CN110625125A - Method for preparing liquid metal nanoparticles by using amino acid as ligand - Google Patents

Method for preparing liquid metal nanoparticles by using amino acid as ligand Download PDF

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Publication number
CN110625125A
CN110625125A CN201910910002.7A CN201910910002A CN110625125A CN 110625125 A CN110625125 A CN 110625125A CN 201910910002 A CN201910910002 A CN 201910910002A CN 110625125 A CN110625125 A CN 110625125A
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liquid metal
amino acid
metal nanoparticles
preparing liquid
ligand
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CN110625125B (en
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常广涛
徐兵兵
李若欣
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Suzhou University
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Suzhou University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • 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

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  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

The invention discloses a method for preparing liquid metal nanoparticles by using amino acid as a ligand, which comprises the following steps: (1) dissolving amino acid in deionized water to obtain a clear amino acid aqueous solution; (2) adjusting the pH value of the amino acid aqueous solution to 2-10; (3) and (3) dropwise adding liquid metal and zirconium beads into the solution after the pH is adjusted, and vibrating and grinding to prepare the liquid metal nanoparticles with the particle size of 100-5000 nm. The invention also provides the liquid metal nanoparticles prepared by the method. The method for preparing the liquid metal nano-particles by using the amino acid as the ligand solves the problems of low production scale and efficiency, large particle size and poor biocompatibility of the existing liquid metal nano-particles.

Description

Method for preparing liquid metal nanoparticles by using amino acid as ligand
Technical Field
The invention relates to the technical field of liquid metal nanoparticles, in particular to a method for preparing liquid metal nanoparticles by using amino acid as a ligand.
Background
The liquid metal has the advantages of high flexibility, deformability, lower cytotoxicity, easy surface modification, low melting point, convenient operation and processing, obvious infrared ray absorption and temperature rise, degradability in a weakly acidic environment and the like, and the liquid metal-based biomaterial receives more and more attention.
However, the liquid metal has a higher density and a higher surface tension, which is not favorable for dispersing into smaller nanoparticles. And the catalyst is quickly oxidized in water or air, and adjacent particles are easy to agglomerate to generate precipitates. Many researchers modify liquid metal nanoparticles with various surfactants, but most of the surfactants are various chemical substances and have certain biocompatibility problem. Meanwhile, the prior art mostly adopts an ultrasonic method, only can produce liquid metal nano particles in small batch, and has complex operation and larger particle size of the produced particles.
Disclosure of Invention
The invention aims to provide a method for preparing liquid metal nanoparticles by using amino acid as a ligand, and aims to solve the problems of low production scale and efficiency, large particle size and poor biocompatibility of the existing liquid metal nanoparticles.
In order to solve the above technical problems, the present invention provides a method for preparing liquid metal nanoparticles using amino acids as ligands, comprising the steps of:
(1) dissolving amino acid in deionized water to obtain a clear amino acid aqueous solution;
(2) adjusting the pH value of the amino acid aqueous solution to 2-10;
(3) and (3) dropwise adding liquid metal and zirconium beads into the solution after the pH is adjusted, and vibrating and grinding to prepare the liquid metal nanoparticles with the particle size of 100-5000 nm.
In the invention, the addition of the amino acid is equivalent to a dispersant, so that each small liquid metal particle can be effectively isolated, and the agglomeration and the precipitation of the small liquid metal particles are prevented.
Further, in the step (1), the amino acid is one or more of cysteine, phenylalanine, lysine, histidine, tryptophan, aspartic acid, leucine, glycine, alanine, valine, isoleucine, proline, serine, tyrosine, methionine, asparagine, glutamine, threonine, glutamic acid and arginine.
In the step (1), the mass ratio of the amino acid to the deionized water is (0.1-10): 100, preferably 1: 100.
Further, in the step (3), the liquid metal is one or more of gallium, gallium-indium alloy and gallium-indium-tin alloy. The gallium, the gallium indium alloy or the gallium indium tin alloy can be selected from all products sold in the market, and the gallium indium alloy and the gallium indium tin alloy can also be prepared according to the alloy preparation method recorded in the prior art. Preferably the liquid metal is a gallium indium alloy, more preferably Ga60In40、Ga70In30、Ga75In25、Ga75.5In24.5、Ga80In20。
Further, in the step (3), the mass ratio of the liquid metal to the deionized water is (0.1-10): 100, preferably 1: 100.
Further, in the step (3), the diameter of the zirconium beads is one or more of 0.1-0.2 mm, 0.3-0.4 mm, 0.5-0.6 mm and 0.8-1 mm.
Further, in the step (3), the mass ratio of the addition amount of the zirconium beads to the mixed solution is 10: (0.1-10).
Further, in the step (3), an oscillator is adopted for oscillation, and the oscillation grinding time is 1-20 hours.
In another aspect of the invention, liquid metal nanoparticles prepared by the method are provided.
The invention has the beneficial effects that:
1. the invention provides a method for efficiently and conveniently preparing liquid metal nanoparticles by using amino acid as a ligand, which solves the problems of low production scale and efficiency, large particle size and poor biocompatibility of the existing liquid metal nanoparticles. Because different pH has greater influence on the dispersion effect of the liquid metal nanoparticles, the proportion of amino acid, liquid metal and solvent, different pH, grinding time and the like can be flexibly adjusted, so that the liquid metal nanoparticles with different concentrations and particle sizes can be obtained.
2. The invention can realize simple and low-cost preparation of the liquid metal nanoparticles, and broadens the application of the liquid metal nanoparticles in the fields of bioengineering, drug delivery and release, flexible wearing, printed circuit, electronic product heat dissipation and the like.
Drawings
FIG. 1 is a photograph of liquid metal nanoparticle suspensions obtained at pH values of 3, 5, 7, and 9 for aqueous solutions of cysteine, phenylalanine, and lysine, respectively;
fig. 2 is a graph showing a particle size distribution of each of the liquid metal nanoparticles when the pH of the cysteine solution was 7, the pH of the phenylalanine solution was 3, and the pH of the lysine solution was 3.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Example 1
The embodiment provides a method for preparing liquid metal nanoparticles by using amino acid as a ligand, which specifically comprises the following steps:
(1) taking 100g of deionized water in a glass bottle, and taking 1g of cysteine to dissolve in the deionized water to obtain a transparent clear solution;
(2) the pH of the solution in (1) was adjusted to 7, and 1g of liquid metal (Ga) was added75In25)。
(3) And (3) adding 300g of zirconium beads with the diameter of 0.3-0.4 mm into the solution in the step (2), and oscillating in an oscillation grinding machine for 2 hours to obtain liquid metal nanoparticles with the particle size of 300 nm.
Example 2
The embodiment provides a method for preparing liquid metal nanoparticles by using amino acid as a ligand, which specifically comprises the following steps:
(1) taking 100g of deionized water in a glass bottle, and taking 1g of lysine to dissolve in the deionized water to obtain a transparent clear solution;
(2) the pH of the solution in (1) was adjusted to 3, and 1g of liquid metal (Ga) was added75In25)。
(3) And (3) adding 300g of zirconium beads with the diameter of 0.3-0.4 mm into the solution in the step (2), and oscillating in an oscillation grinding machine for 2 hours to obtain liquid metal nanoparticles with the particle size of 250 nm.
Example 3
The embodiment provides a method for preparing liquid metal nanoparticles by using amino acid as a ligand, which specifically comprises the following steps:
(1) taking 100g of deionized water in a glass bottle, taking 1g of phenylalanine to dissolve in the deionized water, and heating and stirring at 50 ℃ to obtain a transparent clear solution;
(2) the pH of the solution in (1) was adjusted to 3, and 1g of liquid metal (Ga) was added75In25)。
(3) And (3) adding 300g of zirconium beads with the diameter of 0.3-0.4 mm into the solution in the step (2), and oscillating in an oscillation grinding machine for 2 hours to obtain liquid metal nanoparticles with the particle size of 200 nm.
Example 4
This example differs from example 1 only in that the pH was adjusted to 6 in step (2) of example 1.
Example 5
This example differs from example 2 only in that the pH was adjusted to 2 in step (2) of example 2.
Example 6
This example differs from example 3 only in that the pH was adjusted to 2 in step (2) of example 3.
Example 7
This embodiment differs from embodiment 3 only in that the liquid metal in step (2) of embodiment 3 is replaced with Ga60In40。
Example 8
This embodiment differs from embodiment 3 only in that the liquid metal in step (2) of embodiment 3 is replaced with Ga70In30。
Example 9
This embodiment differs from embodiment 3 only in that the liquid metal in step (2) of embodiment 3 is replaced with Ga75.5In24.5。
Example 10
This embodiment differs from embodiment 3 only in that the liquid metal in step (2) of embodiment 3 is replaced with Ga80In20。
In conclusion, the invention provides a method for efficiently and conveniently preparing liquid metal nanoparticles by using amino acid, and solves the problems of low production scale and efficiency, large particle size and poor biocompatibility of the existing liquid metal nanoparticles. Different pH values have great influence on the dispersion effect of the liquid metal nanoparticles, and the proportion of amino acid, liquid metal and solvent, different pH values, grinding time and the like can be flexibly adjusted, so that the liquid metal nanoparticles with different concentrations and particle sizes can be obtained. The invention can realize simple and low-cost preparation of the liquid metal nanoparticles, and broadens the application of the liquid metal nanoparticles in the fields of bioengineering, drug delivery and release, flexible wearing, printed circuit, electronic product heat dissipation and the like.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.

Claims (10)

1. A method for preparing liquid metal nanoparticles using amino acids as ligands, comprising the steps of:
(1) dissolving amino acid in deionized water to obtain a clear amino acid aqueous solution;
(2) adjusting the pH value of the amino acid aqueous solution to 2-10;
(3) and (3) dropwise adding liquid metal and zirconium beads into the solution after the pH is adjusted, and vibrating and grinding to obtain the liquid metal nanoparticles with the particle size of 100-5000 nm.
2. The method for preparing liquid metal nanoparticles using an amino acid as a ligand according to claim 1, wherein in the step (1), the amino acid is one or more of cysteine, phenylalanine, lysine, histidine, tryptophan, aspartic acid, leucine, glycine, alanine, valine, isoleucine, proline, serine, tyrosine, methionine, asparagine, glutamine, threonine, glutamic acid and arginine.
3. The method for preparing liquid metal nanoparticles by using amino acid as a ligand according to claim 1, wherein in the step (1), the mass ratio of the amino acid to the deionized water is (0.1-10): 100.
4. The method for preparing liquid metal nanoparticles using amino acids as ligands according to claim 3, wherein the mass ratio of the amino acids to the deionized water in step (1) is 1: 100.
5. The method for preparing liquid metal nanoparticles by using amino acids as ligands according to claim 1, wherein in the step (3), the liquid metal is one or more of gallium, gallium-indium alloy and gallium-indium-tin alloy.
6. The method for preparing liquid metal nanoparticles by using amino acid as a ligand according to claim 1, wherein in the step (3), the mass ratio of the liquid metal to the deionized water is (0.1-10): 100.
7. the method for preparing liquid metal nanoparticles by using amino acid as a ligand according to claim 1, wherein in the step (3), the diameter of the zirconium beads is one or more of 0.1-0.2 mm, 0.3-0.4 mm, 0.5-0.6 mm and 0.8-1 mm.
8. The method for preparing liquid metal nanoparticles using amino acid as a ligand according to claim 1, wherein in the step (3), the mass ratio of the addition amount of the zirconium beads to the mixed solution is 10: (0.1-10).
9. The method for preparing liquid metal nanoparticles by using amino acid as a ligand according to claim 1, wherein in the step (3), the duration of the shaking and grinding is 1-20 h.
10. Liquid metal nanoparticles prepared according to the method of any one of claims 1-9.
CN201910910002.7A 2019-09-25 2019-09-25 Method for preparing liquid metal nanoparticles by using amino acid as ligand Active CN110625125B (en)

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CN113501860B (en) * 2020-03-24 2023-06-16 国家纳米科学中心 Assembled nano liquid metal particles and preparation method and application thereof

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