CN108996478B - MN (Mobile node)xSuper crystal and preparation method and application thereof - Google Patents

MN (Mobile node)xSuper crystal and preparation method and application thereof Download PDF

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CN108996478B
CN108996478B CN201810962581.5A CN201810962581A CN108996478B CN 108996478 B CN108996478 B CN 108996478B CN 201810962581 A CN201810962581 A CN 201810962581A CN 108996478 B CN108996478 B CN 108996478B
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crystal
surfactant
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CN108996478A (en
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巩飞龙
李峰
弓丽华
彭丽芳
刘梦梦
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Zhengzhou University of Light Industry
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/20—Methods for preparing sulfides or polysulfides, in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/007—Tellurides or selenides of metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer

Abstract

The invention relates to a MNxA super crystal and a preparation method and application thereof belong to the field of functional material structure control. Under the conditions of 120 ℃ and 260 ℃ and an acidic environment, taking M salt as a raw material, a mixture of alcohol and water as a solvent, and thiourea as a sulfur (selenium) source, and reacting in a high-pressure reaction kettle for 1 hour to 1 week to obtain MNxA super-crystalline material. The invention is characterized in that: by adjusting the type of metal salt, reaction temperature, reaction time, surfactant and the amount of thiourea, MN with a solid, hollow and core-shell structure with uniform size and adjustable composition, which is formed by self-assembly of two-dimensional flaky materials, can be obtainedxSuper crystal spheres, sheets and butterfly materials. Of particular importance are: the semiconductor phase (2H phase) and the metal phase (1T phase) MN can be selectively prepared by controlling the reaction temperature conditionxA superlattice sphere and a sheet material.

Description

MN (Mobile node)xSuper crystal and preparation method and application thereof
Technical Field
The invention relates to a MNxA super crystal and a preparation method and application thereof belong to the field of functional material structure control.
Background
2D nanomaterials, such as: the graphene and the layered transition metal sulfide have excellent optical, thermal, electrical and other properties. Research on the regulation and cutting of the properties of 2D materials such as light, heat, electricity and the like is directly to determine the important fields of the materials in energy storage, sensors, catalysts and the likeApplication of the domain. Among 2D materials, graphene has attracted much attention in recent years, but due to its lack of an intrinsic band gap, the potential of chemical modification to regulate its band gap is also limited, and its applications are therefore limited. In contrast, graphene-like materials have received much attention because of their wide band gap. In MoS2For example, the following steps are carried out: the nano electronics and structure laboratory of the swiss los federal institute of technology, known as molybdenite (MoS), published in 2011 in Nature Nanotechnology (nat. Nanotechnology 2011, 6, 147)2) Not only has a graphene-like structure, but also has a wider band gap. Using a monolayer semiconductor phase MoS2(2H-MoS2) The semiconductor device made of the material is more advanced and energy-saving than graphene, and is expected to be applied to next-generation electronic devices. Therefore, in recent years, the MoS is in a layered form2The research of the 2D transition metal sulfide material as a representative is rapidly developed and becomes a new hotspot and focus in the research field of functional materials. MoS2The preparation method of the material mainly comprises a solvothermal method, a hydrothermal method, a template method, a mechanical stripping method, a chemical cleavage method, a gas phase deposition method and the like. For example: flaky MoS can be obtained by hydrothermal method2The material is nano-sized, the super-capacitance performance of the material is studied, 85.1 percent of capacity can be maintained after 500 cycles, but the current density is 0.1 Ag-1The capacitance capacity of the capacitor is only 129.2F g-1. The patent is CN: 103617893B, a hydrothermal method is used to prepare a composite material of molybdenum sulfide and multi-walled carbon nanotubes, and the electrolyte is 1.0 mol/L of Na2SO4In the solution, the specific capacitance of the capacitor is 452.7F/g, the synthesis time is at least 48 h, the reaction time is longer, and the cost is higher by using L-cysteine as a sulfur source. Literature reports using SiO2As a template, the product obtained is MoO3And SiO2After the microspheres are formed, SiO is etched by HF2Preparation of hollow MoO3Microspheres, subsequently in H2S and H2Calcining at high temperature in mixed atmosphere to obtain MoS2The nano-sheet assembled hollow microsphere (J. Am. chem. Soc. 2005, 127, 2368-2369) has the disadvantages of complicated operation process, dangerous atmosphere and unsuitability for actual production requirements. In addition, the massive MoS is peeled off2Time of materialBy means of Li+, Na+And K+The teaching of Chhowalla et al gave a 1T-MoS with a high concentration content2Nanosheets, but the preparation conditions are harsh and the cost is relatively high (Nano Lett. 2011, 11, 5111-. Therefore, in order to reduce environmental pollution, improve chemical efficiency of material synthesis, and reduce cost, it is necessary to develop new 2D material production technologies. Meanwhile, the shape and structure of the material are effectively regulated to obtain a uniform and stable functional material, so that the method is one of effective ways for improving the performance of the energy storage device, is also a challenge in the research and production of energy materials, is very important for the popularization and application of related materials, and has important application value, and the requirements are still difficult to meet by the existing numerous manufacturing methods and technologies.
Disclosure of Invention
The invention provides MN (manganese nitrate) for solving the technical problems of complicated process, environmental pollution and low efficiency of preparing a material with a super-crystal structurexSuper crystal and its preparation method and application.
In order to solve the technical problems, the following technical scheme is adopted:
the present invention relates to MNxThe preparation method of the super crystal material comprises the specific steps of taking a mixture of alcohol and water as a solvent, providing an acid environment with an acid solution, providing a sulfur (selenium) source with thiourea, placing the mixture into a high-pressure reaction kettle, and reacting for 1h-1 week at the temperature of (120-xA super-crystalline material. Then selectively selecting a semiconductor phase (2H phase) or a metal phase (1T phase) MN through high-temperature calcination or notxA super-crystalline material.
MN of the inventionxThe preparation method of the super-crystal material comprises the following specific steps:
MN (Mobile node)xA super crystal of said MNxThe super crystal is formed by self-assembling two-dimensional sheet materials, MNxThe super crystal structure is a semiconductor phase or metal phase crystal with a disc-shaped, solid, hollow or core-shell structure.
MNxThe preparation method of the super crystal comprises the following steps:
(1) preparing an oil phase solution: completely dissolving surfactant 1 in long-chain alcohol to form a uniform and stable oil phase solution, wherein (2-12) mmoL surfactant is dissolved in per 100mL of long-chain alcohol;
(2) preparing an aqueous phase solution: dissolving the M salt in deionized water to form a uniform and stable aqueous solution, wherein 0.1-10 mmol of the M salt is dissolved in every 300mL of the deionized water;
(3) under the condition of magnetic stirring of 100-;
(4) placing the emulsion obtained in the step (3) into a high-pressure reaction kettle for reaction, and washing, drying and calcining the obtained product to obtain MNxA super crystal.
In the step (1), the surfactant is an anionic surfactant or a cationic surfactant, the anionic surfactant is a sodium succinate anionic surfactant, and the cationic surfactant is an amine salt cationic surfactant, a quaternary ammonium salt cationic surfactant, an onium salt cationic surfactant, an amine oxide cationic surfactant or a heterocyclic cationic surfactant; the long-chain alcohol is butanol, pentanol, hexanol, heptanol or octanol.
In the step (2), the M salt is molybdenum salt, tungsten salt, nickel salt, cobalt salt, manganese salt, zinc salt, tin salt, iron salt or cadmium salt.
In the step (3), the acid solution is a hydrochloric acid solution, a nitric acid solution or an acetic acid solution, the mass fraction of the hydrochloric acid solution is 35-37%, the mass fraction of the nitric acid solution is 65-70%, and the concentration of the acetic acid solution is 95-99.5%.
The quantity ratio of the surfactant in the step (1) to the M salt in the step (2) is (0.2-120): 1; in the step (3), oil phase: water phase: ethylene glycol: the volume ratio of the acid solution is (0.17-0.67): 1: (0-1): (0.0003-0.03), the mass ratio of thiourea or selenourea to M salt is (0.1-100): 1.
in the step (4), the reaction temperature is (160- & ltSUB & gt 220- & gt DEG C, the reaction time is 1h-1 week, the calcination temperature is (250- & ltSUB & gt 1300- & gt DEG C, and the calcination time is (0.5-12) h.
In the step (4), the reaction temperature is 220 ℃, the reaction time is 20 hours, and the semiconductor phase MN is obtainedxA super crystal.
The calcination temperature in the step (4) is 250-1300 ℃ and the calcination time is 1-3 h, so as to obtain the metal phase MNxA super crystal.
MNxThe application of the super crystal in manufacturing an energy storage device is that the energy storage device is a lithium ion battery, a sodium ion battery, an electro-catalysis hydrogen evolution device or a super capacitor.
According to the method, the water phase is added into the excessive oil phase to form the water-in-oil (W/O) micelle, the micelle state is gradually changed into the oil-in-water (O/W) type along with the increase of the water phase, and different amounts of different types of surfactants are added, so that the micelle forms different forms in the solution. The metal acid radical ions are stabilized by adding an acid solution, and finally, the sulfur (selenium) urea is added to provide a sulfur (selenium) source. The whole process finally controls MN by controlling micelle formxThe morphology and structure of the super-crystalline material; preparing high-purity 1T-MN by high-temperature calcinationxAnd (5) producing the product.
The invention has the beneficial effects that: the basic reaction process conditions are unchanged, and different nanocrystalline materials with more uniform appearance can be obtained only by changing the amount of 1-2 reactants. For example: weighing 12 mmol of Sapamine A cationic surfactant, adding 100mL of n-butyl alcohol, and ultrasonically dissolving for 30min to form a uniform oil phase solution; weighing 0.8 mmol of sodium molybdate, adding 300mL of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution; under the condition of vigorous stirring at room temperature, dropwise adding a sodium molybdate aqueous phase solution into a Sapamine A oil phase solution, vigorously stirring for 2 hours after the addition of the aqueous phase solution is finished, dropwise adding 50 mL of ethylene glycol into the mixed solution, vigorously stirring for 10 minutes, dropwise adding 1mL of hydrochloric acid into the mixed solution, vigorously stirring for 1 hour, dropwise adding 6 mmol of thiourea into the mixed solution, and vigorously stirring for 3 hours until the solution forms a uniform and stable emulsion. Placing the emulsion in a container with polytetrafluoroethyleneSealing in an autoclave with an olefin inner container, reacting at 160 deg.C for 20h, washing the product with distilled water and anhydrous ethanol for 3 times, and drying at 60 deg.C for 12 h to obtain MNxThe yield of the super crystal product is about 91 percent. Three additional types of nanocrystalline materials were obtained by varying the reaction temperatures of 180, 200 and 220 ℃ during the above process. In addition, a series of super-crystal materials can be obtained by only changing the amount of hydrochloric acid, the type of the surfactant and the type of the salt. The method has strong process universality, high yield and low preparation cost; the shape and size of the material are uniform; and industrialization is easy to realize.
The invention is characterized in that: by adjusting the type of metal salt, reaction temperature, reaction time, surfactant and the amount of thiourea, MN with a solid, hollow and core-shell structure with uniform size and adjustable composition, which is formed by self-assembly of two-dimensional flaky materials, can be obtainedxSuper crystal spheres, sheets and butterfly materials. Of particular importance are: the semiconductor phase (2H phase) and the metal phase (1T phase) MN can be selectively prepared by controlling the reaction temperature conditionxA superlattice sphere and a sheet material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an XRD diffraction pattern and FESEM photograph of a nanocrystalline material of example 1 of the present invention.
FIG. 2 is an XRD diffraction pattern and FESEM photograph of the nanocrystalline material of example 2 of the present invention.
FIG. 3 is an XRD diffraction pattern and FESEM photograph of the nanocrystalline material of example 3 of the present invention.
FIG. 4 is an XRD diffraction pattern and FESEM photograph of the nanocrystalline material of example 4 of the present invention.
FIG. 5 is a histogram of the variation of Mo and S elements in the superlattice material in examples 1-4 of the present invention.
FIG. 6 is a FESEM photograph of a nanocrystalline material of example 5 of the present invention.
FIG. 7 is a FESEM photograph of a nanocrystalline material of example 6 of the present invention.
FIG. 8 is a FESEM photograph of a nanocrystalline material of example 7 of the present invention.
FIG. 9 is a FESEM photograph of a nanocrystalline material of example 8 of the present invention.
FIG. 10 is an XRD diffraction pattern and FESEM photograph of a nanocrystalline material of example 17 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
An MN of the present embodimentxThe preparation method of the super crystal comprises the following steps:
(1) weighing 12 mmol of Sapamine A cationic surfactant, adding 100mL of n-butyl alcohol, and ultrasonically dissolving for 30min to form a uniform oil phase solution;
(2) weighing 0.8 mmol of sodium molybdate, adding 300mL of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(3) under the condition of vigorous stirring at room temperature, dropwise adding a sodium molybdate aqueous phase solution into a Sapamine A oil phase solution, vigorously stirring for 2 hours after the addition of the aqueous phase solution is finished, dropwise adding 50 mL of ethylene glycol into the mixed solution, vigorously stirring for 10 minutes, dropwise adding 1mL of hydrochloric acid into the mixed solution, vigorously stirring for 1 hour, dropwise adding 6 mmol (0.4567g) of thiourea into the mixed solution, and vigorously stirring for 3 hours until the solution forms a uniform and stable emulsion.
(4) Putting the emulsion into an autoclave with a polytetrafluoroethylene inner container, sealing, reacting at constant temperature of 160 ℃ for 20h to obtain the productWashing with distilled water and anhydrous ethanol for 3 times respectively, and drying at 60 deg.C for 12 hr to obtain MNxThe yield of the super crystal product is about 91 percent.
FIG. 1b shows the MN obtained in the present embodimentxThe XRD spectrum of the super crystal material is that the product is a molybdenum sulfide compound with a large amount of oxygen doping. FIG. 1a is a FESEM photograph of a material. The material is a monodisperse solid super crystal spherical material with a smooth surface, and the particle size distribution is 1050 +/-230 nm.
Example 2
An MN of the present embodimentxThe preparation method of the super crystal comprises the following steps:
(1) weighing 12 mmol of Ahcovel A cationic surfactant, adding 100mL of n-butyl alcohol, and ultrasonically dissolving for 30min to form a uniform oil phase solution;
(2) weighing 0.8 mmol of sodium molybdate, adding 300mL of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(3) under the condition of vigorous stirring at room temperature, dropwise adding a sodium molybdate water phase solution into an Ahcovel A oil phase solution, vigorously stirring for 2 hours after the water phase solution is added, dropwise adding 50 mL of ethylene glycol into the mixed solution, vigorously stirring for 10 minutes, dropwise adding 1mL of hydrochloric acid into the mixed solution, vigorously stirring for 1 hour, dropwise adding 6 mmol (0.4567g) of thiourea into the mixed solution, and vigorously stirring for 3 hours until the solution forms a uniform and stable emulsion;
(4) putting the emulsion into a high-pressure kettle with a polytetrafluoroethylene inner container, sealing, and reacting at the constant temperature of 180 ℃ for 20 hours; washing the product with distilled water and anhydrous ethanol for 3 times respectively, and drying at 60 deg.C for 12 hr to obtain MNxThe yield of the super crystal product is about 92 percent.
FIG. 2b shows the MN obtained in the present embodimentxThe XRD spectrum of the super crystal material is that the product is a molybdenum sulfide compound with a large amount of oxygen doping. FIG. 2a is an FESEM photograph of the material, which shows that the material is a monodisperse solid super crystal spherical material with rough surface, and the diameter distribution of the prepared super crystal spherical particles is 915 +/-77 nm.
Example 3
An MN of the present embodimentxOf super crystalsThe preparation method comprises the following steps:
(1) weighing 12 mmol of CTAB cationic surfactant, adding 100mL of n-butyl alcohol, and ultrasonically dissolving for 30min to form a uniform oil phase solution;
(2) weighing 0.8 mmol of sodium molybdate, adding 300mL of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(3) under the condition of vigorous stirring at room temperature, dropwise adding a sodium molybdate aqueous phase solution into a CTAB oil phase solution, vigorously stirring for 2 hours after the aqueous phase solution is added, dropwise adding 50 mL of ethylene glycol into a mixed solution, vigorously stirring for 10 minutes, dropwise adding 0.09 mL of hydrochloric acid into the mixed solution, vigorously stirring for 1 hour, dropwise adding 6 mmol (0.4567g) of thiourea into the mixed solution, and vigorously stirring for 3 hours until the solution forms a uniform and stable emulsion;
(4) sealing the emulsion in an autoclave with a polytetrafluoroethylene inner container, reacting at a constant temperature of 200 ℃ for 20h, washing the product with distilled water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃ for 12 h to obtain MNxA super-crystalline product with a yield of about 92%;
FIG. 3b is the XRD spectrum of the resulting material of this example, with the product being a molybdenum sulfide compound with substantial oxygen doping. FIG. 3a is a FESEM photograph of a material which is a surface-wrinkled monodisperse solid super crystal spherical material, and the prepared super crystal spherical particle has a diameter distribution of 813 + -53 nm.
Example 4
An MN of the present embodimentxThe preparation method of the super crystal comprises the following steps:
(1) weighing 12 mmol of Cationic amine 220 Cationic surfactant, adding 100mL of n-butyl alcohol, and ultrasonically dissolving for 30min to form a uniform oil phase solution;
(2) weighing 0.8 mmol of sodium molybdate, adding 300mL of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(3) under the condition of vigorous stirring at room temperature, dropwise adding a sodium molybdate aqueous phase solution into a Cationic amine 220 oil phase solution, vigorously stirring for 2 hours after the aqueous phase solution is added, dropwise adding 50 mL of ethylene glycol into a mixed solution, vigorously stirring for 10 minutes, dropwise adding 1mL of hydrochloric acid into the mixed solution, vigorously stirring for 1 hour, dropwise adding 6 mmol (0.4567g) of thiourea into the mixed solution, and vigorously stirring for 3 hours until the solution forms a uniform and stable emulsion;
(4) sealing the emulsion in an autoclave with a polytetrafluoroethylene inner container, reacting at 220 deg.C for 20h, washing the product with distilled water and anhydrous ethanol for 3 times, and drying at 60 deg.C for 12 h to obtain MNxA super-crystalline product with a yield of about 93%;
FIG. 4b shows the MN obtained in the present embodimentxThe XRD spectrogram of the super crystal material has the product of molybdenum sulfide compound with a large amount of oxygen doping; FIG. 4a is an FESEM photograph of the material, which shows that the material is a core-shell super-crystalline spherical material with a surface-wrinkled ultra-thin nanosheet monodisperse, and the diameter distribution of the prepared super-crystalline spherical particles is 780 +/-48 nm; according to the content change diagram of Mo, S and O elements in FIG. 5.
Example 5
An MN of the present embodimentxThe preparation method of the super crystal comprises the following steps:
(1) weighing 5 mmol of CTAC cationic surfactant, adding 100mL of n-butyl alcohol, and ultrasonically dissolving for 30min to form a uniform oil phase solution;
(2) weighing 0.2mmol of sodium molybdate, adding 300mL of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(3) under the condition of vigorous stirring at room temperature, dropwise adding a sodium molybdate aqueous phase solution into a CTAC oil phase solution, vigorously stirring for 2 hours after the aqueous phase solution is added, dropwise adding 30 mL of ethylene glycol into a mixed solution, vigorously stirring for 10 minutes, dropwise adding 0.5 mL of nitric acid into the mixed solution, vigorously stirring for 1 hour, dropwise adding 6 mmol of thiourea into the mixed solution, and vigorously stirring for 3 hours until the solution forms a uniform and stable emulsion;
(4) sealing the emulsion in an autoclave with a polytetrafluoroethylene inner container, reacting at 220 deg.C for 20h, washing the product with distilled water and anhydrous ethanol for 3 times, and drying at 60 deg.C for 12 h to obtain MNxThe nanocrystalline product, designated sample S1;
(5) keeping other reaction conditions unchanged, changing the amount of sodium molybdate to be 0.4 mmol and 0.6 mmol respectively, reacting at constant temperature of 220 ℃ for 20h, and marking the obtained samples as S2 samples and S3 samples respectively;
fig. 6(a-c) are FESEM photographs of the S1, S2 and S3 materials, respectively, and it can be seen that the materials are all surface-wrinkled super-crystalline materials, but the morphology of the materials is greatly changed with the change of molybdenum salt.
Example 6
An MN of the present embodimentxThe preparation method of the super crystal comprises the following steps:
(1) weighing 5 mmol of Soromine A cationic surfactant, adding 100mL of n-amyl alcohol, and ultrasonically dissolving for 30min to form a uniform oil phase solution;
(2) weighing 0.1 mmol of sodium molybdate, adding 300mL of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(3) under the condition of vigorous stirring at room temperature, dropwise adding the aqueous phase solution of sodium molybdate into the oil phase solution of Soromine A, vigorously stirring for 2h after the aqueous phase solution is added, dropwise adding 80 mL of ethylene glycol into the mixed solution, vigorously stirring for 10min, dropwise adding 10 mL of acetic acid into the mixed solution, vigorously stirring for 1h, dropwise adding 6 mmol of selenourea into the mixed solution, vigorously stirring for 3 h until the solution forms uniform and stable emulsion,
(4) sealing the emulsion in an autoclave with a polytetrafluoroethylene inner container, reacting at 220 ℃ for 20h at constant temperature, washing the product with distilled water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃ for 12 h to obtain MoOx(Se2)ySezThe nanocrystalline product, designated sample S4;
(5) keeping other reaction conditions unchanged, changing the amount of hydrochloric acid to be 1.5 mL and 2.5 mL respectively, reacting at constant temperature of 220 ℃ for 20h, and marking the obtained samples as S5 samples and S6 samples respectively;
FIGS. 7(a-c) are FESEM photographs of materials S5, S6 and S7, respectively, and it can be seen that the materials are S5 which is a surface smooth monodisperse core-shell superlattice material, the particle size is 810 + -110 nm, and the materials S6 and S7 which are surface wrinkled superlattice materials, and the particle size is 660 + -50 nm.
Example 7
An MN of the present embodimentxThe preparation method of the super crystal comprises the following steps:
(1) weighing 2mmol of CTAC cationic surfactant, adding 200 mL of n-hexanol, and ultrasonically dissolving for 30min to form a uniform oil phase solution;
(2) weighing 1.0 mmol of sodium molybdate, adding 300mL of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(3) under the condition of vigorous stirring at room temperature, dropwise adding a sodium molybdate aqueous phase solution into a CTAB oil phase solution, vigorously stirring for 2 hours after the aqueous phase solution is added, dropwise adding 20 mL of ethylene glycol into a mixed solution, vigorously stirring for 10 minutes, dropwise adding 0.5 mL of hydrochloric acid into the mixed solution, vigorously stirring for 1 hour, dropwise adding 1 mmol (0.4567g) of selenourea into the mixed solution, and vigorously stirring for 3 hours until the solution forms a uniform and stable emulsion;
(4) and (3) sealing the emulsion in an autoclave with a polytetrafluoroethylene inner container, reacting for 20 hours at a constant temperature of 220 ℃, washing the product for 3 times respectively by using distilled water and absolute ethyl alcohol, and drying for 12 hours at 60 ℃ to obtain the product, namely the molybdenum selenide super-crystal product doped with a large amount of oxygen, which is marked as an S10 sample.
(5) Keeping other reaction conditions unchanged, changing the amount of CTAC into 4 mmol and 10 mmol respectively, reacting at 220 ℃ for 20h at constant temperature, and recording the obtained samples as S11 samples and S12 samples respectively.
FIG. 8(a-c) is the FESEM photographs of the materials S10, S11 and S12, and it can be seen that the material S10 is a monodisperse core-shell superlattice material, the particle size is 804 + -105 nm, and S11 and S12 are both surface-folded irregular superlattice materials.
Example 8
An MN of the present embodimentxThe preparation method of the super crystal comprises the following steps:
(1) weighing 12 mmol of Soromine A cationic surfactant, adding 200 mL of diheptanol, and ultrasonically dissolving for 30min to form a uniform oil phase solution;
(2) weighing 2mmol of sodium molybdate, adding 300mL of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(3) under the condition of vigorous stirring at room temperature, dropwise adding a sodium molybdate aqueous phase solution into a Soromine A oil phase solution, vigorously stirring for 2 hours after the addition of the aqueous phase solution is finished, dropwise adding 300mL of ethylene glycol into a mixed solution, vigorously stirring for 10 minutes, dropwise adding 0.5 mL of hydrochloric acid into the mixed solution, vigorously stirring for 1 hour, dropwise adding 4 mmol of thiourea into the mixed solution, and vigorously stirring for 3 hours until the solution forms a uniform and stable emulsion;
(4) sealing the emulsion in an autoclave with a polytetrafluoroethylene inner container, reacting at 220 ℃ for 20h at constant temperature, washing the product with distilled water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃ for 12 h to obtain a molybdenum sulfide super-crystal product doped with a large amount of oxygen;
(5) keeping other reaction conditions unchanged, changing the amount of thiourea into 10 mmol and 16 mmol respectively, reacting at 220 ℃ for 20h at constant temperature, and marking the obtained samples as S14 samples and S15 samples respectively.
FIG. 9(a-c) is FESEM photographs of materials S13, S14 and S15, and it can be seen that the materials are all monodisperse nanocrystalline materials with wrinkles on the surface, and the particle sizes are 734 + -67 nm, 805 + -166 nm and 669 + -76 nm, respectively.
Example 9
An MN of the present embodimentxThe preparation method of the super crystal comprises the following steps:
the product prepared in example 1 is calcined at the high temperature of 250-1300 ℃ for 3 h under the protection of high-purity argon. Namely obtaining the hollow structure MoS with 1T phase up to 90 percent and coated by carbon2A nanocrystalline product.
Example 10
An MN of the present embodimentxThe preparation method of the super crystal comprises the following steps:
(1) weighing 2mmol of Soromine A cationic surfactant, adding 100mL of n-octanol, and ultrasonically dissolving for 30min to form a uniform oil phase solution;
(2) weighing 0.1 mmol of sodium tungstate, adding 300mL of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(3) under the condition of vigorous stirring at room temperature, dropwise adding a sodium tungstate aqueous phase solution into a Soromine A oil phase solution, vigorously stirring for 2 hours after the aqueous phase solution is added, dropwise adding 80 mL of ethylene glycol into a mixed solution, vigorously stirring for 10 minutes, dropwise adding 0.1 mL of hydrochloric acid into the mixed solution, vigorously stirring for 1 hour, dropwise adding 4 mmol (0.4567g) of thiourea into the mixed solution, and vigorously stirring for 3 hours until the solution forms a uniform and stable emulsion;
(4) and (3) sealing the emulsion in an autoclave with a polytetrafluoroethylene inner container, reacting at a constant temperature of 200 ℃ for 20h, washing the product with distilled water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃ for 12 h to obtain the product, namely the tungsten sulfide super-crystal product doped with a large amount of oxygen.
Example 11
An MN of the present embodimentxThe preparation method of the super crystal comprises the following steps:
(1) weighing 5 mmol sodium succinate (NaAOT) anionic surfactant, adding 100mL glycerol, and ultrasonically dissolving for 30min to form uniform oil phase solution;
(2) weighing 5 mmol (0.2908 g) of nickel nitrate, adding 300mL of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(3) under the condition of vigorous stirring at room temperature, dropwise adding a nickel nitrate aqueous phase solution into a NaAOT oil phase solution, vigorously stirring for 2 hours after the aqueous phase solution is added, dropwise adding 10 mL of ethylene glycol into a mixed solution, vigorously stirring for 10 minutes, dropwise adding 0.1 mL of hydrochloric acid into the mixed solution, dropwise adding 4 mmol (0.4567g) of thiourea into the mixed solution, and vigorously stirring for 3 hours until the solution forms a uniform and stable emulsion;
(4) putting the emulsion into a high-pressure kettle with a polytetrafluoroethylene inner container, sealing, and reacting at 220 ℃ for 20 hours at constant temperature; washing the product with distilled water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃ for 12 hours to obtain the nickel sulfide super crystal product doped with a large amount of oxygen.
Example 12
An MN of the present embodimentxThe preparation method of the super crystal comprises the following steps:
(1) weighing 10 mmol sodium succinate (NaAOT) anionic surfactant, adding 200 mL glycerol, and ultrasonically dissolving for 30min to form uniform oil phase solution;
(2) weighing 1 mmol of cobalt nitrate, adding 300mL of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution; under the condition of vigorous stirring at room temperature, dropwise adding a cobalt nitrate aqueous phase solution into a NaAOT oil phase solution, vigorously stirring for 2 hours after the addition of the aqueous phase solution is finished, dropwise adding 30 mL of ethylene glycol into the mixed solution, vigorously stirring for 10 minutes, dropwise adding 0.8 mL of hydrochloric acid into the mixed solution, dropwise adding 4 mmol of thiourea into the mixed solution, and vigorously stirring for 3 hours until the solution forms a uniform and stable emulsion;
(3) and (3) sealing the emulsion in an autoclave with a polytetrafluoroethylene inner container, reacting at a constant temperature of 200 ℃ for 20h, washing the product for 3 times by using distilled water and absolute ethyl alcohol respectively, and drying at 60 ℃ for 12 h to obtain the product, namely the cobalt sulfide super-crystal product doped with a large amount of oxygen.
Example 13
An MN of the present embodimentxThe preparation method of the super crystal comprises the following steps:
(1) weighing 3 mmol sodium succinate (NaAOT) anionic surfactant, adding 100mL n-octanol, and ultrasonically dissolving for 30min to form uniform oil phase solution;
(2) weighing 10 mmol of manganese nitrate, adding 300mL of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(3) under the condition of vigorous stirring at room temperature, dropwise adding a manganese nitrate aqueous phase solution into a NaAOT oil phase solution, vigorously stirring for 2 hours after the addition of the aqueous phase solution is finished, dropwise adding 30 mL of ethylene glycol into a mixed solution, vigorously stirring for 10 minutes, dropwise adding 7mL of hydrochloric acid into the mixed solution, dropwise adding 10 mmol of thiourea into the mixed solution, and vigorously stirring for 3 hours until the solution forms a uniform and stable emulsion;
(4) and (3) sealing the emulsion in an autoclave with a polytetrafluoroethylene inner container, reacting at a constant temperature of 200 ℃ for 20h, washing the product for 3 times by using distilled water and absolute ethyl alcohol respectively, and drying at 60 ℃ for 12 h to obtain the product, namely the manganese sulfide super-crystal product doped with a large amount of oxygen.
Example 14
An MN of the present embodimentxThe preparation method of the super crystal comprises the following steps:
(1) weighing 6 mmol sodium succinate (NaAOT) anionic surfactant, adding 100mL n-amyl alcohol, and ultrasonically dissolving for 30min to form uniform oil phase solution;
(2) weighing 1 mmol of zinc nitrate, adding 300mL of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(3) under the condition of vigorous stirring at room temperature, dropwise adding a zinc nitrate aqueous phase solution into a NaAOT oil phase solution, vigorously stirring for 2 hours after the aqueous phase solution is added, dropwise adding 1mL of hydrochloric acid into a mixed solution, vigorously stirring for 10 minutes, dropwise adding 6 mmol of thiourea into the mixed solution, and vigorously stirring for 3 hours until the solution forms a uniform and stable emulsion;
(4) and (3) sealing the emulsion in an autoclave with a polytetrafluoroethylene inner container, reacting at a constant temperature of 180 ℃ for 20h, washing the product with distilled water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃ for 12 h to obtain the product, namely the zinc sulfide super-crystal product doped with a large amount of oxygen.
Example 15
An MN of the present embodimentxThe preparation method of the super crystal comprises the following steps:
(1) weighing 10 mmol sodium succinate (NaAOT) anionic surfactant, adding 500 mL isopropanol, and ultrasonically dissolving for 30min to form uniform oil phase solution;
(2) weighing 1 mmol of tin chloride, adding 300mL of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(3) under the condition of vigorous stirring at room temperature, dropwise adding a tin chloride aqueous phase solution into a NaAOT oil phase solution, vigorously stirring for 2 hours after the aqueous phase solution is added, dropwise adding 30 mL of ethylene glycol into the mixed solution, vigorously stirring for 10 minutes, dropwise adding 3 mL of hydrochloric acid into the mixed solution, dropwise adding 4 mmol of thiourea into the mixed solution, and vigorously stirring for 3 hours until the solution forms a uniform and stable emulsion;
(4) and (3) sealing the emulsion in an autoclave with a polytetrafluoroethylene inner container, reacting at a constant temperature of 180 ℃ for 20h, washing the product with distilled water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃ for 12 h to obtain the product, namely the tin sulfide super-crystal product doped with a large amount of oxygen.
Example 16
An MN of the present embodimentxThe preparation method of the super crystal comprises the following steps:
(1) weighing 120mmol sodium succinate (NaAOT) anionic surfactant, adding 100mL isopropanol, and ultrasonically dissolving for 30min to form uniform oil phase solution;
(2) weighing 1 mmol of ferric chloride, adding 300mL of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(3) under the condition of vigorous stirring at room temperature, dropwise adding a ferric chloride aqueous phase solution into a NaAOT oil phase solution, vigorously stirring for 2 hours after the addition of the aqueous phase solution is finished, dropwise adding 30 mL of ethylene glycol into the mixed solution, vigorously stirring for 10 minutes, dropwise adding 9 mL of hydrochloric acid into the mixed solution, dropwise adding 100mmol of thiourea into the mixed solution, and vigorously stirring for 3 hours until the solution forms a uniform and stable emulsion;
(4) and (3) sealing the emulsion in an autoclave with a polytetrafluoroethylene inner container, reacting at 220 ℃ for 20h at constant temperature, washing the product for 3 times by using distilled water and absolute ethyl alcohol respectively, and drying at 60 ℃ for 12 h to obtain the product, namely the iron sulfide super-crystal product doped with a large amount of oxygen.
Example 17
An MN of the present embodimentxThe preparation method of the super crystal comprises the following steps:
(1) weighing 8 mmol of Soromine A cationic surfactant, adding 100mL of n-butyl alcohol, and ultrasonically dissolving for 30min to form a uniform oil phase solution;
(2) weighing 2mmol of sodium molybdate, adding 300mL of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(3) under the condition of vigorous stirring at room temperature, dropwise adding a sodium tungstate aqueous phase solution into a Soromine A oil phase solution, vigorously stirring for 2 hours after the aqueous phase solution is added, dropwise adding 80 mL of ethylene glycol into a mixed solution, vigorously stirring for 10 minutes, dropwise adding 0.5 mL of hydrochloric acid into the mixed solution, vigorously stirring for 1 hour, dropwise adding 4 mmol (0.4567g) of thiourea into the mixed solution, and vigorously stirring for 3 hours until the solution forms a uniform and stable emulsion;
(4) sealing the emulsion in an autoclave with a polytetrafluoroethylene inner container, reacting at 260 ℃ for 20h at constant temperature, washing the product with distilled water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃ for 12 h to obtain the oxygen-doped dish-shaped MoS2A nanocrystalline product.
Example 18
An MN of the present embodimentxThe preparation method of the super crystal comprises the following steps:
(1) weighing 0.2mmol of Soromine A cationic surfactant, adding 100mL of n-butyl alcohol, and ultrasonically dissolving for 30min to form a uniform oil phase solution;
(2) weighing 2mmol of sodium molybdate, adding 300mL of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(3) under the condition of vigorous stirring at room temperature, dropwise adding a sodium tungstate aqueous phase solution into a Soromine A oil phase solution, vigorously stirring for 2 hours after the aqueous phase solution is added, dropwise adding 80 mL of ethylene glycol into a mixed solution, vigorously stirring for 10 minutes, dropwise adding 0.5 mL of hydrochloric acid into the mixed solution, vigorously stirring for 1 hour, dropwise adding 0.2mmol (0.023 g) of thiourea into the mixed solution, and vigorously stirring for 3 hours until the solution forms a uniform and stable emulsion;
(4) sealing the emulsion in an autoclave with a polytetrafluoroethylene inner container, reacting at 260 ℃ for 20h at constant temperature, washing the product with distilled water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃ for 12 h to obtain the oxygen-doped dish-shaped MoS2A nanocrystalline product.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (5)

1. MN (Mobile node)xSuper gradeA method for producing a crystal, characterized by: the MNxThe super crystal is formed by self-assembling two-dimensional sheet materials, MNxThe super crystal structure is a semiconductor phase or metal phase crystal with a disc-shaped, solid, hollow or core-shell structure; wherein N is sulfur or selenium, and the preparation steps are as follows:
(1) preparing an oil phase solution: completely dissolving a surfactant in a long-chain alcohol to form a uniform and stable oil phase solution, wherein (2-12) mmoL of the surfactant is dissolved in each 100mL of the long-chain alcohol;
(2) preparing an aqueous phase solution: dissolving the M salt in deionized water to form a uniform and stable aqueous solution, wherein 0.1-10 mmol of the M salt is dissolved in every 300mL of the deionized water;
(3) under the condition of magnetic stirring of 100-;
(4) placing the emulsion obtained in the step (3) into a high-pressure reaction kettle for reaction, and washing, drying and calcining the obtained product to obtain MNxA super crystal;
in the step (2), the M salt is molybdenum salt, tungsten salt, nickel salt, cobalt salt, manganese salt, zinc salt, tin salt, iron salt or cadmium salt;
in the step (3), the acid solution is a hydrochloric acid solution, a nitric acid solution or an acetic acid solution, the mass fraction of the hydrochloric acid solution is 35-37%, the mass fraction of the nitric acid solution is 65-70%, and the concentration of the acetic acid solution is 95-99.5%;
the quantity ratio of the surfactant in the step (1) to the M salt in the step (2) is (0.2-120): 1; in the step (3), oil phase: water phase: ethylene glycol: the volume ratio of the acid solution is (0.17-0.67): 1: (0-1): (0.0003-0.03), the mass ratio of thiourea or selenourea to M salt is (0.1-100): 1;
in the step (4), the reaction temperature is (160- & ltSUB & gt 220- & gt DEG C, the reaction time is 1h-1 week, the calcination temperature is (250- & ltSUB & gt 1300- & gt DEG C, and the calcination time is (0.5-12) h.
2. The MN of claim 1xThe preparation method of the super crystal is characterized by comprising the following steps: in the step (1), the surfactant is an anionic surfactant or a cationic surfactant, the anionic surfactant is a sodium succinate anionic surfactant, and the cationic surfactant is an amine salt cationic surfactant, a quaternary ammonium salt cationic surfactant, an onium salt cationic surfactant, an amine oxide cationic surfactant or a heterocyclic cationic surfactant; the long-chain alcohol is butanol, pentanol, hexanol, heptanol or octanol.
3. The MN of claim 1xThe preparation method of the super crystal is characterized by comprising the following steps: in the step (4), the reaction temperature is 220 ℃, the reaction time is 20 hours, and the semiconductor phase MN is obtainedxA super crystal.
4. The MN of claim 1xThe preparation method of the super crystal is characterized by comprising the following steps: the calcination temperature in the step (4) is 250-1300 ℃ and the calcination time is 1-3 h, so as to obtain the metal phase MNxA super crystal.
5. MN prepared according to any one of claims 1 to 4xUse of a superlattice as a component in the manufacture of an energy storage device.
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