CN111349808B - AgCl/Ag composite material and preparation method thereof - Google Patents

AgCl/Ag composite material and preparation method thereof Download PDF

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CN111349808B
CN111349808B CN202010171337.4A CN202010171337A CN111349808B CN 111349808 B CN111349808 B CN 111349808B CN 202010171337 A CN202010171337 A CN 202010171337A CN 111349808 B CN111349808 B CN 111349808B
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agcl
composite material
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alloy
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CN111349808A (en
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赵远云
常春涛
赵成亮
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Dongguan University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C1/00—Making non-ferrous alloys
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1089—Alloys containing non-metals by partial reduction or decomposition of a solid metal compound

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Abstract

The invention relates to an AgCl/Ag composite material and a preparation method thereof, wherein the preparation method comprises the steps of firstly providing an amorphous initial alloy, then reacting the initial alloy with a hydrochloric acid solution under the auxiliary action of ultrasound to enable the initial alloy to be dissolved in the hydrochloric acid solution, enabling AgCl to form nuclei, grow and precipitate when the ultrasound is stopped, obtaining the AgCl material similar to a flower ball, decomposing part of the AgCl material through further irradiation treatment to obtain nano Ag particles, and thus obtaining the AgCl/Ag composite material similar to the flower ball. The preparation method disclosed by the invention is simple in process, and the obtained AgCl/Ag composite material has a high specific surface area, excellent photocatalysis and sterilization effects and good application prospects in the fields of sterilization, photocatalysis and the like.

Description

AgCl/Ag composite material and preparation method thereof
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to an AgCl/Ag composite material and a preparation method thereof.
Background
AgCl has a very wide application prospect as a novel photocatalytic material, and meanwhile, nano Ag has super-strong activity and permeability, and the bactericidal effect is hundreds of times of that of common block Ag. Therefore, the AgCl/Ag composite material obtained by compounding the two materials has the bactericidal performance of Ag and the photocatalytic performance of AgCl. However, the current preparation of the AgCl/Ag composite material usually takes raw materials such as polyvinylpyrrolidone, sodium chloride, silver nitrate and the like as precursors, and the method is complex.
Disclosure of Invention
In view of the above, it is necessary to provide an AgCl/Ag composite material and a method for preparing the same; the preparation method is simple, and the obtained AgCl/Ag composite material has good photocatalysis and sterilization effects.
A preparation method of an AgCl/Ag composite material comprises the following steps:
providing an amorphous starting alloy having a composition of CuaAgbCacMgdWherein a, b, c and d represent the atom percentage content of each element, and a is more than or equal to 15% and less than or equal to 25%, b is more than or equal to 15% and less than or equal to 25%, c is more than or equal to 35% and less than or equal to 45%, and a + b + c + d is 100%;
mixing the initial alloy with a hydrochloric acid solution, and reacting under the assistance of ultrasound to obtain an intermediate solution;
stopping ultrasound, enabling AgCl to nucleate and precipitate from the intermediate solution to obtain an AgCl material, and enabling the surface part of the AgCl material to be decomposed into Ag particles to obtain the AgCl/Ag composite material.
In one embodiment, the starting alloy is obtained by:
weighing metal raw materials according to the proportion and melting to obtain an alloy melt;
solidifying the alloy melt to obtain the initial alloy, wherein the solidification rate is 102K/s～107K/s, the thickness of the obtained initial alloy is 10 mu m-5 mm.
In one embodiment, the concentration of the hydrochloric acid solution is 4 mol/L-8 mol/L.
In one embodiment, the oscillation frequency of the ultrasonic wave is 5 kHz-100 kHz.
In one embodiment, the reaction temperature is 20-80 ℃, and the reaction time is 0.5-5 h.
In one embodiment, the AgCl material has a particle size of 1-100 μm.
In one embodiment, a method of partially decomposing the AgCl material into Ag particles includes: and irradiating the surface of the AgCl material by at least one of light and electron beams.
In one embodiment, the Ag particles have a size of 2nm to 200 nm.
The AgCl/Ag composite material is obtained by the preparation method, and comprises an AgCl carrier and Ag particles loaded on the AgCl carrier.
In one embodiment, the grain size of the AgCl material is 1-100 μm; the grain diameter of the Ag particles is 2 nm-200 nm.
In the preparation method of the invention, amorphous Cu is usedaAgbCacMgdMixing the initial alloy with hydrochloric acid solution, and reacting under the assistance of ultrasound to obtain CuaAgbCacMgdThe starting alloy was slowly dissolved in hydrochloric acid solution. It is worth mentioning that in general, Ag is insoluble in aqueous hydrochloric acid. However, the invention proves that under the action of ultrasonic wave, CuaAgbCacMgdThe silver in the amorphous alloy can be slowly dissolved in a hydrochloric acid aqueous solution with a certain concentration like other elements in the alloy. When the ultrasonic assistance is stopped, the balance is broken, and AgCl can nucleate, grow and separate out from the intermediate solution in a standing state. Meanwhile, the growth mode of the AgCl material has strong directionality, and micron-sized AgCl materials similar to 'flower balls' can be obtained. Then, part of the surface of the AgCl material is decomposed into nanoscale Ag particles, and the AgCl/Ag composite material formed by in-situ compounding of the nano Ag particles and the flower-ball-shaped AgCl material can be obtained.
Therefore, in the AgCl/Ag composite material, AgCl similar to a flower ball is used as a carrier, and Ag particles are compounded in situ, so that the AgCl/Ag composite material has a high specific surface area, is excellent in photocatalysis and sterilization effects, and has a good application prospect in the fields of sterilization, photocatalysis and the like.
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FIG. 1 is a scanning electron microscope photomicrograph of an AgCl material prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope photomicrograph of an AgCl material prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope photomicrograph of the AgCl/Ag composite material prepared in example 1 of the invention.
Detailed Description
The AgCl/Ag composite material and the preparation method thereof provided by the invention are further explained below.
The preparation method of the AgCl/Ag composite material provided by the invention comprises the following steps:
s1, providing an amorphous initial alloy, wherein the composition of the initial alloy is CuaAgbCacMgdWherein a, b, c and d represent the atom percentage content of each element, and a is more than or equal to 15% and less than or equal to 25%, b is more than or equal to 15% and less than or equal to 25%, c is more than or equal to 35% and less than or equal to 45%, and a + b + c + d is 100%;
s2, mixing the initial alloy with a hydrochloric acid solution, and reacting under the assistance of ultrasound to obtain an intermediate solution;
and S3, stopping ultrasound, nucleating and separating AgCl from the intermediate solution to obtain an AgCl material, and decomposing the surface part of the AgCl material into Ag particles to obtain the AgCl/Ag composite material.
In step S1, the initial alloy is obtained by:
weighing metal raw materials according to the proportion and melting to obtain an alloy melt;
solidifying the alloy melt to obtain the initial alloy, wherein the solidification rate is 102K/s～107K/s, the thickness of the obtained initial alloy is 10 mu m-5 mm.
In step S2, the oscillation frequency of the ultrasound is 5 KHz-100 KHz, the hydrochloric acid solution is a hydrochloric acid aqueous solution with the concentration of 4 mol/L-8 mol/L, the reaction temperature is 20 ℃ to 80 ℃, and the reaction time is 0.5 h-5 h.
Under the action of ultrasonic assistance, Ca, Mg and Cu in the initial alloy are dissolved in a hydrochloric acid solution in sequence, and meanwhile, Ag is slowly dissolved in the hydrochloric acid solution under the special condition. After 0.5-5 h, the initial alloy is completely dissolved to obtain a clear intermediate solution. The process is completely different from the traditional dealloying reaction which can directly obtain the nano-porous metal or the nano-metal oxide.
Therefore, in step S3, after the ultrasonic assistance is stopped, the chemical equilibrium in the intermediate solution is broken, and AgCl can form nuclei, grow and be precipitated from the intermediate solution in a standing state, and meanwhile, the growth mode of AgCl has strong directionality, and an AgCl material similar to a flower ball can be obtained, wherein the size of the AgCl material is 1-100 μm, and the specific surface area is large.
And then, when the AgCl material is irradiated by at least one of light and electron beams, the surface of the AgCl material is subjected to photolysis to generate Ag particles with a nano scale, so that the AgCl/Ag composite material formed by in-situ compounding of Ag and AgCl is obtained.
Specifically, the light includes sunlight, ultraviolet light, and the like, and the particle size of the Ag particles is 2nm to 200 nm.
Therefore, the invention also provides an AgCl/Ag composite material which is obtained by the preparation method and comprises an AgCl carrier and Ag particles loaded on the AgCl carrier.
Specifically, the size of the AgCl carrier is 1-100 μm, and the size of the Ag particles is 2-200 nm.
The invention takes AgCl similar to 'flower ball' as a carrier and is compounded with Ag particles in situ, so that the AgCl/Ag composite material has high specific surface area, excellent photocatalysis and sterilization effects and good application prospect in the fields of sterilization, photocatalysis and the like.
Hereinafter, the AgCl/Ag composite material and the method for preparing the same will be further described by the following specific examples.
Example 1
According to the formula Cu20Ag20Ca40Mg20(atomic percent) weighing raw materials, and vacuum induction melting to obtain Cu20Ag20Ca40Mg20The alloy melt of (1). The alloy melt is spun by a copper roller and is rapidly solidified by 106The rate of K/s was made to be Cu with a thickness of-20 μm20Ag20Ca40Mg20A thin ribbon of amorphous starting alloy.
0.1 g of Cu prepared as described above was added at room temperature20Ag20Ca40Mg20The amorphous initial alloy ribbon was immersed in 25mL of a 6mol/L hydrochloric acid aqueous solution, and subjected to ultrasonic treatment at a frequency of 40kHz while reacting. After reacting for 1.5h, the initial alloy was completely dissolved to obtain a yellowish clear intermediate solution.
Stopping ultrasound, standing the intermediate solution for 5min, and nucleating, growing and separating out the flower-ball-shaped AgCl particles with the particle size of 10-20 mu m from the intermediate solution. After separation, cleaning and drying, the AgCl particles with the shape of a flower ball as shown in figure 1 and figure 2 are obtained.
And exposing the 'flower-ball' -shaped AgCl particles to ultraviolet light for 5min to carry out photolysis on the surfaces of the 'flower-ball' -shaped AgCl particles to generate Ag particles with the particle size of 20-50 nm, thereby obtaining the 'flower-ball' -shaped AgCl/Ag composite material shown in figure 3.
Example 2
According to the formula Cu25Ag20Ca35Mg20(atomic percent) weighing raw materials, and vacuum induction melting to obtain Cu25Ag20Ca35Mg20The alloy melt of (1). The alloy melt is spun by a copper roller and is rapidly solidified by 105The rate of K/s is prepared into Cu with the thickness of 40 mu m25Ag20Ca35Mg20A thin ribbon of amorphous starting alloy.
0.1 g of Cu prepared as described above was added at room temperature25Ag20Ca35Mg20The amorphous initial alloy ribbon was immersed in 25mL of a 5mol/L hydrochloric acid aqueous solution, and subjected to ultrasonic treatment at a frequency of 40kHz while reacting. After reacting for 1.5h, the initial alloy was completely dissolved to obtain a yellowish clear intermediate solution.
Stopping ultrasound, standing the intermediate solution for 5min, and nucleating, growing and separating out the flower-ball-shaped AgCl particles with the particle size of 10-20 mu m from the intermediate solution. Separating, cleaning and drying to obtain the 'flower ball' -shaped AgCl particles with the particle size of 10-20 mu m.
Exposing the 'flower-ball' -shaped AgCl particles to sunlight for 10 hours to carry out photolysis on the surfaces of the 'flower-ball' -shaped AgCl particles to generate Ag particles with the particle size of 30-80 nm, thereby obtaining the 'flower-ball' -shaped AgCl/Ag composite material.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A preparation method of an AgCl/Ag composite material is characterized by comprising the following steps:
providing an amorphous starting alloy having a composition of CuaAgbCacMgdWherein a, b, c and d represent the atom percentage content of each element, and a is more than or equal to 15% and less than or equal to 25%, b is more than or equal to 15% and less than or equal to 25%, c is more than or equal to 35% and less than or equal to 45%, and a + b + c + d is 100%;
mixing the initial alloy with a hydrochloric acid solution, and reacting under the assistance of ultrasound to obtain an intermediate solution;
stopping ultrasound, enabling AgCl to nucleate and precipitate from the intermediate solution to obtain an AgCl material, and enabling the surface part of the AgCl material to be decomposed into Ag particles to obtain the AgCl/Ag composite material.
2. Method for the preparation of an AgCl/Ag composite according to claim 1, characterized in that the starting alloy is obtained by:
weighing metal raw materials according to the proportion and melting to obtain an alloy melt;
solidifying the alloy melt to obtain the initial alloy, wherein the solidification rate is 102K/s～107K/s, the thickness of the obtained initial alloy is 10 mu m-5 mm.
3. The method of preparing an AgCl/Ag composite according to claim 1, wherein the concentration of the hydrochloric acid solution is 4 to 8 mol/L.
4. The preparation method of the AgCl/Ag composite material according to claim 1, wherein the oscillation frequency of the ultrasound is 40 kHz-100 kHz.
5. The preparation method of AgCl/Ag composite material according to claim 1, wherein the reaction temperature is 20-80 ℃ and the reaction time is 0.5-5 h.
6. The method of preparing an AgCl/Ag composite material according to claim 1, wherein the grain size of the AgCl material is 1 μm to 100 μm.
7. The method of making an AgCl/Ag composite of claim 1 wherein the method of partially decomposing the AgCl material into Ag particles comprises: and irradiating the surface of the AgCl material by at least one of light and electron beams.
8. The method of preparing an AgCl/Ag composite material according to claim 1, wherein the Ag particles have a particle size of 2nm to 200 nm.
9. An AgCl/Ag composite material, which is obtained by the preparation method of any one of claims 1 to 8, and comprises an AgCl carrier and Ag particles loaded on the AgCl carrier.
10. The AgCl/Ag composite of claim 9 wherein the AgCl material has a particle size of 1 to 100 μ ι η; the size of the Ag particles is 2 nm-200 nm.
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JP2008302308A (en) * 2007-06-08 2008-12-18 Ebara Corp Photocatalyst and method for manufacturing thereof, method and apparatus for water treatment using thereof
CN102489321B (en) * 2011-12-28 2013-07-31 郑州大学 Preparation method of Ag/AgCl hybrid photocatalyst
CN103285894B (en) * 2013-05-23 2015-08-12 河北科技大学 Photochemical catalyst of a kind of organic matter halogenation and preparation method thereof
CN103623851A (en) * 2013-10-14 2014-03-12 陕西盛迈石油有限公司 Preparation method of Ag @ AgCl catalyst
CN104400001B (en) * 2014-11-14 2016-03-16 东北林业大学 A kind of method utilizing the mould extracellular fluid of hook-shaped wood to prepare Ag/AgCl nano composite material
CN108325542B (en) * 2018-02-02 2020-12-08 华北理工大学 Net-shaped Ag/Ag3PO4Synthetic method of/AgCl composite photocatalytic material

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