oxygen-deficient oxidized group VIB element quantum dots according to claim 1, wherein the group VIB element in the step (1) is molybdenum or tungsten; the VIB group element sulfide is molybdenum disulfide or tungsten disulfide.

3. The method for preparing oxygen-deficient oxidized group VIB element quantum dots according to claim 1, wherein 10-60 mgVIB element sulfide powder is mixed with 50mL dimethylformamide in step (1) to form a mixed solution.

4. The method for preparing oxygen-deficient oxidized VIB group element quantum dots according to claim 1, wherein the mixed solution in the step (2) is subjected to ultrasonic treatment for 60-300 minutes preferably under the condition of 240W power to obtain a black solution.

5. The method for preparing the oxygen-deficient oxidized VIB group element quantum dot according to claim 1, wherein the black solution in the step (3) is refluxed for 1-7 hours at the temperature of 120-160 ℃ under stirring to obtain a reflux solution.

6. The preparation method of the oxygen-deficient oxidized VIB group element quantum dot according to claim 1, wherein the reflux solution in the step (4) is centrifuged for 30min at 1000-6000 rpm to obtain a supernatant; heating the supernatant for 1-6 hours at 50-70 ℃ under a vacuum condition, and washing the precipitate with ultrapure water.

7. The method for preparing oxygen-deficient oxidized VIB group element quantum dots according to claim 1, wherein the precipitate obtained in the step (5) is subjected to rotary evaporation drying at a constant temperature of 40-80 ℃.

8. The oxygen-deficient oxidized VIB element quantum dot prepared by the method for preparing the oxygen-deficient oxidized VIB element quantum dot according to claim 1.

9. The oxygen deficient group VIB oxide element quantum dot of claim 8, wherein the oxygen deficient group VIB oxide element quantum dot is an oxygen deficient tungsten oxide quantum dot (WO)_3-xQDs) or oxygen deficient molybdenum oxide quantum dots (MoO)_3-xQDs)。

10. An application of the oxygen-deficient oxidized VIB element quantum dot prepared by the preparation method of the oxygen-deficient oxidized VIB element quantum dot in photocatalysis, supercapacitors, lithium battery information storage materials and biological medicines.

Technical Field

The invention belongs to the technical field of novel nano material preparation, relates to preparation of tungsten oxide and molybdenum oxide quantum dots, and particularly relates to oxygen-deficient type VIB group oxide element quantum dots and a preparation method and application thereof.

Background

Tungsten oxide, molybdenum oxide and other materials are novel transition metal oxide materials and have unique physical properties such as photochromism, electrochromism, gas sensitivity and the like, so that the transition metal molybdenum oxide can be applied to the fields of various sensors, electronic devices and the like. Because of its excellent properties, research and development and utilization have been receiving much attention. The particle size, aggregation structure of the material often enables the properties of the material to be controlled. Compared with a bulk raw material, the molybdenum oxide quantum dot has novel optical performance, good water dispersibility, excellent stability and the like, and can be used for electrochemiluminescence, sensor devices and the like.

Although tungsten oxide and molybdenum oxide quantum dots have good application prospects in various fields, the tungsten oxide and molybdenum oxide quantum dots are few in synthesis method and harsh in synthesis conditions, so that the mass production of VIB group element quantum dots such as tungsten oxide and molybdenum oxide is difficult.

The invention content is as follows:

the purpose of the invention is as follows: the invention provides a preparation method of oxygen-deficient type oxidation VIB group element quantum dots, and provides a brand-new preparation method of VIB group element quantum dots such as tungsten or molybdenum quantum dots, and a preparation method of oxygen-deficient type oxidation VIB group element quantum dots, so that the problem that the synthesis method of tungsten oxide and molybdenum oxide quantum dots or oxygen-deficient type tungsten oxide and molybdenum oxide quantum dots is few in the prior art is solved, and the preparation method has the advantages of simple preparation process and large-scale preparation.

The invention also provides an oxygen-deficient molybdenum oxide group VIB element quantum dot and application thereof, and the oxygen-deficient molybdenum oxide quantum dot prepared by the invention is a novel nano material, and due to the existence of oxygen vacancies, the energy band structure of the material is obviously changed, and the performance of the material is improved.

The technical scheme is as follows: in order to achieve the above object, the present invention provides a method for preparing oxygen-deficient oxidized group VIB element quantum dots, which is characterized by comprising the following steps:

(1) mixing VIB group element sulfide powder with dimethyl formamide to form a mixed solution;

(2) carrying out ultrasonic treatment on the mixed solution to obtain a black solution;

(3) stirring and refluxing the black solution to obtain a reflux solution;

(4) centrifuging the reflux solution to obtain supernatant, heating the supernatant, and washing the precipitate;

(5) drying the precipitate to obtain oxygen-deficient oxidized VIB group element quantum dot solid;

(6) and dispersing the solid in ultrapure water to obtain an oxygen-deficient oxidized VIB group element quantum dot solution.

Wherein the VIB group element in the step (1) is molybdenum or tungsten; the VIB group element sulfide is molybdenum disulfide or tungsten disulfide.

Preferably, the sulfide of the group VIB element is molybdenum disulfide or tungsten disulfide.

And (2) mixing 10-60 mgVIB group element sulfide powder with 50mL of dimethylformamide to form a mixed solution in the step (1).

Preferably, 50mg of tungsten disulfide powder or 40mg of molybdenum disulfide powder is mixed with 50mL of dimethylformamide to form a mixed solution for later use.

And (3) carrying out ultrasonic treatment on the mixed solution in the step (2) for 60-300 minutes under the condition of 240W of power to obtain a black solution.

Preferably, the mixed solution of tungsten disulfide is subjected to ultrasonic treatment for 80-280 minutes under the condition of power of 240W to obtain a black solution. More preferably, sonication is carried out at 240W for 240 minutes.

And (3) performing ultrasonic treatment on the mixed solution of molybdenum disulfide for 60-300 minutes under the condition of power of 240W to obtain a black solution. More preferably, sonication is carried out at 240W for 240 minutes.

Wherein, the black solution in the step (3) is refluxed for 1-7 hours at the temperature of 120-160 ℃ and the rotating speed under the stirring condition of 700rpm to obtain a reflux solution.

Preferably, the black solution is refluxed with tungsten disulfide at 140 ℃ for 2 to 7 hours under stirring to obtain a refluxed solution. More preferably, it is refluxed at 140 ℃ for 6 hours with stirring.

Preferably, the black solution of molybdenum disulfide is refluxed for 1 to 5 hours at 140 ℃ under stirring to obtain a refluxed solution. More preferably, reflux is carried out at 140 ℃ for 4 hours with stirring.

Wherein, the tungsten disulfide reflux solution is adopted in the step (4) and centrifuged for 30min at the condition of 1000-6000 rpm to obtain supernatant; heating the supernatant for 1-6 hours at 50-70 ℃ under vacuum condition, preferably 60 ℃, and washing the precipitate with ultrapure water. Preferably, the reflux solution is centrifuged for 30min at 5000rpm to obtain a supernatant; the supernatant was heated under vacuum for 5 hours, and the precipitate was washed with ultrapure water.

Wherein, the molybdenum disulfide reflux solution is adopted in the step (4) and centrifuged for 30min under the condition of 1000-5000 rpm to obtain supernatant; heating the supernatant for 1-5 hours at 50-70 ℃ under vacuum condition, preferably 60 ℃, and washing the precipitate with ultrapure water. Preferably, the reflux solution is centrifuged for 30min at 5000rpm to obtain a supernatant; the supernatant was heated under vacuum for 4 hours, and the precipitate was washed with ultrapure water.

And (3) carrying out rotary evaporation drying on the precipitate in the step (5) at a constant temperature of 40-80 ℃, preferably 80 ℃.

The oxygen-deficient oxidized VIB group element quantum dot prepared by the preparation method of the oxygen-deficient oxidized VIB group element quantum dot is provided by the invention.

Preferably, the oxygen-deficient group VIB oxide element quantum dots are oxygen-deficient tungsten oxide quantum dots (WO)_{3- x}QDs) or oxygen deficient molybdenum oxide quantum dots (MoO)_3-xQDs)。

The oxygen-deficient oxidized VIB element quantum dot prepared by the preparation method of the oxygen-deficient oxidized VIB element quantum dot is applied to the related fields of photocatalysis, super capacitors, lithium battery information storage materials, biomedicine and the like.

The invention mainly provides a brand-new preparation method aiming at the problem that oxygen-deficient molybdenum oxide/tungsten quantum dots are difficult to prepare or the preparation method is complicated. Although the oxygen-deficient quantum dots prepared by the method belong to tungsten oxide or molybdenum quantum dots, the oxygen-deficient quantum dots are novel oxygen-deficient quantum dot nano materials with better performance. The oxygen defect of the material can be regulated and controlled, the material performance can be improved, the traditional tungsten oxide or molybdenum quantum dot material can be replaced, and the material is applied to the fields of photocatalysis, electrochemiluminescence, biomedicine and the like.

Has the advantages that: compared with the prior art, the invention has the following advantages:

1. the invention prepares oxygen-deficient type oxidized VIB group element quantum dots, such as oxygen-deficient type tungsten oxide quantum dots (WO)_3-xQDs), oxygen deficient molybdenum oxide quantum dots (MoO)_3-xQDs), X-ray photoelectron spectroscopy showed WO_3-xW in QDs is +5/+6 valent, MoO_3-xIn QDs, Mo has a valence of +5/+6, and is therefore defective.

2. The invention relates to a brand-new preparation method of oxygen-deficient oxidized VIB group element quantum dots, which solves the problem that the synthesis method of oxygen-deficient quantum dots in the prior art is few, and has the advantages of simple preparation process and large-scale preparation.

3. The oxygen-deficient oxidized VIB group element quantum dot prepared by the invention is a novel nano material with better performance than the traditional tungsten oxide or molybdenum quantum dot, and the oxygen-deficient oxidized VIB group element quantum dot prepared by the invention obviously changes the energy band structure of the material and improves the performance of the material due to the existence of oxygen vacancies, so the oxygen-deficient oxidized VIB group element quantum dot has important application value in the related fields of photocatalysis, supercapacitors, lithium battery information storage materials, biological medicines and the like.

Drawings

FIG. 1 shows oxygen-deficient tungsten oxide quantum dots (WO) prepared by the present invention_3-xQDs);

FIG. 2 shows oxygen-deficient tungsten oxide quantum dots (WO) prepared by the present invention_3-xQDs) high resolution X-ray photoelectron spectrum of W4 f;

FIG. 3 shows oxygen deficient molybdenum oxide quantum dots (MoO) prepared by the present invention_3-xQDs);

FIG. 4 shows oxygen deficient molybdenum oxide quantum dots (MoO) prepared by the present invention_3-xQDs) Mo3d in the spectrum.

Detailed Description

The present invention is further described in detail below with reference to the drawings and examples so that those skilled in the art can practice the invention with reference to the description.