CN113772752A - PdO2Preparation method of irregular conical nano-particle material - Google Patents

PdO2Preparation method of irregular conical nano-particle material Download PDF

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CN113772752A
CN113772752A CN202110893782.6A CN202110893782A CN113772752A CN 113772752 A CN113772752 A CN 113772752A CN 202110893782 A CN202110893782 A CN 202110893782A CN 113772752 A CN113772752 A CN 113772752A
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gold tube
pdo
reaction kettle
irregular
gold
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严海波
丁兴
刘灼瑜
孙卫东
刘芳
郭佳
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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
    • 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
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX 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
    • C01P2004/42—(bi)pyramid-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • 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 a PdO2The preparation method of the irregular tapered nano-particle material mainly comprises the following steps: (1) selecting potassium chloropalladate (K)2PdCl6) Dissolving in deionized water to obtain potassium chloropalladate (K)2PdCl6) Diluted solution of potassium chloropalladate (K)2PdCl6) 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 300-600 ℃, and performing hydrolysis reaction at the reaction pressure of 100-300 MPa for 12-24 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 PdO2Irregular tapered nanoparticle materials. The method has the advantages of single raw material, easy obtainment, simple process and synthesized PdO2The nanometer particles are irregular cone-shaped, the crystal form is intact, and the particle diameter is dozens of nanometersTo a few microns.

Description

PdO2Irregular tapered nanoparticle materialPreparation method of (1)
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a PdO2A method for preparing irregular tapered nano-particle material.
Background
In recent years, nano materials such as palladium and palladium oxide have been developed rapidly, and have good application prospects in various fields. At present, the main research and application fields of palladium and its oxide include catalysts, hydrogen-absorbing materials, surface modification dopants for sensitive materials, electrode sensors, semiconductor gas-sensitive materials, electronic industry resistors, thick film circuit materials, and the like, and among them, PdO is the most widely researched, prepared, and applied.
At present, a common preparation method of the PdO nano material comprises the following steps: the method is characterized by comprising the steps of preparing palladium chloride by a hydrothermal method, adding activated iron particles into a mixed solution of palladium nitrate, glycine and sodium hydroxide, heating and mixing, preparing by utilizing the difference and the property of the potentials of a metal palladium electrode and a metal nickel electrode, preparing based on a biological template method, preparing by an active sputtering deposition method, preparing by a precipitation hydrolysis method, preparing by suspension regulation and mixing, and the like. The prepared PdO nano material has different morphological structures, such as nanoclusters, nanosheet films, hollow nanospheres, nanowires, nanoparticles and the like. However, currently for PdO2The research and preparation of the palladium oxide are extremely lacking, which can seriously restrict PdO2The application and popularization of the nano material in industry.
Disclosure of Invention
The invention aims to provide a PdO2The preparation method of the irregular conical nanoparticle material has the advantages of single raw material, easy obtainment, simple process and capability of synthesizing the PdO2The nano particles are irregular cone-shaped, the crystal form is intact, and the particle size is dozens of nanometers to several micrometers.
The above object of the present invention can be achieved by the following technical solutions: PdO2The preparation method of the irregular tapered nano-particle material mainly comprises the following steps:
(1) selecting potassium chloropalladate (K)2PdCl6) Dissolving in deionized water to obtain potassium chloropalladate (K)2PdCl6) Diluted solution of potassium chloropalladate (K)2PdCl6) 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 300-600 ℃, and performing hydrolysis reaction at the reaction pressure of 100-300 MPa for 12-24 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 PdO2Irregular tapered nanoparticle materials.
In the above PdO2The preparation method of the irregular tapered nano-particle material comprises the following steps:
optionally, the potassium chloropalladate (K) in step (1)2PdCl6) The concentration of the dilute solution is 0.002-0.005 mol/L.
More preferably, the potassium chloropalladate (K) in the step (1)2PdCl6) The concentration of the dilute solution is 0.002mol/L or 0.005 mol/L.
Optionally, the potassium chloropalladate (K) in step (1)2PdCl6) The volume of the dilute solution accounts for 30-50% 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, during the step (1), a gold tube is sealed by adopting a welding seal treatment, and after the welding seal, the gold tube is subjected to tightness detection, wherein during the tightness detection, potassium chloropalladate (K) is filled in the gold tube2PdCl6) Placing the gold tube of the dilute solution in an oven at 100-120 ℃ for baking for 1-3 h, and weighing again the gold tube filled with potassium chloropalladate (K)2PdCl6) 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 the step (1) by welding, and the sealing performance is detected after welding, and the gold tube is filled with potassium chloropalladate (K) during the sealing performance detection2PdCl6) Placing the gold tube in the dilute solution in an oven at 110 deg.C, baking for 2 hr, weighing again and filling with potassium chloropalladate (K)2PdCl6) 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 injected into the hydrothermal reaction kettle to reach a pressure of 40-100 MPa 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 a target reaction temperature, argon gas is injected to make the reaction pressure reach the target pressure.
Preferably, 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 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 enable the reaction pressure to 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.
As a preferable technical scheme of the invention, in the step (2), the sealed gold tube is placed in a hydrothermal reaction kettle, the temperature in the hydrothermal reaction kettle is adjusted to be 300 ℃, the reaction pressure is 300MPa, and the hydrolysis reaction is carried out for 12-24 hours.
As another preferable technical scheme of the invention, in the step (2), the sealed gold tube is placed in a hydrothermal reaction kettle, the temperature in the hydrothermal reaction kettle is adjusted to be 400-600 ℃, the reaction pressure is 100MPa, and the hydrolysis reaction is carried out for 12-24 hours.
For example, in the step (2), the sealed gold tube is placed in a hydrothermal reaction kettle, the temperature in the hydrothermal reaction kettle is adjusted to 400 ℃, the reaction pressure in the hydrothermal reaction kettle is adjusted to 100MPa by adopting inert gas such as argon, and 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, the temperature in the hydrothermal reaction kettle is adjusted to 500 ℃, the reaction pressure in the hydrothermal reaction kettle is adjusted to 100MPa by adopting inert gas such as argon, and 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, the temperature in the hydrothermal reaction kettle is adjusted to 600 ℃, the reaction pressure in the hydrothermal reaction kettle is adjusted to 100MPa by adopting inert gas such as argon, and 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, the temperature in the hydrothermal reaction kettle is adjusted to 300 ℃, the reaction pressure in the hydrothermal reaction kettle is adjusted to 300MPa by adopting inert gas such as argon, and 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, the temperature in the hydrothermal reaction kettle is adjusted to 300 ℃, the reaction pressure in the hydrothermal reaction kettle is adjusted to 300MPa by adopting inert gas such as argon, and 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 the gold tube, recovering the residual solution in the gold tube, soaking and washing the inner wall of the gold tube by using deionized water and absolute ethyl alcohol respectively, so that PdO attached to the inner wall of the gold tube is obtained2Cleaning the sample, and then carrying out PdO attached to the inner wall of the gold tube2Drying the sample to obtain PdO2Irregular tapered nanoparticle materials.
Specifically, 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 the gold tube, recovering residual solution in the gold tube, soaking and washing the inner wall of the gold tube for 2-3 times respectively by using deionized water and absolute ethyl alcohol to ensure that PdO attached to the inner wall of the gold tube is attached2Cleaning the sample, and then carrying out PdO attached to the inner wall of the gold tube2Drying the sample to obtain PdO2Irregular tapered 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 the step (3) is potassium chloropalladate, hydrochloric acid and potassium chloride, and the solution can be recycled and has less environmental pollution.
Optionally, the drying in the step (3) is natural air drying or drying.
Optionally, PdO is obtained in step (3)2The irregular conical nano-particle material has perfect crystal form and the particle size of tens of nanometers to several micrometers.
The invention relates to a PdO2The core of the preparation method of the irregular conical nano-particle material is that the PdO is generated by the hydrolysis reaction of a single reagent of potassium chloropalladate dilute solution under different temperature and pressure conditions2The only reagent used by the nano-particles is potassium chloropalladate dilute solution, and the potassium chloropalladate and water have the following hydrolysis reaction under the hydrothermal condition:
K2PdCl6+2H2O＝2KCl+PdO2↓+4HCl
the invention has the following beneficial effects:
(1) PdO of the invention2The preparation method of the irregular tapered nano-particle material adopts the self-hydrolysis reaction of a single reagent, and the initial reagent is single and easy to obtain;
(2) PdO of the invention2The preparation method of the irregular tapered nanoparticle material has the advantages that the operation process is simple in process and easy to control, the high-purity gold tube is used as the outer sleeve, so that the reactants can be prevented from reacting with other substances, the sealing performance and effectiveness in the reaction process are guaranteed, the cost is low, and the energy consumption is low;
(3) PdO of the invention2In the preparation method of the irregular tapered nano-particle material, the residual solution has simple components, can be recycled, has less environmental pollution, maintains the process safety and pays attention to environmental protection;
(4) PdO of the invention2Preparation method of irregular conical nanoparticle material and prepared PdO2The nano-particle material is irregular cone-shaped, the crystal form is intact, and the particle size is dozens of nanometers to several micrometers.
(5) PdO of the invention2Preparation of irregular tapered nano-particle materialMethod, PdO prepared2The nanoparticle size shows a tendency to gradually increase with the increase in the reaction temperature, the increase in the initial concentration and the increase in the reaction time.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 shows PdO prepared at 300 ℃ in examples 1 to 3 of the present invention2An EDS spectrum of the nanoparticle material;
FIG. 2 shows PdO prepared at 400 ℃ in example 4 of the present invention2An EDS spectrum of the nanoparticle material;
FIG. 3 shows PdO prepared at 500 ℃ in example 5 of the present invention2An EDS spectrum of the nanoparticle material;
FIG. 4 shows PdO prepared at 600 ℃ in example 6 of the present invention2An EDS spectrum of the nanoparticle material;
FIG. 5 shows PdO prepared at 200-650 ℃ in examples 1-6 and comparative examples 1-3 of the present invention2An XRD spectrum of the nano-particle material;
FIG. 6 shows PdO prepared in examples 1 to 6 of the present invention2Scanning electron micrograph of irregular tapered nanoparticle, wherein: (A) for the preparation in example 1, irregular taper type PdO was obtained2Nanoparticles, (B) irregular tapered PdO prepared in example 22Nanoparticles, (C) irregular tapered PdO prepared in example 32Nanoparticles, (D) irregular tapered PdO prepared in example 42Nanoparticles, (E) irregular tapered PdO prepared in example 52Nanoparticles, (F) irregular tapered PdO prepared in example 62And (3) nanoparticles.
FIG. 7 shows PdO prepared in comparative examples 1 to 3 according to the present invention2Scanning electron micrograph of nanoparticles, wherein (A) is PdO prepared in comparative example 12Nanoparticles, (B) PdO prepared in comparative example 22Nanoparticles, (C) PdO prepared in comparative example 32And (3) nanoparticles.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings, but the scope of the present invention as claimed is not limited to the examples, as the reaction apparatus and the reaction temperature, the reaction time and the volume of the reaction liquid.
Example 1
PdO provided by the embodiment2The preparation method of the irregular tapered nanoparticles comprises the following steps:
(1) cutting a high-purity gold tube with the diameter of 5mm into a length (2-3 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) 0.0795g of analytically pure potassium chloropalladate (K)2PdCl6) The powder is dissolved in 100mL deionized water and fully dissolved to obtain 0.002mol/L K2PdCl6The 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 through a vent pipe to the pressure of 100MPa, taking the argon as the starting 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 300MPa, 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 the gold tube in the reaction kettle, cleaning, drying and weighing to ensureMaintaining the sealing performance and effectiveness of the reaction process, breaking the gold tube after confirming no errors, recovering the residual solution, washing the inner wall of the gold tube with deionized water and alcohol for 2-3 times respectively to ensure that PdO attached to the inner wall of the gold tube2Cleaning the sample, and then air-drying with natural wind or drying with a drying dish to obtain the irregular conical PdO2A nanoparticle;
(6) the obtained irregular conical PdO2Carrying out EDS, XRD qualitative analysis and scanning electron microscope morphology analysis on the nano particle sample to obtain irregular conical PdO2EDS of the nanoparticle sample is shown in figure 1, XRD is shown in figure 5(300 ℃), and EDS and XRD analysis results show that the obtained nanoparticles are PdO2FIG. 6 (A) is a scanning electron micrograph showing that PdO having an irregular tapered shape is synthesized2The crystal form of the nano-particles is complete, and the diameter of the particles is 50-150 nm;
(7) the residual solution mainly comprises potassium chloropalladate, hydrochloric acid and potassium chloride, and the solution can be recycled and has small environmental pollution.
Example 2
PdO provided by the embodiment2The preparation method of the irregular tapered nanoparticles comprises the following steps:
(1) pretreatment of the gold tube was the same as in example 1;
(2) 0.0795g of analytically pure potassium chloropalladate (K)2PdCl6) The powder is dissolved in 100mL deionized water and fully dissolved to obtain 0.002mol/L K2PdCl6The 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 through an air duct to reach the pressure of 100MPa 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 300MPa, 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 the gold tube is confirmed to be correct, recovering the residual solution, washing the inner wall of the gold tube with deionized water and alcohol 2-3 times respectively to ensure that PdO attached to the inner wall of the gold tube2Cleaning the sample, and then air-drying with natural wind or drying with a drying dish to obtain the irregular conical PdO2A nanoparticle;
(6) the obtained irregular conical PdO2EDS, XRD qualitative analysis and scanning electron microscope morphology analysis are carried out on the nano particle sample, EDS and XRD analysis results are shown in figures 1 and 5(300 ℃), and the obtained nano particle is PdO2FIG. 6 (B) is a scanning electron micrograph showing the resultant irregular cone-shaped PdO2The crystal form of the nano-particles is complete, and the diameter of the particles is 100-300 nm;
(7) the residual solution mainly comprises potassium chloropalladate, hydrochloric acid and potassium chloride, and the solution can be recycled and has small environmental pollution.
Comparative examples 1-2 it can be found that PdO is formed as the reaction time is prolonged under the same conditions of initial concentration, reaction temperature and pressure (initial concentration of 0.002mol/L, reaction temperature of 300 ℃ C., reaction pressure of 300MPa)2The nanoparticle size shows a tendency to increase.
Example 3
PdO provided by the embodiment2The preparation method of the irregular tapered nanoparticles comprises the following steps:
(1) pretreatment of the gold tube was the same as in example 1;
(2) 0.199g of potassium chloropalladate (K) of analytical purity2PdCl6) The powder is dissolved in 100mL of deionized water and fully dissolved to obtain 0.005mol/L K2PdCl6The 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 through an air duct to reach the pressure of 100MPa 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 300MPa, 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 the gold tube is confirmed to be correct, recovering the residual solution, washing the inner wall of the gold tube with deionized water and alcohol 2-3 times respectively to ensure that PdO attached to the inner wall of the gold tube2Cleaning the sample, and then air-drying with natural wind or drying with a drying dish to obtain the irregular conical PdO2A nanoparticle;
(6) the obtained irregular conical PdO2EDS, XRD qualitative analysis and scanning electron microscope morphology analysis are carried out on the nano particle sample, EDS and XRD analysis results are shown in figures 1 and 5(300 ℃), and the obtained nano particle is PdO2FIG. 6(C) scanning electron micrograph showing the resultant PdO of irregular taper2The crystal form of the nano-particles is complete, and the diameter of the particles is 100-600 nm;
(7) the residual solution mainly comprises potassium chloropalladate, hydrochloric acid and potassium chloride, and the solution can be recycled and has small environmental pollution.
Comparative examples 2 to 3 can find that in the same reactionTime, reaction temperature and pressure conditions, with increasing initial concentration, PdO2The particle size of the nano-particles tends to increase gradually.
Example 4
PdO provided by the embodiment2The preparation method of the irregular tapered nanoparticles comprises the following steps:
(1) pretreatment of the gold tube was the same as in example 1;
(2) 0.199g of potassium chloropalladate (K) of analytical purity2PdCl6) The powder is dissolved in 100mL of deionized water and fully dissolved to obtain 0.005mol/L K2PdCl6The 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 400 ℃;
(4) after the temperature is increased to 400 ℃, 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 the gold tube is confirmed to be correct, recovering the residual solution, washing the inner wall of the gold tube with deionized water and alcohol 2-3 times respectively to ensure that PdO attached to the inner wall of the gold tube2Cleaning the sample, and then air-drying with natural wind or drying with a drying dish to obtain the irregular conical PdO2A nanoparticle;
(6) to be obtainedIrregular cone-shaped PdO2EDS, XRD qualitative analysis and scanning electron microscope morphology analysis are carried out on the nano particle sample, EDS and XRD analysis results are shown in figures 2 and 5(400 ℃), and the obtained nano particle is PdO2FIG. 6(D) scanning Electron micrograph showing the resultant irregular taper PdO2The crystal form of the nano-particles is complete, and the diameter of the particles is 100-600 nm;
(7) the residual solution mainly comprises potassium chloropalladate, hydrochloric acid and potassium chloride, and the solution can be recycled and has small environmental pollution.
Example 5
PdO provided by the embodiment2The preparation method of the irregular tapered nanoparticles comprises the following steps:
(1) pretreatment of the gold tube was the same as in example 1;
(2) 0.0795g of analytically pure potassium chloropalladate (K)2PdCl6) The powder is dissolved in 100mL deionized water and fully dissolved to obtain 0.002mol/L K2PdCl6The 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 500 ℃;
(4) after the temperature is increased to 500 ℃, 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 the gold tube in the reaction kettle, cleaning, drying and weighing to ensure the reactionBreaking the gold tube after confirming the correctness of the tightness and the validity of the process, recovering the residual solution, washing the inner wall of the gold tube with deionized water and alcohol for 2-3 times respectively to ensure that PdO attached to the inner wall of the gold tube2Cleaning the sample, and then air-drying with natural wind or drying with a drying dish to obtain the irregular conical PdO2A nanoparticle;
(6) the obtained irregular conical PdO2EDS, XRD qualitative analysis and scanning electron microscope morphology analysis are carried out on the nano particle sample, EDS and XRD analysis results are shown in figures 3 and 5(500 ℃), and the obtained nano particle is PdO2FIG. 6(E) SEM photograph shows the synthesized irregular conic PdO2The crystal form of the nano-particles is complete, and the diameter of the particles is 200-1200 nm;
(7) the residual solution mainly comprises potassium chloropalladate, hydrochloric acid and potassium chloride, and the solution can be recycled and has small environmental pollution.
Example 6
PdO provided by the embodiment2The preparation method of the irregular tapered nanoparticles comprises the following steps:
(1) pretreatment of the gold tube was the same as in example 1;
(2) 0.199g of potassium chloropalladate (K) of analytical purity2PdCl6) The powder is dissolved in 100mL of deionized water and fully dissolved to obtain 0.005mol/L K2PdCl6The 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 the gold tube is confirmed to be correct, recovering the residual solution, washing the inner wall of the gold tube with deionized water and alcohol 2-3 times respectively to ensure that PdO attached to the inner wall of the gold tube2Cleaning the sample, and then air-drying with natural wind or drying with a drying dish to obtain the irregular conical PdO2A nanoparticle;
(6) the obtained irregular conical PdO2EDS, XRD qualitative analysis and scanning electron microscope morphology analysis are carried out on the nano particle sample, EDS and XRD analysis results are shown in figures 4 and 5(600 ℃), and the obtained nano particle is PdO2FIG. 6(F) SEM photograph shows the synthesized irregular conic PdO2The crystal form of the nano-particles is complete, and the diameter of the particles is 200-800 nm;
(7) the residual solution mainly comprises potassium chloropalladate, hydrochloric acid and potassium chloride, and the solution can be recycled and has small environmental pollution.
Comparative examples 3 to 4 and 6 show that PdO increases with the reaction temperature under the same conditions of initial concentration, reaction time and pressure2The nanoparticle size gradually increases.
Comparative example 1
The non-irregular tapered nanoparticles PdO prepared by the embodiment2Comprises the following steps:
(1) pretreatment of the gold tube was the same as in example 1;
(2) 0.199g of potassium chloropalladate (K) of analytical purity2PdCl6) The powder is dissolved in 100mL of deionized water and fully dissolved to obtain 0.005mol/L K2PdCl6Filling the prepared reaction solution into a gold tube by using a sample injector, controlling the filling degree to be about 50%, sealing, weighing and recording after sealing, and then filling the gold tube with the solution samplePlacing the gold tube 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 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 200 ℃;
(4) after the temperature is increased to 200 ℃, 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 the gold tube is confirmed to be correct, recovering the residual solution, washing the inner wall of the gold tube with deionized water and alcohol 2-3 times respectively to ensure that PdO 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 PdO2A nanoparticle;
(6) the obtained PdO2XRD qualitative analysis and scanning electron microscope morphology analysis are carried out on the nanoparticle sample, and an XRD analysis result is shown in figure 5(200 ℃), which shows that the obtained nanoparticles are PdO2FIG. 7(A) SEM photograph shows the synthesized PdO2The nano particles are short column-shaped particles and non-irregular conical nano particles;
(7) the residual solution mainly comprises potassium chloropalladate, hydrochloric acid and potassium chloride, and the solution can be recycled and has small environmental pollution.
Comparative example 2
The non-irregular tapered nanoparticles PdO prepared by the embodiment2Comprises the following steps:
(1) pretreatment of the gold tube was the same as in example 1;
(2) 0.199g of analytically pure palladium chloride was addedPotassium salt (K)2PdCl6) The powder is dissolved in 100mL of deionized water and fully dissolved to obtain 0.005mol/L K2PdCl6The 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 through an air duct to reach the pressure of 100MPa 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 200MPa, 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 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 the gold tube is confirmed to be correct, recovering the residual solution, washing the inner wall of the gold tube with deionized water and alcohol 2-3 times respectively to ensure that PdO 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 PdO2A nanoparticle;
(6) the obtained PdO2XRD qualitative analysis and scanning electron microscope morphology analysis are carried out on the nanoparticle sample, and an XRD analysis result is shown in figure 5(300 ℃), which shows that the obtained nanoparticles are PdO2FIG. 7(B) SEM photograph shows the synthesized PdO2The nano particles are not completely irregular cone-shaped nano particles, and the part of the nano particles is columnar;
(7) the residual solution mainly comprises potassium chloropalladate, hydrochloric acid and potassium chloride, and the solution can be recycled and has small environmental pollution.
Comparative example 3
The non-irregular tapered nanoparticles PdO prepared by the embodiment2Comprises the following steps:
(1) pretreatment of the gold tube was the same as in example 1;
(2) 0.199g of potassium chloropalladate (K) of analytical purity2PdCl6) The powder is dissolved in 100mL of deionized water and fully dissolved to obtain 0.005mol/L K2PdCl6The 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 650 ℃;
(4) after the temperature is raised to 650 ℃, opening the stop valve in the step (3), continuously supplementing and injecting argon gas to the pressure of 100MPa, keeping the temperature and the 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 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 the gold tube is confirmed to be correct, recovering the residual solution, washing the inner wall of the gold tube with deionized water and alcohol 2-3 times respectively to ensure that PdO 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 PdO2A nanoparticle;
(6) the obtained PdO2XRD qualitative analysis and scanning electron microscope morphology analysis are carried out on the nanoparticle sample, and an XRD analysis result is shown in figure 5(650 ℃), which shows that the obtained nanoparticles are PdO2FIG. 7(C) SEM photograph shows the synthesized PdO2The nano particles are not irregular conical nano particles and are in a net sheet-shaped structure;
(7) the residual solution mainly comprises potassium chloropalladate, hydrochloric acid and potassium chloride, and the solution can be recycled and has small environmental pollution.
From the above comparative examples 1 to 3, it can be found that PdO is too low (200MPa) at 300 ℃ or too low (200 ℃ C.) or too high (650 ℃ C.) at 100MPa2The nanoparticles do not exhibit an irregular pyramid-type structure. Therefore, the invention preferably synthesizes the irregular cone type PdO2The range of the nano particles is 300MPa at 300 ℃, 400-600 ℃ at 100MPa, and the initial concentration is 0.002-0.005 mol/L.
The irregular conical PdO synthesized by the invention2The nano-particles have higher reducibility and conductivity, and can be used as a catalyst, a reducing agent or an electrode material in the fields of industrial production and the like in the future.
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. PdO2The preparation method of the irregular tapered nano-particle material is characterized by mainly comprising the following steps:
(1) selecting potassium chloropalladate (K)2PdCl6) Dissolving in deionized water to obtain potassium chloropalladate (K)2PdCl6) Diluted solution of potassium chloropalladate (K)2PdCl6) 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 300-600 ℃, and performing hydrolysis reaction at the reaction pressure of 100-300 MPa for 12-24 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 PdO2Irregular tapered nanoparticle materials.
2. The PdO of claim 12The preparation method of the irregular tapered nano-particle material is characterized by comprising the following steps: the potassium chloropalladate (K) in the step (1)2PdCl6) The concentration of the dilute solution is 0.002-0.005 mol/L.
3. The PdO of claim 12The preparation method of the irregular tapered nano-particle material is characterized by comprising the following steps: the potassium chloropalladate (K) in the step (1)2PdCl6) The volume of the dilute solution accounts for 30-50% 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. The PdO of claim 12The preparation method of the irregular tapered nano-particle material is characterized by comprising the following steps: sealing the gold tube in the step (1) by welding, and performing tightness detection after welding, wherein potassium chloropalladate (K) is filled in the gold tube during tightness detection2PdCl6) Placing the gold tube of the dilute solution in an oven at 100-120 ℃ for baking for 1-3 h, and weighing again the gold tube filled with potassium chloropalladate (K)2PdCl6) 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. The PdO of claim 12The preparation method of the irregular tapered nano-particle material is characterized by comprising the following steps: and (2) placing the sealed gold tube in a hydrothermal reaction kettle, injecting argon into the hydrothermal reaction kettle to a pressure of 40-100 MPa as an initial pressure, stopping injecting the gas, heating the hydrothermal reaction kettle by using a heating furnace, and injecting the argon to enable the reaction pressure to reach a target pressure after the temperature reaches a target reaction temperature.
6. The PdO of claim 12Irregular tapered nanoparticlesThe preparation method of the 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 drop, and is reaction time under the specified temperature and pressure; and (2) placing the sealed gold tube in a hydrothermal reaction kettle, adjusting the temperature in the hydrothermal reaction kettle to 300 ℃ and the reaction pressure to 300MPa, or adjusting the temperature in the hydrothermal reaction kettle to 400-600 ℃ and the reaction pressure to 100MPa, and performing hydrolysis reaction for 12-24 hours.
7. The PdO of claim 12The preparation method of the irregular tapered 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 ensure that PdO attached to the inner wall of the gold tube2Cleaning the sample, and then carrying out PdO attached to the inner wall of the gold tube2Drying the sample to obtain PdO2Irregular tapered nanoparticle materials.
8. The PdO of claim 1 or 72The preparation method of the irregular tapered 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. The PdO of claim 12The preparation method of the irregular tapered nano-particle material is characterized by comprising the following steps: the residual solution in the step (3) is potassium chloropalladate, hydrochloric acid and potassium chloride, and the drying in the step (3) is natural air drying or drying.
10. The PdO of claim 12The preparation method of the irregular tapered nano-particle material is characterized by comprising the following steps: PdO obtained in step (3)2The irregular conical nano-particle material has perfect crystal form and the particle size of tens of nanometers to several micrometers.
CN202110893782.6A 2021-08-04 2021-08-04 PdO2Preparation method of irregular conical nano-particle material Pending CN113772752A (en)

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Application publication date: 20211210