CN109079130B - Preparation method of particle size-adjustable yolk-eggshell structure porous composite material with platinum nano-core cerium dioxide nano-shell - Google Patents

Preparation method of particle size-adjustable yolk-eggshell structure porous composite material with platinum nano-core cerium dioxide nano-shell Download PDF

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CN109079130B
CN109079130B CN201810801922.0A CN201810801922A CN109079130B CN 109079130 B CN109079130 B CN 109079130B CN 201810801922 A CN201810801922 A CN 201810801922A CN 109079130 B CN109079130 B CN 109079130B
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蒋妮娜
李丹阳
陈爱政
王士斌
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Abstract

The invention discloses a preparation method of a porous composite material with a particle size-adjustable yolk-eggshell structure of a platinum nano inner core cerium dioxide nano shell, which comprises the following steps: (1) mixing a nonionic surfactant with a platinum precursor solution, adding a reducing agent, reacting under the conditions of ultrasound and room temperature to obtain a nano platinum colloidal solution, (2) adding an alkali liquor into the nano platinum colloidal solution to adjust the pH value, then adding a pore-forming agent, then dropwise adding a cerium nitrate aqueous solution, reacting at room temperature, centrifuging to obtain nano particles, and then placing the nano particles in a muffle furnace to calcine to obtain the yolk-eggshell structure porous composite material with the adjustable particle size. The yolk-eggshell structure porous composite material with the adjustable particle size, which is prepared by the invention, takes platinum nano as an inner core and cerium dioxide nano as an outer shell, can accurately adjust the particle size according to the requirement, and has uniform size.

Description

Preparation method of particle size-adjustable yolk-eggshell structure porous composite material with platinum nano-core cerium dioxide nano-shell
Technical Field
The invention belongs to the technical field of precious metal/semiconductor composite nano materials, and particularly relates to a preparation method of a porous composite material with an adjustable particle size yolk-eggshell structure, wherein the porous composite material is prepared from a platinum nano inner core cerium dioxide nano shell.
Background
Semiconductor nanomaterials are of great interest to scientists as they are capable of converting between solar energy and chemical energy. Specifically, semiconductor nanomaterials generate energetic electron-hole pairs under light conditions, which in turn participate in chemical reactions of substances surrounding the semiconductor nanomaterials through these energetic carriers (Advanced Materials, 2012, 24, 229-. However, since the semiconductor material has limited absorption in the visible light region and the generated electrons and holes are easily recombined, the utilization rate of solar energy is generally low for the semiconductor material alone. In recent years, studies have found that the light absorption performance of semiconductors and the promoted separation efficiency of electrons and holes can be greatly enhanced by using the recombination of noble metal nanoparticles having localized surface plasmon resonance properties with semiconductor Materials (Advanced Materials, 2014, 26, 5274-. The yolk-eggshell structure means that there is a gap between the inner core and the shell layer as if the yolk and the eggshell were. On one hand, the hollow core-shell structure can cause multiple reflection of incident light, thereby greatly prolonging the average path length of incident photons (Journal of the American Chemical Society, 2007, 129, 8406-; on the other hand, this structure facilitates electron-hole separation. Therefore, the noble metal/semiconductor composite nano material with the yolk-eggshell structure has obvious structural advantages in the application of photocatalysis and photodynamic reaction.
Cerium oxide is a unique semiconductor material and has great application potential in the fields of oxygen storage, photo-induced hydrogen production, dye photodegradation and the like. Platinum is a common precious metal material. Platinum nanoparticles have been recently applied to photocatalytic and photothermal therapies because they exhibit broadband absorption throughout the visible region. Therefore, the platinum/cerium oxide composite nano material has great application prospect in the aspect of solar energy utilization. In the existing synthesis research of (platinum nanometer inner core)/(cerium dioxide nanometer outer shell) yolk-eggshell structure, the prepared nanometer structure often has the problems of poor dispersibility and poor size uniformity, and the experimental method is relatively complicated. For example, Chun-Hua Yan et al (Journal of the American Chemical Society, 2010, 132, 4998-. In addition, the surface of the currently reported (platinum nanometer inner core)/(cerium dioxide nanometer outer shell) yolk-eggshell structure does not have a porous structure, and the size of the inner core cannot be regulated. For example, Yi-Jun Xu et al (Journal of Materials Chemistry, 2011, 21, 8152) -8158) utilize the alkaline property of urea solution at high temperature to coat a dense cerium dioxide shell layer on the surface of platinum nanoparticles, and the particle size of the platinum/cerium dioxide material prepared by the method is widely distributed in the range of 250-500 nm, the size is not uniform, and the precise regulation and control cannot be carried out. In addition, no report on the synthesis method of the (platinum nanometer inner core)/(cerium dioxide nanometer outer shell) yolk-eggshell structure with adjustable inner core is found at present.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and discloses a preparation method of a porous composite material with an adjustable yolk-eggshell structure and with a platinum nano inner core cerium dioxide nano shell particle size.
The technical scheme of the invention is as follows:
a preparation method of a porous composite material with a particle size adjustable yolk-eggshell structure and platinum nano inner core cerium dioxide nano shells comprises the following steps:
(1) mixing a non-ionic surfactant with a platinum precursor solution, adding a reducing agent, and reacting under the conditions of ultrasound and room temperature to obtain a nano platinum colloidal solution; the non-ionic surfactant is polyoxyethylene lauryl ether, polyoxyethylene stearate, polyethylene glycol cetyl ether or polyoxyethylene lauryl ether, the platinum precursor is chloroplatinic acid, potassium chloroplatinite or potassium chloroplatinate, and the reducing agent is sodium borohydride, ascorbic acid, glucose or sodium citrate;
(2) adding alkali liquor into the nano platinum colloidal solution to adjust the pH value to 8-14, then adding a pore-forming agent, then dropwise adding a cerium nitrate aqueous solution, reacting at room temperature, centrifuging to obtain nano particles, and then placing the nano particles in a muffle furnace to calcine at 673-1073K to obtain the yolk-eggshell structure porous composite material with the adjustable particle size; the pore-foaming agent is cetyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride or dodecyl trimethyl ammonium bromide.
In a preferred embodiment of the present invention, the concentration of the nonionic surfactant in the nano platinum colloid solution is 1 to 500 g/L.
In a preferred embodiment of the invention, the concentration of the platinum precursor in the nano platinum colloid solution is 0.1-100 mmol/L.
In a preferred embodiment of the present invention, the molar ratio of the platinum precursor to the reducing agent is 1:0.1 to 100.
In a preferred embodiment of the invention, the concentration of the pore-forming agent in the sum of the nano platinum colloid solution and the cerium nitrate aqueous solution is 0.1-100 mmol/L.
In a preferred embodiment of the invention, the molar ratio of the platinum nanoparticles in the nano platinum colloidal solution to the cerium nitrate in the cerium nitrate aqueous solution is 1: 0.01-100.
In a preferred embodiment of the present invention, the power of the ultrasound is 180 to 220W.
In a preferred embodiment of the present invention, the speed of the centrifugation is 2000 to 12000rpm, and the time is 10 to 15 min.
Further preferably, the alkali liquor is an ammonia water solution, a sodium hydroxide solution, a sodium carbonate solution, a sodium bicarbonate solution, a disodium hydrogen phosphate solution or a urea solution.
The invention has the beneficial effects that: the yolk-eggshell structure porous composite material with the adjustable particle size, which is prepared by the invention, takes platinum nano as an inner core and cerium dioxide nano as an outer shell, can accurately adjust the particle size according to the requirement, and has uniform size.
Drawings
FIG. 1 is a transmission electron microscope image of a yolk-eggshell structure of (platinum nano-core)/(cerium oxide nano-shell) obtained in example 1 of the present invention.
Fig. 2 is an element distribution diagram of a yolk-eggshell structure of (platinum nano-core)/(cerium oxide nano-shell) obtained in example 1 of the present invention.
FIG. 3 is a transmission electron microscope image of a yolk-eggshell structure of (platinum nano-core)/(cerium oxide nano-shell) obtained in example 2 of the present invention.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
Example 1:
the potassium chloroplatinite solution was mixed with the polyethylene glycol cetyl ether solution in a centrifuge tube, followed by the addition of ascorbic acid solution. The concentration of the potassium chloroplatinite is controlled to be 8mmol/L, meanwhile, the molar ratio of the potassium chloroplatinite to the ascorbic acid is 1: 13, and the concentration of the polyethylene glycol hexadecyl ether is 120 g/L. The reaction is carried out for 1h in a 200W ultrasonic cleaning machine. Under the condition, a reduction reaction is carried out, thereby preparing the nano platinum particles. Subsequently, a colloidal solution containing 10mg of platinum nanoparticles was taken, and an aqueous ammonia solution was added thereto to adjust the system pH to 10. Cetyl trimethylammonium bromide was added so that the concentration thereof was 10mmol/L, and then an aqueous solution of cerium nitrate was added dropwise so that the molar ratio of platinum nanoparticles to cerium nitrate was 1: 1. Mixing and reacting for 2 h. The product was centrifuged at 10000rpm for 10 min. Removing supernatant, and dispersing with water to obtain colloidal solution with yolk-eggshell structure (platinum nanometer core)/(cerium dioxide nanometer shell). The average size of the yolk-eggshell structure obtained in this example was 57nm, wherein the average size of the inner core was 23nm and the average size of the outer shell was 12nm, and fig. 1 is a transmission electron microscope picture of the yolk-eggshell structure of (platinum nano inner core)/(cerium oxide nano outer shell) prepared in this example. Fig. 2 is an element distribution diagram of a yolk-eggshell structure of (platinum nano-core)/(cerium oxide nano-shell) prepared in this example.
Example 2:
the chloroplatinic acid solution was mixed with the polyethylene glycol cetyl ether solution in a centrifuge tube, followed by the addition of the sodium citrate solution. The concentration of the chloroplatinic acid is controlled to be 32mmol/L, the molar ratio of the chloroplatinic acid to the sodium citrate is 1: 45, and the concentration of the polyethylene glycol hexadecyl ether is 15 g/L. The reaction is carried out for 1h in a 200W ultrasonic cleaning machine. Under the condition, a reduction reaction is carried out, thereby preparing the nano platinum particles. Subsequently, a colloidal solution containing 10mg of platinum nanoparticles was taken, and an aqueous sodium hydroxide solution was added thereto to adjust the system pH to 13. Tetradecyltrimethylammonium bromide was added so that the concentration thereof was 10mmol/L, and then an aqueous solution containing cerium nitrate was added dropwise so that the molar ratio of platinum nanoparticles to cerium nitrate was 1: 5. Mixing and reacting for 2 h. The product was centrifuged at 5000rpm for 10 min. Removing supernatant, and dispersing with water to obtain colloidal solution with yolk-eggshell structure (platinum nanometer core)/(cerium dioxide nanometer shell). The average size of the yolk-eggshell structure obtained in this example was 230nm, wherein the average size of the inner core was 126nm and the average size of the outer shell was 27nm, and fig. 3 is a transmission electron microscope picture of the yolk-eggshell structure of (platinum nano inner core)/(cerium oxide nano outer shell) prepared in this example.
Example 3:
the potassium chloroplatinate solution was mixed with the polyoxyethylene lauryl ether solution in a centrifuge tube, followed by the addition of ascorbic acid solution. The concentration of potassium chloroplatinate is controlled to be 1mmol/L, the molar ratio of the potassium chloroplatinate to ascorbic acid is 1: 45, and the concentration of polyoxyethylene lauryl ether is 80 g/L. The reaction is carried out for 1h in a 200W ultrasonic cleaning machine. Under the condition, a reduction reaction is carried out, thereby preparing the nano platinum particles. Subsequently, a colloidal solution containing 10mg of platinum nanoparticles was taken, and a sodium hydroxide solution was added thereto to adjust the system pH to 12. Cetyltrimethylammonium chloride was added so that the concentration thereof was 50mmol/L, followed by dropwise addition of an aqueous solution containing cerium nitrate so that the molar ratio of platinum nanoparticles to cerium nitrate was 1: 20. Mixing and reacting for 2 h. The product was centrifuged at 11000rpm for 10 min. Removing supernatant, and dispersing with water to obtain colloidal solution with yolk-eggshell structure (platinum nanometer core)/(cerium dioxide nanometer shell). The average size of the yolk-eggshell structure obtained in this example was 40nm, with an average size of the inner core of 15nm and an average size of the outer shell of 7 nm.
Example 4:
mixing the potassium chloroplatinate solution and the polyoxyethylene lauryl ether solution in a centrifuge tube, and then adding the glucose solution. The concentration of the potassium chloroplatinate is controlled to be 1mmol/L, the molar ratio of the potassium chloroplatinate to the glucose is 1: 90, and the concentration of the polyoxyethylene lauryl ether is 300 g/L. The reaction is carried out for 1h in a 200W ultrasonic cleaning machine. Under the condition, a reduction reaction is carried out, thereby preparing the nano platinum particles. Subsequently, a colloidal solution containing 10mg of platinum nanoparticles was taken, and a sodium carbonate solution was added thereto to adjust the system pH to 9. Dodecyltrimethylammonium bromide was added so that the concentration thereof was 1mmol/L, and then an aqueous solution containing cerium nitrate was added dropwise so that the molar ratio of platinum nanoparticles to cerium nitrate was 1: 20. Mixing and reacting for 2 h. The product was centrifuged at 13000rpm for 10 min. Removing supernatant, and dispersing with water to obtain colloidal solution with yolk-eggshell structure (platinum nanometer core)/(cerium dioxide nanometer shell). The average size of the yolk-eggshell structure obtained in this example was 20nm, with an average size of the inner core of 7nm and an average size of the outer shell of 5 nm.
Example 5:
the chloroplatinic acid solution was mixed with the polyoxyethylene lauryl ether solution in a centrifuge tube, followed by the addition of sodium borohydride solution. The concentration of potassium chloroplatinate is controlled to be 50mmol/L, the molar ratio of chloroplatinic acid to sodium borohydride is 1: 90, and the concentration of polyoxyethylene lauryl ether is 200 g/L. The reaction is carried out for 1h in a 200W ultrasonic cleaning machine. Under the condition, a reduction reaction is carried out, thereby preparing the nano platinum particles. Subsequently, a colloidal solution containing 10mg of platinum nanoparticles was taken, and a sodium hydroxide solution was added thereto to adjust the system pH to 13. Dodecyltrimethylammonium bromide was added so that the concentration thereof was 50mmol/L, and then an aqueous solution containing cerium nitrate was added dropwise so that the molar ratio of platinum nanoparticles to cerium nitrate was 1: 2. Mixing and reacting for 2 h. The product was centrifuged at 7000rpm for 10 min. Removing supernatant, and dispersing with water to obtain colloidal solution with yolk-eggshell structure (platinum nanometer core)/(cerium dioxide nanometer shell). The average size of the yolk-eggshell structure obtained in this example was 103nm, with an average size of the inner core of 55nm and an average size of the outer shell of 15 nm.
Example 6:
the potassium chloroplatinate solution was mixed with the polyoxyethylene stearate solution in a centrifuge tube, followed by the addition of ascorbic acid solution. The concentration of the potassium chloroplatinate is controlled to be 80mmol/L, meanwhile, the molar ratio of the potassium chloroplatinate to the ascorbic acid is 1: 90, and the concentration of the polyoxyethylene stearate is 6 g/L. The reaction is carried out for 1h in a 200W ultrasonic cleaning machine. Under the condition, a reduction reaction is carried out, thereby preparing the nano platinum particles. Subsequently, a colloidal solution containing 10mg of platinum nanoparticles was taken, and a sodium hydrogencarbonate solution was added thereto to adjust the system pH to 8. Hexadecyltrimethylammonium bromide was added so that the concentration thereof was 80mmol/L, and then an aqueous solution containing cerium nitrate was added dropwise so that the molar ratio of platinum nanoparticles to cerium nitrate was 1: 0.05. Mixing and reacting for 2 h. The product was centrifuged at 2000rpm for 10 min. Removing supernatant, and dispersing with water to obtain colloidal solution with yolk-eggshell structure (platinum nanometer core)/(cerium dioxide nanometer shell). The average size of the yolk-eggshell structure obtained in this example was 420nm, with an average size of the inner core of 206nm and an average size of the outer shell of 33 nm.
It is obvious to those skilled in the art that the technical solutions of the present invention can still obtain the same or similar technical effects as the above embodiments within the following ranges, and still fall into the protection scope of the present invention:
a preparation method of a porous composite material with a particle size adjustable yolk-eggshell structure and platinum nano inner core cerium dioxide nano shells comprises the following steps:
(1) mixing a non-ionic surfactant with a platinum precursor solution, adding a reducing agent, and reacting under the conditions of ultrasound and room temperature to obtain a nano platinum colloidal solution; the non-ionic surfactant is polyoxyethylene lauryl ether, polyoxyethylene stearate, polyethylene glycol cetyl ether or polyoxyethylene lauryl ether, the platinum precursor is chloroplatinic acid, potassium chloroplatinite or potassium chloroplatinate, and the reducing agent is sodium borohydride, ascorbic acid, glucose or sodium citrate;
(2) adding alkali liquor into the nano platinum colloidal solution to adjust the pH value to 8-14, then adding a pore-forming agent, then dropwise adding a cerium nitrate aqueous solution, reacting at room temperature, centrifuging to obtain nano particles, and then placing the nano particles in a muffle furnace to calcine at 673-1073K to obtain the yolk-eggshell structure porous composite material with the adjustable particle size; the pore-foaming agent is cetyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride or dodecyl trimethyl ammonium bromide.
The concentration of the nonionic surfactant in the nano platinum colloidal solution is 1-500 g/L. The concentration of the platinum precursor in the nano platinum colloidal solution is 0.1-100 mmol/L. The molar ratio of the platinum precursor to the reducing agent is 1: 0.1-100. The concentration of the pore-foaming agent in the total sum of the nano platinum colloid solution and the cerium nitrate aqueous solution is 0.1-100 mmol/L. The molar ratio of the platinum nanoparticles in the nano platinum colloidal solution to the cerium nitrate in the cerium nitrate aqueous solution is 1: 0.01-100. The alkali liquor is ammonia water solution, sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, disodium hydrogen phosphate solution or urea solution.
The power of the ultrasonic is 180-220W, the speed of the centrifugation is 2000-12000 rpm, and the time is 10-15 min.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.

Claims (6)

1. A preparation method of a porous composite material with a particle size adjustable yolk-eggshell structure and platinum nano inner core cerium dioxide nano shells is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing a non-ionic surfactant with a platinum precursor solution, adding a reducing agent, and reacting under the conditions of ultrasound and room temperature to obtain a nano platinum colloidal solution; the non-ionic surfactant is polyoxyethylene lauryl ether, polyoxyethylene stearate, polyethylene glycol cetyl ether or polyoxyethylene lauryl ether, the platinum precursor is chloroplatinic acid, potassium chloroplatinite or potassium chloroplatinate, and the reducing agent is sodium borohydride, ascorbic acid, glucose or sodium citrate; the concentration of the nonionic surfactant in the nano platinum colloidal solution is 1-500 g/L;
(2) adding alkali liquor into the nano platinum colloidal solution to adjust the pH value to 8-14, then adding a pore-forming agent, then dropwise adding a cerium nitrate aqueous solution, reacting at room temperature, centrifuging to obtain nano particles, and then placing the nano particles in a muffle furnace to calcine at 673-1073K to obtain the yolk-eggshell structure porous composite material with the adjustable particle size; the pore-foaming agent is cetyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride or dodecyl trimethyl ammonium bromide.
2. The method of claim 1, wherein: the concentration of the platinum precursor in the nano platinum colloidal solution is 0.1-100 mmol/L.
3. The method of claim 1, wherein: the molar ratio of the platinum precursor to the reducing agent is 1: 0.1-100.
4. The method of claim 1, wherein: the concentration of the pore-foaming agent in the total sum of the nano platinum colloid solution and the cerium nitrate aqueous solution is 0.1-100 mmol/L.
5. The method of claim 1, wherein: the molar ratio of the platinum nanoparticles in the nano platinum colloidal solution to the cerium nitrate in the cerium nitrate aqueous solution is 1: 0.01-100.
6. The production method according to any one of claims 1 to 5, characterized in that: the alkali liquor is ammonia water solution, sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, disodium hydrogen phosphate solution or urea solution.
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