CN105524617A - Preparation method of molybdenum selenide quantum dots - Google Patents
Preparation method of molybdenum selenide quantum dots Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- DORQJBTVNDGTEY-UHFFFAOYSA-N selanylidenemolybdenum Chemical class [Se].[Mo] DORQJBTVNDGTEY-UHFFFAOYSA-N 0.000 title abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 47
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 44
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000002096 quantum dot Substances 0.000 claims abstract description 37
- 239000013078 crystal Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 28
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 28
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 25
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000007791 liquid phase Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000010494 dissociation reaction Methods 0.000 claims description 7
- 230000005593 dissociations Effects 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 3
- 235000010469 Glycine max Nutrition 0.000 claims description 2
- 244000068988 Glycine max Species 0.000 claims description 2
- 239000008267 milk Substances 0.000 claims description 2
- 210000004080 milk Anatomy 0.000 claims description 2
- 235000013336 milk Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 18
- 229910052750 molybdenum Inorganic materials 0.000 claims 18
- 239000011733 molybdenum Substances 0.000 claims 18
- 239000000203 mixture Substances 0.000 claims 4
- 239000002904 solvent Substances 0.000 claims 4
- 238000013019 agitation Methods 0.000 claims 3
- 238000010008 shearing Methods 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 claims 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 claims 1
- 239000006228 supernatant Substances 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- MHWZQNGIEIYAQJ-UHFFFAOYSA-N molybdenum diselenide Chemical compound [Se]=[Mo]=[Se] MHWZQNGIEIYAQJ-UHFFFAOYSA-N 0.000 abstract description 63
- 239000011259 mixed solution Substances 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 229910016001 MoSe Inorganic materials 0.000 description 4
- 238000010411 cooking Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000004299 exfoliation Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- -1 transition metal sulfides Chemical class 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 239000002074 nanoribbon Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01B19/00—Selenium; Tellurium; Compounds thereof
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Abstract
本发明公开了一种硒化钼量子点的制备方法，采用两步法合成硒化钼量子点，具体实现方法为：首先，将氧化钼和硒粉分散在水合肼水溶液中，通过水热离子交换反应得到硒化钼晶体；然后，将硒化钼晶体分散在水和异丙醇混合溶液中，再转移至搅拌桶内，通过高速旋转刀片产生的液相剪切力使硒化钼解离，即可得到硒化钼量子点分散液。本发明方法公开的硒化钼量子点的制备方法具有成本低、可规模化制备、效率高、生产周期短的优点。The invention discloses a method for preparing molybdenum selenide quantum dots. The molybdenum selenide quantum dots are synthesized by a two-step method. The specific implementation method is as follows: first, molybdenum oxide and selenium powder are dispersed in an aqueous solution of hydrazine hydrate, Molybdenum selenide crystals are obtained through the exchange reaction; then, the molybdenum selenide crystals are dispersed in a mixed solution of water and isopropanol, and then transferred to a mixing tank, and the molybdenum selenide is dissociated by the liquid phase shear force generated by the high-speed rotating blade , the molybdenum selenide quantum dot dispersion can be obtained. The preparation method of the molybdenum selenide quantum dot disclosed by the method of the invention has the advantages of low cost, large-scale preparation, high efficiency and short production cycle.
Description
技术领域technical field
本发明涉及一种硒化钼量子点的制备方法，该方法结合水热离子交换和液相剪切力解离方法得到硒化钼量子点分散液，属于纳米材料制备的技术领域。The invention relates to a method for preparing molybdenum selenide quantum dots. The method combines hydrothermal ion exchange and liquid phase shear force dissociation to obtain molybdenum selenide quantum dot dispersion liquid, which belongs to the technical field of nanometer material preparation.
背景技术Background technique
二维纳米材料如石墨烯、过渡金属硫化物等，以其优异的物理和结构特性已经在电子、传感和光电器件等多领域表现出非凡的应用潜力。其中，石墨烯作为最具代表性的二维材料已经被广泛研究。它具有超高的载流子迁移率，但缺乏带隙却严重阻碍了石墨烯在逻辑半导体器件如场效应晶体管中的应用。而作为过渡金属硫化物半导体家族的代表成员，二硫化钼(MoS2)具有明显的带隙，且在n-型晶体管中表现出优异的开关比特性(>108)。然而，MoS2中结构缺陷存在可能会导致电子迁移率的降低，从而影响它的电学性能。因此许多方法被尝试用来在石墨烯中引入带隙，比如将其切成纳米带，引入缺陷和制备量子点。Two-dimensional nanomaterials such as graphene and transition metal sulfides have shown extraordinary application potential in many fields such as electronics, sensing and optoelectronic devices due to their excellent physical and structural properties. Among them, graphene has been widely studied as the most representative two-dimensional material. It has ultrahigh carrier mobility, but the lack of a band gap has severely hindered the application of graphene in logic semiconductor devices such as field-effect transistors. As a representative member of the transition metal sulfide semiconductor family, molybdenum disulfide (MoS 2 ) has an obvious band gap and exhibits excellent switching ratio characteristics (>10 8 ) in n-type transistors. However, the existence of structural defects in MoS2 may lead to the decrease of electron mobility, thereby affecting its electrical properties. Therefore many methods have been tried to introduce band gaps in graphene, such as cutting it into nanoribbons, introducing defects and preparing quantum dots.
近年来，硒化钼以其良好电子迁移率和较高的电催化活性，逐渐成为具有潜力的适用于高性能光电子器件和能源领域的重要二维半导体材料。和石墨类似，硒化钼的原子层间也是通过微弱的层间作用力而相互堆叠，并且这种作用力具有范德华力特征，能够通过机械剥离或者超声剥离得到少层硒化钼纳米片。最近的报告证实硒化钼在电催化析氢反应中表现出低于硫化钼的析氢电位和更高的电流密度。此外，随着硒化钼从块体到纳米片的结构迁移，将表现出更多的活性位点和更低的析氢电位。对于极薄的硒化钼纳米片当限定到零维时，量子效应和边缘作用会更加突出，这些将导致有趣的物理性质。然而对于硒化钼量子点的研究仍旧停留在理论阶段，实验上的制备还没有被实现。为此，开发一种简单易行的制备方法来获得尺寸均匀的硒化钼量子点对于拓宽硒化钼在光电子和电催化领域的工业级应用具有重要价值。In recent years, molybdenum selenide has gradually become an important two-dimensional semiconductor material with potential for high-performance optoelectronic devices and energy fields due to its good electron mobility and high electrocatalytic activity. Similar to graphite, the atomic layers of molybdenum selenide are also stacked by weak interlayer forces, and this force has the characteristics of van der Waals force, and few-layer molybdenum selenide nanosheets can be obtained by mechanical exfoliation or ultrasonic exfoliation. Recent reports have confirmed that molybdenum selenide exhibits lower hydrogen evolution potential and higher current density than molybdenum sulfide in the electrocatalytic hydrogen evolution reaction. In addition, with the structural migration of MoSe from bulk to nanosheets, more active sites and lower hydrogen evolution potential will be exhibited. For extremely thin MoSe nanosheets, quantum effects and edge interactions become more prominent when restricted to zero dimension, which leads to interesting physical properties. However, the research on molybdenum selenide quantum dots is still at the theoretical stage, and the experimental preparation has not been realized yet. Therefore, developing a simple and feasible preparation method to obtain MoSe quantum dots with uniform size is of great value for broadening the industrial application of MoSe in the field of optoelectronics and electrocatalysis.
发明内容Contents of the invention
发明目的：为了克服现有技术中存在的不足，本发明提供一种硒化钼量子点的制备方法，利用高速旋转刀头产生的高液相剪切力解离水热合成的硒化钼，可实现硒化钼量子点的简单、快速制备，具有低成本、规模化制备的潜能。Purpose of the invention: In order to overcome the deficiencies in the prior art, the present invention provides a method for preparing molybdenum selenide quantum dots, using the high liquid phase shear force generated by the high-speed rotating cutter head to dissociate the molybdenum selenide synthesized by hydrothermal, The simple and fast preparation of molybdenum selenide quantum dots can be realized, and the potential of low-cost and large-scale preparation is achieved.
技术方案：为实现上述目的，本发明采用的技术方案为：Technical scheme: in order to achieve the above object, the technical scheme adopted in the present invention is:
一种硒化钼量子点的制备方法，采用两步法合成硒化钼量子点，具体实现方法为：首先，将氧化钼和硒粉分散在水合肼水溶液中，通过水热离子交换反应得到硒化钼晶体；然后，将硒化钼晶体分散在水和异丙醇混合溶液中，再转移至搅拌桶内，通过高速旋转刀片产生的液相剪切力使硒化钼解离，即可得到硒化钼量子点分散液。A method for preparing molybdenum selenide quantum dots, using a two-step method to synthesize molybdenum selenide quantum dots, the specific implementation method is as follows: first, molybdenum oxide and selenium powder are dispersed in hydrazine hydrate aqueous solution, and selenium is obtained by hydrothermal ion exchange reaction Molybdenum selenide crystals; then, molybdenum selenide crystals are dispersed in a mixed solution of water and isopropanol, and then transferred to a mixing tank, and the molybdenum selenide is dissociated by the liquid phase shear force generated by the high-speed rotating blade to obtain Molybdenum selenide quantum dot dispersion.
该方法具体包括如下步骤：The method specifically includes the following steps:
(1)首先配置水合肼水溶液；再分别称取氧化钼和硒粉，氧化钼和硒粉的摩尔比为1:2；接着将称取的硒粉撒入配置的水合肼水溶液中，搅拌均匀形成硒粉分散液；最后将称取的氧化钼撒入硒粉分散液中，搅拌均匀形成氧化钼和硒粉分散液；水合肼水溶液中水合肼和水的体积比为1:40～1:10，每50mL水合肼水溶液撒入0.1～1g硒粉；(1) First configure the hydrazine hydrate aqueous solution; then weigh molybdenum oxide and selenium powder respectively, the molar ratio of molybdenum oxide and selenium powder is 1:2; then sprinkle the weighed selenium powder into the configured hydrazine hydrate aqueous solution and stir evenly Form the selenium powder dispersion liquid; Finally the molybdenum oxide that weighs is sprinkled in the selenium powder dispersion liquid, stirs to form molybdenum oxide and selenium powder dispersion liquid; The volume ratio of hydrazine hydrate and water in the hydrazine hydrate aqueous solution is 1:40～1: 10. Sprinkle 0.1-1g of selenium powder per 50mL of hydrazine hydrate aqueous solution;
(2)将氧化钼和硒粉分散液转移至不锈钢反应釜中进行水热离子交换反应，水热离子交换反应完成后，首先过滤出沉淀物，再使用乙醇和水对沉淀物进行冲洗，然后将沉淀物置于45～55℃的烘箱中烘干，得到硒化钼晶体；水热离子交换反应的反应温度为140～220℃，反应时间为6～18h；(2) Transfer the molybdenum oxide and selenium powder dispersion to a stainless steel reactor for hydrothermal ion exchange reaction. After the hydrothermal ion exchange reaction is completed, first filter out the precipitate, then use ethanol and water to wash the precipitate, and then Dry the precipitate in an oven at 45-55°C to obtain molybdenum selenide crystals; the reaction temperature of the hydrothermal ion exchange reaction is 140-220°C, and the reaction time is 6-18h;
(3)将硒化钼晶体分散在水和异丙醇混合溶液中，搅拌均匀形成硒化钼分散液，将硒化钼分散液转移至搅拌桶内，通过高速旋转刀片产生的液相剪切力使硒化钼晶体解离，即可得到硒化钼量子点分散液；水和异丙醇混合溶液中水和异丙醇的体积比为1:10～1:1，每200～500mL水和异丙醇混合溶液分散0.05～1g硒化钼晶体，高速旋转刀片的转速为15000～25000rpm，解离时间为0.5～2h；(3) Disperse molybdenum selenide crystals in a mixed solution of water and isopropanol, stir evenly to form a molybdenum selenide dispersion, transfer the molybdenum selenide dispersion to the mixing tank, and shear the molybdenum selenide liquid through the high-speed rotating blade Dissociate molybdenum selenide crystals by force to obtain molybdenum selenide quantum dot dispersion liquid; the volume ratio of water and isopropanol in the mixed solution of water and isopropanol is 1:10～1:1, every 200～500mL water Disperse 0.05-1g of molybdenum selenide crystals with a mixed solution of isopropanol, the speed of the high-speed rotating blade is 15000-25000rpm, and the dissociation time is 0.5-2h;
(4)将硒化钼量子点分散液在6000～10000rpm转速下离心分离，取上层液体即为稳定的硒化钼量子点分散液，量子点直径在2～5nm之间。(4) The molybdenum selenide quantum dot dispersion liquid is centrifuged at 6000-10000 rpm, and the upper liquid is obtained as a stable molybdenum selenide quantum dot dispersion liquid, and the diameter of the quantum dots is between 2-5 nm.
所述搅拌桶为家用厨房料理机，比如豆浆机或鲜榨果汁机。The mixing barrel is a household cooking machine, such as a soybean milk machine or a freshly squeezed fruit juice machine.
有益效果：本发明提供的硒化钼量子点的制备方法，结合水热法和液相剪切解离，可实现硒化钼量子点的简单、快速制备，具有低成本、规模化制备的潜能。该制备方法首先利用水热法进行离子交换得到硒化钼，能够实现大规模制备；再通过家用厨房料理机刀头高速旋转产生的液相剪切力解离硒化钼，这一液相剪切原理亦可进一步放大到工业化规模化生产，因而该方法具有高度的扩展性和广泛的应用性。利用这种方法能够得到尺寸均匀且高度分散的硒化钼量子点，这不仅弥补了现有硒化钼纳米结构的不足，还为其他二维材料量子点的制备提供了可能。Beneficial effects: the preparation method of molybdenum selenide quantum dots provided by the present invention, combined with hydrothermal method and liquid phase shear dissociation, can realize the simple and rapid preparation of molybdenum selenide quantum dots, and has the potential of low-cost and large-scale preparation . In the preparation method, molybdenum selenide is obtained by ion exchange using a hydrothermal method, which can realize large-scale preparation; The cutting principle can also be further enlarged to industrial scale production, so this method has high scalability and wide applicability. Using this method, uniform and highly dispersed molybdenum selenide quantum dots can be obtained, which not only makes up for the shortcomings of the existing molybdenum selenide nanostructures, but also provides the possibility for the preparation of other two-dimensional material quantum dots.
附图说明Description of drawings
图1为本发明方法制备的硒化钼晶体的光学照片和晶体衍射(XRD)图谱；其中，1(a)为硒化钼晶体的光学照片，1(b)为硒化钼的XRD图谱，1(b)的横坐标为衍射角2θ(单位：度)，1(b)的纵坐标为衍射相对强度(无量纲)；Fig. 1 is the optical photograph and crystal diffraction (XRD) collection of illustrative plates of the molybdenum selenide crystal prepared by the inventive method; Wherein, 1 (a) is the optical photograph of molybdenum selenide crystal, and 1 (b) is the XRD collection of illustrative plates of molybdenum selenide, The abscissa of 1(b) is the diffraction angle 2θ (unit: degree), and the ordinate of 1(b) is the relative intensity of diffraction (dimensionless);
图2为本发明方法制备的硒化钼晶体的扫描电镜(SEM)图；其中，2(a)为低倍SEM图，2(b)为高倍SEM图；Fig. 2 is the scanning electron microscope (SEM) figure of the molybdenum selenide crystal that the inventive method prepares; Wherein, 2 (a) is low power SEM figure, and 2 (b) is high power SEM figure;
图3为本发明方法制备的硒化钼晶体的透射电镜(TEM)图；其中，3(a)为低倍TEM图，3(b)为高倍TEM图；Fig. 3 is the transmission electron microscope (TEM) figure of the molybdenum selenide crystal that the inventive method prepares; Wherein, 3 (a) is low power TEM figure, and 3 (b) is high power TEM figure;
图4为本发明方法制备的硒化钼量子点的TEM图；其中，4(a)为低倍TEM图，4(b)为高倍TEM图；Fig. 4 is the TEM figure of the molybdenum selenide quantum dot prepared by the inventive method; Wherein, 4 (a) is low power TEM figure, 4 (b) is high power TEM figure;
图5为本发明方法制备的硒化钼量子点的丁达尔效应的光学照片；Fig. 5 is the optical photograph of the Tyndall effect of the molybdenum selenide quantum dot prepared by the inventive method;
图6为本发明方法制备的硒化钼晶体硒化钼量子点的吸收光谱和发光光谱；其中，6(a)为低倍吸收光谱，6(b)为发光光谱，6(a)和6(b)的横坐标为波长(单位：nm)，6(a)和6(b)的纵坐标为相对强度(无量纲)。Fig. 6 is the absorption spectrum and the emission spectrum of the molybdenum selenide crystal molybdenum selenide quantum dot prepared by the method of the present invention; Wherein, 6 (a) is low power absorption spectrum, 6 (b) is emission spectrum, 6 (a) and 6 The abscissa in (b) is the wavelength (unit: nm), and the ordinate in 6(a) and 6(b) is the relative intensity (dimensionless).
具体实施方式detailed description
下面结合附图对本发明作更进一步的说明。The present invention will be further described below in conjunction with the accompanying drawings.
实施例1Example 1
(1)配制50mL水合肼水溶液，水合肼水溶液中水合肼和水体积比为1:20；再分别称取氧化钼和硒粉，氧化钼和硒粉的摩尔比为1:2，硒粉质量为0.2g；将称取的硒粉撒入配置的水合肼水溶液中，搅拌均匀形成硒粉分散液；将称取的氧化钼撒入硒粉分散液中，搅拌均匀形成氧化钼和硒粉分散液；(1) prepare 50mL hydrazine hydrate aqueous solution, the volume ratio of hydrazine hydrate and water in the hydrazine hydrate aqueous solution is 1:20; then weigh molybdenum oxide and selenium powder respectively, the molar ratio of molybdenum oxide and selenium powder is 1:2, the mass of selenium powder Sprinkle the weighed selenium powder into the prepared hydrazine hydrate aqueous solution, stir evenly to form a selenium powder dispersion; sprinkle the weighed molybdenum oxide into the selenium powder dispersion, stir evenly to form a molybdenum oxide and selenium powder dispersion liquid;
(2)氧化钼和硒粉分散液转移至容量为80mL的不锈钢反应釜中，在140℃条件下进行水热离子交换反应6h；水热离子交换反应完成后，首先过滤出沉淀物，再使用乙醇和水对沉淀物进行冲洗，然后将沉淀物置于50℃的烘箱中烘干，得到硒化钼晶体；(2) The molybdenum oxide and selenium powder dispersions were transferred to a stainless steel reactor with a capacity of 80 mL, and the hydrothermal ion exchange reaction was carried out at 140 ° C for 6 hours; after the hydrothermal ion exchange reaction was completed, the precipitate was first filtered out, and then used washing the precipitate with ethanol and water, and then drying the precipitate in an oven at 50°C to obtain molybdenum selenide crystals;
(3)称取0.1g硒化钼晶体分散到300mL的水和异丙醇混合溶液中，水和异丙醇混合溶液中水和异丙醇的体积比为1:1；将硒化钼分散液转移至厨房料理机内，通过高速旋转刀片产生的液相剪切力使硒化钼晶体解离，即可得到硒化钼量子点分散液；高速旋转刀片的转速为17000rpm，解离时间为1h；(3) Weigh 0.1g of molybdenum selenide crystals and disperse them into 300mL of water and isopropanol mixed solution, the volume ratio of water and isopropanol in the water and isopropanol mixed solution is 1:1; disperse molybdenum selenide The liquid is transferred to the kitchen cooking machine, and the molybdenum selenide crystal is dissociated by the liquid phase shear force generated by the high-speed rotating blade to obtain the molybdenum selenide quantum dot dispersion liquid; the speed of the high-speed rotating blade is 17000rpm, and the dissociation time is 1h;
(4)将硒化钼量子点分散液在6000rpm转速下离心分离，取上层液体即为稳定的硒化钼量子点分散液，量子点直径在2～5nm之间。(4) The molybdenum selenide quantum dot dispersion is centrifuged at 6000 rpm, and the upper liquid is taken as a stable molybdenum selenide quantum dot dispersion, and the diameter of the quantum dots is between 2 and 5 nm.
实施例2Example 2
(1)配制50mL水合肼水溶液，水合肼水溶液中水合肼和水体积比为1:40；再分别称取氧化钼和硒粉，氧化钼和硒粉的摩尔比为1:2，硒粉质量为0.1g；将称取的硒粉撒入配置的水合肼水溶液中，搅拌均匀形成硒粉分散液；将称取的氧化钼撒入硒粉分散液中，搅拌均匀形成氧化钼和硒粉分散液；(1) prepare 50mL hydrazine hydrate aqueous solution, the volume ratio of hydrazine hydrate and water in the hydrazine hydrate aqueous solution is 1:40; then weigh molybdenum oxide and selenium powder respectively, the molar ratio of molybdenum oxide and selenium powder is 1:2, the mass of selenium powder Sprinkle the weighed selenium powder into the prepared hydrazine hydrate aqueous solution, stir evenly to form a selenium powder dispersion; sprinkle the weighed molybdenum oxide into the selenium powder dispersion, stir evenly to form a molybdenum oxide and selenium powder dispersion liquid;
(2)氧化钼和硒粉分散液转移至容量为80mL的不锈钢反应釜中，在160℃条件下进行水热离子交换反应12h；水热离子交换反应完成后，首先过滤出沉淀物，再使用乙醇和水对沉淀物进行冲洗，然后将沉淀物置于50℃的烘箱中烘干，得到硒化钼晶体；(2) Molybdenum oxide and selenium powder dispersions were transferred to a stainless steel reactor with a capacity of 80 mL, and the hydrothermal ion exchange reaction was carried out at 160 °C for 12 hours; after the hydrothermal ion exchange reaction was completed, the precipitate was first filtered out, and then used washing the precipitate with ethanol and water, and then drying the precipitate in an oven at 50°C to obtain molybdenum selenide crystals;
(3)称取0.05g硒化钼晶体分散到200mL的水和异丙醇混合溶液中，水和异丙醇混合溶液中水和异丙醇的体积比为1:3；将硒化钼分散液转移至厨房料理机内，通过高速旋转刀片产生的液相剪切力使硒化钼晶体解离，即可得到硒化钼量子点分散液；高速旋转刀片的转速为23000rpm，解离时间为1.5h；(3) Weigh 0.05g of molybdenum selenide crystals and disperse them into 200mL of water and isopropanol mixed solution, the volume ratio of water and isopropanol in the water and isopropanol mixed solution is 1:3; disperse molybdenum selenide The liquid is transferred to the kitchen cooking machine, and the molybdenum selenide crystal is dissociated by the liquid phase shear force generated by the high-speed rotating blade to obtain the molybdenum selenide quantum dot dispersion liquid; the speed of the high-speed rotating blade is 23000rpm, and the dissociation time is 1.5h;
(4)将硒化钼量子点分散液在9000rpm转速下离心分离，取上层液体即为稳定的硒化钼量子点分散液，量子点直径在2～5nm之间。(4) The molybdenum selenide quantum dot dispersion liquid is centrifuged at 9000 rpm, and the upper liquid is taken as a stable molybdenum selenide quantum dot dispersion liquid, and the diameter of the quantum dots is between 2 and 5 nm.
实施例3Example 3
(1)配制50mL水合肼水溶液，水合肼水溶液中水合肼和水体积比为1:12；再分别称取氧化钼和硒粉，氧化钼和硒粉的摩尔比为1:2，硒粉质量为0.5g；将称取的硒粉撒入配置的水合肼水溶液中，搅拌均匀形成硒粉分散液；将称取的氧化钼撒入硒粉分散液中，搅拌均匀形成氧化钼和硒粉分散液；(1) prepare 50mL hydrazine hydrate aqueous solution, the volume ratio of hydrazine hydrate and water in the hydrazine hydrate aqueous solution is 1:12; then weigh molybdenum oxide and selenium powder respectively, the molar ratio of molybdenum oxide and selenium powder is 1:2, the mass of selenium powder Sprinkle the weighed selenium powder into the prepared hydrazine hydrate aqueous solution, stir evenly to form a selenium powder dispersion; sprinkle the weighed molybdenum oxide into the selenium powder dispersion, stir evenly to form a molybdenum oxide and selenium powder dispersion liquid;
(2)氧化钼和硒粉分散液转移至容量为80mL的不锈钢反应釜中，在180℃条件下进行水热离子交换反应8h；水热离子交换反应完成后，首先过滤出沉淀物，再使用乙醇和水对沉淀物进行冲洗，然后将沉淀物置于50℃的烘箱中烘干，得到硒化钼晶体；(2) Molybdenum oxide and selenium powder dispersions were transferred to a stainless steel reactor with a capacity of 80 mL, and the hydrothermal ion exchange reaction was carried out at 180 °C for 8 hours; after the hydrothermal ion exchange reaction was completed, the precipitate was first filtered out, and then used washing the precipitate with ethanol and water, and then drying the precipitate in an oven at 50°C to obtain molybdenum selenide crystals;
(3)称取0.2g硒化钼晶体分散到500mL的水和异丙醇混合溶液中，水和异丙醇混合溶液中水和异丙醇的体积比为1:1；将硒化钼分散液转移至厨房料理机内，通过高速旋转刀片产生的液相剪切力使硒化钼晶体解离，即可得到硒化钼量子点分散液；高速旋转刀片的转速为20000rpm，解离时间为2h；(3) Weigh 0.2g molybdenum selenide crystals and disperse them into 500mL of water and isopropanol mixed solution, the volume ratio of water and isopropanol in the water and isopropanol mixed solution is 1:1; disperse molybdenum selenide The liquid is transferred to the kitchen cooking machine, and the molybdenum selenide crystal is dissociated by the liquid phase shear force generated by the high-speed rotating blade to obtain the molybdenum selenide quantum dot dispersion liquid; the speed of the high-speed rotating blade is 20000rpm, and the dissociation time is 2h;
(4)将硒化钼量子点分散液在10000rpm转速下离心分离，取上层液体即为稳定的硒化钼量子点分散液，量子点直径在2～5nm之间。(4) The molybdenum selenide quantum dot dispersion liquid is centrifuged at 10000 rpm, and the upper liquid is obtained as a stable molybdenum selenide quantum dot dispersion liquid, and the diameter of the quantum dots is between 2 and 5 nm.
图1为本实施例制备的硒化钼晶体的光学照片和晶体衍射图谱，图2为本实施例制备的硒化钼晶体的扫描电镜图，图3为本实施例制备的硒化钼晶体的透射电镜图；以上表征充分证明了硒化钼的成功制备。图4为本实施例制备的硒化钼量子点的TEM图，可以清楚看到，尺寸均匀的量子点已经被成功制备。图5为本实施例制备的硒化钼量子点的丁达尔效应的光学照片，证明了硒化钼量子点稳定的分散性。图6为本实施例制备的硒化钼晶体和硒化钼量子点的吸收光谱和发光光谱；可以看到，硒化钼量子点比硒化钼粉体具有更强的紫外发光性能，体现了量子点的优越性。Fig. 1 is the optical photo and the crystal diffraction spectrum of the molybdenum selenide crystal prepared by the present embodiment, Fig. 2 is the scanning electron micrograph of the molybdenum selenide crystal prepared by the present embodiment, Fig. 3 is the molybdenum selenide crystal prepared by the present embodiment Transmission electron microscope image; the above characterization fully proves the successful preparation of molybdenum selenide. FIG. 4 is a TEM image of the molybdenum selenide quantum dots prepared in this example. It can be clearly seen that quantum dots with uniform size have been successfully prepared. FIG. 5 is an optical photograph of the Tyndall effect of the molybdenum selenide quantum dots prepared in this example, which proves the stable dispersion of the molybdenum selenide quantum dots. Fig. 6 is the absorption spectrum and the luminescent spectrum of molybdenum selenide crystal and molybdenum selenide quantum dots prepared in this embodiment; it can be seen that molybdenum selenide quantum dots have stronger ultraviolet luminescence performance than molybdenum selenide powder, reflecting the The advantages of quantum dots.
以上所述仅是本发明的优选实施方式，应当指出：对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications are also possible. It should be regarded as the protection scope of the present invention.
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