CN111233041B - Preparation method of ionic liquid intercalated nano molybdenum disulfide - Google Patents
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Abstract
The invention discloses a preparation method of ionic liquid intercalated nano molybdenum disulfide. The method comprises the following steps: (1) respectively adding aqueous solutions of a molybdenum source and a sulfur source with certain concentrations into two prepared emulsion solutions, emulsifying to form reverse micro-emulsions A and B, mixing the reverse micro-emulsions A and B to obtain a reverse micro-emulsion C, carrying out micro-emulsion heat treatment on the C, and then separating, washing and drying to obtain nano molybdenum disulfide; (2) dispersing the nano molybdenum disulfide prepared in the step (1) in an ionic liquid aqueous solution, carrying out ion exchange for 2-72 h at 15-80 ℃, separating, washing and drying the obtained product, and obtaining the ionic liquid intercalated nano molybdenum disulfide. The synthetic method has the advantages that the preparation process is mild in condition, the operation process is simple and safe, subsequent impurity treatment is not needed, the prepared ionic liquid intercalated nano molybdenum disulfide has the interlayer spacing of 1.0-4.0 nm, high dispersibility and the particle size of 5-30 nm, and the highest side active site exposure rate is achieved.
Description
Technical Field
The invention relates to a preparation method of nano molybdenum disulfide for ionic liquid intercalation, in particular to a method for preparing nano molybdenum disulfide for ionic liquid intercalation by carrying out ion exchange on nano molybdenum disulfide thermally synthesized by microemulsion in a reverse ionic liquid microemulsion system.
Background
Molybdenum disulfide has a graphene-like layered structure. A monolayer of molybdenum disulfide can be viewed as a "sandwich-like" structure formed by one atomic layer of molybdenum sandwiched between two atomic layers of sulfur. In the S-Mo-S monolayer, each molybdenum atom and six sulfur atoms form covalent bonds and are in a triangular prism shape or an octahedron shape. The layers are connected through weak van der Waals force to form a multi-layer stacked structure, the direct distance between the layers is 0.62nm, and the layers are connected through strong chemical bonds. The molybdenum disulfide with the intercalation structure has the characteristics of larger interlayer spacing, fewer stacked layers, more defect sites and the like, and the characteristics are all beneficial to increasing the exposure of the active sites of the molybdenum disulfide nanosheets, so that the reaction activity of the molybdenum disulfide nanosheets in the processes of catalytic hydrogenation, electrochemical catalysis and the like of oil products is improved.
The intercalation is to insert a guest substance into the molybdenum disulfide layer without causing the breakage of chemical bonds in the layer by utilizing the characteristic of the layered structure of the molybdenum disulfide. At present, the synthesis of two-dimensional molybdenum disulfide nanosheets with intercalation structures has been reported, for example, metal ions, organic macromolecules and O atoms (P atoms or NH) are prepared by hydrothermal solvothermal methods and the like4 +) Isoheteroatom intercalated molybdenum sulfide materials.
CN108067257A discloses a method for preparing a nano molybdenum disulfide hydrogenation catalyst with exposed high-activity sites by adopting high-viscosity solvent solvothermal method, wherein the interlayer spacing of the prepared nano molybdenum disulfide catalyst is enlarged from 0.62nm to 0.98nm by intercalation of ammonium radicals, metal ions and the like. CN 10660865 discloses a preparation method of a metal cation doped molybdenum disulfide material. Adding a metal complex solution protected by a coordination reagent into a molybdenum source sulfur source reaction solution to obtain solid powder, and then carrying out high-temperature treatment to obtain a metal cation doped molybdenum disulfide material with the interlayer spacing of 0.62-1.0 nm. CN 107540019A discloses a preparation method of a molybdenum disulfide/graphene alternate intercalation structure material, in the invention, a surfactant is added into a molybdenum source sulfur source reaction solution, a solid product obtained by hydrothermal reaction is roasted at 800 ℃ in an inert atmosphere, and then the molybdenum disulfide/graphene alternate intercalation structure material is obtained, wherein the interlayer spacing of the molybdenum disulfide material is 0.95 nm. In conclusion, the molybdenum disulfide with enlarged interlayer spacing prepared in the invention is mostly caused by insertion of inorganic cations or carbon-containing substances and the like between layers, and the interlayer spacing is less than 1.0 nm.
CN103275355A discloses an organicThe preparation method of the modified molybdenum disulfide nanosheet layer comprises the steps of carrying out intercalation treatment on layered molybdenum disulfide by using an intercalation agent such as n-butyllithium and the like through a solvothermal method, hydrolyzing the intercalated molybdenum disulfide to obtain a molybdenum disulfide suspension, adding an organic modifier into the suspension to react to generate the organic modified molybdenum disulfide nanosheet layer, wherein the interlayer spacing is 1.1-3.0 nm. The prepared organic modified molybdenum disulfide nanosheet layer has good dispersibility in an organic solvent. In this invention, lithium ions (e.g. butyllithium, n-C)4H9Li) is firstly embedded into the molybdenum disulfide powder layers to form a compound with an intercalation structure, and then reacts with water (protic solvent) to generate hydrogen, so that stripping of molybdenum disulfide is realized, and a single-layer or few-layer molybdenum disulfide nanosheet is formed. But due to n-C4H9Li is very active, the required working environment is harsh, Li ion insertion reaction must be performed in an oxygen-free and water-free environment, and post-treatment is required to remove lithium ions after reaction with water.
In order to increase the exposure of the active site of the molybdenum disulfide nanosheet and improve the reaction activity of the molybdenum disulfide nanosheet in the processes of oil product catalytic hydrogenation, electrochemical catalysis and the like, a synthesis method needs to be further developed to prepare the molybdenum disulfide nanocatalyst with an intercalation structure.
Disclosure of Invention
Based on the problems, the invention provides the preparation method of the ionic liquid intercalated nano molybdenum disulfide, which has the advantages of mild preparation conditions, simple and safe operation, no need of subsequent treatment and high side exposure.
The method adopted by the invention is as follows:
(1) respectively dissolving soluble molybdenum source and biological sulfur source in deionized water, respectively adding aqueous solution of molybdenum source and sulfur source with certain concentration into two prepared emulsion solutions, emulsifying to form reversed-phase microemulsions A and B, mixing the reversed-phase microemulsions A and B to obtain reversed-phase microemulsion C, carrying out microemulsion heat treatment on the C, separating, washing and drying to obtain nano molybdenum disulfide;
(2) dispersing the nano molybdenum disulfide prepared in the step (1) in an ionic liquid aqueous solution, carrying out ion exchange for 2-72 h at 15-80 ℃, separating, washing and drying the obtained product, and obtaining the ionic liquid intercalated nano molybdenum disulfide.
(3) And performing characterization analysis on the prepared molybdenum disulfide product. The obtained product is characterized by the crystal phase structure and the interlayer spacing by XRD (X-ray powder diffraction). The result shows that the black powder obtained by microemulsion heating is molybdenum disulfide, the crystallization degree is good, the calculated interlayer spacing is 1.0nm, the crystallization degree is increased after the ionic liquid is intercalated, and the interlayer spacing is increased to 1.12 nm. Compared with molybdenum disulfide prepared by microemulsion heat, the interlayer spacing of the ionic liquid is obviously increased after intercalation (see figure 1); the particle size and the dispersity of the molybdenum disulfide are characterized by SEM (scanning electron microscope), and SEM pictures show that the prepared molybdenum disulfide is high-dispersity nanoflower with the particle size of 5-30 nm (see figure 2). The size of the lamella of the molybdenum disulfide nano-particles is characterized by TEM (transmission electron microscope), and TEM photos show that the length of the lamella size of the prepared molybdenum disulfide nano-particles is 5-20 nm (see figure 3).
The soluble molybdenum source adopted in the microemulsion thermal process is one or more than two of ammonium heptamolybdate, ammonium molybdate, sodium molybdate and phosphomolybdic acid, and the concentration of molybdenum in the prepared molybdenum source aqueous solution is 0.05-0.50 mol/L.
The sulfur source used in the invention is one or a mixture of two of biological sulfur source L-cysteine and glutathione, and the concentration of the prepared sulfur source aqueous solution is 0.20-2.00 mol/L.
The emulsifying solution used in the invention is polyethylene glycol octyl phenyl ether (Triton X-100): alcohol: the cyclohexane is (1-5) to (1-50) in mass ratio.
The aqueous solution in the reverse microemulsion used in the present invention: the mass ratio of (Triton X-100+ alcohol + cyclohexane) is 0.005-0.50.
The heat treatment temperature of the microemulsion is 120-220 ℃, and the treatment time is 2-72 hours.
The ionic liquid used in the invention can be 1-ethyl-3-methylimidazole bromine salt EMIMBr, 1-ethyl-3-methylimidazole chlorine salt EMIMCl, 1-butyl-3-methylimidazole bromine salt BMIMBr, 1-butyl-3-methylimidazole chlorine salt BMIMCl, 1-butyl-3-methylimidazole tetrafluoroborate BMIMBF41-butyl-3-methylimidazolium tetrafluorophosphate BMIMPF4One or more than two hydrophilic ionic liquids are added, and the concentration of the ionic liquid aqueous solution is 0.01-5.00 mol/L.
The molar ratio of the nano molybdenum disulfide to the intercalation ionic liquid is 1 (0.1-10).
The molybdenum disulfide prepared by the invention has the advantages of nanoflower appearance, particle size of 5-30 nm, ionic liquid inserted interlayer and interlayer spacing expanded by 1.0-4.0 nm, and compared with the interlayer spacing of 0.62nm of commercial molybdenum disulfide, the interlayer spacing is increased by 0.38-3.38 nm, so that the molybdenum disulfide of the ionic liquid intercalation has high exposure of side active sites.
Compared with the prior art, the invention has the following advantages and effects:
the invention adopts a microemulsion thermal process to prepare the nano molybdenum disulfide sample with micromolecules such as ammonium radicals, sodium ions and other cation intercalation, and further prepares the nano molybdenum disulfide sample with ionic liquid intercalation through a simple low-temperature ion exchange process. The nano molybdenum disulfide sample can be prepared by carrying out ion exchange on a molybdenum disulfide sample prepared by microemulsion heat at a low temperature (100 ℃), the preparation process is mild in condition, the operation process is simple and safe, and the ionic liquid intercalated nano molybdenum disulfide material with high side exposure can be obtained without subsequent impurity treatment.
The micro-emulsion adopted by the invention can form a micro-reactor, also called as an intelligent micro-reactor, which has self-organization and self-reproduction functions under certain conditions, the size of the reactor is generally controlled to be about tens of nanometers and separated from each other, and the prepared nano product has uniform particle size and good dispersion. And after the reaction is finished, a demulsifier is used for destroying the microemulsion system, and the nano particles and the surfactant are separated to obtain the product, wherein the surfactant can be recycled. The process has the advantages of simple operation, controllable particle size, narrow particle size distribution range, good particle dispersibility, easy realization of continuous operation and the like.
The molybdenum disulfide sample of the ionic liquid intercalation prepared by the invention has enlarged interlayer spacing, and the adjustment and control of the interlayer spacing can be realized by adjusting and controlling the amount of the inserted ionic liquid. In addition, the nano molybdenum disulfide sample of the ionic liquid intercalation has nano size and high dispersibility, and is beneficial to realizing high-activity exposure in the application of the nano molybdenum disulfide sample in the fields of hydrogenation, electrocatalysis and the like.
Drawings
FIG. 1a) XRD spectrum of microemulsion heat prepared and ionic liquid intercalated molybdenum disulfide sample at 5-70 degrees, b) XRD spectrum of microemulsion heat prepared and ionic liquid intercalated molybdenum disulfide sample at 5-20 degrees.
FIG. 2 SEM photograph of ionic liquid intercalated nano molybdenum disulfide.
FIG. 3 TEM photograph of ionic liquid intercalated nano molybdenum disulfide.
FIG. 4 shows a) an XRD spectrum, b) an SEM photograph, and c, d) a TEM photograph of commercial molybdenum disulfide.
Detailed Description
Example 1
Polyethylene glycol octyl phenyl ether (Triton X-100), n-hexanol and cyclohexane are prepared into two parts of emulsified solution according to the mass ratio of 1:1:1, wherein each part comprises 16.25g of Triton X-100, 16.25g of n-hexanol and 16.25g of cyclohexane. Adding 2.45mL of 0.05mol/L sodium molybdate aqueous solution into the emulsified solution under the condition of emulsification and stirring, and stirring for 30min to form the inverse microemulsion A. Adding 2.45mL of glutathione aqueous solution with the concentration of 0.4mol/L into the emulsified solution under the condition of emulsification and stirring, and stirring for 30min to form the reverse microemulsion B. And mixing the reversed-phase microemulsion A and the reversed-phase microemulsion B to obtain reversed-phase microemulsion C, carrying out microemulsion heat treatment on the reversed-phase microemulsion C at 120 ℃ for 72 hours, and then separating, washing and drying to obtain the nano molybdenum disulfide. XRD characterization of the prepared nano molybdenum disulfide is shown in figure 1, the molybdenum sulfide has better crystallinity, the interlayer spacing of 1.0nm is calculated according to a Bragg equation, and the interlayer spacing of the molybdenum disulfide prepared by the method is increased by 0.38nm compared with the interlayer spacing of 0.62nm of a commercial molybdenum disulfide.
Dispersing 0.8g of the nano molybdenum disulfide prepared in the steps in 50mL of 0.01M 1-ethyl-3-methylimidazole bromine salt EMIMBr ionic liquid aqueous solution, carrying out ion exchange for 72 hours at 15 ℃, separating, washing and drying the obtained product, and obtaining the ionic liquid intercalated nano molybdenum disulfide.
The obtained ionic liquid intercalation product is characterized by the crystalline phase structure and the interlayer spacing by XRD (X-ray powder diffraction). The results show that the crystallization degree of the molybdenum disulfide ionic liquid obtained by microemulsion heat is increased after intercalation, and the interlayer spacing is increased to 1.12 nm. Compared with the interlayer spacing of the commercial molybdenum sulfide in the figure 4 of 0.62nm, the interlayer spacing of the ionic liquid intercalated sample is increased by 0.39 nm. And (3) characterizing the morphology, the particle size and the dispersion degree by using an SEM (scanning electron microscope), wherein the SEM photo shows that the prepared molybdenum disulfide is in a highly dispersed nano flower shape, and the particle size is 10-20 nm (see figure 2). The size of the lamella of the prepared ionic liquid intercalated molybdenum disulfide nanoparticles is characterized by TEM (transmission electron microscope), and TEM photographs show that the length of the lamella size of the prepared ionic liquid intercalated molybdenum disulfide nanoparticles is 5-10 nm (see figure 3).
Example 2
Polyethylene glycol octyl phenyl ether (Triton X-100), n-hexanol and cyclohexane are prepared into two parts of emulsified solution according to the mass ratio of 2:1:10, wherein each part comprises 7.50g of Triton X-100, 3.75g of n-hexanol and 37.50g of cyclohexane. Adding 0.245mL of 0.5mol/L sodium molybdate aqueous solution into the emulsified solution under the condition of emulsification and stirring, and stirring for 30min to form the reverse microemulsion A. Adding 0.245mL of 2.0 mol/L-cysteine aqueous solution into the emulsified solution under the condition of emulsification and stirring, and stirring for 30min to form the inverse microemulsion B. And mixing the reversed-phase microemulsion A and the reversed-phase microemulsion B to obtain reversed-phase microemulsion C, carrying out microemulsion heat treatment on the reversed-phase microemulsion C at 160 ℃ for 24 hours, and then separating, washing and drying to obtain the nano molybdenum disulfide.
Dispersing 0.8g of the nano molybdenum disulfide prepared in the steps in 50mL of 1.0M 1-butyl-3-methylimidazolium chloride BMIMCl ionic liquid aqueous solution, carrying out ion exchange at 40 ℃ for 24 hours, separating, washing and drying the obtained product, and obtaining the ionic liquid intercalated nano molybdenum disulfide.
Example 3
Polyethylene glycol octyl phenyl ether (Triton X-100), n-hexanol and cyclohexane are prepared into two parts of emulsified solution according to the mass ratio of 5:1:50, wherein each part comprises 4.35g of Triton X-100, 0.87g of n-hexanol and 43.50g of cyclohexane. Adding 24.5mL of 0.25mol/L sodium molybdate aqueous solution into the emulsified solution under the condition of emulsification and stirring, and stirring for 30min to form the inverse microemulsion A. Adding 24.5mL of glutathione aqueous solution with the concentration of 1.0mol/L into the emulsified solution under the condition of emulsification and stirring, and stirring for 30min to form the reverse microemulsion B. And mixing the reversed-phase microemulsion A and the reversed-phase microemulsion B to obtain reversed-phase microemulsion C, carrying out microemulsion heat treatment on the reversed-phase microemulsion C at the temperature of 140 ℃ for 48 hours, and then separating, washing and drying to obtain the nano molybdenum disulfide.
Dispersing 0.8g of nano molybdenum disulfide prepared in the steps in 50mL of 5.0M 1-butyl-3-methylimidazolium tetrafluoroborate BMIMBF4And (3) carrying out ion exchange for 2 hours in an ionic liquid aqueous solution at 80 ℃, separating, washing and drying the obtained product to obtain the ionic liquid intercalated nano molybdenum disulfide.
Example 4
Polyethylene glycol octyl phenyl ether (Triton X-100), n-hexanol and cyclohexane are prepared into two parts of emulsified solution according to the mass ratio of 2:1:10, wherein each part comprises 7.50g of Triton X-100, 3.75g of n-hexanol and 37.50g of cyclohexane. Adding 0.245mL of 0.5mol/L sodium molybdate aqueous solution into the emulsified solution under the condition of emulsification and stirring, and stirring for 30min to form the reverse microemulsion A. Adding 0.245mL of 2.0 mol/L-cysteine aqueous solution into the emulsified solution under the condition of emulsification and stirring, and stirring for 30min to form the inverse microemulsion B. And mixing the reversed-phase microemulsion A and the reversed-phase microemulsion B to obtain reversed-phase microemulsion C, carrying out microemulsion heat treatment on the reversed-phase microemulsion C at 160 ℃ for 24 hours, and then separating, washing and drying to obtain the nano molybdenum disulfide.
Dispersing 0.8g of the nano molybdenum disulfide prepared in the steps in 50mL of 1.0M 1-butyl-3-methylimidazolium chloride BMIMCl ionic liquid aqueous solution, carrying out ion exchange at 60 ℃ for 12 hours, separating, washing and drying the obtained product, and obtaining the ionic liquid intercalated nano molybdenum disulfide.
Example 5
Polyethylene glycol octyl phenyl ether (Triton X-100), n-hexanol and cyclohexane are prepared into two parts of emulsified solution according to the mass ratio of 2:1:10, wherein each part comprises 7.50g of Triton X-100, 3.75g of n-hexanol and 37.50g of cyclohexane. Adding 2.45mL of ammonium heptamolybdate aqueous solution with the concentration of 0.05mol/L into the emulsified solution under the condition of emulsification and stirring, and stirring for 30min to form the inverse microemulsion A. Adding 2.45mL of 1.4mol/L glutathione aqueous solution into the emulsified solution under the condition of emulsification and stirring, and stirring for 30min to form the reverse microemulsion B. And mixing the reversed-phase microemulsion A and the reversed-phase microemulsion B to obtain reversed-phase microemulsion C, carrying out microemulsion heat treatment on the reversed-phase microemulsion C at the temperature of 200 ℃ for 12 hours, and then separating, washing and drying to obtain the nano molybdenum disulfide.
Dispersing 0.8g of nano molybdenum disulfide prepared in the steps in 50mL of 0.5M 1-butyl-3-methylimidazolium tetrafluorophosphate BMIMPF4And (3) carrying out ion exchange in an ionic liquid aqueous solution at 20 ℃ for 60 hours, and separating, washing and drying the obtained product to obtain the ionic liquid intercalated nano molybdenum disulfide.
Comparative example
Commercial molybdenum disulfide 0.8g was dispersed in 50mL of 0.5M 1-butyl-3-methylimidazolium tetrafluorophosphate BMIMPF4And (3) carrying out ion exchange in an ionic liquid aqueous solution at 20 ℃ for 60 hours, and separating, washing and drying the obtained product to obtain the commercial molybdenum disulfide.
XRD characterization of the prepared commercial molybdenum disulfide is shown in figure 4a, the molybdenum sulfide has better crystallinity, and the layer spacing of the commercial molybdenum disulfide is calculated to be 0.62nm according to the Bragg equation. The SEM photograph of commercial molybdenum disulfide in FIG. 4b shows that the commercial molybdenum disulfide is in the form of agglomerated chunks with a particle size of 0.5-5 μm (see FIG. 4 b). TEM photographs showed that commercial molybdenum disulfide sheets were prepared with layer sizes ranging from 200 to 500nm in length (see FIGS. 4c and 4 d).
Claims (4)
1. A preparation method of ionic liquid intercalated nano molybdenum disulfide is characterized by comprising the following steps:
(1) respectively dissolving a soluble molybdenum source and a biological sulfur source in water, respectively adding aqueous solutions of the molybdenum source and the sulfur source into two prepared emulsion solutions, respectively emulsifying to form reverse micro-emulsions A and B, mixing the reverse micro-emulsions A and B to obtain a reverse micro-emulsion C, carrying out micro-emulsion heat treatment on the C, and then separating, washing and drying to obtain nano molybdenum disulfide; the heat treatment temperature of the microemulsion is 120-220 ℃, and the treatment time is 2-72 h;
(2) dispersing the nano molybdenum disulfide prepared in the step (1) in an ionic liquid aqueous solution, carrying out ion exchange for 2-72 h at 15-80 ℃, separating, washing and drying the obtained product to obtain the ionic liquid intercalated nano molybdenum disulfide, wherein the prepared molybdenum disulfide has a particle size of 5-30 nm, the ionic liquid is inserted between layers, the interlayer spacing is 1.0-4.0 nm, and the molybdenum disulfide has high side active site exposure;
the microemulsion thermal process in the step (1) adopts one or more than two soluble molybdenum sources of ammonium heptamolybdate, ammonium molybdate, sodium molybdate and phosphomolybdic acid, and the concentration of molybdenum in the prepared molybdenum source aqueous solution is 0.05-0.50 mol/L;
the micro-emulsion thermal process in the step (1) adopts a sulfur source which is one or a mixture of two of biological sulfur source L-cysteine and glutathione, and the concentration of the prepared sulfur source water solution is 0.20-2.00 mol/L;
the emulsified solution in the step (1) is polyethylene glycol octyl phenyl ether Triton X-100: n-pentanol: the cyclohexane is prepared according to the mass ratio of (1-5) to (1-50).
2. The method for preparing ionic liquid intercalated nano molybdenum disulfide according to claim 1, wherein the reverse microemulsion of step (1) contains an aqueous solution: the mass ratio of Triton X-100+ n-amyl alcohol + cyclohexane is 0.005-0.50; the volume ratio of the inverse microemulsion A and the inverse microemulsion B is 1:1 when mixing.
3. The method for preparing nano molybdenum disulfide by ionic liquid intercalation according to claim 1, wherein the ionic liquid in step (2) is 1-ethyl-3-methylimidazole bromide EMIMBr, 1-ethyl-3-methylimidazole chloride EMIMCl, 1-butyl-3-methylimidazole bromide BMIMBr, 1-butyl-3-methylimidazole chloride BMIMCl, 1-butyl-3-methylimidazole tetrafluoroborate BMIMBF41-butyl-3-methylimidazolium tetrafluorophosphate BMIMPF4One or more than two hydrophilic ionic liquids, wherein the concentration of the ionic liquid aqueous solution is 0.01-5.00 mol/L.
4. The method for preparing the ionic liquid intercalated nano molybdenum disulfide according to claim 1, wherein the molar ratio of the nano molybdenum disulfide to the intercalated ionic liquid in the step (2) is 1 (0.1-10).
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