TWI813976B - Carboxylate, use of carboxylate for producing metal sulfide with nanostructure, method of preparation of metal sulfide with nanostructure, use of liguid medium ,and use of gaseous sulfuric source - Google Patents

Abstract

A carboxylate, a use of a carboxylate for producing metal sulfide with nanostructure, a method of preparation of metal sulfide with nanostructure, a use of liquid medium, and a use of gaseous sulfuric source are provided. The carboxylate is represented by formula (I), wherein R ₁, R ₂, and R ₃are linear alkyl groups, branched alkyl groups, or hydrogen, x is an integer between 1 and3, M is a transition metal.

Description

Carboxylate, its use as a preparation method of metal sulfide with nanostructure, preparation method of metal sulfide with nanostructure, use of liquid medium, and use of gaseous sulfur source

The present invention relates to a carboxylate, its use as a preparation method of metal sulfide with nanostructure, the preparation method of metal sulfide with nanostructure, the use of liquid medium, and the use of gaseous sulfur source.

Conventional manufacturing methods of semiconductor materials with nanostructures include two major technical fields: (1) Top-down and (2) Bottom up. (1) Top-down mainly uses mechanical methods to gradually reduce the size of the material through high-pressure, high-speed and other grinding methods. The main shortcomings of this technology are the large size distribution and poor geometric uniformity of the prepared nanopowders. The phenomenon of aggregation between powders is easy to occur, so there are limitations in practical application. (2) Bottom-up is the mainstream technology for nanopowder preparation. Compared with the above-mentioned Top-down method, it can control various conditions of nanomaterials more accurately.

Bottom-up can be further divided into three major categories of technical fields: (1) gas phase method, (2) solid phase method, and (3) liquid phase method. (1) Vapor phase methods include Vapor-liquid-solid (VLS) method, chemical vapor deposition (CVD), thermal evaporation (Thermal evaporation), etc., although nanomaterials can be precisely controlled The growth rate, shape and size, but its main shortcoming is that the synthesis environmental conditions are relatively harsh, including expensive equipment, high vacuum environment, and high-purity metal precursors, so the preparation cost is high. (2) The solid-phase method does not use solvents, but must crack the metal precursor in a high-temperature environment. The chemical composition of the precursor must include metal and sulfur, but its limitation is that the source of the precursor is small and difficult to obtain. And expensive. (3) The liquid phase method is also called the wet chemical method. The manufacturing process uses solvents or liquid media. It is characterized by diverse choices of metal precursors, solvents, and protective agents. It can be changed by changing the concentration, temperature, and time of the reactants. Various nanostructured metal sulfides are prepared under the same conditions, and also have better nanometer size uniformity and dispersion.

However, the previous technology for preparing nanostructured metal sulfide by wet chemical method is limited to higher reaction temperature, which even needs to reach 400°C. The reason is that (a) the solid metal source usually uses metal oxidation Materials (such as cadmium oxide, CdO), inorganic metal salts (such as zinc chloride, copper chloride, cadmium chloride), acetylacetone metal salts (such as copper acetylacetone), thiol metal salts (such as copper dodecanethiolate), linear alkanes Carboxylic acid metal salts (such as copperoleate) must reach high temperature conditions in the liquid phase to dissolve and crack to produce metal ions; (b) Liquid and solid sulfur sources usually use mercaptans (such as octanethiol, dodecanethiol, octadecanethiol), sulfur powder ( S), carbon disulfide, ammonium diethyldithiocarbamate, thioacetamide, alkyl mercaptans, etc., must reach high temperatures in the liquid phase to produce sulfide ions. ; (c) Liquid media usually use high boiling point solvents, such as 9-octylamine (tri-n-octylphosphine, boiling point about 348°C), trioctylamine (trooctylamine, boiling point about 365°C), tri-n-octylamine Phosphorus oxide (tri-n-octylphosphine oxide, boiling point is about 411°C), hexadecylamine (boiling point is about 330°C), and dodecanethiol (boiling point is about 266°C) to provide a high-temperature synthesis environment ; (d) After the reaction is completed, an antisolvent (such as ethanol, acetone, etc.) must be added to the liquid medium to precipitate the nanostructured metal sulfide from the liquid medium, and then filtered or centrifuged, rinsed (such as ethanol, acetone, etc.) ), drying and other multiple procedures to obtain metal sulfide products with nanostructures.

The object of the present invention is to provide a carboxylate that can be dissolved in a low boiling point (less than or equal to 125°C) organic solvent at low temperature (less than or equal to 150°C).

Another object of the present invention is to provide a carboxylate for use in preparing metal sulfides with nanostructures, which can prepare metal sulfides with nanostructures at low temperatures.

Another object of the present invention is to provide a method for preparing metal sulfide with nanostructure, which can be carried out at low temperature.

The carboxylate salt of the present invention is represented by the following formula (I), Formula (I); wherein, R ₁ , R ₂ , R ₃ are linear alkyl groups, branched alkyl groups or hydrogen containing 1-22 carbon atoms, X is an integer between 1 and 3, and M is Transition metals.

In one embodiment of the present invention, R ₁ and R ₂ are respectively a linear or branched alkyl group having a carbon number of 1-22 and having a tert-butyl group.

In one embodiment of the present invention, R ₁ and R ₂ together are a cycloalkyl group having a carbon number of 2-22 and having a tert-butyl group.

In one embodiment of the invention, M is not silver or palladium.

The preparation method of metal sulfide with nanostructure of the present invention includes the following steps in sequence: (A1000) providing the aforementioned carboxylate; (A2000) mixing and dissolving the carboxylate and liquid medium to form a liquid reactant slurry; (A3000) Mix and react the liquid reaction slurry with the gaseous sulfur source to generate nanostructured metal sulfides.

In one embodiment of the present invention, step A1000 includes the following steps in sequence: (A1100) Mix branched alkyl carboxylic acid, sodium salt or potassium salt, and solvent to form a first liquid slurry, wherein the carboxylic acid is of the following formula ( II) means, Formula (II); wherein, R ₁ , R ₂ and R ₃ are linear alkyl groups, branched alkyl groups or hydrogen containing 1-22 carbon atoms, and the solvent is water, methanol, ethanol, acetone or a mixture thereof; (A1200) The first liquid slurry is mixed and reacted with a salt of a water-soluble transition metal M to form a carboxylate salt.

In one embodiment of the present invention, the liquid medium is an organic solvent with a boiling point less than or equal to 125°C.

In one embodiment of the present invention, the organic solvent is a hydrocarbon containing 4-12 carbon atoms, chloroform, tetrahydrofuran or a mixture thereof.

In one embodiment of the present invention, the organic solvent is hexane, cyclohexane, heptane, cycloheptane, octane, toluene, xylene, or mixtures thereof.

In an embodiment of the present invention, step A2000 further includes mixing a carboxylate, a liquid medium and a dispersant.

In one embodiment of the present invention, the dispersant is an amine, a carboxylic acid, or a mercaptan having an alkyl group, and the alkyl group contains 1-22 carbon atoms.

In one embodiment of the invention, the dispersant is butylamine, second-butylamine, isobutylamine, third-butylamine, 3-methoxypropylamine, (2-methylbutyl)amine, 1,2- Dimethylpropylamine, 1-ethylpropylamine, 2-aminopentane, pentylamine, isopentylamine, tertiarypentylamine, 3-ethoxypropylamine, 3, 3-dimethylbutylamine, hexylamine, 3-isopropoxypropylamine, heptylamine, 2-heptylamine, 1, 4-dimethylpentylamine, 1, 5-dimethylhexylamine, 1-methylheptylamine, 2-ethyl-1- Hexylamine, octylamine, 1, 1, 3, 3-tetramethylbutylamine, nonylamine, decylamine, dodecaamine, tridecaamine, tetradecalyamine, hexadecylamine, oleylamine, octadecylamine, hexylamine Acid, caprylic acid, nonanoic acid, capric acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, stearic acid, nonadecaic acid, 20 Acid, eicosanoid acid, behenic acid, eicosanoid acid, eicosanoid acid, hexadecanoic acid, 8-methylnonanoic acid, 1 1-methyllauric acid, 12-methyltridecanoic acid, 1 2-methyltetradecanoic acid, 13-methyltetradecanoic acid, isohexadecanoic acid, 1 4-methylhexadecanoic acid, 1 5-methylhexadecanoic acid, 1 6-methylhexadecanoic acid, 17 -Methyl stearic acid, 18-methylnonadecanoic acid, 2, 6, 10, 14-tetramethylhexadecanoic acid, 19-methyl eicosanoic acid or 2,2,4,8,10,10- Hexamethylundecan-5-carboxylic acid (2, 2, 4, 8, 10, 10-hexamethylundecane-5-carboxylic acid), propanethiol, 2-methyl-1-propanethiol , Butanethiol, 2-methyl-1-butanethiol, 2-butanethiol, 2,3-butanediol, 3-methyl-1-butanethiol, pentanethiol, hexanethiol, Heptylmercaptan, Octylmercaptan, Decanethiol, Undecylmercaptan, Dodecylmercaptan, Tetradecylmercaptan, Pentadecylmercaptan, Octadecylmercaptan, Eicosylmercaptan or Behenylmercaptan.

In one embodiment of the present invention, the concentration of the dispersant dissolved in the liquid medium is less than or equal to 5000 mM.

In one embodiment of the present invention, the gaseous sulfur source includes hydrogen sulfide and an inert gas, and the inert gas includes nitrogen, helium, and carbon dioxide.

In one embodiment of the present invention, step A3000 includes mixing and reacting the liquid reaction slurry and the gaseous sulfur source at a temperature of 40°C to 150°C.

In one embodiment of the present invention, the metal sulfide with nanostructure is processed at a temperature less than or equal to 150°C.

In one embodiment of the present invention, the method for preparing a metal sulfide with a nanostructure further includes: (A4000) separating the metal sulfide with a nanostructure and a liquid medium.

The use of the liquid medium of the present invention is to mix the liquid medium with the aforementioned carboxylate to form a liquid reactant slurry for preparing metal sulfides with nanostructures, wherein the liquid medium is an organic solvent with a boiling point less than or equal to 125°C.

In the use of the gaseous sulfur source of the present invention, the gaseous sulfur source reacts with the aforementioned carboxylate to generate a metal sulfide with a nanostructure.

The carboxylate salt of the present invention is represented by the following formula (I), Formula (I); wherein, R ₁ , R ₂ , R ₃ are linear alkyl groups, branched alkyl groups or hydrogen containing 1-22 carbon atoms, X is an integer between 1 and 3, and M is Transition metals. The carboxylic acid salt of the present invention can be dissolved in a low-boiling point solvent at low temperature. More specifically, the carboxylic acid salt of the present invention has a branched chain and can be dissolved in a solvent with a boiling point of less than or equal to 125°C at an operating temperature of less than or equal to 150°C. .

Furthermore, in one embodiment, R ₁ and R ₂ are respectively a linear or branched alkyl group having a carbon number of 1-22 and having a tert-butyl group. In different embodiments, R ₁ and R ₂ together are a cycloalkyl group having a carbon number of 2-22 and having a tert-butyl group. In one embodiment, M is not silver or palladium.

As shown in the schematic flow chart of the embodiment shown in FIG. 1A , the method for preparing a metal sulfide with a nanostructure of the present invention includes, for example, the following steps in sequence.

Step A1000 (preparation step of metal source) provides the aforementioned carboxylate (metal source). More specifically, step A1000 includes, for example, the following steps in sequence.

Step A1100: Mix branched alkyl carboxylic acid, sodium salt or potassium salt, and solvent to form a first liquid slurry, wherein the carboxylic acid is represented by the following formula (II), Formula (II); wherein, R ₁ , R ₂ and R ₃ are linear alkyl groups, branched alkyl groups or hydrogen containing 1 to 22 carbon atoms, and the solvent is water, methanol, ethanol, acetone or a mixture thereof. More specifically, in this step, the branched alkyl carboxylic acid undergoes a cation exchange reaction with the sodium salt or potassium salt and forms a first liquid slurry.

Step A1200, mix and react the first liquid slurry and the salt of the water-soluble transition metal M to form a carboxylate. More specifically, in this step, the first liquid slurry and the salt of the transition metal M undergo a cation exchange reaction to form a second liquid slurry, and then the liquid can be removed through procedures such as filtration to obtain the carboxylate salt. .

Step A2000 (preparation step of liquid reactant slurry), mix carboxylate and liquid medium to form liquid reactant slurry. In one embodiment, the organic solvent is a hydrocarbon containing 4-12 carbon atoms, chloroform, tetrahydrofuran or a mixture thereof. In another embodiment, the organic solvent is hexane, cyclohexane, heptane, cycloheptane, octane, toluene, xylene, or mixtures thereof. More specifically, the liquid medium is an organic solvent with a boiling point less than or equal to 125°C. Among them, because the carboxylate has a branched chain, it can be dissolved in a liquid medium with a boiling point of less than or equal to 125°C at an operating temperature of less than or equal to 150°C. The boiling point of the liquid medium is less than or equal to 125°C, and can be recycled by low-temperature distillation or other methods. Utilization makes operation more convenient. Viewed from a different angle, the liquid medium is mixed with the carboxylate to form a liquid reactant slurry for preparing metal sulfides with nanostructures.

On the other hand, step A2000 further includes mixing the carboxylate salt, the liquid vehicle and the dispersant. In other words, in step A2000, a dispersant can be added to mix with the carboxylate and the liquid medium to promote the dissolution of the carboxylate in the liquid medium. Among them, the concentration of the dispersant dissolved in the liquid medium is preferably less than or equal to 5000 mM. In one embodiment, the dispersant is an amine, a carboxylic acid, or a mercaptan having an alkyl group, and the alkyl group contains 1-22 carbon atoms. In another embodiment, the dispersant is butylamine, second-butylamine, isobutylamine, third-butylamine, 3-methoxypropylamine, (2-methylbutyl)amine, 1,2-dimethylamine Propylamine, 1-ethylpropylamine, 2-aminopentane, pentylamine, isopentylamine, tertiarypentylamine, 3-ethoxypropylamine, 3, 3-dimethylbutylamine, hexylamine, 3- Isopropoxypropylamine, heptylamine, 2-heptylamine, 1, 4-dimethylpentylamine, 1, 5-dimethylhexylamine, 1-methylheptylamine, 2-ethyl-1-hexylamine , octylamine, 1, 1, 3, 3-tetramethylbutylamine, nonylamine, decylamine, dodecaamine, tridecaamine, tetradecalyamine, hexadecylamine, oleylamine, stearylamine, hexanoic acid, Octanoic acid, nonanoic acid, capric acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, eicosanoic acid, Heconic acid, behenic acid, hexaconic acid, icosanoic acid, hexacosonic acid, 8-methylnonanoic acid, 1 1-methyllauric acid, 12-methyltridecanoic acid, 1 2 -Methyl myristanoic acid, 13-methyltetradecanoic acid, isohexadecanoic acid, 1 4-methyl hexadecanoic acid, 1 5-methyl hexadecanoic acid, 1 6-methyl heptadecanoic acid, 17-methyl Stearic acid, 18-methylnonadecanoic acid, 2, 6, 10, 14-tetramethylhexadecanoic acid, 19-methyleicosanoids or 2,2,4,8,10,10-hexamethyl Undecane-5-carboxylic acid (2, 2, 4, 8, 10, 10-hexamethylundecane-5-carboxylic acid), propanethiol, 2-methyl-1-propanethiol, butyl Thiol, 2-methyl-1-butanethiol, 2-butanethiol, 2,3-butanedithiol, 3-methyl-1-butanethiol, pentylthiol, hexanethiol, heptylthiol alcohol, octyl mercaptan, deca mercaptan, undeca mercaptan, dodecyl mercaptan, tetradecyl mercaptan, pentadecyl mercaptan, octadecyl mercaptan, eicosyl mercaptan or eicosyl mercaptan. Dialkylmercaptans.

Step A3000 (generation step of metal sulfide with nanostructure), the liquid reaction slurry and the gaseous sulfur source are mixed and reacted to generate metal sulfide with nanostructure. More specifically, the gaseous sulfur source includes hydrogen sulfide and inert gases, and the inert gases include nitrogen, helium, and carbon dioxide. In one embodiment, the liquid reaction slurry and the gaseous sulfur source are mixed and reacted at a temperature of 40°C to 150°C. Viewed from a different perspective, the gaseous sulfur source reacts with the carboxylate to generate nanostructured metal sulfides.

Furthermore, when the gaseous sulfur source dissolves into the liquid medium, the sulfidation reaction of the metal source starts, which decomposes to produce metal sulfides with nanostructures and carboxylate free ligands of branched chain alkyl groups with nanostructures. The outer surface of the metal sulfide is combined with free ligands to form a stable metal sulfide with a nanostructure without aggregation, forming a liquid slurry containing the metal sulfide with a nanostructure. In the presence of an added dispersant, the outer surface of the nanostructured metal sulfide combines with the free ligands and the added dispersant to form a stable nanostructured metal sulfide without aggregation. , forming a liquid slurry containing metal sulfides with nanostructures. Since this liquid slurry contains the aforementioned liquid medium and has a low boiling point, the liquid medium can be removed and recovered at low temperature and used as a liquid medium for another batch. The residue is a nanostructured metal sulfide. Solid products. Methods for separating the liquid medium for recovery may include, but are not limited to, heating and condensation, atmospheric distillation, vacuum distillation, etc.

Based on the above, the method for preparing the metal sulfide with nanostructure of the present invention is carried out at a temperature of less than or equal to 150°C, which is more convenient in operation. The following further provides examples to illustrate the present invention.

Preparation of carboxylic acid salts

Example A Synthesis of 2,2,4,8,10,10-hexamethylundecan-5-carboxylic acid metal salt

In this embodiment, the carboxylate salt of the present invention can be prepared using a carboxylic acid functional group with a branched alkyl group and a transition metal ion. 2,2,4,8,10,10-hexamethylundecan-5-carboxylic acid has a branched chain alkyl group, where R ₁ =C ₉ H ₁₈ , R ₂ =C ₇ H ₁₅ , R ₃ =H . With 2.85 g 2,2,4,8,10,10-hexamethylundecan-5-carboxylic acid (10mmol), 0.4g sodium hydroxide (10 mmol) and 100 ml deionized water at 70°C , mixed evenly and stirred for 30 minutes, a transparent aqueous solution containing 2,2,4,8,10,10-hexamethylundecan-5-carboxylic acid sodium salt was formed.

After adding zinc sulfate (1.44 g, 5 mmol) aqueous solution dropwise to the above solution, react for 1 hour, 2,2,4,8,10,10-hexamethylundecan-5-carboxylic acid sodium salt and zinc sulfate The hydrate undergoes a cation exchange reaction to prepare 2,2,4,8,10,10-hexamethylundecan-5-carboxylic acid zinc salt, whose molecular formula is (C ₁₇ H ₃₆ CO ₂ ) ₂ Zn, which is collected After washing, place to dry at 40°C for 24 hours. The preparation method of 2,2,4,8,10,10-hexamethylundecan-5-carboxylate cadmium salt, lead salt, cobalt salt, nickel salt, manganese salt and copper salt is the same as 2,2,4, 8,10,10-Hexamethylundecan-5-carboxylic acid zinc salt is similar to 2,2,4,8,10,10-hexamethylundecane-5-carboxylic acid sodium salt and acetic acid respectively. Cadmium, lead nitrate, cobalt chloride, nickel sulfate, manganese sulfate, and ketone sulfate undergo cation exchange reactions. The products are transparent, milky white, white, blue, light green, brown, and dark green 2, 2, 4, respectively. 8,10,10-Hexamethylundecan-5-carboxylic acid cadmium salt (C ₁₇ H ₃₆ CO ₂ ) ₂ Cd, 2,2,4,8,10,10-Hexamethylundecane-5 - Lead carboxylate salt (C ₁₇ H ₃₆ CO ₂ ) ₂ Pb, 2,2,4,8,10,10-hexamethylundecan-5-carboxylic acid cobalt salt (C ₁₇ H ₃₆ CO ₂ ) ₂ Co, 2,2,4,8,10,10-hexamethylundecan-5-carboxylic acid nickel salt (C ₁₇ H ₃₆ CO ₂ ) ₂ Ni, 2,2,4,8,10,10- Hexamethylundecane-5-carboxylic acid manganese salt (C ₁₇ H ₃₆ CO ₂ ) ₂ Mn, 2,2,4,8,10,10-hexamethylundecane-5-carboxylic acid copper salt ( C ₁₇ H ₃₆ CO ₂ ) ₂ Cu. The finished product appearance is shown in Figure 1B.

Preparation of metal sulfide with nanostructure

The liquid reactant slurry of the present invention and the gaseous sulfur source are mixed in a reaction vessel, and after wet chemical vulcanization reaction under low temperature conditions, metal sulfides with nanostructures can be prepared. The reactor can be, but is not limited to, a 100 ml double-necked glass round-bottomed bottle with a magnet placed inside it. The reactor was heated in an oil bath containing silicone oil. The magnetic heating platform is connected to the temperature controller, and a thermocouple is used to measure the temperature of the oil bath to feed back the temperature setting of the thermostat. In addition to being able to be heated, temperature controlled, and stirred, the reactor also has air inlets/outlets and a feed port.

Example 2 Preparation of zinc sulfide with nanostructure

In this example, 10 mM of 2,2,4,8,10,10-hexamethylundecan-5-carboxylic acid zinc salt/toluene (50 ml)/oleylamine dispersant (10 mM) Place it into a 100 ml reactor and pass nitrogen into the reactor for 30 minutes to eliminate water vapor and air inside the reactor. After the temperature controller is set to the required reaction temperature, turn on the heating and stirring functions, and set the rotation speed to 300 rpm to dissolve 2,2,4,8,10,10-hexamethylundecan-5-carboxylic acid zinc salt , forming a liquid reactant slurry. After the oil bath temperature reaches the set reaction temperature, and after balancing for 10 minutes, inject 10 ml of hydrogen sulfide gas into the reactor to start the reaction. The first group was subjected to a 40°C vulcanization reaction with a reaction time of 2 hours; the second group was subjected to a 100°C vulcanization reaction with a reaction time of 8 hours. The two sets of reaction product liquids are vacuum distilled, and the solid product obtained is zinc sulfide with nanostructure. The transmission electron microscope observation photos of the first and second groups of zinc sulfide with nanostructures prepared at different reaction temperatures and reaction times are shown in Figures 2A and 2B, and the scale bar is 50 nanometers.

Example 3 Preparation of cadmium sulfide with nanostructure

In this example, 5 mM of cadmium salt of 2,2,4,8,10,10-hexamethylundecan-5-carboxylate/xylene (50 ml)/hexadecanoic acid (10 mM) Place it into a 100 ml reactor and pass nitrogen into the reactor for 30 minutes to eliminate water vapor and air inside the reactor. After the temperature controller is set to the required reaction temperature, turn on the heating and stirring functions, and set the rotation speed to 300 rpm to dissolve the cadmium salt of 2,2,4,8,10,10-hexamethylundecan-5-carboxylate. , forming a liquid reactant slurry. After the oil bath temperature reaches the set reaction temperature, and after balancing for 10 minutes, inject 10 ml of hydrogen sulfide gas into the reactor to start the reaction. The first group was subjected to a vulcanization reaction at 40°C, with a reaction time of 2 hours; the second group was subjected to a vulcanization reaction at 80°C, with a reaction time of 8 hours; and the third group was subjected to a 120°C vulcanization reaction, with a reaction time of 12 hours. The two sets of reaction product liquids are vacuum distilled, and the solid product obtained is zinc sulfide with nanostructure. The transmission electron microscope observation photos of the first, second and third groups of cadmium sulfide with nanostructures prepared at different reaction temperatures and reaction times are shown in Figures 3A, 3B and 3C. The scale bar is 50 Nano.

Example 4 Preparation of lead sulfide with nanostructure

In this example, 0.5 mM of lead salt of 2,2,4,8,10,10-hexamethylundecan-5-carboxylate/toluene (50 ml) was placed in a 100 ml reactor to Pour nitrogen into the reactor for 30 minutes to eliminate water vapor and air inside the reactor. After the temperature controller is set to the required reaction temperature, turn on the heating and stirring functions, and set the rotation speed to 300 rpm to dissolve the 2,2,4,8,10,10-hexamethylundecan-5-carboxylate lead salt. , forming a liquid reactant slurry. After the oil bath temperature reaches the set reaction temperature, and after balancing for 10 minutes, inject 10 ml of hydrogen sulfide gas into the reactor to start the 60°C sulfurization reaction, with a reaction time of 24 hours. The reaction product liquid of this group is vacuum distilled, and the solid product obtained is lead sulfide with a nanostructure. The transmission electron microscope observation photo is shown in Figure 4, and the scale is 50 nanometers.

Example 5 Preparation of cobalt sulfide with nanostructure

In this example, 5 mM of 2,2,4,8,10,10-hexamethylundecan-5-carboxylic acid cobalt salt/toluene (50 ml)/dodecylamine (10 mM) was placed. into a 100 ml reactor, and flow nitrogen into the reactor for 30 minutes to eliminate water vapor and air inside the reactor. After the temperature controller is set to the required reaction temperature, turn on the heating and stirring functions, and set the rotation speed to 300 rpm to dissolve the 2,2,4,8,10,10-hexamethylundecan-5-carboxylic acid cobalt salt. , forming a liquid reactant slurry. After the oil bath temperature reaches the set reaction temperature, and after balancing for 10 minutes, inject 10 ml of hydrogen sulfide gas into the reactor to start the 100°C sulfurization reaction. The reaction time is 24 hours. The reaction product liquid is vacuum distilled, and the solid product obtained is cobalt sulfide with a nanostructure. Its transmission electron microscope observation photo is shown in Figure 5, and the scale bar is 50 nanometers.

Example 6 Preparation of nickel sulfide with nanostructure

In this example, 2 mM of 2,2,4,8,10,10-hexamethylundecan-5-carboxylic acid nickel salt/toluene and xylene (volume ratio 1:1) (50 ml ) into a 100 ml reactor, and pass nitrogen into the reactor for 30 minutes to eliminate water vapor and air inside the reactor. After the temperature controller is set to the required reaction temperature, turn on the heating and stirring functions, and set the rotation speed to 300 rpm to dissolve 2,2,4,8,10,10-hexamethylundecan-5-carboxylic acid nickel salt , forming a liquid reactant slurry. After the oil bath temperature reaches the set reaction temperature, and after balancing for 10 minutes, inject 10 ml of hydrogen sulfide gas into the reactor to start the 80°C sulfurization reaction, with a reaction time of 8 hours. The reaction product liquid is vacuum distilled, and the solid product obtained is nickel sulfide with a nanostructure. The transmission electron microscope observation photo is shown in Figure 6, and the scale bar is 50 nanometers.

Example 7 Preparation of Manganese Sulfide with Nanostructure

In this example, 1 mM of 2,2,4,8,10,10-hexamethylundecan-5-carboxylic acid manganese salt/chloroform (50 ml) was placed in a 100 ml reactor to Pour nitrogen into the reactor for 30 minutes to eliminate water vapor and air inside the reactor. After the temperature controller is set to the required reaction temperature, turn on the heating and stirring functions, and set the rotation speed to 300 rpm to dissolve 2,2,4,8,10,10-hexamethylundecan-5-carboxylic acid manganese salt. , forming a liquid reactant slurry. After the oil bath temperature reaches the set reaction temperature, and after balancing for 10 minutes, inject 10 ml of hydrogen sulfide gas into the reactor to start the 40°C sulfurization reaction, with a reaction time of 8 hours. The reaction product liquid is vacuum distilled, and the solid product obtained is manganese sulfide with a nanostructure. Its transmission electron microscope observation photo is shown in Figure 7, and the scale bar is 50 nanometers.

Example 8 Preparation of nanostructured copper sulfide

In this example, 20 mM of 2,2,4,8,10,10-hexamethylundecan-5-carboxylic acid copper salt/octane (50 ml)/octadecylmercaptan ( 10 mM) was placed into a 100 ml reactor, and nitrogen was introduced into the reactor for 30 minutes to eliminate water vapor and air inside the reactor. After the temperature controller is set to the required reaction temperature, turn on the heating and stirring functions, and set the rotation speed to 300 rpm to dissolve the 2,2,4,8,10,10-hexamethylundecan-5-carboxylic acid copper salt. A liquid reactant slurry is formed. After the oil bath temperature reaches the set reaction temperature, and after balancing for 10 minutes, inject 10 ml of hydrogen sulfide gas into the reactor to start the reaction. The first group performed a vulcanization reaction at 40°C, with a reaction time of 8 hours; the second group performed a vulcanization reaction at 80°C, with a reaction time of 8 hours. The two sets of reaction product liquids are vacuum distilled, and the solid product obtained is zinc sulfide with nanostructure. The transmission electron microscope observation photos of the first and second groups of zinc sulfide with nanostructures prepared at different reaction temperatures and reaction times are shown in Figures 8A and 8B, and the scale bar is 50 nanometers.

Although the foregoing description and drawings disclose the preferred embodiments of the present invention, it must be understood that various additions, many modifications and substitutions may be made to the preferred embodiments of the present invention without departing from the scope of the appended claims. spirit and scope of the principles of the invention. One of ordinary skill in the art to which this invention pertains will appreciate that the invention is susceptible to modifications in many forms, structures, arrangements, proportions, materials, elements and assemblies. Therefore, the embodiments disclosed herein should be regarded as illustrating the present invention rather than limiting the present invention. The scope of the present invention should be defined by the appended patent claims and cover their legal equivalents, and is not limited to the previous description.

A1000: Steps A1100: Steps A1200: Steps A2000: Steps A3000: Steps

FIG. 1A is a schematic flowchart of a method for preparing a metal sulfide with a nanostructure according to an embodiment of the present invention.

Figure 1B is a schematic diagram of the appearance of an embodiment of the carboxylic acid salt of the present invention.

Figures 2A and 2B are transmission electron microscope photos of zinc sulfide with nanostructures made according to the present invention.

Figures 3A, 3B, and 3C are transmission electron microscope photos of the nanostructured cadmium sulfide produced in the present invention.

Figure 4 is a transmission electron microscope observation photo of the lead sulfide with nanostructure made according to the present invention.

Figure 5 is a transmission electron microscope observation photo of the cobalt sulfide with nanostructure made by the present invention.

Figure 6 is a transmission electron microscope observation photo of the nickel sulfide with nanostructure made according to the present invention.

Figure 7 is a transmission electron microscope observation photo of the manganese sulfide with nanostructure made according to the present invention.

Figures 8A and 8B are transmission electron microscope photos of the copper sulfide with nanostructure made according to the present invention.

A1000: Steps

A1100: Steps

A1200: Steps

A2000: Steps

A3000: Steps

Claims (15)

A method for preparing metal sulfides with nanostructures, including the following steps in sequence: (A1000) using a one-stage temperature rise program at 70°C to prepare a monocarboxylate, represented by the following formula (I),

Among them, R ₁ , R ₂ and R ₃ are linear alkyl groups, branched alkyl groups or hydrogen containing 1-22 carbon atoms, X is an integer between 1 and 3, and M is a transition metal; (A2000 ) Mix the carboxylate and a liquid medium to form a liquid reactant slurry, wherein the liquid medium is an organic solvent with a boiling point less than or equal to 125°C; (A3000) Mix the liquid reaction slurry with a gaseous sulfur The sources mix and react to create a nanostructured metal sulfide. The method for preparing a metal sulfide with a nanostructure as described in claim 1, wherein R ₁ and R ₂ are respectively a linear alkyl group or a branched alkyl group having a tert-butyl group and containing 1-22 carbon atoms. The method for preparing a metal sulfide with a nanostructure as described in claim 1, wherein R ₁ and R ₂ together are a cycloalkyl group having a tert-butyl group containing 2-22 carbon atoms. The method for preparing a metal sulfide with a nanostructure as described in claim 1, wherein M is not silver or palladium. The method for preparing a metal sulfide with a nanostructure as described in claim 1, wherein step A1000 includes the following steps in sequence: (A1100) adding a branched chain alkyl carboxylic acid, a sodium salt or a potassium salt, and a solvent Mix to form a first liquid slurry, wherein the carboxylic acid is represented by the following formula (II),

Among them, R ₁ , R ₂ and R ₃ are linear alkyl groups, branched alkyl groups or hydrogen containing 1-22 carbon atoms, and the solvent is water, methanol, ethanol, acetone or mixtures thereof; (A1200) convert the The first liquid slurry is mixed and reacted with a water-soluble salt of transition metal M to form the carboxylate salt. The method for preparing a metal sulfide with a nanostructure as described in claim 1, wherein the organic solvent is a hydrocarbon containing 4-12 carbon atoms, chloroform, tetrahydrofuran or a mixture thereof. The method for preparing a metal sulfide with a nanostructure as described in claim 1, wherein the organic solvent is hexane, cyclohexane, heptane, cycloheptane, octane, toluene, xylene, or a mixture thereof. The method for preparing a metal sulfide with a nanostructure as described in claim 1, wherein step A2000 further includes mixing the carboxylate, the liquid medium and a dispersant. The method for preparing a metal sulfide with a nanostructure as described in claim 8, wherein the dispersant is an amine, a carboxylic acid, or a thiol having an alkyl group, and the alkyl group contains 1-22 carbon atoms. The preparation method of metal sulfide with nanostructure as described in claim 8, wherein the dispersant is butylamine, second-butylamine, isobutylamine, third-butylamine, 3-methoxypropylamine, (2- Methylbutyl)amine, 1,2-dimethylpropylamine, 1-ethylpropylamine, 2-aminopentane, pentylamine, isopentylamine, tertiarypentylamine, 3-ethoxypropylamine, 3, 3-dimethylbutylamine, hexylamine, 3-isopropoxypropylamine, heptylamine, 2-heptylamine, 1,4-di Methylpentylamine, 1,5-dimethylhexylamine, 1-methylheptylamine, 2-ethyl-1-hexylamine, octylamine, 1,1,3,3-tetramethylbutylamine, nonane Amine, decylamine, dodecylamine, tridecylamine, tetradecylamine, hexadecylamine, oleylamine, stearylamine, hexanoic acid, heptanoic acid, nonanoic acid, capric acid, undecanoic acid, dodecanoic acid, ten Trisaccharide, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, stearic acid, nonadecaic acid, eicosanoic acid, 21 acid, 22 acid, 23 acid, 24 acid , Hexadecanoic acid, 8-methylnonanoic acid, 11-methyllauric acid, 12-methyltridecanoic acid, 12-methyltetradecanoic acid, 13-methyltetradecanoic acid, isohexadecanoic acid, 14 -Methyl hexadecanoic acid, 15-methyl hexadecanoic acid, 16-methyl heptadecanoic acid, 17-methylstearic acid, 18-methyl nonadecanoic acid, 2,6,10,14-tetramethyldecanoic acid Hexadecanoic acid, 19-methyleicosanoic acid or 2,2,4,8,10,10-hexamethylundecan-5-carboxylic acid (2,2,4,8,10,10-hexamethyl (Undecane-5-carboxylic acid), propanethiol, 2-methyl-1-propanethiol, butanethiol, 2-methyl-1-butanethiol, 2-butanethiol, 2,3- Butanethiol, 3-methyl-1-butanethiol, pentylthiol, hexanethiol, heptylthiol, octylthiol, decamercaptan, undecanethiol, dodecylthiol, tetradecyl Thiol, pentadecylmercaptan, stearylmercaptan, eicosylmercaptan or behenylmercaptan. The method for preparing a metal sulfide with a nanostructure as described in claim 8, wherein the concentration of the dispersant dissolved in the liquid medium is less than or equal to 5000mM. The method for preparing a metal sulfide with a nanostructure as described in claim 1, wherein the gaseous sulfur source includes hydrogen sulfide and an inert gas, and the inert gas includes nitrogen, helium, and carbon dioxide. The method for preparing a metal sulfide with a nanostructure as described in claim 1, wherein the step A3000 includes mixing and reacting the liquid reaction slurry and the gaseous sulfur source at a temperature of 40°C to 150°C. The method for preparing a metal sulfide with a nanostructure as described in claim 1 is carried out at a temperature less than or equal to 150°C. The method for preparing a metal sulfide with a nanostructure as described in claim 1 further includes: (A4000) separating the metal sulfide with a nanostructure and the liquid medium.

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