CN101555040A - Preparation method of manganese sulfide nano material - Google Patents
Preparation method of manganese sulfide nano material Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 18
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims description 19
- 239000000243 solution Substances 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000003607 modifier Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 5
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims 4
- 238000001556 precipitation Methods 0.000 claims 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims 2
- 235000010265 sodium sulphite Nutrition 0.000 claims 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 235000019628 coolness Nutrition 0.000 claims 1
- 229960000935 dehydrated alcohol Drugs 0.000 claims 1
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 abstract description 14
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 abstract description 14
- 235000002867 manganese chloride Nutrition 0.000 abstract description 14
- 239000011565 manganese chloride Substances 0.000 abstract description 14
- 229940099607 manganese chloride Drugs 0.000 abstract description 14
- 229910052979 sodium sulfide Inorganic materials 0.000 abstract description 11
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 9
- -1 polytetrafluoroethylene Polymers 0.000 abstract description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 16
- 229910006275 γ-MnS Inorganic materials 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 239000002073 nanorod Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- HBLUTSPORGTSEC-UHFFFAOYSA-N dioctadecoxy-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCCCCCCCCCCCCCCCOP(S)(=S)OCCCCCCCCCCCCCCCCCC HBLUTSPORGTSEC-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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- Luminescent Compositions (AREA)
Abstract
一种无机纳米材料领域的硫化锰纳米材料的制备方法，该方法包括如下步骤：步骤一，制备溶液a和溶液b：溶液a：将氯化锰溶解在纯水中，然后加入修饰剂，搅拌，形成溶液a；或者，将氯化锰溶解在纯水中，搅拌，形成溶液a；溶液b：将硫化钠溶解在纯水中，形成溶液b；步骤二，将步骤一中的溶液a和溶液b混合，混合按照氯化锰与硫化钠的摩尔比为2∶3的比例进行；搅拌，之后将混合液转入到含有聚四氟乙烯内胆的高压釜中，120℃～180℃下反应6～12小时，自然冷却；步骤三，洗涤步骤二冷却后得到的产物，干燥，得到硫化锰纳米材料。本发明的方法具有操作简便，产量高，产物晶型以及形貌均匀可控等优点。
A method for preparing manganese sulfide nanomaterials in the field of inorganic nanomaterials, the method comprising the following steps: step 1, preparing solution a and solution b: solution a: dissolving manganese chloride in pure water, then adding a modifier, stirring , to form solution a; or, manganese chloride is dissolved in pure water and stirred to form solution a; solution b: sodium sulfide is dissolved in pure water to form solution b; step 2, solution a and The solution b is mixed, and the mixing is carried out according to the molar ratio of manganese chloride and sodium sulfide as 2:3; after stirring, the mixed solution is transferred to an autoclave containing a polytetrafluoroethylene liner at 120°C to 180°C Reacting for 6-12 hours, cooling naturally; step 3, washing the product obtained after cooling in step 2, and drying to obtain manganese sulfide nanometer material. The method of the invention has the advantages of simple and convenient operation, high yield, uniform and controllable crystal form and morphology of the product, and the like.
Description
技术领域 technical field
本发明涉及一种无机纳米材料领域的制备方法，具体是一种硫化锰纳米材料的制备方法。The invention relates to a preparation method in the field of inorganic nanometer materials, in particular to a preparation method of manganese sulfide nanomaterials.
技术背景technical background
MnS是VIIB-VIA族的弱磁性半导体材料，带隙宽度为3.7eV，在制备太阳能电池的窗口/缓冲材料，短波光电器件方面有着潜在的应用。所以近些年来纳米MnS制备的研究引起了人们的广泛关注。MnS一般有α-，β-，γ-三种晶型，绿色的α-MnS是一种稳态的岩盐结构，β-MnS和γ-MnS则分别属于闪锌矿和纤锌矿结构。亚稳态的β-，γ-MnS在100～400℃或高压下易转变为α-MnS，因此控制合成单相的MnS成为了研究焦点。常见的制备方法是采用水热、溶剂热法在控制一定的温度条件下得到纯相的β-，γ-MnS。还有许多方法如化学沉积法、射频辐照法、分子束外延法和微波照射法可用来制备γ-MnS，但这些方法都较为复杂。MnS is a weakly magnetic semiconductor material of the VIIB-VIA family, with a bandgap width of 3.7eV. It has potential applications in the preparation of window/buffer materials for solar cells and short-wave optoelectronic devices. Therefore, in recent years, the research on the preparation of nano-MnS has attracted widespread attention. MnS generally has three crystal forms of α-, β-, and γ-. Green α-MnS is a stable rock-salt structure, while β-MnS and γ-MnS belong to sphalerite and wurtzite structures, respectively. The metastable β-, γ-MnS is easy to transform into α-MnS at 100-400℃ or under high pressure, so the controlled synthesis of single-phase MnS has become the focus of research. The common preparation method is to obtain pure phase β-, γ-MnS under certain temperature conditions by using hydrothermal and solvothermal methods. There are also many methods such as chemical deposition, radio frequency irradiation, molecular beam epitaxy and microwave irradiation that can be used to prepare γ-MnS, but these methods are relatively complicated.
经对现有技术的文献检索发现，祈元春、赵彦保、许红涛在《化学研究》2006年12月第17卷第4期第60～62页发表了题为“形貌可控γ-硫化锰纳米晶的制备及表征”一文，文中提及：在表面修饰剂聚乙烯吡咯烷酮(PVP)存在的条件下，使氯化锰和硫化钠发生反应，在76℃无水乙醇溶液中，制备出了亚稳态的γ-MnS纳米晶；马良、徐洮、张治军、赵家政在《物理化学学报》1999年1月第15卷第1期第5～9页发表了题为“亲油性硫化锰纳米微粒的化学制备和结构”一文，文中提及：采用表面修饰的方法，在醇水体系中利用双十八烷基二硫代磷酸(DDP)进行表面修饰制备出了γ-MnS纳米微粒。但是，这些方法都用到了复杂的表面修饰剂和乙醇，使得生产成本比较高，而且有些产物的形貌不规则，甚至团聚，这对产品的性能有很大的影响。因此，利用简单的技术合成出不同形貌/晶型的单分散纳米硫化锰具有很重要的现实意义。After searching the literature of the prior art, it was found that Qi Yuanchun, Zhao Yanbao, and Xu Hongtao published a paper entitled "Controllable Morphology of γ-Manganese Sulfide Nanoparticles" in "Chemical Research" in December 2006, Vol. In the article "Preparation and Characterization of Crystal", it is mentioned in the article that in the presence of the surface modifier polyvinylpyrrolidone (PVP), manganese chloride and sodium sulfide were reacted, and a sub Steady-state γ-MnS nanocrystals; Ma Liang, Xu Tao, Zhang Zhijun, and Zhao Jiazheng published a paper entitled "Oleophilic manganese sulfide nanoparticle In the article "Chemical Preparation and Structure of Chemical Preparation and Structure", it is mentioned in the article that γ-MnS nanoparticles were prepared by surface modification using dioctadecyl dithiophosphoric acid (DDP) in an alcohol-water system. However, these methods all use complex surface modifiers and ethanol, which makes the production cost relatively high, and some products have irregular shapes or even agglomerates, which have a great impact on the performance of the product. Therefore, it is of great practical significance to synthesize monodisperse nano-manganese sulfide with different morphology/crystal forms by using simple technology.
发明内容 Contents of the invention
本发明的目的在于克服现有技术的不足，提供一种硫化锰纳米材料的制备方法。本发明的方法使硫化锰纳米材料的合成方法简单化，具有操作简便，产量高，产物晶型以及形貌均匀可控等优点。The purpose of the present invention is to overcome the deficiencies of the prior art and provide a preparation method of manganese sulfide nanomaterials. The method of the invention simplifies the synthesis method of the manganese sulfide nanometer material, and has the advantages of simple and convenient operation, high yield, uniform and controllable product crystal form and appearance, and the like.
本发明是通过以下技术方案实现的，本发明包括如下步骤：The present invention is realized through the following technical solutions, and the present invention comprises the following steps:
步骤一，制备溶液a和溶液b：Step 1, prepare solution a and solution b:
溶液a的配制：Preparation of solution a:
将氯化锰溶解在纯水中，然后加入修饰剂，搅拌，形成溶液a，其中，氯化锰与修饰剂的摩尔量比为1∶25～1∶50；Dissolving manganese chloride in pure water, then adding a modifier and stirring to form a solution a, wherein the molar ratio of manganese chloride to the modifier is 1:25 to 1:50;
或者，将氯化锰溶解在纯水中，搅拌，形成溶液a；Alternatively, dissolve manganese chloride in pure water and stir to form solution a;
溶液b的配制：将硫化钠溶解在纯水中，形成溶液b；Preparation of solution b: Dissolve sodium sulfide in pure water to form solution b;
步骤二，将步骤一中的溶液a和溶液b混合，混合按照氯化锰与硫化钠的摩尔比为2∶3的比例进行；搅拌，之后将混合液转入到含有聚四氟乙烯内胆的高压釜中，120℃～180℃下反应6～12小时，自然冷却；Step 2, mix solution a and solution b in step 1, and mix according to the molar ratio of manganese chloride and sodium sulfide being 2:3; stir, and then transfer the mixed solution into a polytetrafluoroethylene-containing liner In an autoclave, react at 120°C to 180°C for 6 to 12 hours, and cool naturally;
步骤三，洗涤步骤二冷却后得到的产物，干燥，得到硫化锰纳米材料。Step 3, washing the product obtained after cooling in Step 2, and drying to obtain manganese sulfide nanomaterials.
步骤一中，所述修饰剂为一水合肼、一水合氨或N，N-二甲基甲酰胺中的一种。In step 1, the modifying agent is one of hydrazine monohydrate, ammonia monohydrate or N,N-dimethylformamide.
步骤三中，所述洗涤具体为：将得到的产物离心分离，得到沉淀；之后将沉淀超声分散在纯水中，离心分离得到沉淀，重复3～4次；最后将沉淀超声分散在无水乙醇中，离心分离得到沉淀，重复2～3次；离心转速为3000～5000rpm。In step 3, the washing specifically includes: centrifuging the obtained product to obtain a precipitate; then ultrasonically dispersing the precipitate in pure water, centrifuging to obtain the precipitate, repeating 3 to 4 times; finally ultrasonically dispersing the precipitate in absolute ethanol , centrifugation to obtain a precipitate, repeated 2 to 3 times; the centrifugation speed is 3000 to 5000 rpm.
步骤三中，所述干燥为60℃下烘干4～6小时。In step 3, the drying is drying at 60° C. for 4 to 6 hours.
本发明在改变简单修饰剂的种类同时改变产物的晶型和形貌，本发明所得到的产物有α-MnS和γ-MnS，在电镜下可以发现产物具有多种形貌，加入不同的修饰剂得到的产物形貌不同，可制备得到纳米八面体状，纳米棒状以及纳米立方块状等材料。The present invention changes the crystal form and morphology of the product while changing the types of simple modifiers. The products obtained in the present invention include α-MnS and γ-MnS. It can be found under the electron microscope that the products have various morphologies, adding different modifications The morphology of the product obtained by the agent is different, and materials such as nano-octahedron, nano-rod and nano-cube can be prepared.
本发明具有如下的有益效果：本发明可一步法合成出硫化锰纳米材料，并且在改变简单修饰剂的同时改变产物的晶型和形貌；本发明的方法简便，操作易行，产量高，便于控制；本发明制备的硫化锰可以广泛应用于光学，电子，磁学，光电子以及发光等工业和生活领域。The present invention has the following beneficial effects: the present invention can synthesize manganese sulfide nanomaterials in one step, and change the crystal form and shape of the product while changing the simple modifier; the method of the present invention is simple, easy to operate, high in yield, It is easy to control; the manganese sulfide prepared by the invention can be widely used in the industrial and living fields such as optics, electronics, magnetism, optoelectronics and luminescence.
附图说明 Description of drawings
图1是实施例1制备出的纳米八面体不同放大倍率的扫描电子显微镜照片；Fig. 1 is the scanning electron micrograph of the different magnifications of the nano-octahedron that embodiment 1 prepares;
图2是实施例4制备出的纳米棒不同放大倍率的扫描电子显微镜照片；Fig. 2 is the scanning electron micrograph of the nanorod prepared in embodiment 4 different magnifications;
图3是实施例5制备出的纳米立方块透射电子显微镜照片；Fig. 3 is the transmission electron micrograph of the nano cube that embodiment 5 prepares;
图4是实施例6制备出的纳米立方块透射电子显微镜照片。FIG. 4 is a transmission electron micrograph of nanocubes prepared in Example 6. FIG.
具体实施方式 Detailed ways
以下实例将结合附图对本发明作进一步说明。本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和过程，但本发明的保护范围不限于下述的实施例。下列实施例中未注明具体条件的实验方法，通常按照常规条件，或按照制造厂商所建议的条件。The following examples will further illustrate the present invention in conjunction with the accompanying drawings. This embodiment is carried out on the premise of the technical solution of the present invention, and detailed implementation methods and processes are given, but the protection scope of the present invention is not limited to the following embodiments. For the experimental methods without specific conditions indicated in the following examples, the conventional conditions or the conditions suggested by the manufacturer are usually followed.
实施例1Example 1
在50毫升的烧杯中注入10毫升的纯水，将1毫摩尔氯化锰溶于水中形成澄清溶液，再将35毫摩尔一水合肼溶于其中得到溶液a。另外取50毫升烧杯注入10毫升的纯水，将1.5毫摩尔硫化钠溶于水中得到溶液b。将溶液a和溶液b混合搅拌30分钟后转入容积为35毫升的含聚四氟乙烯内胆的不锈钢高压釜中，补充纯水至釜容积的70％～90％，将釜密封，放入180℃的高温烘箱中反应12小时。得到的产物自然冷却后用纯水和乙醇洗涤离心分离数次后放入60℃烘箱中烘干6小时，得到α-MnS纳米材料。图1是本实施例制备出的纳米八面体扫描电子显微镜照片。Inject 10 ml of pure water into a 50 ml beaker, dissolve 1 mmol of manganese chloride in water to form a clear solution, and then dissolve 35 mmol of hydrazine monohydrate therein to obtain solution a. Another 50 ml beaker was injected with 10 ml of pure water, and 1.5 mmol of sodium sulfide was dissolved in water to obtain solution b. Mix and stir solution a and solution b for 30 minutes, then transfer to a 35 ml stainless steel autoclave containing polytetrafluoroethylene liner, add pure water to 70% to 90% of the volume of the autoclave, seal the autoclave, and put React in a high-temperature oven at 180°C for 12 hours. After natural cooling, the obtained product was washed and centrifuged several times with pure water and ethanol, and then dried in an oven at 60° C. for 6 hours to obtain α-MnS nanomaterials. Fig. 1 is a scanning electron microscope photo of the nano-octahedron prepared in this embodiment.
实施例2Example 2
在50毫升的烧杯中注入10毫升的纯水，将1毫摩尔氯化锰溶于水中形成澄清溶液，再将35毫摩尔一水合肼溶于其中得到溶液a。另外取50毫升烧杯注入10毫升的纯水，将1.5毫摩尔硫化钠溶于水中得到溶液b。将溶液a和溶液b混合搅拌30分钟后转入容积为35毫升的含聚四氟乙烯内胆的不锈钢高压釜中，补充纯水至釜容积的70％～90％，将釜密封，放入180℃的高温烘箱中反应6小时。得到的产物自然冷却后用纯水和乙醇洗涤离心分离数次后放入60℃烘箱中烘干6小时，得到α-MnS纳米材料。本实施例制备出的纳米粒子扫描电子显微镜照片类似于图1。Inject 10 ml of pure water into a 50 ml beaker, dissolve 1 mmol of manganese chloride in water to form a clear solution, and then dissolve 35 mmol of hydrazine monohydrate therein to obtain solution a. Another 50 ml beaker was injected with 10 ml of pure water, and 1.5 mmol of sodium sulfide was dissolved in water to obtain solution b. Mix and stir solution a and solution b for 30 minutes, then transfer to a 35 ml stainless steel autoclave containing polytetrafluoroethylene liner, add pure water to 70% to 90% of the volume of the autoclave, seal the autoclave, and put React in a high-temperature oven at 180°C for 6 hours. After natural cooling, the obtained product was washed and centrifuged several times with pure water and ethanol, and then dried in an oven at 60° C. for 6 hours to obtain α-MnS nanomaterials. The scanning electron micrograph of the nanoparticles prepared in this example is similar to that shown in FIG. 1 .
实施例3Example 3
在50毫升的烧杯中注入10毫升的纯水，将1毫摩尔氯化锰溶于水中形成澄清溶液，再将35毫摩尔一水合肼溶于其中得到溶液a。另外取50毫升烧杯注入10毫升的纯水，将1.5毫摩尔硫化钠溶于水中得到溶液b。将溶液a和溶液b混合搅拌30分钟后转入容积为35毫升的含聚四氟乙烯内胆的不锈钢高压釜中，补充纯水至釜容积的70％～90％。将釜密封，放入120℃的高温烘箱中反应12小时。得到的产物自然冷却后用纯水和乙醇洗涤离心分离数次后放入60℃烘箱中烘干6小时，得到α-MnS纳米材料。本实施例制备出的纳米粒子扫描电子显微镜照片类似于图1。Inject 10 ml of pure water into a 50 ml beaker, dissolve 1 mmol of manganese chloride in water to form a clear solution, and then dissolve 35 mmol of hydrazine monohydrate therein to obtain solution a. Another 50 ml beaker was injected with 10 ml of pure water, and 1.5 mmol of sodium sulfide was dissolved in water to obtain solution b. Solution a and solution b were mixed and stirred for 30 minutes and then transferred to a stainless steel autoclave with a polytetrafluoroethylene liner with a volume of 35 milliliters, and pure water was added to 70% to 90% of the volume of the kettle. The kettle was sealed and put into a high-temperature oven at 120°C to react for 12 hours. After natural cooling, the obtained product was washed and centrifuged several times with pure water and ethanol, and then dried in an oven at 60° C. for 6 hours to obtain α-MnS nanomaterials. The scanning electron micrograph of the nanoparticles prepared in this example is similar to that shown in FIG. 1 .
实施例4Example 4
在50毫升的烧杯中注入10毫升的纯水，将1毫摩尔氯化锰溶于水中形成澄清溶液a。另外取50毫升烧杯注入10毫升的纯水，将1.5毫摩尔硫化钠溶于水中得到溶液b。将溶液a和溶液b混合搅拌30分钟后转入容积为35毫升的含聚四氟乙烯内胆的不锈钢高压釜中，补充纯水至釜容积的70％～90％。将釜密封，放入180℃的高温烘箱中反应12小时。得到的产物自然冷却后用纯水和乙醇洗涤离心分离数次后放入60℃烘箱中烘干6小时，得到γ-MnS纳米材料。图2是本实施例制备出的纳米棒扫描电子显微镜照片。Inject 10 ml of pure water into a 50 ml beaker, and dissolve 1 mmol of manganese chloride in water to form a clear solution a. Another 50 ml beaker was injected with 10 ml of pure water, and 1.5 mmol of sodium sulfide was dissolved in water to obtain solution b. Solution a and solution b were mixed and stirred for 30 minutes and then transferred to a stainless steel autoclave with a polytetrafluoroethylene liner with a volume of 35 milliliters, and pure water was added to 70% to 90% of the volume of the kettle. The kettle was sealed and put into a high-temperature oven at 180° C. to react for 12 hours. The obtained product was naturally cooled, washed with pure water and ethanol and centrifuged several times, and then put into an oven at 60° C. for 6 hours to obtain γ-MnS nanomaterials. Fig. 2 is a scanning electron micrograph of nanorods prepared in this example.
实施例5Example 5
在50毫升的烧杯中注入10毫升的纯水，将1毫摩尔氯化锰溶于水中形成澄清溶液，再将50毫摩尔一水合氨溶于其中得到溶液a。另外取50毫升烧杯注入10毫升的纯水，将1.5毫摩尔硫化钠溶于水中得到溶液b。将溶液a和溶液b混合搅拌30分钟后转入容积为35毫升的含聚四氟乙烯内胆的不锈钢高压釜中，补充纯水至釜容积的70％～90％，将釜密封，放入120℃的高温烘箱中反应12小时。得到的产物自然冷却后用纯水和乙醇洗涤离心分离数次后放入60℃烘箱中烘干6小时，得到α-MnS纳米材料。图3是本实施例制备出的纳米立方块透射电子显微镜照片。Inject 10 ml of pure water into a 50 ml beaker, dissolve 1 mmol of manganese chloride in water to form a clear solution, and then dissolve 50 mmol of ammonia monohydrate therein to obtain solution a. Another 50 ml beaker was injected with 10 ml of pure water, and 1.5 mmol of sodium sulfide was dissolved in water to obtain solution b. Mix and stir solution a and solution b for 30 minutes, then transfer to a 35 ml stainless steel autoclave containing polytetrafluoroethylene liner, add pure water to 70% to 90% of the volume of the autoclave, seal the autoclave, and put React in a high-temperature oven at 120°C for 12 hours. After natural cooling, the obtained product was washed and centrifuged several times with pure water and ethanol, and then dried in an oven at 60° C. for 6 hours to obtain α-MnS nanomaterials. Fig. 3 is a transmission electron microscope photo of nanocubes prepared in this embodiment.
实施例6Example 6
在50毫升的烧杯中注入10毫升的纯水，将1毫摩尔氯化锰溶于水中形成澄清溶液，再将25毫摩尔N，N-二甲基甲酰胺溶于其中得到溶液a。另外取50毫升烧杯注入10毫升的纯水，将1.5毫摩尔硫化钠溶于水中得到溶液b。将溶液a和溶液b混合搅拌30分钟后转入容积为35毫升的含聚四氟乙烯内胆的不锈钢高压釜中，补充纯水至釜容积的70％～90％，将釜密封，放入120℃的高温烘箱中反应12小时。得到的产物自然冷却后用纯水和乙醇洗涤离心分离数次后放入60℃烘箱中烘干6小时，得到α-MnS纳米材料。图4是本实施例制备出的纳米立方块透射电子显微镜照片。Inject 10 ml of pure water into a 50 ml beaker, dissolve 1 mmol of manganese chloride in water to form a clear solution, and then dissolve 25 mmol of N,N-dimethylformamide in it to obtain solution a. Another 50 ml beaker was injected with 10 ml of pure water, and 1.5 mmol of sodium sulfide was dissolved in water to obtain solution b. Mix and stir solution a and solution b for 30 minutes, then transfer to a 35 ml stainless steel autoclave containing polytetrafluoroethylene liner, add pure water to 70% to 90% of the volume of the autoclave, seal the autoclave, and put React in a high-temperature oven at 120°C for 12 hours. After natural cooling, the obtained product was washed and centrifuged several times with pure water and ethanol, and then dried in an oven at 60° C. for 6 hours to obtain α-MnS nanomaterials. Fig. 4 is a transmission electron microscope photo of nanocubes prepared in this embodiment.
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| CN113415827A (en) * | 2021-05-31 | 2021-09-21 | 中南大学 | Preparation method and application of manganese sulfide/porous carbon energy storage material |
| CN113415827B (en) * | 2021-05-31 | 2022-05-27 | 中南大学 | Preparation method and application of manganese sulfide/porous carbon energy storage material |
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