CN113620357A - OsO (OsO)2Preparation method of spherical nano-particle material - Google Patents

OsO (OsO)2Preparation method of spherical nano-particle material Download PDF

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CN113620357A
CN113620357A CN202110893783.0A CN202110893783A CN113620357A CN 113620357 A CN113620357 A CN 113620357A CN 202110893783 A CN202110893783 A CN 202110893783A CN 113620357 A CN113620357 A CN 113620357A
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oso
gold tube
reaction kettle
spherical
pressure
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CN113620357B (en
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严海波
丁兴
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Guangzhou Institute of Geochemistry of CAS
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Guangzhou Institute of Geochemistry of CAS
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
    • C01G55/004—Oxides; Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • 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
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • 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
    • 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
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Abstract

The invention discloses an OsO2The preparation method of the spherical nano-particle material mainly comprises the following steps: (1) dissolving potassium cloosmate in deionized water to obtain diluted solution, placing the potassium cloosmate in a gold tube, and sealing the gold tube; (2) placing the sealed gold tube in a hydrothermal reaction kettle, adjusting the temperature in the hydrothermal reaction kettle to be 150-550 ℃ and the reaction pressure to be 100MPa, and carrying out hydrolysis reaction for 12-36 hours; (3) after the hydrolysis reaction, opening the hydrothermal reaction kettle, taking out the gold tube and breaking the gold tube, recovering residual solution in the gold tube, cleaning the inner wall of the gold tube, and then drying to obtain spherical OsO2And (3) nanoparticles. The method has the advantages of single raw material, easy obtainment, simple process and synthesized OsO2The nano-particles are spherical, the crystal form is perfect, and the OsO2The particle size of the nanoparticles is several tens to several hundreds of nanometers.

Description

OsO (OsO)2Preparation method of spherical nano-particle material
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to OsO2A preparation method of spherical nano-particle material.
Background
Because of its good oxidation, magnetic property and electric conductivity, osmium oxide is widely used in the fields of microbiological reagents, photoprotection materials, catalysts, biological samples and gas fixatives, electrode conductive materials and the like (Millonig G J.1961.Advantages of a phosphate buffer for OSO)4 solutions in fixation.Journal of Applied Physics；Mattheiss L F.1976.Electronic structure of RuO2,OsO2,and IrO2Physical Review B.13: 2433-; mimai and pink Zhao Xiao V1990 osmium tetroxide (OsO)4) Secondary utilization of fixative electron microscopy, 3: 118). However, because of the oxidative and toxic properties of osmium oxides, research and preparation thereof is currently extremely limited. Wherein osmium dioxide (OsO)2) OsO synthesized mainly by chemical vapor transport method2Has a tetragonal rutile structure and special magnetism and electric conductivity, thereby having good application prospect in the aspects of electrode materials, electric storage elements and the like (Yen et al 2004.growth and characterization of OsO)2 single crystals.Journal of Crystal Growth.262:271–276；Yen et al.2004.Preparation and characterization of OsO2Journal of Alloys and Compounds.383: 277-. However, OsO is currently available2There are few reports on the research and preparation of other crystal structures, which severely restrict the OsO2The nano material has application prospect in the fields of future electrodes, catalysis and the like.
Disclosure of Invention
The invention aims to provide OsO2The preparation method of the spherical nano-particle material has the advantages of single raw material, easy obtainment, simple process and synthesized OsO2The nano-particles are spherical, the crystal form is perfect, and the OsO2The particle size of the nanoparticles is several tens to several hundreds of nanometers.
The above object of the present invention can be achieved by the following technical solutions: OsO (OsO)2The preparation method of the spherical nano-particle material mainly comprises the following steps:
(1) selecting potassium chloro osmate (K)2OsCl6) Dissolving in deionized water to obtain potassium chloroosmate (K)2OsCl6) Diluted solution of potassium chloroosmate (K)2OsCl6) Placing the dilute solution in a gold tube, and sealing the gold tube;
(2) placing the sealed gold tube in a hydrothermal reaction kettle, adjusting the temperature in the hydrothermal reaction kettle to be 150-550 ℃ and the reaction pressure to be 100MPa, and carrying out hydrolysis reaction for 12-36 hours;
(3) after the hydrolysis reaction, opening the hydrothermal reaction kettle, taking out the gold tube and breaking the gold tube, recovering residual solution in the gold tube, cleaning the inner wall of the gold tube, and then drying to obtain spherical OsO2And (3) nanoparticles.
In the above-mentioned OsO2The preparation method of the spherical nano-particle material comprises the following steps:
optionally, the potassium chloro osmate (K) in step (1)2OsCl6) The concentration of the dilute solution is 0.002-0.005 mol/L.
More preferably, potassium chloro osmate (K) in step (1)2OsCl6) The concentration of the dilute solution is 0.002mol/L or 0.005 mol/L.
Optionally, the potassium chloro osmate (K) in step (1)2OsCl6) The volume of the dilute solution accounts for 40-60% of the total volume of the gold tube.
Optionally, the gold tube in the step (1) is a gold tube with a mass percentage of more than 99%, and the gold tube is subjected to pretreatment including cutting, acid boiling, washing, ultrasonic treatment and quenching before use.
More preferably, the gold tube in the step (1) is a gold tube with a mass percentage of more than 99.9%, and the gold tube is subjected to pretreatment including cutting, acid boiling, washing, ultrasonic treatment and quenching before use.
Optionally, in the step (1), a welding seal treatment is adopted during the sealing of the gold tube, the sealing performance detection is carried out after the welding seal, and during the sealing performance detection, potassium osmate chloride (K) is filled in2OsCl6) Placing the gold tube in the diluted solution in an oven at 100-120 deg.C for baking for 1-3 h, weighing again and adding potassium chloroosmate (K)2OsCl6) And the gold tube with the diluted solution ensures that the weighing error before and after the gold tube is less than 0.001g, which indicates that the gold tube has good sealing property.
Preferably, the gold tube is sealed in step (1) by welding, and then the tightness is detected, wherein the potassium chloro osmate (K) is filled in the tube during the tightness detection2OsCl6) The gold tube in diluted solution was baked in an oven at 110 ℃ for 2h, and weighed again with potassium chloro osmate (K)2OsCl6) And the gold tube with the diluted solution ensures that the weighing error before and after the gold tube is less than 0.001g, which indicates that the gold tube has good sealing property.
Optionally, in the step (2), the sealed gold tube is placed in a hydrothermal reaction kettle, argon gas is firstly injected into the hydrothermal reaction kettle to reach the pressure of 40MPa as an initial pressure, then the gas injection is stopped, the hydrothermal reaction kettle is heated by a heating furnace, and when the temperature reaches the target reaction temperature, argon gas is injected to make the reaction pressure reach the target pressure.
Alternatively, the hydrolysis reaction time in the step (2) does not include the time taken for temperature rise and temperature fall, and is a reaction time at a specified temperature and pressure.
For example, in the step (2), the sealed gold tube is placed in a hydrothermal reaction kettle, after the hydrothermal reaction kettle is sealed, argon gas is firstly injected into the hydrothermal reaction kettle to the pressure of 40MPa as the initial pressure, then the gas injection is stopped, the hydrothermal reaction kettle is heated by a heating furnace, the temperature in the hydrothermal reaction kettle is adjusted to 150 ℃, the reaction pressure in the hydrothermal reaction kettle is adjusted to 100MPa by adopting inert gas such as argon gas, and the hydrolysis reaction is carried out for 24 hours.
For example, in the step (2), the sealed gold tube is placed in a hydrothermal reaction kettle, after the hydrothermal reaction kettle is sealed, argon gas is firstly injected into the hydrothermal reaction kettle to the pressure of 40MPa as the initial pressure, then the gas injection is stopped, the hydrothermal reaction kettle is heated by a heating furnace, the temperature in the hydrothermal reaction kettle is adjusted to 250 ℃, the reaction pressure in the hydrothermal reaction kettle is adjusted to 100MPa by adopting inert gas such as argon gas, and the hydrolysis reaction is carried out for 24 hours.
For example, in the step (2), the sealed gold tube is placed in a hydrothermal reaction kettle, after the hydrothermal reaction kettle is sealed, argon gas is firstly injected into the hydrothermal reaction kettle to the pressure of 40MPa as the initial pressure, then the gas injection is stopped, the hydrothermal reaction kettle is heated by a heating furnace, the temperature in the hydrothermal reaction kettle is adjusted to 300 ℃, the reaction pressure in the hydrothermal reaction kettle is adjusted to 100MPa by adopting inert gas such as argon gas, and the hydrolysis reaction is carried out for 12 hours.
For example, in the step (2), the sealed gold tube is placed in a hydrothermal reaction kettle, after the hydrothermal reaction kettle is sealed, argon gas is firstly injected into the hydrothermal reaction kettle to the pressure of 40MPa as the initial pressure, then the gas injection is stopped, the hydrothermal reaction kettle is heated by a heating furnace, the temperature in the hydrothermal reaction kettle is adjusted to 300 ℃, the reaction pressure in the hydrothermal reaction kettle is adjusted to 100MPa by adopting inert gas such as argon gas, and the hydrolysis reaction is carried out for 24 hours.
For example, in the step (2), the sealed gold tube is placed in a hydrothermal reaction kettle, after the hydrothermal reaction kettle is sealed, argon gas is firstly injected into the hydrothermal reaction kettle to the pressure of 40MPa as the initial pressure, then the gas injection is stopped, the hydrothermal reaction kettle is heated by a heating furnace, the temperature in the hydrothermal reaction kettle is adjusted to 300 ℃, the reaction pressure in the hydrothermal reaction kettle is adjusted to 100MPa by adopting inert gas such as argon gas, and the hydrolysis reaction is carried out for 36 hours.
For example, in the step (2), the sealed gold tube is placed in a hydrothermal reaction kettle, after the hydrothermal reaction kettle is sealed, argon gas is firstly injected into the hydrothermal reaction kettle to the pressure of 40MPa as the initial pressure, then the gas injection is stopped, the hydrothermal reaction kettle is heated by a heating furnace, the temperature in the hydrothermal reaction kettle is adjusted to 350 ℃, the reaction pressure in the hydrothermal reaction kettle is adjusted to 100MPa by adopting inert gas such as argon gas, and the hydrolysis reaction is carried out for 24 hours.
For example, in the step (2), the sealed gold tube is placed in a hydrothermal reaction kettle, after the hydrothermal reaction kettle is sealed, argon gas is firstly injected into the hydrothermal reaction kettle to the pressure of 40MPa as the initial pressure, then the gas injection is stopped, the hydrothermal reaction kettle is heated by a heating furnace, the temperature in the hydrothermal reaction kettle is adjusted to 450 ℃, the reaction pressure in the hydrothermal reaction kettle is adjusted to 100MPa by adopting inert gas such as argon gas, and the hydrolysis reaction is carried out for 24 hours.
For example, in the step (2), the sealed gold tube is placed in a hydrothermal reaction kettle, after the hydrothermal reaction kettle is sealed, argon gas is firstly injected into the hydrothermal reaction kettle to the pressure of 40MPa as the initial pressure, then the gas injection is stopped, the hydrothermal reaction kettle is heated by a heating furnace, the temperature in the hydrothermal reaction kettle is adjusted to 550 ℃, the reaction pressure in the hydrothermal reaction kettle is adjusted to 100MPa by adopting inert gas such as argon gas, and the hydrolysis reaction is carried out for 24 hours.
Optionally, after the hydrolysis reaction in the step (3), using ice water to rapidly cool the hydrothermal reaction kettle to normal temperature, opening the hydrothermal reaction kettle, taking out the gold tube and breaking open, recovering residual solution in the gold tube, and respectively soaking with deionized water and anhydrous ethanolSoaking and washing the inner wall of the gold tube to make the OsO attached to the inner wall of the gold tube2Cleaning the sample, and then carrying out OsO attached to the inner wall of the gold tube2Drying the sample to obtain OsO2Spherical nanoparticle materials.
Preferably, after the hydrolysis reaction in the step (3), using ice water to rapidly cool the hydrothermal reaction kettle to normal temperature, opening the hydrothermal reaction kettle, taking out the gold tube and breaking open, recovering the residual solution in the gold tube, soaking and washing the inner wall of the gold tube for 2-3 times by using deionized water and absolute ethyl alcohol respectively to enable the OsO attached to the inner wall of the gold tube2Cleaning the sample, and then carrying out OsO attached to the inner wall of the gold tube2Drying the sample to obtain OsO2Spherical nanoparticle materials.
Optionally, after the gold tube is taken out in the step (3), the gold tube is cleaned, dried and weighed to ensure the effectiveness of the reaction process and the sealing performance of the experimental process, and then the gold tube is broken.
Optionally, the residual solution in step (3) is potassium chloroosmate, hydrochloric acid and potassium chloride.
Optionally, the drying in the step (3) is natural air drying or drying.
Optionally, the spherical OsO in step (3)2The crystalline form of the nanoparticles is intact, the spherical OsO2The particle size of the nanoparticles is several tens to several hundreds of nanometers.
OsO of the invention2The core of the preparation method of the spherical nano-particle material is that OsO is generated by utilizing the hydrolysis reaction of potassium chloroosmate single reagent under different temperature and time conditions2Nanoparticles, the reagent used was only a dilute solution of potassium cloosmate, which underwent the following hydrolysis reaction with water under hydrothermal conditions:
K2OsCl6+2H2O＝2KCl+OsO2↓+4HCl。
the invention has the following beneficial effects:
(1) OsO in the invention2The preparation method of the spherical nano-particle material adopts the self-hydrolysis reaction of a single reagent, and the initial reagent is single and easy to obtain;
(2) OsO in the invention2The preparation method of the spherical nano-particle material has the advantages of simple operation process, lower reaction pressure and easy control, and the adoption of the high-purity gold tube as the outer sleeve can ensure that reactants do not react with other substances, the sealing property and the effectiveness in the reaction process, low cost and low energy consumption;
(3) OsO in the invention2The preparation method of the spherical nano-particle material has the advantages that the residual solution is simple in component, can be recycled, has little pollution to the environment, maintains the process safety and pays attention to environmental protection;
(4) OsO in the invention2Preparation method of spherical nano-particle material and obtained OsO2The nano-particles are spherical, the crystal form is perfect, and the OsO2The particle size of the nanoparticles is several tens to several hundreds of nanometers.
(5) OsO in the invention2Preparation method of spherical nano-particle material and spherical OsO obtained by preparation method2The nanoparticle morphology is closely related to the reaction temperature, initial concentration and reaction time, and as the reaction time is prolonged, the OsO2The crystal form of the nano-particles is more and more complete, and the particle size is gradually increased; in a preferred temperature range, OsO2The particle size of the nano particles is gradually increased along with the temperature; furthermore, an increase in the initial concentration within the preferred range results in OsO2The crystal form of the nano-particles is more complete, and the particle size tends to increase.
Drawings
FIG. 1 shows OsO prepared at 150-600 ℃ in examples 1-9 and comparative examples 1-2 of the present invention2A Raman spectrum of the nanoparticle material;
FIG. 2 shows OsO prepared in examples 1 to 4 of the present invention2Scanning electron micrograph of spherical nanoparticle material, (A) spherical OsO prepared in example 12Nanoparticles, (B) spherical OsO prepared in example 22Nanoparticles, (C) spherical OsO prepared in example 32Nanoparticles, (D) spherical OsO prepared in example 42A nanoparticle;
FIG. 3 shows OsO prepared in examples 5 to 9 of the present invention2Scanning electron micrograph of spherical nanoparticles, (A) prepared in example 5Obtaining spherical OsO2Nanoparticles, (B) spherical OsO prepared in example 62Nanoparticles, (C) spherical OsO prepared in example 72Nanoparticles, (D) spherical OsO prepared in example 82Nanoparticles, (E-F) spherical OsO prepared in example 92And (3) nanoparticles.
FIG. 4 shows OsO prepared in comparative examples 1-2 of the present invention2Scanning electron micrograph of nanoparticles, (A) OsO prepared in comparative example 12Nanoparticles, (B) OsO prepared in comparative example 22And (3) nanoparticles.
Detailed Description
The present invention will be further described with reference to the following specific examples and the accompanying drawings, but the scope of the present invention as claimed is not limited to the following examples as exemplified by the reaction apparatus and the reaction temperature, the reaction time and the volume of the reaction liquid.
Example 1
OsO provided in this example2A method for preparing nanoparticles, comprising the steps of:
(1) cutting a high-purity gold tube with the diameter of 5mm into a length (2-2.5 cm) required by an experiment, performing early-stage treatment such as acid boiling, washing, quenching, welding and sealing one end in advance and the like to ensure that no impurities or cracks exist in the gold tube;
(2) 0.0962g of potassium chloroosmate (K) in analytical purity2OsCl6) The powder is dissolved in 100mL deionized water and fully dissolved to obtain 0.002mol/L K2OsCl6The solution is prepared by filling the prepared reaction solution into a gold tube by using a sample injector, controlling the filling degree to be about 50%, welding and sealing, weighing and recording after welding and sealing, then putting the gold tube filled with the solution sample into a drying box at 110 ℃ for 2h, and then weighing again, ensuring that the mass error before and after weighing is less than 0.001g, and indicating that the gold tube is complete in sealing;
(3) putting a gold tube which is confirmed to have perfect tightness and is filled with a solution sample into a high-temperature high-pressure reaction kettle (the high-temperature high-pressure reaction kettle can meet the temperature and pressure requirements of the application only by adopting conventional use in the field, and also can refer to the high-temperature high-pressure reaction kettle disclosed in the inventor's early application of the application), screwing the reaction kettle, checking the tightness of the reaction kettle, confirming that no error exists, injecting argon into the kettle to 40MPa through a vent pipeline, taking the argon as initial pressure, closing a stop valve to stop gas injection, heating the reaction kettle through a heating furnace, and setting the reaction temperature to 300 ℃;
(4) after the temperature is increased to 300 ℃, opening the stop valve in the step (3), continuously supplementing and injecting argon to the pressure of 100MPa, keeping the stable temperature and pressure condition for reaction for 5 hours, and after the reaction is finished, using ice water to pour the reaction kettle in the step (3) for rapid cooling or constant pressure cooling to normal temperature;
(5) opening the reaction kettle in the step (3), taking out, cleaning, drying and weighing the gold tube in the reaction kettle, ensuring the sealing property and effectiveness of the reaction process, breaking the gold tube after confirming that no error exists, recovering the residual solution, washing the inner wall of the gold tube with deionized water and absolute ethyl alcohol for 2-3 times respectively to ensure that the OsO attached to the inner wall of the gold tube2Cleaning the sample, and air-drying with natural wind or oven-drying to obtain OsO2A nanoparticle;
(6) the obtained OsO2Raman qualitative analysis and scanning electron microscope morphology analysis are carried out on the nanoparticle sample, Raman analysis results are shown in figure 1 (300 ℃), and the obtained nanoparticles are OsO2FIG. 2 (A) is a scanning electron micrograph showing the synthesized OsO2The nano particles are in a crystal nucleus structure, the crystal form is not completely developed, and the particle size is 40-150 nm;
(7) the residual solution is mainly potassium osmate chloride, hydrochloric acid and potassium chloride, and the solution can be recycled and has less environmental pollution.
Example 2
OsO provided in this example2The preparation method of the spherical nano-particles comprises the following steps:
(1) pretreatment of the gold tube was the same as in example 1;
(2) 0.0962g of potassium chloroosmate (K) in analytical purity2OsCl6) The powder is dissolved in 100mL deionized water and fully dissolved to obtain 0.002mol/L K2OsCl6The prepared reaction solution is filled into a gold tube by using a sample injector, and the filling degree is controlled to be about 50 percentWelding and sealing, weighing and recording after welding and sealing, then putting the gold tube filled with the solution sample into a drying box at 110 ℃ for 2h, and then weighing again to ensure that the mass error before and after weighing is less than 0.001g, which indicates that the gold tube is intact in sealing;
(3) placing a gold tube which is confirmed to have perfect tightness and is filled with a solution sample into a high-temperature high-pressure reaction kettle, screwing down the reaction kettle, checking the tightness of the reaction kettle, confirming that no error exists, injecting argon into the kettle to the pressure of 40MPa through an air duct to serve as an initial pressure, closing a stop valve to stop gas injection, heating the reaction kettle through a heating furnace, and setting the reaction temperature to 300 ℃;
(4) after the temperature is increased to 300 ℃, opening the stop valve in the step (3), continuously supplementing and injecting argon to the pressure of 100MPa, keeping the stable temperature and pressure condition for reaction for 12 hours, and after the reaction is finished, using ice water to pour the reaction kettle in the step (3) for rapid cooling or constant pressure cooling to normal temperature;
(5) opening the reaction kettle in the step (3), taking out, cleaning, drying and weighing the gold tube in the reaction kettle, ensuring the sealing property and effectiveness of the reaction process, breaking the gold tube after confirming that no error exists, recovering the residual solution, washing the inner wall of the gold tube with deionized water and absolute ethyl alcohol for 2-3 times respectively to ensure that the OsO attached to the inner wall of the gold tube2Cleaning the sample, and air-drying with natural wind or oven-drying to obtain OsO2A nanoparticle;
(6) the obtained OsO2Raman qualitative analysis and scanning electron microscope morphology analysis are carried out on the nanoparticle sample, Raman analysis results are shown in figure 1 (300 ℃), and the obtained nanoparticles are OsO2FIG. 2 (B) is a scanning electron micrograph showing the synthesized OsO2The nano particles initially have a spherical structure, and the particle size is 100-200 nm;
(7) the residual solution is mainly potassium osmate chloride, hydrochloric acid and potassium chloride, and the solution can be recycled and has less environmental pollution.
Example 3
OsO provided in this example2The preparation method of the spherical nano-particles comprises the following steps:
(1) pretreatment of the gold tube was the same as in example 1;
(2) 0.0962g of potassium chloroosmate (K) in analytical purity2OsCl6) The powder is dissolved in 100mL deionized water and fully dissolved to obtain 0.002mol/L K2OsCl6The solution is prepared by filling the prepared reaction solution into a gold tube by using a sample injector, controlling the filling degree to be about 50%, welding and sealing, weighing and recording after welding and sealing, then putting the gold tube filled with the solution sample into a drying box at 110 ℃ for 2h, and then weighing again, ensuring that the mass error before and after weighing is less than 0.001g, and indicating that the gold tube is complete in sealing;
(3) placing a gold tube which is confirmed to have perfect tightness and is filled with a solution sample into a high-temperature high-pressure reaction kettle, screwing down the reaction kettle, checking the tightness of the reaction kettle, confirming that no error exists, injecting argon into the kettle to the pressure of 40MPa through an air duct to serve as an initial pressure, closing a stop valve to stop gas injection, heating the reaction kettle through a heating furnace, and setting the reaction temperature to 300 ℃;
(4) after the temperature is increased to 300 ℃, opening the stop valve in the step (3), continuously supplementing and injecting argon to the pressure of 100MPa, keeping the stable temperature and pressure condition for reaction for 24 hours, and after the reaction is finished, using ice water to pour the reaction kettle in the step (3) for rapid cooling or constant pressure cooling to normal temperature;
(5) opening the reaction kettle in the step (3), taking out, cleaning, drying and weighing the gold tube in the reaction kettle, ensuring the sealing property and effectiveness of the reaction process, breaking the gold tube after confirming that no error exists, recovering the residual solution, washing the inner wall of the gold tube with deionized water and absolute ethyl alcohol for 2-3 times respectively to ensure that the OsO attached to the inner wall of the gold tube2Cleaning the sample, and air-drying with natural wind or drying in a drying dish to obtain spherical OsO2A nanoparticle;
(6) spherical OsO to be obtained2Raman qualitative analysis and scanning electron microscope morphology analysis are carried out on the nanoparticle sample, Raman analysis results are shown in figure 1 (300 ℃), and the obtained nanoparticles are OsO2FIG. 2 (C) is a scanning electron micrograph showing the synthesized OsO2The nano particles have a spherical structure, complete crystal form and particle size of 100-500 nm;
(7) the residual solution is mainly potassium osmate chloride, hydrochloric acid and potassium chloride, and the solution can be recycled and has less environmental pollution.
Example 4
OsO provided in this example2The preparation method of the spherical nano-particles comprises the following steps:
(1) pretreatment of the gold tube was the same as in example 1;
(2) 0.0962g of potassium chloroosmate (K) in analytical purity2OsCl6) The powder is dissolved in 100mL deionized water and fully dissolved to obtain 0.002mol/L K2OsCl6The solution is prepared by filling the prepared reaction solution into a gold tube by using a sample injector, controlling the filling degree to be about 50%, welding and sealing, weighing and recording after welding and sealing, then putting the gold tube filled with the solution sample into a drying box at 110 ℃ for 2h, and then weighing again, ensuring that the mass error before and after weighing is less than 0.001g, and indicating that the gold tube is complete in sealing;
(3) placing a gold tube which is confirmed to have perfect tightness and is filled with a solution sample into a high-temperature high-pressure reaction kettle, screwing down the reaction kettle, checking the tightness of the reaction kettle, confirming that no error exists, injecting argon into the kettle to the pressure of 40MPa through an air duct to serve as an initial pressure, closing a stop valve to stop gas injection, heating the reaction kettle through a heating furnace, and setting the reaction temperature to 300 ℃;
(4) after the temperature is increased to 300 ℃, opening the stop valve in the step (3), continuously supplementing and injecting argon to the pressure of 100MPa, keeping the stable temperature and pressure condition for reacting for 36 hours, and after the reaction is finished, using ice water to pour the reaction kettle in the step (3) for rapidly cooling or cooling to normal temperature at constant pressure;
(5) opening the reaction kettle in the step (3), taking out, cleaning, drying and weighing the gold tube in the reaction kettle, ensuring the sealing property and effectiveness of the reaction process, breaking the gold tube after confirming that no error exists, recovering the residual solution, washing the inner wall of the gold tube with deionized water and absolute ethyl alcohol for 2-3 times respectively to ensure that the OsO attached to the inner wall of the gold tube2Cleaning the sample, and air-drying with natural wind or drying in a drying dish to obtain spherical OsO2A nanoparticle;
(6) spherical OsO to be obtained2Raman characterization of nanoparticle samplesAnalysis and shape analysis of a scanning electron microscope, and Raman analysis results are shown in figure 1 (300 ℃), which shows that the obtained nano-particles are OsO2FIG. 2 (D) is a scanning electron micrograph showing the synthesized OsO2The nano particles have a spherical structure, complete crystal form and particle size of 200-600 nm;
(7) the residual solution is mainly potassium osmate chloride, hydrochloric acid and potassium chloride, and the solution can be recycled and has less environmental pollution.
The results of the experiments in examples 1 to 4 show that different reaction times for OsO at a reaction temperature of 300 ℃ and a reaction pressure of 100MPa2The structure of the nanoparticles has an influence, OsO with prolonged reaction time2The crystal structure of the nano-particles gradually tends to be complete, the particle size of the particles is gradually increased, and the OsO formed in more than 12h2The nanoparticles have an intact spherical structure.
Example 5
OsO provided in this example2The preparation method of the spherical nano-particles comprises the following steps:
(1) pretreatment of the gold tube was the same as in example 1;
(2) 0.2405g of potassium chloroosmate (K) are analyzed for purity2OsCl6) The powder is dissolved in 100mL of deionized water and fully dissolved to obtain 0.005mol/L K2OsCl6The solution is prepared by filling the prepared reaction solution into a gold tube by using a sample injector, controlling the filling degree to be about 50%, welding and sealing, weighing and recording after welding and sealing, then putting the gold tube filled with the solution sample into a drying box at 110 ℃ for 2h, and then weighing again, ensuring that the mass error before and after weighing is less than 0.001g, and indicating that the gold tube is complete in sealing;
(3) placing a gold tube which is confirmed to have perfect tightness and is filled with a solution sample into a high-temperature high-pressure reaction kettle, screwing down the reaction kettle, checking the tightness of the reaction kettle, confirming that no error exists, injecting argon into the kettle to the pressure of 40MPa through an air duct to serve as an initial pressure, closing a stop valve to stop gas injection, heating the reaction kettle through a heating furnace, and setting the reaction temperature to be 150 ℃;
(4) after the temperature is raised to 150 ℃, opening the stop valve in the step (3), continuously supplementing and injecting argon to the pressure of 100MPa, keeping the temperature and pressure stable, reacting for 24 hours, and after the reaction is finished, using ice water to pour the reaction kettle in the step (3) for rapidly cooling or cooling to normal temperature at constant pressure;
(5) opening the reaction kettle in the step (3), taking out, cleaning, drying and weighing the gold tube in the reaction kettle, ensuring the sealing property and effectiveness of the reaction process, breaking the gold tube after confirming that no error exists, recovering the residual solution, washing the inner wall of the gold tube with deionized water and absolute ethyl alcohol for 2-3 times respectively to ensure that the OsO attached to the inner wall of the gold tube2Cleaning the sample, and air-drying with natural wind or drying in a drying dish to obtain spherical OsO2A nanoparticle;
(6) spherical OsO to be obtained2Raman qualitative analysis and scanning electron microscope morphology analysis are carried out on the nanoparticle sample, Raman analysis results are shown in figure 1 (150 ℃), and the obtained nanoparticles are OsO2FIG. 3 (A) is a scanning electron micrograph showing the synthesized OsO2The nano particles have a spherical structure, complete crystal form and particle size of 80-400 nm;
(7) the residual solution is mainly potassium osmate chloride, hydrochloric acid and potassium chloride, and the solution can be recycled and has less environmental pollution.
Example 6
OsO provided in this example2The preparation method of the spherical nano-particles comprises the following steps:
(1) pretreatment of the gold tube was the same as in example 1;
(2) 0.2405g of potassium chloroosmate (K) are analyzed for purity2OsCl6) The powder is dissolved in 100mL of deionized water and fully dissolved to obtain 0.005mol/L K2OsCl6The solution is prepared by filling the prepared reaction solution into a gold tube by using a sample injector, controlling the filling degree to be about 50%, welding and sealing, weighing and recording after welding and sealing, then putting the gold tube filled with the solution sample into a drying box at 110 ℃ for 2h, and then weighing again, ensuring that the mass error before and after weighing is less than 0.001g, and indicating that the gold tube is complete in sealing;
(3) placing a gold tube which is confirmed to have perfect tightness and is filled with a solution sample into a high-temperature high-pressure reaction kettle, screwing down the reaction kettle, checking the tightness of the reaction kettle, confirming that no error exists, injecting argon into the kettle to the pressure of 40MPa through an air duct to serve as an initial pressure, closing a stop valve to stop gas injection, heating the reaction kettle through a heating furnace, and setting the reaction temperature to be 250 ℃;
(4) after the temperature is increased to 250 ℃, opening the stop valve in the step (3), continuously supplementing and injecting argon to the pressure of 100MPa, keeping the stable temperature and pressure condition for reaction for 24 hours, and after the reaction is finished, using ice water to pour the reaction kettle in the step (3) for rapid cooling or constant pressure cooling to normal temperature;
(5) opening the reaction kettle in the step (3), taking out, cleaning, drying and weighing the gold tube in the reaction kettle, ensuring the sealing property and effectiveness of the reaction process, breaking the gold tube after confirming that no error exists, recovering the residual solution, washing the inner wall of the gold tube with deionized water and absolute ethyl alcohol for 2-3 times respectively to ensure that the OsO attached to the inner wall of the gold tube2Cleaning the sample, and air-drying with natural wind or drying in a drying dish to obtain spherical OsO2A nanoparticle;
(6) spherical OsO to be obtained2Raman qualitative analysis and scanning electron microscope morphology analysis are carried out on the nanoparticle sample, Raman analysis results are shown in figure 1 (250 ℃), and the obtained nanoparticles are OsO2FIG. 3 (B) is a scanning electron micrograph showing the synthesized OsO2The nano particles have a spherical structure, complete crystal form and particle size of 80-400 nm;
(7) the residual solution is mainly potassium osmate chloride, hydrochloric acid and potassium chloride, and the solution can be recycled and has less environmental pollution.
Example 7
OsO provided in this example2The preparation method of the spherical nano-particles comprises the following steps:
(1) pretreatment of the gold tube was the same as in example 1;
(2) 0.2405g of potassium chloroosmate (K) are analyzed for purity2OsCl6) The powder is dissolved in 100mL of deionized water and fully dissolved to obtain 0.005mol/L K2OsCl6Filling the prepared reaction solution into a gold tube by using a sample injector, controlling the filling degree to be about 50%, welding and sealing, and sealingWeighing and recording, then putting the gold tube filled with the solution sample into a drying box at 110 ℃ for 2h, and then weighing again, wherein the mass error of the previous weighing and the next weighing is ensured to be less than 0.001g, which indicates that the gold tube is complete in sealing property;
(3) placing a gold tube which is confirmed to have perfect tightness and is filled with a solution sample into a high-temperature high-pressure reaction kettle, screwing down the reaction kettle, checking the tightness of the reaction kettle, confirming that no error exists, injecting argon into the kettle to the pressure of 40MPa through an air duct to serve as an initial pressure, closing a stop valve to stop gas injection, heating the reaction kettle through a heating furnace, and setting the reaction temperature to 350 ℃;
(4) after the temperature is increased to 350 ℃, opening the stop valve in the step (3), continuously supplementing and injecting argon to the pressure of 100MPa, keeping the stable temperature and pressure condition for reaction for 24 hours, and after the reaction is finished, using ice water to pour the reaction kettle in the step (3) for rapid cooling or constant pressure cooling to normal temperature;
(5) opening the reaction kettle in the step (3), taking out, cleaning, drying and weighing the gold tube in the reaction kettle, ensuring the sealing property and effectiveness of the reaction process, breaking the gold tube after confirming that no error exists, recovering the residual solution, washing the inner wall of the gold tube with deionized water and absolute ethyl alcohol for 2-3 times respectively to ensure that the OsO attached to the inner wall of the gold tube2Cleaning the sample, and air-drying with natural wind or drying in a drying dish to obtain spherical OsO2A nanoparticle;
(6) spherical OsO to be obtained2Raman qualitative analysis and scanning electron microscope morphology analysis are carried out on the nanoparticle sample, Raman analysis results are shown in figure 1 (350 ℃), and the obtained nanoparticles are OsO2FIG. 3 (C) is a scanning electron micrograph showing the synthesized OsO2The nano particles have a spherical structure and complete crystal forms. The particle size is 50-200 nm;
(7) the residual solution is mainly potassium osmate chloride, hydrochloric acid and potassium chloride, and the solution can be recycled and has less environmental pollution.
Example 8
OsO provided in this example2The preparation method of the spherical nano-particles comprises the following steps:
(1) pretreatment of the gold tube was the same as in example 1;
(2) 0.2405g of potassium chloroosmate (K) are analyzed for purity2OsCl6) The powder is dissolved in 100mL of deionized water and fully dissolved to obtain 0.005mol/L K2OsCl6The method comprises the following steps of preparing a solution, namely filling the prepared reaction solution into a gold tube by using a sample injector, controlling the filling degree to be about 50%, carrying out welding sealing, carrying out weighing recording after welding sealing, then putting the gold tube filled with a solution sample into a drying box at 110 ℃ for 2 hours, weighing again, ensuring that the mass error before and after weighing is less than 0.001g, and indicating that the gold tube is complete in sealing property;
(3) placing a gold tube which is confirmed to have perfect tightness and is filled with a solution sample into a high-temperature high-pressure reaction kettle, screwing down the reaction kettle, checking the tightness of the reaction kettle, confirming that no error exists, injecting argon into the kettle to the pressure of 40MPa through an air duct to serve as an initial pressure, closing a stop valve to stop gas injection, heating the reaction kettle through a heating furnace, and setting the reaction temperature to be 450 ℃;
(4) after the temperature is increased to 450 ℃, opening the stop valve in the step (3), continuously supplementing and injecting argon gas to the pressure of 100MPa, keeping the stable temperature and pressure condition for reaction for 24 hours, and after the reaction is finished, using ice water to pour the reaction kettle in the step (3) for rapid cooling or constant pressure cooling to normal temperature;
(5) opening the reaction kettle in the step (3), taking out, cleaning, drying and weighing the gold tube in the reaction kettle, ensuring the sealing property and effectiveness of the reaction process, breaking the gold tube after confirming that no error exists, recovering the residual solution, washing the inner wall of the gold tube with deionized water and absolute ethyl alcohol for 2-3 times respectively to ensure that the OsO attached to the inner wall of the gold tube2Cleaning the sample, and air-drying with natural wind or drying in a drying dish to obtain spherical OsO2A nanoparticle;
(6) spherical OsO to be obtained2Raman qualitative analysis and scanning electron microscope morphology analysis are carried out on the nanoparticle sample, Raman analysis results are shown in figure 1 (450 ℃), and the obtained nanoparticles are OsO2FIG. 3 (D) is a scanning electron micrograph showing the synthesized OsO2The nano particles have a spherical structure, complete crystal form and particle size of 100-600 nm;
(7) the residual solution is mainly potassium osmate chloride, hydrochloric acid and potassium chloride, and the solution can be recycled and has less environmental pollution.
Example 9
OsO provided in this example2The preparation method of the spherical nano-particles comprises the following steps:
(1) pretreatment of the gold tube was the same as in example 1;
(2) 0.2405g of potassium chloroosmate (K) are analyzed for purity2OsCl6) The powder is dissolved in 100mL of deionized water and fully dissolved to obtain 0.005mol/L K2OsCl6The solution is prepared by filling the prepared reaction solution into a gold tube by using a sample injector, controlling the filling degree to be about 50%, welding and sealing, weighing and recording after welding and sealing, then putting the gold tube filled with the solution sample into a drying box at 110 ℃ for 2h, and then weighing again, ensuring that the mass error before and after weighing is less than 0.001g, and indicating that the gold tube is complete in sealing;
(3) placing a gold tube which is confirmed to have perfect tightness and is filled with a solution sample into a high-temperature high-pressure reaction kettle, screwing down the reaction kettle, checking the tightness of the reaction kettle, confirming that no error exists, injecting argon into the kettle to the pressure of 40MPa through an air duct to serve as an initial pressure, closing a stop valve to stop gas injection, heating the reaction kettle through a heating furnace, and setting the reaction temperature to be 550 ℃;
(4) after the temperature is increased to 550 ℃, opening the stop valve in the step (3), continuously supplementing and injecting argon gas to the pressure of 100MPa, keeping the stable temperature and pressure condition for reaction for 24 hours, and after the reaction is finished, using ice water to pour the reaction kettle in the step (3) for rapid cooling or constant pressure cooling to normal temperature;
(5) opening the reaction kettle in the step (3), taking out, cleaning, drying and weighing the gold tube in the reaction kettle, ensuring the sealing property and effectiveness of the reaction process, breaking the gold tube after confirming that no error exists, recovering the residual solution, washing the inner wall of the gold tube with deionized water and absolute ethyl alcohol for 2-3 times respectively to ensure that the OsO attached to the inner wall of the gold tube2Cleaning the sample, and air-drying with natural wind or drying in a drying dish to obtain spherical OsO2A nanoparticle;
(6) spherical OsO to be obtained2Performing Raman qualitative analysis and scanning on nanoparticle sampleThe morphology analysis of a scanning electron microscope shows that the Raman analysis result in figure 1 (550 ℃) shows that the obtained nano-particles are OsO2FIG. 3 (E-F) is a scanning electron micrograph showing the synthesized OsO2The nano particles have a spherical structure, complete crystal form and particle size of 50-300 nm;
(7) the residual solution is mainly potassium osmate chloride, hydrochloric acid and potassium chloride, and the solution can be recycled and has less environmental pollution.
Example 5-the results in example 9 show that potassium chloroaosmate (K)2OsCl6) The concentration of the dilute solution is 0.002-0.005 mol/L, the reaction temperature is 150-550 ℃, the reaction pressure is 100MPa, and the reaction time is 24h, so that better OsO can be prepared2Spherical nanoparticles.
Comparative example 1
Preparation of non-spherical OsO as provided in this example2In the case of nanoparticles, comprising the steps of:
(1) pretreatment of the gold tube was the same as in example 1;
(2) 0.0481g of potassium chloroosmate (K) are analyzed for purity2OsCl6) The powder is dissolved in 100mL of deionized water and fully dissolved to obtain 0.001mol/L K2OsCl6The solution is prepared by filling the prepared reaction solution into a gold tube by using a sample injector, controlling the filling degree to be about 50%, welding and sealing, weighing and recording after welding and sealing, then putting the gold tube filled with the solution sample into a drying box at 110 ℃ for 2h, and then weighing again, ensuring that the mass error before and after weighing is less than 0.001g, and indicating that the gold tube is complete in sealing;
(3) placing a gold tube which is confirmed to have perfect tightness and is filled with a solution sample into a high-temperature high-pressure reaction kettle, screwing down the reaction kettle, checking the tightness of the reaction kettle, confirming that no error exists, injecting argon into the kettle to the pressure of 40MPa through an air duct to serve as an initial pressure, closing a stop valve to stop gas injection, heating the reaction kettle through a heating furnace, and setting the reaction temperature to be 150 ℃;
(4) after the temperature is raised to 150 ℃, opening the stop valve in the step (3), continuously supplementing and injecting argon to the pressure of 100MPa, keeping the temperature and pressure stable, reacting for 24 hours, and after the reaction is finished, using ice water to pour the reaction kettle in the step (3) for rapidly cooling or cooling to normal temperature at constant pressure;
(5) opening the reaction kettle in the step (3), taking out, cleaning, drying and weighing the gold tube in the reaction kettle, ensuring the sealing property and effectiveness of the reaction process, breaking the gold tube after confirming that no error exists, recovering the residual solution, washing the inner wall of the gold tube with deionized water and absolute ethyl alcohol for 2-3 times respectively to ensure that the OsO attached to the inner wall of the gold tube2Cleaning the sample, and air-drying with natural wind or oven-drying to obtain OsO2A nanoparticle;
(6) the obtained OsO2Raman qualitative analysis and scanning electron microscope morphology analysis are carried out on the nanoparticle sample, Raman analysis results are shown in figure 1 (150 ℃), and the obtained nanoparticles are OsO2FIG. 4 (A) is a SEM photograph showing the synthesized OsO2The nano particles are of a crystal nucleus structure, have incomplete crystal forms and are distributed sporadically;
(7) the residual solution is mainly potassium osmate chloride, hydrochloric acid and potassium chloride, and the solution can be recycled and has less environmental pollution.
Comparative example 2
Preparation of non-spherical OsO as provided in this example2In the case of nanoparticles, comprising the steps of:
(1) pretreatment of the gold tube was the same as in example 1;
(2) 0.2405g of potassium chloroosmate (K) are analyzed for purity2OsCl6) The powder is dissolved in 100mL of deionized water and fully dissolved to obtain 0.005mol/L K2OsCl6The solution is prepared by filling the prepared reaction solution into a gold tube by using a sample injector, controlling the filling degree to be about 50%, welding and sealing, weighing and recording after welding and sealing, then putting the gold tube filled with the solution sample into a drying box at 110 ℃ for 2h, and then weighing again, ensuring that the mass error before and after weighing is less than 0.001g, and indicating that the gold tube is complete in sealing;
(3) placing a gold tube which is confirmed to have perfect tightness and is filled with a solution sample into a high-temperature high-pressure reaction kettle, screwing down the reaction kettle, checking the tightness of the reaction kettle, confirming that no error exists, injecting argon into the kettle to the pressure of 40MPa through an air duct to serve as an initial pressure, closing a stop valve to stop gas injection, heating the reaction kettle through a heating furnace, and setting the reaction temperature to 600 ℃;
(4) after the temperature is increased to 600 ℃, opening the stop valve in the step (3), continuously supplementing and injecting argon to the pressure of 100MPa, keeping the stable temperature and pressure condition for reaction for 24 hours, and after the reaction is finished, using ice water to pour the reaction kettle in the step (3) for rapid cooling or constant pressure cooling to normal temperature;
(5) opening the reaction kettle in the step (3), taking out, cleaning, drying and weighing the gold tube in the reaction kettle, ensuring the sealing property and effectiveness of the reaction process, breaking the gold tube after confirming that no error exists, recovering the residual solution, washing the inner wall of the gold tube with deionized water and absolute ethyl alcohol for 2-3 times respectively to ensure that the OsO attached to the inner wall of the gold tube2Cleaning the sample, and air-drying with natural wind or oven-drying to obtain OsO2A nanoparticle;
(6) the obtained OsO2Raman qualitative analysis and scanning electron microscope morphology analysis are carried out on the nanoparticle sample, Raman analysis results are shown in figure 1 (600 ℃), and the obtained nanoparticles are OsO2FIG. 4 (B) is a scanning electron micrograph showing the synthesized OsO2The nano particles are in a cone-shaped structure and are non-spherical;
(7) the residual solution is mainly potassium osmate chloride, hydrochloric acid and potassium chloride, and the solution can be recycled and has less environmental pollution.
As can be seen from comparative examples 1-2, OsO2The formation of the spherical nano particles is sensitive to the initial concentration and the reaction temperature, and when the concentration is lower than 0.002mol/L, the formed nano particles are of a crystal nucleus structure and do not have a spherical crystal form; OsO is formed at a temperature higher than 550 DEG C2The nanoparticles are also not spherical particles. In addition, early experiments showed that when the initial concentration of the experiment was too high (>0.005mol/L), the initial solution can generate an infusibility phenomenon, so that the experiment can not be carried out orderly. Moreover, in preliminary experiments in the early stage of the application, OsO is found2The formation of spherical nanoparticles is not sensitive to the reaction pressure, so the reaction pressure is selected to be 100MPa in the present application in consideration of the optimal pressure interval of the instrument equipment. Taken together, the present application synthesizes spherical OsO2The preferable range of the nano particles is that the initial concentration is 0.002-0.005 mol/L, the pressure is 100MPa, the temperature is 150-550 ℃, and the time is 12-36 hours.
Spherical OsO synthesized by the invention2The nano particles have stable structural characteristics and high exposure area, can be used as a catalyst or a fixing agent, and have important application in the aspects of chemical catalysis, electronic materials and the like.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. OsO (OsO)2The preparation method of the spherical nano-particle material is characterized by mainly comprising the following steps:
(1) selecting potassium chloro osmate (K)2OsCl6) Dissolving in deionized water to obtain potassium chloroosmate (K)2OsCl6) Diluted solution of potassium chloroosmate (K)2OsCl6) Placing the dilute solution in a gold tube, and sealing the gold tube;
(2) placing the sealed gold tube in a hydrothermal reaction kettle, adjusting the temperature in the hydrothermal reaction kettle to be 150-550 ℃ and the reaction pressure to be 100MPa, and carrying out hydrolysis reaction for 12-36 hours;
(3) after the hydrolysis reaction, opening the hydrothermal reaction kettle, taking out the gold tube and breaking the gold tube, recovering residual solution in the gold tube, cleaning the inner wall of the gold tube, and then drying to obtain spherical OsO2And (3) nanoparticles.
2. OsO according to claim 12The preparation method of the spherical nano-particle material is characterized by comprising the following steps: potassium chloro osmate (K) in step (1)2OsCl6) The concentration of the dilute solution is 0.002-0.005 mol/L.
3. OsO according to claim 12The preparation method of the spherical nano-particle material is characterized by comprising the following steps: potassium chloro osmate (K) in step (1)2OsCl6) The volume of the dilute solution accounts for 40-60% of the total volume of the gold tube; the gold tube in the step (1) is a gold tube with the mass percentage of more than 99 percent, and the gold tube is subjected to pretreatment including truncation, acid boiling, washing, ultrasonic treatment and quenching before use.
4. OsO according to claim 12The preparation method of the spherical nano-particle material is characterized by comprising the following steps: sealing the gold tube in step (1) by welding, detecting the sealing property after welding, and loading potassium chloro osmate (K) during the sealing property detection2OsCl6) Placing the gold tube in the diluted solution in an oven at 100-120 deg.C for baking for 1-3 h, weighing again and adding potassium chloroosmate (K)2OsCl6) And the gold tube with the diluted solution ensures that the weighing error before and after the gold tube is less than 0.001g, which indicates that the gold tube has good sealing property.
5. OsO according to claim 12The preparation method of the spherical nano-particle material is characterized by comprising the following steps: and (2) placing the sealed gold tube in a hydrothermal reaction kettle, injecting argon gas into the hydrothermal reaction kettle to a pressure of 40MPa as an initial pressure, stopping injecting the gas, heating the hydrothermal reaction kettle by using a heating furnace, and injecting argon gas to enable the reaction pressure to reach a target pressure after the temperature reaches a target reaction temperature.
6. OsO according to claim 12The preparation method of the spherical nano-particle material is characterized by comprising the following steps: the hydrolysis reaction time in the step (2) does not include time consumed by temperature rise and temperature fall, and is reaction time under the specified temperature and pressure.
7. OsO according to claim 12The preparation method of the spherical nano-particle material is characterized by comprising the following steps: after the hydrolysis reaction in the step (3), using ice water to quickly cool the hydrothermal reaction kettle to normal temperature, opening the hydrothermal reaction kettle, taking out the gold tube and breaking the gold tube, recovering residual solution in the gold tube, respectively soaking and washing the inner wall of the gold tube by using deionized water and absolute ethyl alcohol to enable the OsO attached to the inner wall of the gold tube2The sample is clean and the sample is clean,then OsO attached to the inner wall of the gold tube2Drying the sample to obtain OsO2Spherical nanoparticle materials.
8. OsO according to claim 12The preparation method of the spherical nano-particle material is characterized by comprising the following steps: and (4) after the gold tube is taken out in the step (3), cleaning, washing, drying and weighing the gold tube to ensure the effectiveness of the reaction process and the tightness of the experiment process, and then breaking the gold tube.
9. OsO according to claim 12The preparation method of the spherical nano-particle material is characterized by comprising the following steps: and (3) the residual solution is potassium chloro osmate, hydrochloric acid and potassium chloride, and the drying in the step (3) is natural air drying or baking.
10. OsO according to claim 12The preparation method of the spherical nano-particle material is characterized by comprising the following steps: the spherical OsO in the step (3)2The crystalline form of the nanoparticles is intact, the spherical OsO2The particle size of the nanoparticles is several tens to several hundreds of nanometers.
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