技术领域technical field
本发明属于化学领域，具体涉及一种硫化物包覆型颗粒及其制备方法与应用。The invention belongs to the field of chemistry, and in particular relates to a sulfide-coated particle and a preparation method and application thereof.
背景技术Background technique
许多硫化物都具有优异的电化学性质，诸如硫化镉、硫化钼的光电催化分解水性质，硫化铅、硫化镉、硫化锌的量子点敏化太阳能电池方面的应用，硫化钼、硫化钴、硫化亚铜在催化加氢、电池负极、超级电容器等多个方面的性质。Many sulfides have excellent electrochemical properties, such as photocatalytic water splitting properties of cadmium sulfide and molybdenum sulfide, applications in quantum dot-sensitized solar cells of lead sulfide, cadmium sulfide, and zinc sulfide, molybdenum sulfide, cobalt sulfide, The properties of cuprous in catalytic hydrogenation, battery negative electrode, supercapacitor and so on.
目前对硫化物的应用主要集中在量子点、纳米球和纳米管等方面，例如CN200710171388.1公开了一种硒化镉/硫化镉/硫化锌核壳量子点的制备方法。CN201310614267.5公开了一种二硫化钼修饰的一维硫化镉纳米棒结构具有太阳光解水制氢性能。CN201410676448.5公开了一种二硫化钼纳米管的制备方法。CN201510148981.9公开了一种掺杂二硫化钼石墨烯纤维的制备方法。CN201410758505.4公开了一种碳包覆硫化钴材料作为电催化裂解水产氢催化剂方面的应用。但上述各方法均存在原料价格昂贵、工艺复杂而不易控制、难于工业化推广等缺陷，亟待开发全新的硫化物的应用方式。At present, the application of sulfide mainly focuses on quantum dots, nanospheres and nanotubes. For example, CN200710171388.1 discloses a preparation method of cadmium selenide/cadmium sulfide/zinc sulfide core-shell quantum dots. CN201310614267.5 discloses a one-dimensional cadmium sulfide nanorod structure modified by molybdenum disulfide, which has the performance of solar photolysis of water to produce hydrogen. CN201410676448.5 discloses a method for preparing molybdenum disulfide nanotubes. CN201510148981.9 discloses a method for preparing graphene fibers doped with molybdenum disulfide. CN201410758505.4 discloses the application of a carbon-coated cobalt sulfide material as a hydrogen production catalyst for electrocatalytic cracking of water. However, the above-mentioned methods all have defects such as expensive raw materials, complicated processes that are not easy to control, and are difficult to promote in an industrialized manner. It is urgent to develop a new application method of sulfide.
发明内容Contents of the invention
本发明的目的在于克服现有技术中的不足，提供一种硫化物包覆型颗粒及其制备方法与应用。The purpose of the present invention is to overcome the deficiencies in the prior art, and provide a sulfide-coated granule and its preparation method and application.
本发明所谓“硫化物包覆”是指在物质(通常称为基底)表面覆盖上一层硫化物。通过“硫化物包覆”，可以调节基底的一些性质，同时也能起到保护基底的作用；而且，把硫化物均匀可控的包覆在基底材料上能够对硫化物的性质进行更加有效的利用。现有技术中没有关于利用硫化物在其它材料上进行包覆的报道，本发明中通过选择价格便宜的原料、合适简单可控的方法实现了硫化物在基底表面的可控、连续、完整地包覆，为硫化物的应用开拓了全新的方向。The so-called "sulfide coating" in the present invention means that a layer of sulfide is covered on the surface of a material (usually referred to as a substrate). Through "sulfide coating", some properties of the substrate can be adjusted, and at the same time, it can also protect the substrate; moreover, the uniform and controllable coating of sulfide on the substrate material can more effectively control the properties of the sulfide. use. There is no report about using sulfide to coat other materials in the prior art. In the present invention, the controllable, continuous and complete coating of sulfide on the substrate surface is realized by selecting cheap raw materials and a suitable, simple and controllable method. Coating opens up a new direction for the application of sulfide.
本发明提供的具有核壳结构的硫化物包覆型颗粒，由核和包覆所述核的壳组成；The sulfide-coated particles with a core-shell structure provided by the present invention are composed of a core and a shell covering the core;
其中，构成所述核的材料选自金属单质、金属氧化物、金属氢氧化物、金属无机盐、碳单质或其氧化体、碳化物、氮化物、半导体和有机物中的至少一种；Wherein, the material constituting the core is selected from at least one of metal element, metal oxide, metal hydroxide, metal inorganic salt, carbon element or its oxide, carbide, nitride, semiconductor and organic matter;
构成所述壳的材料为金属硫化物。The material constituting the shell is a metal sulfide.
上述颗粒中，构成所述壳的金属硫化物选自硫化锌、硫化镉、硫化钴、硫化铅、硫化亚铜、硫化钼、硫化钨、硫化镍中的至少一种。优选地，所述金属硫化物为晶相的金属硫化物。In the above particles, the metal sulfide constituting the shell is at least one selected from zinc sulfide, cadmium sulfide, cobalt sulfide, lead sulfide, cuprous sulfide, molybdenum sulfide, tungsten sulfide, and nickel sulfide. Preferably, the metal sulfide is a crystalline metal sulfide.
上述颗粒中，构成所述核的材料中，所述金属单质选自金、银、铂、铑、钯、钌、铁、锰、钴、镍、钛、镁、铝和锡中的至少一种；In the above particles, among the materials constituting the core, the metal element is selected from at least one of gold, silver, platinum, rhodium, palladium, ruthenium, iron, manganese, cobalt, nickel, titanium, magnesium, aluminum and tin ;
所述金属氧化物选自二氧化钛、二氧化锡、一氧化锡、二氧化铈、三氧化二铁、四氧化三铁、氧化锌、氧化镁、氧化钙、氧化锆、氧化钪、二氧化钒、五氧化二钒、三氧化二铬、氧化镓、氧化锗、氧化钇、氧化铌、氧化钌、氧化银、氧化金、氧化铂、氧化钯、氧化汞、氧化铅、氧化铟、氧化镉、氧化铱、三氧化钨、二氧化钨、氧化镧、氧化铋、氧化钍、氧化锂、氧化钴、二氧化锰、三氧化二锰、四氧化三锰、氧化镍、氧化铝、氧化钼、氧化铜、氧化镁、氧化钠、二氧化硅和五氧化二磷中的至少一种；The metal oxide is selected from titanium dioxide, tin dioxide, tin oxide, cerium oxide, ferric oxide, ferric oxide, zinc oxide, magnesium oxide, calcium oxide, zirconium oxide, scandium oxide, vanadium dioxide, Vanadium pentoxide, chromium oxide, gallium oxide, germanium oxide, yttrium oxide, niobium oxide, ruthenium oxide, silver oxide, gold oxide, platinum oxide, palladium oxide, mercury oxide, lead oxide, indium oxide, cadmium oxide, oxide Iridium, tungsten trioxide, tungsten dioxide, lanthanum oxide, bismuth oxide, thorium oxide, lithium oxide, cobalt oxide, manganese dioxide, manganese trioxide, trimanganese tetraoxide, nickel oxide, aluminum oxide, molybdenum oxide, copper oxide , at least one of magnesium oxide, sodium oxide, silicon dioxide and phosphorus pentoxide;
所述金属氢氧化物选自氢氧化铝、氢氧化铁、氢氧化锰、氢氧化钴、氢氧化镍、氢氧化铱、氢氧化锌、氢氧化铜、氢氧化钛、氢氧化铈和氢氧化锡中的至少一种；The metal hydroxide is selected from aluminum hydroxide, iron hydroxide, manganese hydroxide, cobalt hydroxide, nickel hydroxide, iridium hydroxide, zinc hydroxide, copper hydroxide, titanium hydroxide, cerium hydroxide and hydroxide at least one of tin;
所述金属无机盐选自磷酸铝、磷酸铁、磷酸锰、磷酸铁锂、磷酸锰锂、磷酸锰铁锂、磷酸钒锂、氟化铝、碳酸锰、碳酸钴、碳酸镍、碳酸钙、碳酸镁、碳酸铈和碳酸锌中的至少一种；The metal inorganic salt is selected from aluminum phosphate, iron phosphate, manganese phosphate, lithium iron phosphate, lithium manganese phosphate, lithium iron manganese phosphate, lithium vanadium phosphate, aluminum fluoride, manganese carbonate, cobalt carbonate, nickel carbonate, calcium carbonate, carbonic acid At least one of magnesium, cerium carbonate and zinc carbonate;
所述碳单质或其氧化体选自碳、碳纳米管、富勒烯、石墨烯、氧化石墨烯中的至少一种；The carbon element or its oxidant is selected from at least one of carbon, carbon nanotubes, fullerenes, graphene, and graphene oxide;
所述碳化物选自碳化钙、碳化铬、碳化钽、碳化钒、碳化锆、碳化钨、碳化硼和碳化硅中的至少一种；The carbide is selected from at least one of calcium carbide, chromium carbide, tantalum carbide, vanadium carbide, zirconium carbide, tungsten carbide, boron carbide and silicon carbide;
所述氮化物选自氮化锂、氮化钛、氮化钽、氮化硼、氮化镓、五氮化三磷和四氮化三硅中的至少一种；The nitride is selected from at least one of lithium nitride, titanium nitride, tantalum nitride, boron nitride, gallium nitride, phosphorus pentanitride and silicon nitride;
所述半导体选自硼、硅、硒、锗、碲、GaAs、ZnS、CdTe、HgTe、CuBr、CuI、Bi2Te3、Bi2Se3、Bi2S3、As2Te3、ZnSiP2、ZnGeP2、ZnGeAs2、CdGeAs2、CdSnSe2、CuGaSe2、AgInTe2、AgTlTe2、CuInSe2、CuAlS2、Cu3AsSe4、Ag3AsTe4、Cu3SbS4和Ag3SbSe4中的至少一种；The semiconductor is selected from boron, silicon, selenium, germanium, tellurium, GaAs, ZnS, CdTe, HgTe, CuBr, CuI, Bi2 Te3 , Bi2 Se3 , Bi2 S3 , As2 Te3 , ZnSiP2 , At least one of ZnGeP2 , ZnGeAs2 , CdGeAs2 , CdSnSe2 , CuGaSe2 , AgInTe 2 , AgTlTe2 , CuInSe2 , CuAlS2, Cu3 AsSe4 , Ag3 AsTe4 , Cu3 SbS4 and Ag3 SbSe4 kind;
所述有机物选自聚苯乙烯、酚醛树脂、脲醛树脂、聚乙烯吡咯烷酮、十六烷基三甲基溴化铵(CTAB)、十六烷基三甲基氯化铵(CTAC)、十二烷基硫酸钠(SDS)、多巴胺、葡萄糖和果糖中的至少一种。The organic matter is selected from polystyrene, phenolic resin, urea-formaldehyde resin, polyvinylpyrrolidone, cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC), dodecane at least one of sodium disulfate (SDS), dopamine, glucose and fructose.
所述核的平均粒径为1nm-25μm，优选2nm-15μm，具体为35nm、500nm、10μm、55nm-100nm、55nm-10μm或100nm-10μm；The average particle diameter of the core is 1nm-25μm, preferably 2nm-15μm, specifically 35nm, 500nm, 10μm, 55nm-100nm, 55nm-10μm or 100nm-10μm;
所述壳的平均厚度为1nm-200nm，优选1nm-50nm，更优选1nm-20nm。The average thickness of the shell is 1 nm-200 nm, preferably 1 nm-50 nm, more preferably 1 nm-20 nm.
本发明提供的制备所述硫化物包覆型颗粒的方法，所述方法包括如下步骤：将前述构成所述核的材料、金属盐、还原剂和硫源于溶剂中混匀，进行溶剂热反应，反应完毕，得硫化物包覆型颗粒。The method for preparing the sulfide-coated particles provided by the present invention includes the following steps: mixing the aforementioned materials constituting the core, the metal salt, the reducing agent and the sulfur source in a solvent, and performing a solvothermal reaction , after the reaction is completed, sulfide-coated particles are obtained.
上述方法中，反应完毕后进一步包括：在惰性气氛下煅烧，得到硫化物包覆型颗粒。其中，溶剂热反应后制备的硫化物包覆型颗粒中的硫化物可以是无定型的硫化物、多硫化物或晶相的硫化物；若得到的是无定型的硫化物或多硫化物，则通过所述煅烧步骤，可将无定型的硫化物或多硫化物转化为晶相的硫化物。In the above method, after the reaction is completed, it further includes: calcining under an inert atmosphere to obtain sulfide-coated particles. Wherein, the sulfides in the sulfide-coated particles prepared after the solvothermal reaction can be amorphous sulfides, polysulfides or crystal phase sulfides; if amorphous sulfides or polysulfides are obtained, Then, through the calcination step, the amorphous sulfide or polysulfide can be converted into crystalline sulfide.
上述方法中，所述溶剂热反应为水解反应。In the above method, the solvothermal reaction is a hydrolysis reaction.
上述方法中，所述金属盐选自金属醋酸盐、金属硝酸盐、钨酸钠、钨酸铵、钼酸铵、钼酸钠、磷钼酸中的至少一种。所述金属醋酸盐或金属硝酸盐中的金属选自锌、镉、钴、铅、铜或镍中的至少一种。In the above method, the metal salt is selected from at least one of metal acetate, metal nitrate, sodium tungstate, ammonium tungstate, ammonium molybdate, sodium molybdate, and phosphomolybdic acid. The metal in the metal acetate or metal nitrate is selected from at least one of zinc, cadmium, cobalt, lead, copper or nickel.
上述方法中，所述还原剂选自草酸、盐酸羟胺、甘氨酸、L-抗坏血酸、水合肼、硼氢化钠、甲醛、苯酚中的至少一种。In the above method, the reducing agent is selected from at least one of oxalic acid, hydroxylamine hydrochloride, glycine, L-ascorbic acid, hydrazine hydrate, sodium borohydride, formaldehyde, and phenol.
上述方法中，所述硫源选自硫化钠、硫脲、硫代甲酰胺、硫代乙酰胺、硫代硫酸钠、蛋氨酸、半胱氨酸中的至少一种。In the above method, the sulfur source is at least one selected from sodium sulfide, thiourea, thioformamide, thioacetamide, sodium thiosulfate, methionine, and cysteine.
上述方法中，所述溶剂选自水、乙醇、甲醇、丙醇、异丙醇、丁醇、乙二醇、二乙二醇和聚乙二醇中的至少一种。In the above method, the solvent is selected from at least one of water, ethanol, methanol, propanol, isopropanol, butanol, ethylene glycol, diethylene glycol and polyethylene glycol.
上述方法中，构成所述核的材料在反应体系中的浓度为0.01g/L-1000g/L，优选为0.1g/L-100g/L，还优选为4g/L-5g/L；In the above method, the concentration of the material constituting the core in the reaction system is 0.01g/L-1000g/L, preferably 0.1g/L-100g/L, and preferably 4g/L-5g/L;
金属盐在反应体系中的浓度为1*10-6mol/L-0.1mol/L，优选为1*10-5mol/L-0.01mol/L，还优选为0.25*10-3mol/L-0.5*10-3mol/L；The concentration of the metal salt in the reaction system is 1*10-6 mol/L-0.1 mol/L, preferably 1*10-5 mol/L-0.01 mol/L, and preferably 0.25*10-3 mol/L -0.5*10-3 mol/L;
还原剂在反应体系中的浓度为1*10-3mol/L-10mol/L，优选为0.01mol/L-1mol/L，还优选为0.25mol/L-0.5mol/L；The concentration of the reducing agent in the reaction system is 1*10-3 mol/L-10mol/L, preferably 0.01mol/L-1mol/L, and preferably 0.25mol/L-0.5mol/L;
硫源在在反应体系中的浓度为1*10-3mol/L-10mol/L，优选0.01mol/L-1mol/L，还优选为0.25mol/L、0.5mol/L或0.25-0.5mol/L。The concentration of the sulfur source in the reaction system is 1*10-3 mol/L-10mol/L, preferably 0.01mol/L-1mol/L, and preferably 0.25mol/L, 0.5mol/L or 0.25-0.5mol /L.
上述方法的溶剂热反应步骤中，pH值为0.5-10.0，优选3.0-8.0；温度为10℃-250℃，优选30℃-80℃；时间为45min-24h，优选3h-12h。In the solvothermal reaction step of the above method, the pH value is 0.5-10.0, preferably 3.0-8.0; the temperature is 10°C-250°C, preferably 30°C-80°C; the time is 45min-24h, preferably 3h-12h.
上述方法的煅烧步骤中，温度为300-1500℃，具体为600℃；时间为0.5-20小时，具体为8小时。In the calcining step of the above method, the temperature is 300-1500° C., specifically 600° C.; the time is 0.5-20 hours, specifically 8 hours.
上述方法中，在所述溶剂热反应过程中通入氮气、氩气、氢氩气等保护；煅烧时保护气氛取氮气、氩气、氢氩气等中一种。In the above method, nitrogen, argon, hydrogen and argon are introduced into the protective atmosphere during the solvothermal reaction; one of nitrogen, argon, hydrogen and argon is used as the protective atmosphere during calcination.
本发明提供的具有核壳结构的硫化物包覆型颗粒在催化、能源存储、表面增强拉曼、生物医学等领域具有广泛的应用。The sulfide-coated particles with a core-shell structure provided by the invention have a wide range of applications in the fields of catalysis, energy storage, surface-enhanced Raman, biomedicine and the like.
本发明的有益效果：Beneficial effects of the present invention:
本发明提供的硫化物包覆型颗粒，其制备方法是一种通用的包覆方法，可以在不同的核上得到了一层均匀的硫化物包覆层，并且包覆层的厚度可以精确调节和控制。本发明采用液相法，将所要包覆的核与金属盐混合，通过原位在核表面沉积硫化物，使之在核表面实现均一、连续、可控的包覆。本发明提供的包覆方法简单，反应条件温和，普适性强，包覆层厚度可控、完整、均一。本发明提供的硫化物包覆型颗粒在催化、能源存储、表面增强拉曼、生物医学等领域有着很高的实用性应用前景。The preparation method of the sulfide-coated particles provided by the invention is a general coating method, which can obtain a uniform sulfide coating layer on different cores, and the thickness of the coating layer can be precisely adjusted and control. The invention adopts a liquid phase method, mixes the core to be coated with a metal salt, and deposits sulfide on the surface of the core in situ to realize uniform, continuous and controllable coating on the surface of the core. The coating method provided by the invention is simple, the reaction conditions are mild, the universality is strong, and the thickness of the coating layer is controllable, complete and uniform. The sulfide-coated particles provided by the invention have high practical application prospects in the fields of catalysis, energy storage, surface-enhanced Raman, biomedicine and the like.
附图说明Description of drawings
图1为实施例1的硫化钴包覆的聚苯乙烯小球透射电子显微镜(TEM)图。FIG. 1 is a transmission electron microscope (TEM) image of cobalt sulfide-coated polystyrene beads in Example 1.
图2为实施例2的硫化锌包覆的二氧化硅小球的TEM图。FIG. 2 is a TEM image of the zinc sulfide-coated silica pellets of Example 2. FIG.
图3为实施例3的煅烧前得到的硫化钼包覆的碳纳米管的透射电子显微镜图。FIG. 3 is a transmission electron microscope image of the molybdenum sulfide-coated carbon nanotubes obtained before calcination in Example 3. FIG.
图4为实施例3的煅烧后得到的硫化钼包覆的碳纳米管的透射电子显微镜图。FIG. 4 is a transmission electron microscope image of the molybdenum sulfide-coated carbon nanotube obtained after calcination in Example 3. FIG.
具体实施方式Detailed ways
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外，应理解，在阅读了本发明所记载的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本发明所限定的范围。Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the contents of the present invention, those skilled in the art may make various changes or modifications to the present invention, and these equivalent forms also fall within the scope of the present invention.
实施例1Example 1
制备硫化钴包覆的聚苯乙烯Preparation of cobalt sulfide-coated polystyrene
将聚苯乙烯颗粒0.2g(平均粒径为500nm)、乙酸钴0.124g(1*10-3mol/L)还原剂水合肼400微升、硫源硫代乙酰胺0.075g(2*10-3mol/L)在溶剂水50ml中混合，在搅拌下40℃回流进行水解反应12h，经离心、洗涤、干燥得到硫化钴包覆的聚苯乙烯颗粒。Add 0.2g of polystyrene particles (average particle size of 500nm), 0.124g of cobalt acetate (1*10-3 mol/L), 400 microliters of reducing agent hydrazine hydrate, and 0.075g of sulfur source thioacetamide (2*10-3 mol/L). 3 mol/L) in 50ml of solvent water, and reflux at 40°C under stirring for 12h for hydrolysis reaction, centrifugation, washing, and drying to obtain cobalt sulfide-coated polystyrene particles.
该硫化钴包覆的聚苯乙烯颗粒为核壳结构，其电镜照片如图1所示。构成核的材料为粒径约为500nm的聚苯乙烯，构成壳的材料为晶相的硫化钴，厚度约为30nm，且硫化钴均匀覆盖在聚苯乙烯表面。The cobalt sulfide-coated polystyrene particles have a core-shell structure, and its electron micrograph is shown in FIG. 1 . The material constituting the core is polystyrene with a particle size of about 500nm, and the material constituting the shell is cobalt sulfide in crystal phase with a thickness of about 30nm, and the cobalt sulfide uniformly covers the surface of polystyrene.
实施例2Example 2
硫化锌包覆的二氧化硅颗粒Zinc sulfide coated silica particles
将二氧化硅颗粒0.1g(平均粒径为400nm)、六水合硝酸锌0.149g(1*10-3mol/L)还原剂水合肼400微升、硫源硫脲0.076g(2*10-3mol/L)在溶剂水50ml中混合，在搅拌下55℃回流进行水解反应8h，经离心、洗涤、干燥得到硫化锌包覆的二氧化硅颗粒。Mix 0.1g of silica particles (average particle diameter of 400nm), 0.149g of zinc nitrate hexahydrate (1*10-3 mol/L), 400 microliters of reducing agent hydrazine hydrate, and 0.076g of sulfur source thiourea (2*10- 3 mol/L) in 50ml of solvent water, and reflux at 55°C under stirring for 8h for hydrolysis reaction, centrifugation, washing, and drying to obtain zinc sulfide-coated silica particles.
该硫化锌包覆的二氧化硅颗粒为核壳结构，其电镜照片如图2所示。构成核的材料为粒径约为400nm的二氧化硅球，构成壳的材料为晶相的硫化锌，厚度约为20nm；且硫化锌均匀覆盖在硅颗粒表面。The silicon dioxide particles coated with zinc sulfide have a core-shell structure, and its electron microscope photo is shown in FIG. 2 . The material constituting the core is silicon dioxide spheres with a particle size of about 400nm, and the material constituting the shell is zinc sulfide in the crystalline phase with a thickness of about 20nm; and the zinc sulfide uniformly covers the surface of the silicon particles.
实施例3Example 3
制备硫化钼包覆的碳纳米管Preparation of carbon nanotubes coated with molybdenum sulfide
将碳纳米管0.2g、钼酸铵0.242g(1*10-3mol/L)还原剂水合肼800微升、硫源硫代乙酰胺0.15g(2*10-3mol/L)在溶剂水100ml中混合，在搅拌下35℃回流进行水解反应24h，经离心、洗涤、干燥得到无定型的硫化钼包覆的碳纳米管，再在惰性气氛600℃下煅烧7h，得到晶相的硫化钼包覆的碳纳米管。Mix 0.2 g of carbon nanotubes, 0.242 g of ammonium molybdate (1*10-3 mol/L) of 800 microliters of reducing agent hydrazine hydrate, and 0.15 g of sulfur source thioacetamide (2*10-3 mol/L) in a solvent Mix in 100ml of water, reflux at 35°C under stirring for 24h for hydrolysis reaction, centrifuge, wash, and dry to obtain amorphous molybdenum sulfide-coated carbon nanotubes, and then calcined at 600°C for 7h in an inert atmosphere to obtain sulfide in the crystal phase Molybdenum-coated carbon nanotubes.
该无定型的硫化钼包覆的碳纳米管和晶相的硫化钼包覆的碳纳米管的电镜照片如图3和图4所示。硫化钼层厚度为10nm；且硫化钼均匀覆盖在碳纳米管表面。The electron micrographs of the amorphous molybdenum sulfide-coated carbon nanotubes and the crystalline molybdenum sulfide-coated carbon nanotubes are shown in FIGS. 3 and 4 . The thickness of the molybdenum sulfide layer is 10nm; and the molybdenum sulfide evenly covers the surface of the carbon nanotubes.
以上，对本发明的实施方式进行了说明。但是，本发明不限定于上述实施方式。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The embodiments of the present invention have been described above. However, the present invention is not limited to the above-mentioned embodiments. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.
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| CN201610943827.5ACN107983272A (en) | 2016-10-26 | 2016-10-26 | Sulfide encapsulated particles and preparation method and application |
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| CN201610943827.5ACN107983272A (en) | 2016-10-26 | 2016-10-26 | Sulfide encapsulated particles and preparation method and application |
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| CN201610943827.5APendingCN107983272A (en) | 2016-10-26 | 2016-10-26 | Sulfide encapsulated particles and preparation method and application |
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| RJ01 | Rejection of invention patent application after publication | Application publication date:20180504 |