CN114455599B - Preparation method and application of rare earth or alkaline earth hexaboride liquid phase dispersion - Google Patents

Preparation method and application of rare earth or alkaline earth hexaboride liquid phase dispersion Download PDF

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CN114455599B
CN114455599B CN202011247903.1A CN202011247903A CN114455599B CN 114455599 B CN114455599 B CN 114455599B CN 202011247903 A CN202011247903 A CN 202011247903A CN 114455599 B CN114455599 B CN 114455599B
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rare earth
aqueous solution
water
alkaline earth
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CN114455599A (en
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肖立华
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Guizhou Jiaotong College
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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
    • C01B35/00—Boron; Compounds thereof
    • C01B35/02—Boron; Borides
    • C01B35/04—Metal borides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/14—Treatment of water, waste water, or sewage by heating by distillation or evaporation using solar energy
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/61—Additives non-macromolecular inorganic
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/20—Controlling water pollution; Waste water treatment
    • Y02A20/208—Off-grid powered water treatment
    • Y02A20/212—Solar-powered wastewater sewage treatment, e.g. spray evaporation

Abstract

A preparation method and application of a rare earth or alkaline earth hexaboride liquid phase dispersion are provided, wherein the preparation method comprises the following steps: (1) Uniformly mixing rare earth salt or alkaline earth salt with a boron source, heating and reacting in vacuum or inert atmosphere, and cooling to room temperature to obtain an initial product; (2) Emulsifying the initial product in water, performing ultrasonic vibration, filtering or centrifuging, washing, adding an alkaline aqueous solution into the washed product, performing emulsification treatment, and performing ultrasonic vibration to obtain a water phase dispersion; or washing the water washing product with alcohol, adding an organic solvent, emulsifying, and performing ultrasonic oscillation to obtain an organic phase dispersion. The liquid phase dispersion is applied to preparing transparent heat insulation coating, solar photo-thermal conversion nano fluid and sea water desalination device. The liquid phase dispersoid obtained by the method provided by the invention is not settled after standing for 12 months, and has good dispersibility and stability. The method has simple process and low cost, does not need to be dried, does not add any dispersing agent or surface treating agent, and can realize industrial production.

Description

Preparation method and application of rare earth or alkaline earth hexaboride liquid phase dispersion
Technical Field
The invention particularly relates to a preparation method and application of a rare earth or alkaline earth hexaboride liquid-phase dispersion.
Background
Rare earth and alkaline earth hexaboride (MB) having CsCl type cubic crystal structure 6 ) Not only has the characteristics of high melting point, large hardness and strong chemical stability, but also has respective functionality. Wherein trivalent rare earth hexaboride (LaB) with abundant electrons 6 、CeB 6 And PrB 6 Etc.) has the characteristics of low volatility, low work function, etc., not only is a cathode material with excellent thermionic emission performance applied in industry, but also is an ideal field emission cathode material; mixed valence compound SmB 6 Has the property of topological rattan insulator; divalent rare earth hexaboron compound EuB 6 Is a narrow bandgap semiconductor; divalent alkaline earth hexaboride (CaB) 6 、SrB 6 And BaB 6 ) Can be used for thermoelectric materials. In particular, trivalent rare earth hexaboride (YB 6 、LaB 6 And GaB 6 Etc.) nanomaterials with localized surface plasmon resonance absorptionNear infrared radiation with the wavelength of 800-2500 nm has strong absorption to the whole solar radiation, so that the method can be applied to transparent solar radiation shielding materials for windows, solar photo-thermal conversion and sea water desalination. However, in the conventional preparation, solid rare earth or alkaline earth hexaboride nano powder is prepared, then a surface treatment agent is added, and the surface of the powder is modified by ball milling to prepare a liquid phase dispersion, and the rare earth or alkaline earth hexaboride nano particles prepared by the method are partially agglomerated before modification, so that the particle size after modification is large and the distribution is uneven, the monodispersion of the rare earth or alkaline earth hexaboride nano material is difficult to realize, the dispersion performance of the rare earth or alkaline earth hexaboride nano material is poor, and the absorption characteristic and the efficient solar energy absorption performance of the rare earth or alkaline earth hexaboride are difficult to realize. Therefore, the dispersibility and stability of rare earth or alkaline earth hexaboride dispersions are critical indicators in their applications.
CN 106395843A and literature (Powder Technology,2018, 323:203-207) disclose a preparation method of lanthanum hexaboride powder and a study on sintering performance thereof, wherein lanthanum source, boron source and molten salt are mixed and heated, and then washed, filtered and dried to prepare the lanthanum hexaboride nano powder. However, this method tends to form a layer of lanthanum oxide, boron oxide or amorphous boron on the surface of the nanoparticles, thereby affecting the dispersion stability of the aqueous dispersion thereof.
CN 1923686A discloses a method for preparing nano hexaboride nano powder, which is to mix rare earth or alkaline earth source with boron source, and make them undergo the process of high-pressure reaction in high-pressure reactor. However, the method needs to seal high pressure, and is not easy for industrial production; in addition, due to the sealing reaction, the rare earth or alkaline earth source and the boron source are difficult to form boron defects in the nano powder, so that the surface of the nano particles is positively charged, and the aqueous dispersion is difficult to prepare; the rare earth or alkaline earth source also absorbs water easily, and part of impurity rare earth or alkaline earth borate is easily generated.
CN 106009884A discloses a lanthanum hexaboride nano heat-insulating aqueous slurry and a preparation method thereof, which are characterized in that the surface activity of lanthanum hexaboride nano particles is improved by adding different active agents, so as to prepare the nano lanthanum hexaboride heat-insulating aqueous slurry. However, it is impossible to directly disperse nano lanthanum hexaboride in water without adding a dispersing agent.
In summary, the rare earth hexaboride prepared by the existing method must be pickled to remove the impurity rare earth borate, and in order to ensure the stability of the dispersion prepared by the method, a surface treatment agent must be added into the rare earth hexaboride, and hard agglomeration is formed after drying, so that the particle size of the modified particles is large, the distribution is uneven, and the dispersibility is seriously affected. Therefore, it is needed to find a preparation method of rare earth or alkaline earth hexaboride liquid-phase dispersion which is simple in process, low in cost, free from drying and adding any dispersing agent, and excellent in dispersibility and stability of the obtained dispersion.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects in the prior art, and provides a preparation method and application of a rare earth or alkaline earth hexaboride liquid-phase dispersion, which have the advantages of simple process, low cost, no need of drying, no addition of any dispersing agent, realization of industrial production, excellent dispersion and stability of the obtained dispersion, and strong near infrared absorption and scattering capability.
The technical scheme adopted for solving the technical problems is as follows: a method for preparing a rare earth or alkaline earth hexaboride liquid phase dispersion, comprising the steps of:
(1) Uniformly mixing rare earth salt or alkaline earth salt with a boron source, heating and reacting in vacuum or inert atmosphere, and cooling to room temperature to obtain an initial product;
(2) Emulsifying the initial product obtained in the step (1) in water, carrying out ultrasonic vibration, filtering or centrifuging, washing, adding an alkaline aqueous solution into the washed product, carrying out emulsification treatment, and carrying out ultrasonic vibration to obtain a rare earth or alkaline earth hexaboride aqueous phase dispersion; or washing the water washing product with alcohol, adding an organic solvent, emulsifying, and performing ultrasonic oscillation to obtain the rare earth or alkaline earth hexaboride organic phase dispersion.
Preferably, in step (1), the molar ratio of the rare earth element in the rare earth salt or the alkaline earth element in the alkaline earth salt to the boron element in the boron source is 1:2 to 12 (more preferably 1:5 to 10). The boron source is easy to decompose into gas phase and is lost, so that the consumption of the boron source is properly excessive compared with that of rare earth or alkaline earth elements, but the excessive consumption or the excessive consumption can cause boron defects in the synthesized nano hexaboride powder, thereby leading the surface of the hexaboride nano particles to be positively charged.
Preferably, in the step (1), the rare earth salt is one or more of rare earth chloride, rare earth oxychloride, rare earth fluoride, rare earth bromide and the like. More preferably, the rare earth salt is rare earth chloride and/or rare earth oxychloride. The melting points of the rare earth chloride and the rare earth oxychloride are low, a liquid phase is easier to form, the liquid phase is easy to reduce, and the particle size of the synthesized hexaboride nano particles is small, so that the dispersion is facilitated. The rare earth element in the rare earth salt is one or more of rare earth metal element with atomic number of 57-71, metal element Sc and metal element Y.
Preferably, in the step (1), the alkaline earth salt is one or more of chlor alkaline earth, fluoridated alkaline earth or brominated alkaline earth. More preferably, the alkaline earth salt is alkaline earth chloride and/or alkaline earth oxychloride. The alkaline earth element in the alkaline earth salt is one or more of calcium, strontium or barium.
Preferably, in step (1), the boron source is an alkali metal boron hydride compound.
Preferably, the alkali metal boron hydride is NaBH 4 、KBH 4 Or LiBH 4 One or more of the following.
Preferably, in the step (1), the vacuum degree of the vacuum is 0 to 100Pa.
Preferably, in step (1), the inert atmosphere is argon and/or helium. The inert atmosphere used in the method is high-purity gas with the purity more than or equal to 99.9 percent.
Preferably, in the step (1), the specific operation of the heating reaction is: heating to 300-400 ℃ at a speed of 5-20 ℃/min, preserving heat for 1-5 h, heating to 400-1200 ℃ (more preferably 600-1000 ℃) at a speed of 1-30 ℃/min, and preserving heat for 1-10 h. The method of the invention firstly keeps the temperature at a lower temperature of 300-400 ℃ to sufficiently remove the residual moisture, wherein the moisture mainly comes from: firstly, the water contained in the raw materials; secondly, the rare earth salt or alkaline earth salt which is easier to absorb water absorbs the moisture in the air in the mixing process; if too much moisture remains, rare earth borate or alkaline earth borate is easy to generate, which not only seriously affects the purity of the hexaboride nano material, but also can be removed by acid washing, and the acid washing damages the surface charge of the hexaboride nano particles, thereby seriously affecting the dispersion of rare earth or alkaline earth hexaboride in water.
Preferably, in step (1), the cooling is at a rate of 5 to 40 ℃/min (more preferably 10 to 30 ℃/min) to room temperature.
Preferably, in step (1), a low melting point medium corresponding to 1 to 20 times (more preferably 1 to 10 times) the total mass thereof is added to the rare earth salt or alkaline earth salt and the boron source.
Preferably, the low-melting-point medium is low-melting-point elemental metal or low-melting-point molten salt.
Preferably, the low-melting-point elemental metal is one or more of elemental Sn, elemental In, elemental Bi and the like. The melting point of the low-melting-point simple substance metal is lower than 300 ℃, which is beneficial to reducing the reaction temperature. The high-temperature metal liquid phase environment provided by the low-melting-point simple metal can reduce the loss of borane generated by the thermal decomposition of the boron source, so that the rare earth salt or alkaline earth salt reacts with the boron source more quickly and fully, the yield is improved, and the method is suitable for industrial production; on the other hand, the inherent problems of high reaction temperature, long atom diffusion path, serious boron source loss, incomplete reaction and the like of the rare earth or alkaline earth hexaboride nano powder prepared by the existing solid phase reaction method are skillfully solved. The low-melting-point simple substance metal can be recycled after the reaction is completed.
Preferably, the low melting point molten salt is LiCl, KCl, naCl or ZnCl 2 One or more of the following. More preferably, the low melting point molten salt is KCl, liCl and ZnCl 2 The mass ratio of the mixture is 1-4:1.
Preferably, in the step (2), the volume-to-mass ratio (mL/g) of the water to the total mass of the raw materials in the step (1) is 3-10:1. The raw materials are rare earth salt or alkaline earth salt and boron source, or also comprise low-melting point medium.
Preferably, in the step (2), the power of the emulsification treatment is 0.5-40 kW (more preferably 1-10 kW), the rotating speed is 1000-30000 r/min, and the time of each emulsification treatment is 20-40 min. The mechanical shearing force in the emulsification treatment process reduces the size of solid particles in the nano material by grinding or crushing, and can rapidly play a role in loosening the mass.
Preferably, in the step (2), the frequency of the ultrasonic oscillation is 10 to 50kHz (more preferably 20 to 50 kHz), and the time of each ultrasonic oscillation is 10 to 180 minutes (more preferably 50 to 150 minutes). The effect of the ultrasonic vibration is to disperse the hexaboride starting material more so that the halide salt or also the low melting point molten salt formed in the hexaboride starting material is dissolved in water.
Preferably, in the step (2), the temperature of the water washing is 10 to 80 ℃ (more preferably 40 to 70 ℃). The purpose of the water wash is to remove the halide salts formed or also the low melting point molten salts.
Preferably, in the step (2), the repeated operations of emulsification, ultrasonic vibration, filtration or centrifugation and water washing are carried out for more than or equal to 3 times, and AgNO is added into the water washing liquid in a dropwise manner 3 Or Ca (OH) 2 The solution had no white precipitate. When the rare earth salt or alkaline earth salt contains chlorine or bromine, agNO is added dropwise 3 The solution, no white precipitate indicates that chloride or bromide ions in the solution have been completely removed; when the rare earth salt or alkaline earth salt contains fluorine, ca (OH) is added dropwise 2 The solution, without white precipitate, indicated that the fluoride ions in the solution had been completely removed.
Preferably, in the step (2), when the low-melting-point medium is low-melting-point simple substance metal, after the first emulsification treatment and ultrasonic oscillation, adjusting the pH value to 9-10 with an alkaline aqueous solution, standing, separating the low-melting-point simple substance metal, filtering or centrifuging, washing with water, repeating the emulsification treatment, ultrasonic oscillation, filtering or centrifuging, performing the washing operation for more than or equal to 2 times, and dripping AgNO into the washing liquid 3 Or Ca (OH) 2 The solution had no white precipitate. After the pH value is regulated to 9-10, rare earth or alkaline earth hexaboride can be dispersed in water, and the mixture is calmIn the process, low-melting-point simple substance metal can be precipitated, thereby being beneficial to separation and recycling.
Preferably, the pH value of the alkaline aqueous solution with the pH value adjusted is more than or equal to 10.
Preferably, the alkaline aqueous solution is an aqueous sodium hydroxide solution or an aqueous ammonia solution.
Preferably, the time of the standing is 5 to 30 hours.
Preferably, in step (2), the volume to mass ratio (L/g) of the alkaline aqueous solution or organic solvent to the dry weight of the water-washed product is from 5 to 1000:1 (more preferably from 6 to 600:1). After the dry weight proportion of the water-washed product is determined by a conventional method, the water-washed product to be added under a certain dry weight can be converted, and the water-washed product does not need to be dried. The method of the invention is to directly add alkaline aqueous solution or organic solvent into wet-based water washing products for dispersion, which can reduce drying steps and save energy sources, and is more important because the inventor researches that once rare earth or alkaline earth hexaboride is dried, ball milling is needed and dispersing agents are added to disperse the rare earth or alkaline earth hexaboride in water, the dispersion performance of the rare earth or alkaline earth hexaboride is greatly reduced and even cannot be dispersed, while wet-based water is directly dispersed, no surface treatment agent is needed to be added, and after the pH value is regulated to 9-10, stable hexaboride liquid phase dispersion which can be kept for 12 months and does not settle can be realized.
Preferably, in the step (2), the pH of the alkaline aqueous solution is 9 to 10.
Preferably, in the step (2), the alkaline aqueous solution is an aqueous sodium hydroxide solution or an aqueous ammonia solution.
Preferably, in the step (2), the number of times of washing water with alcohol is not less than 2.
Preferably, in the step (2), the organic solvent is one or more of alcohol solution, ionic liquid, grease or liquid resin.
Preferably, in the step (2), the alcohol used for washing water with alcohol and the alcohol solution are one or more of ethanol, ethylene glycol or n-butanol.
Preferably, in the step (2), the ionic liquid is 1-hexyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt and/or 1-butyl-3-methylimidazole tetrafluoroborate and the like. The ionic liquid is in a wide liquid temperature range (namely liquid range).
The technical scheme adopted by the invention for further solving the technical problems is as follows: the rare earth or alkaline earth hexaboride liquid phase dispersion obtained by the preparation method is applied to the preparation of transparent heat insulation coating, solar photo-thermal conversion nano-fluid and sea water desalination device. Compared with the existing dispersion, the dispersion obtained by the method has better dispersibility, and can avoid aggregation of nano particles to form larger secondary particles, so that the transparent heat insulation performance of a coating and the photo-thermal conversion efficiency of nano fluid and a seawater desalination device thereof are improved.
The beneficial effects of the invention are as follows:
(1) The rare earth or alkaline earth hexaboride liquid phase dispersoid obtained by the method of the invention can realize sealing and standing for 12 months without sedimentation by utilizing positive charges on the surfaces of nano particles and adjusting the pH value of the solution, and has good stability, the one-dimensional size of the nano particles of the dispersoid is 5-30 nm, and the dispersibility is good;
(2) The method has simple process and low cost, does not need to be dried, does not add any dispersing agent or surface treating agent, and can realize industrial production;
(3) The rare earth or alkaline earth hexaboride liquid phase dispersion obtained by the method has strong near infrared absorption and scattering capability, and can be widely used for preparing transparent heat insulation coating, solar photo-thermal conversion nano-fluid and sea water desalination devices.
Drawings
FIG. 1 is an X-ray diffraction pattern of an aqueous lanthanum hexaboride dispersion obtained in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the aqueous lanthanum hexaboride dispersion obtained in example 1 of the present invention;
FIG. 3 is a graph showing the UV-visible near-infrared absorption spectrum of nanoparticles in the aqueous lanthanum hexaboride dispersion obtained in example 1 of the present invention;
FIG. 4 is a sedimentation diagram of the aqueous lanthanum hexaboride dispersion obtained in example 1 of the present invention after standing for 12 months.
Detailed Description
The invention is further described below with reference to examples and figures.
The density of the ethanol used in the embodiment of the invention is 0.79g/mL, and the density of the n-butanol is 0.81g/mL; the 1-hexyl-3-methylimidazole bistrifluoromethylsulfonylimide salt used in the examples of the present invention was purchased from Mini chemical technology (Shanghai) Co., ltd, and had a density of 1.37g/mL, and 1-butyl-3-methylimidazole tetrafluoroborate was purchased from Beijing carbofuran technology Co., ltd, and had a density of 1.21g/mL; the purity of the high-purity gas used by the method is more than or equal to 99.9 percent; the chemical reagents used in the examples of the present invention, unless otherwise specified, were all obtained by conventional commercial means.
Example 1
(1) 1.25 g (5 mmol) LaCl 3 With 1.52 g (40 mmol) NaBH 4 After being uniformly mixed, the mixture is put into an alumina crucible, and the temperature rising and heating reaction is carried out under the atmosphere of high-purity argon, the temperature is firstly increased to 400 ℃ at the speed of 10 ℃/min, the heat is preserved for 1h, the temperature is then increased to 750 ℃ at the speed of 20 ℃/min, the heat is preserved for 3h, and the mixture is cooled to the room temperature at the speed of 20 ℃/min, so that the initial product is obtained;
(2) Emulsifying the initial product obtained in the step (1) in 15mL of water (with the power of 3kW, the rotating speed of 20000r/min, the time of each emulsifying treatment being 30 min), performing ultrasonic vibration (with the frequency of 40kHz, the time of each ultrasonic vibration being 100 min), filtering, washing with 50 ℃ water for 3 times, and dropwise adding AgNO into the washing liquid 3 Adding 9.5mL of sodium hydroxide solution with pH value of 9.5 into 0.5g (dry weight) of water washing product until the solution has no white precipitate, emulsifying for 30min under the conditions of power of 3kW and rotating speed of 20000r/min, and carrying out ultrasonic oscillation for 100min under the condition of frequency of 40kHz to obtain lanthanum hexaboride aqueous phase dispersion;
after 0.5g (dry weight) of the water washing product is washed with ethanol for 3 times, 6.9ml of 1-hexyl-3-methylimidazole bistrifluoromethanesulfonimide salt is added, the emulsion is carried out for 30min under the conditions of the power of 3kW and the rotating speed of 20000r/min, and the ultrasonic oscillation is carried out for 100min under the frequency of 40kHz, thus obtaining the lanthanum hexaboride ion liquid phase dispersion.
As shown in FIG. 1, the lanthanum hexaboride in the aqueous dispersion of lanthanum hexaboride obtained in the example of the present invention is LaB 6 Pure phase, without any other impurity phase.
As shown in figure 2, the lanthanum hexaboride aqueous dispersion obtained by the embodiment of the invention has good dispersibility, no agglomeration phenomenon and the one-dimensional size of the nano particles of the dispersion is 10-30 nm.
As shown in FIG. 3, the lanthanum hexaboride aqueous dispersion obtained by the embodiment of the invention has high absorption capacity in ultraviolet, visible and near infrared bands, and can be used in the fields of heat insulation and optics.
As shown in FIG. 4, the lanthanum hexaboride aqueous dispersion obtained in the example of the present invention is black, has a solid content of 5wt%, and is sealed and left to stand for 12 months without sedimentation.
Through detection, the lanthanum hexaboride ion liquid phase dispersion obtained by the embodiment of the invention is black, has the solid content of 5 weight percent, and is sealed and stood for 12 months without sedimentation.
Example 2
(1) 1.24 g (5 mmol) CeCl 3 And 1.14 g (30 mmol) NaBH 4 With 6.64g KCl, 5.21g LiCl and 2.38g ZnCl 2 After being uniformly mixed, the mixture is put into an alumina crucible, and the temperature rising and heating reaction is carried out under the atmosphere of high-purity argon, the temperature is firstly increased to 300 ℃ at the speed of 15 ℃/min, the heat is preserved for 2 hours, the temperature is then increased to 700 ℃ at the speed of 30 ℃/min, the heat is preserved for 5 hours, and the mixture is cooled to the room temperature at the speed of 30 ℃/min, so that the initial product is obtained;
(2) Emulsifying the initial product obtained in the step (1) in 100mL of water (with the power of 4kW, the rotating speed of 30000r/min, the time of each emulsifying treatment of 20 min), ultrasonically oscillating (with the frequency of 40kHz, the time of each ultrasonic oscillating of 50 min), filtering and washing with water at 60 ℃ for 4 times, and dropwise adding AgNO into the washing liquid 3 Until the solution had no white precipitate, 4.5mL of an aqueous ammonia solution having a pH of 9.0 was added to 0.5g (dry weight) of the water-washed product, and the water-washed product was washed with water at a power of 4kW,emulsifying for 20min at 30000r/min, and ultrasonically oscillating for 50min at 40kHz to obtain cerium hexaboride aqueous dispersion;
after washing 0.5g (dry weight) of the water washing product with n-butanol for 4 times, adding 3.7mL of 1-butyl-3-methylimidazole tetrafluoroborate, emulsifying for 20min under the power of 4kW and the rotating speed of 30000r/min, and carrying out ultrasonic oscillation for 50min under the frequency of 40kHz to obtain the cerium hexaboride ion liquid phase dispersion.
Through detection, cerium hexaboride in the cerium hexaboride aqueous phase dispersion obtained in the embodiment of the invention is CeB 6 Pure phase, without any other impurity phase.
Through detection, the cerium hexaboride aqueous dispersion obtained by the embodiment of the invention has good dispersibility, no agglomeration phenomenon and the one-dimensional size of the nano particles of the dispersion is 5-20 nm.
Through detection, the cerium hexaboride aqueous dispersion obtained by the embodiment of the invention has high absorption capacity of ultraviolet, visible and near infrared bands, and can be used in the fields of heat insulation and optics.
Through detection, the cerium hexaboride aqueous phase dispersoid obtained by the embodiment of the invention is black, the solid content is 10 weight percent, and the cerium hexaboride aqueous phase dispersoid is sealed and stood for 12 months without sedimentation; the cerium hexaboride ion liquid phase dispersoid obtained by the embodiment of the invention is black, the solid content is 10 weight percent, and the cerium hexaboride ion liquid phase dispersoid is sealed and kept stand for 12 months without sedimentation.
Example 3
(1) 2.45 g (10 mmol) LaCl 3 And 2.65 g (70 mmol) NaBH 4 Uniformly mixing 5.11g (43 mmol) of Sn powder, loading into an alumina crucible, heating to react under the atmosphere of high-purity helium, heating to 400 ℃ at a speed of 5 ℃/min, preserving heat for 1h, heating to 750 ℃ at a speed of 10 ℃/min, preserving heat for 1h, and cooling to room temperature at a speed of 10 ℃/min to obtain a primary product;
(2) Emulsifying the primary product obtained in the step (1) in 100mL of water (power is 2kW, rotation speed is 10000r/min, time of each emulsifying treatment is 40 min), ultrasonic oscillating (frequency is 50kHz, time of each ultrasonic oscillating is 120 min), and regulating pH value to 11 with sodium hydroxide solution9.3, standing for 24 hours, separating Sn powder, filtering and washing with water at 40 ℃, repeating the emulsification treatment, ultrasonic oscillating, filtering, washing with water for 3 times, and dripping AgNO into the washing liquid 3 Adding 99mL of ammonia water solution with pH value of 9.5 into 1g (dry weight) of water washing product until the solution has no white precipitate, emulsifying for 40min under the conditions of power of 2kW and rotating speed of 10000r/min, and ultrasonically oscillating for 120min under the condition of frequency of 50kHz to obtain lanthanum hexaboride aqueous phase dispersion;
washing 1g (dry weight) of the water washing product with ethanol for 3 times, adding 125.3mL of ethanol, emulsifying for 40min under the power of 2kW and the rotating speed of 10000r/min, and ultrasonically oscillating for 120min under the frequency of 50kHz to obtain lanthanum hexaboride alcohol phase dispersion.
Through detection, lanthanum hexaboride in the lanthanum hexaboride aqueous phase dispersion obtained by the embodiment of the invention is LaB 6 Pure phase, without any other impurity phase.
Through detection, the lanthanum hexaboride aqueous dispersion obtained by the embodiment of the invention has good dispersibility, no agglomeration phenomenon and the one-dimensional size of the nano particles of the dispersion is 10-30 nm.
Through detection, the lanthanum hexaboride aqueous dispersion obtained by the embodiment of the invention has high absorption capacity of ultraviolet, visible and near infrared bands, and can be used in the fields of heat insulation and optics.
Through detection, the lanthanum hexaboride aqueous dispersion obtained by the embodiment of the invention is black, has the solid content of 1 weight percent, and is sealed and stood for 12 months without sedimentation; the lanthanum hexaboride alcohol phase dispersion obtained by the embodiment of the invention is black, has the solid content of 1 weight percent, and has no sedimentation after being sealed and stood for 12 months.
Example 4
(1) 1.75g (10 mmol) of BaF are reacted 2 With 2.70g (50 mmol) KBH 4 After being uniformly mixed, the mixture is put into an alumina crucible, and is heated up and heated up for reaction under the vacuum of 60 Pa, the temperature is firstly increased to 350 ℃ at the speed of 20 ℃/min, the heat is preserved for 3 hours, then the temperature is increased to 800 ℃ at the speed of 20 ℃/min, the heat is preserved for 2 hours, and the mixture is cooled to the room temperature at the speed of 20 ℃/min, so that a primary product is obtained;
(2) Emulsifying the initial product obtained in the step (1) in 20mL of waterTreating (power is 3kW, rotating speed is 20000r/min, time of each emulsification treatment is 30 min), ultrasonic oscillating (frequency is 30kHz, time of each ultrasonic oscillating is 100 min), filtering and washing with 50deg.C water repeatedly for 3 times, and dripping Ca (OH) into the washing liquid 2 Adding 199mL of sodium hydroxide solution with pH value of 10.0 into 1g (dry weight) of water washing product until the solution does not have white precipitate, emulsifying for 30min under the conditions of power of 3kW and rotating speed of 20000r/min, and carrying out ultrasonic oscillation for 100min under the condition of frequency of 30kHz to obtain barium hexaboride aqueous phase dispersion;
washing 1g (dry weight) of the water washing product with n-butanol for 3 times, adding 245.7mL of n-butanol, emulsifying for 30min at the power of 3kW and the rotating speed of 20000r/min, and ultrasonically oscillating for 100min at the frequency of 30kHz to obtain the lanthanum hexaboride alcohol phase dispersion.
Through detection, the barium hexaboride in the barium hexaboride aqueous phase dispersion obtained in the embodiment of the invention is BaB 6 Pure phase, without any other impurity phase.
Through detection, the barium hexaboride aqueous dispersion obtained by the embodiment of the invention has good dispersibility, no agglomeration phenomenon and the one-dimensional size of the nano particles of the dispersion is 5-30 nm.
Through detection, the barium hexaboride aqueous dispersion obtained by the embodiment of the invention has high absorption capacity of ultraviolet, visible and near infrared bands, and can be used in the fields of heat insulation and optics.
Through detection, the barium hexaboride aqueous phase dispersoid obtained by the embodiment of the invention is black, the solid content is 0.5 weight percent, and the barium hexaboride aqueous phase dispersoid is sealed and stood for 12 months without sedimentation; the barium hexaboride alcohol phase dispersion obtained by the embodiment of the invention is black, has the solid content of 0.5 weight percent, and has no sedimentation after being sealed and stood for 12 months.
Comparative example 1
This comparative example differs from example 1 only in that: after the water washing operation, the product is dried and then subjected to subsequent operation. Example 1 was followed.
Through detection, the lanthanum hexaboride aqueous dispersion obtained in the comparative example is black, has a solid content of 5wt%, and is settled after being sealed and stood for 0.5 days.
Application examples 1 to 3 of rare earth hexaboride liquid phase Dispersion
The lanthanum hexaboride aqueous dispersion and the ionic liquid dispersion obtained in the embodiment 1 of the invention are applied to preparing transparent heat-insulating paint;
the cerium hexaboride aqueous phase dispersion and the ion liquid phase dispersion obtained in the embodiment 2 of the invention are applied to the preparation of solar photothermal conversion nanofluid;
the lanthanum hexaboride aqueous dispersion and the alcohol phase dispersion obtained in the embodiment 3 of the invention are applied to the preparation of sea water desalination devices.
Application example 4 of alkaline-earth hexaboride liquid phase Dispersion
The aqueous phase dispersion and the alcohol phase dispersion of barium hexaboride obtained in the example 4 of the invention are applied to the preparation of transparent heat insulation coating.

Claims (22)

1. A method for preparing a liquid phase dispersion of rare earth or alkaline earth hexaboride, comprising the steps of:
(1) Uniformly mixing rare earth salt or alkaline earth salt with a boron source, heating and reacting in vacuum or inert atmosphere, and cooling to room temperature to obtain an initial product;
(2) Emulsifying the initial product obtained in the step (1) in water, carrying out ultrasonic vibration, filtering or centrifuging, washing, adding an alkaline aqueous solution into the washed product, carrying out emulsification treatment, and carrying out ultrasonic vibration to obtain a rare earth or alkaline earth hexaboride aqueous phase dispersion; or washing the water washing product with alcohol, adding an organic solvent, emulsifying, and performing ultrasonic oscillation to obtain the rare earth or alkaline earth hexaboride organic phase dispersion.
2. The method for preparing a liquid phase dispersion of rare earth or alkaline earth hexaboride according to claim 1, characterized in that: in the step (1), the molar ratio of the rare earth element in the rare earth salt or the alkaline earth element in the alkaline earth salt to the boron element in the boron source is 1:2-12; the rare earth salt is one or more of rare earth chloride, rare earth oxychloride, rare earth fluoride or rare earth bromide; the alkaline earth salt is one or more of chloridized alkaline earth, fluoridized alkaline earth or bromized alkaline earth;the boron source is an alkali metal boron hydride compound; the alkali metal boron hydride is NaBH 4 、KBH 4 Or LiBH 4 One or more of them.
3. Process for the preparation of a liquid phase dispersion of rare earth or alkaline earth hexaboride according to claim 1 or 2, characterized in that: in the step (1), the vacuum degree of the vacuum is 0-100 Pa; the inert atmosphere is argon and/or helium.
4. Process for the preparation of a liquid phase dispersion of rare earth or alkaline earth hexaboride according to claim 1 or 2, characterized in that: in the step (1), the specific operation of the temperature rising and heating reaction is as follows: firstly, heating to 300-400 ℃ at the speed of 5-20 ℃/min, preserving heat for 1-5 h, then heating to 400-1200 ℃ at the speed of 1-30 ℃/min, and preserving heat for 1-10 h; the cooling is to cool to room temperature at a rate of 5-40 ℃/min.
5. A process for the preparation of a liquid phase dispersion of rare earth or alkaline earth hexaboride according to claim 3, characterized in that: in the step (1), the specific operation of the temperature rising and heating reaction is as follows: firstly, heating to 300-400 ℃ at the speed of 5-20 ℃/min, preserving heat for 1-5 h, then heating to 400-1200 ℃ at the speed of 1-30 ℃/min, and preserving heat for 1-10 h; the cooling is to cool to room temperature at a rate of 5-40 ℃/min.
6. Process for the preparation of a liquid phase dispersion of rare earth or alkaline earth hexaboride according to claim 1 or 2, characterized in that: in the step (1), a low-melting-point medium which is 1 to 20 times of the total mass of the rare earth salt or alkaline earth salt and a boron source is added; the low-melting-point medium is low-melting-point simple metal or low-melting-point molten salt; the low-melting-point simple substance metal is one or more of simple substance Sn, simple substance In or simple substance Bi; the low-melting-point molten salt is LiCl, KCl, naCl or ZnCl 2 One or more of them.
7. The rare earth or alkaline earth hexaboride liquid according to claim 3A process for preparing a phase dispersion characterized by: in the step (1), a low-melting-point medium which is 1 to 20 times of the total mass of the rare earth salt or alkaline earth salt and a boron source is added; the low-melting-point medium is low-melting-point simple metal or low-melting-point molten salt; the low-melting-point simple substance metal is one or more of simple substance Sn, simple substance In or simple substance Bi; the low-melting-point molten salt is LiCl, KCl, naCl or ZnCl 2 One or more of them.
8. The method for preparing a liquid phase dispersion of rare earth or alkaline earth hexaboride according to claim 4, wherein: in the step (1), a low-melting-point medium which is 1 to 20 times of the total mass of the rare earth salt or alkaline earth salt and a boron source is added; the low-melting-point medium is low-melting-point simple metal or low-melting-point molten salt; the low-melting-point simple substance metal is one or more of simple substance Sn, simple substance In or simple substance Bi; the low-melting-point molten salt is LiCl, KCl, naCl or ZnCl 2 One or more of them.
9. Process for the preparation of a liquid phase dispersion of rare earth or alkaline earth hexaboride according to claim 1 or 2, characterized in that: in the step (2), the volume-mass ratio of the water to the total mass of the raw materials in the step (1) is 3-10:1; the power of the emulsification treatment is 0.5-40 kW, the rotating speed is 1000-30000 r/min, and the time of each emulsification treatment is 20-40 min; the frequency of ultrasonic oscillation is 10-50 kHz, and the time of each ultrasonic oscillation is 10-180 min; the temperature of the water washing is 10-80 ℃; the repeated operations of emulsification treatment, ultrasonic vibration, filtration or centrifugation and water washing are more than or equal to 3 times, and AgNO is added into the water washing liquid in a dropwise manner 3 Or Ca (OH) 2 The solution had no white precipitate.
10. A process for the preparation of a liquid phase dispersion of rare earth or alkaline earth hexaboride according to claim 3, characterized in that: in the step (2), the volume-mass ratio of the water to the total mass of the raw materials in the step (1) is 3-10:1; the power of the emulsification treatment is 0.5-40 kW, the rotating speed is 1000-30000 r/min, and the time of each emulsification treatment is 20-40 min; the saidThe frequency of ultrasonic oscillation is 10-50 kHz, and the time of each ultrasonic oscillation is 10-180 min; the temperature of the water washing is 10-80 ℃; the repeated operations of emulsification treatment, ultrasonic vibration, filtration or centrifugation and water washing are more than or equal to 3 times, and AgNO is added into the water washing liquid in a dropwise manner 3 Or Ca (OH) 2 The solution had no white precipitate.
11. The method for preparing a liquid phase dispersion of rare earth or alkaline earth hexaboride according to claim 4, wherein: in the step (2), the volume-mass ratio of the water to the total mass of the raw materials in the step (1) is 3-10:1; the power of the emulsification treatment is 0.5-40 kW, the rotating speed is 1000-30000 r/min, and the time of each emulsification treatment is 20-40 min; the frequency of ultrasonic oscillation is 10-50 kHz, and the time of each ultrasonic oscillation is 10-180 min; the temperature of the water washing is 10-80 ℃; the repeated operations of emulsification treatment, ultrasonic vibration, filtration or centrifugation and water washing are more than or equal to 3 times, and AgNO is added into the water washing liquid in a dropwise manner 3 Or Ca (OH) 2 The solution had no white precipitate.
12. The method for preparing a liquid phase dispersion of rare earth or alkaline earth hexaboride according to claim 6, wherein: in the step (2), the volume-mass ratio of the water to the total mass of the raw materials in the step (1) is 3-10:1; the power of the emulsification treatment is 0.5-40 kW, the rotating speed is 1000-30000 r/min, and the time of each emulsification treatment is 20-40 min; the frequency of ultrasonic oscillation is 10-50 kHz, and the time of each ultrasonic oscillation is 10-180 min; the temperature of the water washing is 10-80 ℃; the repeated operations of emulsification treatment, ultrasonic vibration, filtration or centrifugation and water washing are more than or equal to 3 times, and AgNO is added into the water washing liquid in a dropwise manner 3 Or Ca (OH) 2 The solution had no white precipitate.
13. The method for preparing a liquid phase dispersion of rare earth or alkaline earth hexaboride according to claim 6, wherein: in the step (2), when the low-melting-point medium is low-melting-point simple substance metal, after the first emulsification treatment and ultrasonic oscillation, regulating the pH value to 9-10 by using an alkaline aqueous solution, standing, and separating the low melting pointFiltering or centrifuging after simple substance metal, washing with water, repeating emulsification treatment, ultrasonic oscillating, filtering or centrifuging, washing with water for more than or equal to 2 times, and dripping AgNO into the washing liquid 3 Or Ca (OH) 2 The solution had no white precipitate; the pH value of the alkaline aqueous solution with the pH value adjusted is more than or equal to 10; the alkaline aqueous solution is sodium hydroxide aqueous solution or ammonia water solution; the standing time is 5-30 h.
14. The method for preparing a liquid phase dispersion of rare earth or alkaline earth hexaboride according to claim 12, characterized in that: in the step (2), when the low-melting-point medium is low-melting-point simple substance metal, after the first emulsification treatment and ultrasonic oscillation, regulating the pH value to 9-10 by using an alkaline aqueous solution, standing, separating the low-melting-point simple substance metal, filtering or centrifuging, washing with water, repeating the emulsification treatment, ultrasonic oscillation, filtering or centrifuging, performing the washing operation for more than or equal to 2 times, and dripping AgNO into the washing liquid 3 Or Ca (OH) 2 The solution had no white precipitate; the pH value of the alkaline aqueous solution with the pH value adjusted is more than or equal to 10; the alkaline aqueous solution is sodium hydroxide aqueous solution or ammonia water solution; the standing time is 5-30 h.
15. Process for the preparation of a liquid phase dispersion of rare earth or alkaline earth hexaboride according to claim 1 or 2, characterized in that: in the step (2), the volume-mass ratio of the alkaline aqueous solution or the organic solvent to the dry weight of the water washing product is 5-1000:1; the pH value of the alkaline aqueous solution is 9-10; the alkaline aqueous solution is sodium hydroxide aqueous solution or ammonia water solution; the times of water washing by alcohol are more than or equal to 2 times; the organic solvent is one or more of alcohol solution, ionic liquid, grease or liquid resin; the alcohol used for washing water with alcohol is one or more of ethanol, glycol or n-butanol; the ionic liquid is 1-hexyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt and/or 1-butyl-3-methylimidazole tetrafluoroborate.
16. A process for the preparation of a liquid phase dispersion of rare earth or alkaline earth hexaboride according to claim 3, characterized in that: in the step (2), the volume-mass ratio of the alkaline aqueous solution or the organic solvent to the dry weight of the water washing product is 5-1000:1; the pH value of the alkaline aqueous solution is 9-10; the alkaline aqueous solution is sodium hydroxide aqueous solution or ammonia water solution; the times of water washing by alcohol are more than or equal to 2 times; the organic solvent is one or more of alcohol solution, ionic liquid, grease or liquid resin; the alcohol used for washing water with alcohol is one or more of ethanol, glycol or n-butanol; the ionic liquid is 1-hexyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt and/or 1-butyl-3-methylimidazole tetrafluoroborate.
17. The method for preparing a liquid phase dispersion of rare earth or alkaline earth hexaboride according to claim 4, wherein: in the step (2), the volume-mass ratio of the alkaline aqueous solution or the organic solvent to the dry weight of the water washing product is 5-1000:1; the pH value of the alkaline aqueous solution is 9-10; the alkaline aqueous solution is sodium hydroxide aqueous solution or ammonia water solution; the times of water washing by alcohol are more than or equal to 2 times; the organic solvent is one or more of alcohol solution, ionic liquid, grease or liquid resin; the alcohol used for washing water with alcohol is one or more of ethanol, glycol or n-butanol; the ionic liquid is 1-hexyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt and/or 1-butyl-3-methylimidazole tetrafluoroborate.
18. The method for preparing a liquid phase dispersion of rare earth or alkaline earth hexaboride according to claim 6, wherein: in the step (2), the volume-mass ratio of the alkaline aqueous solution or the organic solvent to the dry weight of the water washing product is 5-1000:1; the pH value of the alkaline aqueous solution is 9-10; the alkaline aqueous solution is sodium hydroxide aqueous solution or ammonia water solution; the times of water washing by alcohol are more than or equal to 2 times; the organic solvent is one or more of alcohol solution, ionic liquid, grease or liquid resin; the alcohol used for washing water with alcohol is one or more of ethanol, glycol or n-butanol; the ionic liquid is 1-hexyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt and/or 1-butyl-3-methylimidazole tetrafluoroborate.
19. The method for preparing a liquid phase dispersion of rare earth or alkaline earth hexaboride according to claim 9, characterized in that: in the step (2), the volume-mass ratio of the alkaline aqueous solution or the organic solvent to the dry weight of the water washing product is 5-1000:1; the pH value of the alkaline aqueous solution is 9-10; the alkaline aqueous solution is sodium hydroxide aqueous solution or ammonia water solution; the times of water washing by alcohol are more than or equal to 2 times; the organic solvent is one or more of alcohol solution, ionic liquid, grease or liquid resin; the alcohol used for washing water with alcohol is one or more of ethanol, glycol or n-butanol; the ionic liquid is 1-hexyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt and/or 1-butyl-3-methylimidazole tetrafluoroborate.
20. The method for preparing a liquid phase dispersion of rare earth or alkaline earth hexaboride according to claim 13, characterized in that: in the step (2), the volume-mass ratio of the alkaline aqueous solution or the organic solvent to the dry weight of the water washing product is 5-1000:1; the pH value of the alkaline aqueous solution is 9-10; the alkaline aqueous solution is sodium hydroxide aqueous solution or ammonia water solution; the times of water washing by alcohol are more than or equal to 2 times; the organic solvent is one or more of alcohol solution, ionic liquid, grease or liquid resin; the alcohol used for washing water with alcohol is one or more of ethanol, glycol or n-butanol; the ionic liquid is 1-hexyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt and/or 1-butyl-3-methylimidazole tetrafluoroborate.
21. The method for preparing a liquid phase dispersion of rare earth or alkaline earth hexaboride according to claim 14, characterized in that: in the step (2), the volume-mass ratio of the alkaline aqueous solution or the organic solvent to the dry weight of the water washing product is 5-1000:1; the pH value of the alkaline aqueous solution is 9-10; the alkaline aqueous solution is sodium hydroxide aqueous solution or ammonia water solution; the times of water washing by alcohol are more than or equal to 2 times; the organic solvent is one or more of alcohol solution, ionic liquid, grease or liquid resin; the alcohol used for washing water with alcohol is one or more of ethanol, glycol or n-butanol; the ionic liquid is 1-hexyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt and/or 1-butyl-3-methylimidazole tetrafluoroborate.
22. Use of a liquid phase dispersion of rare earth or alkaline earth hexaboride obtained by the process according to any one of claims 1 to 21, characterized in that: use of the rare earth or alkaline earth hexaboride liquid phase dispersion obtained by the preparation method according to any one of claims 1 to 21 for preparing transparent heat insulation coating, solar photo-thermal conversion nanofluid and sea water desalination device.
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