CN110576191B

CN110576191B - Method for preparing copper-nickel alloy nano material with bevel bipyramid morphology characteristics in hydrophobic phase

Info

Publication number: CN110576191B
Application number: CN201910993325.7A
Authority: CN
Inventors: 郑逸群; 侯士峰
Original assignee: Jining University
Current assignee: Jining University
Priority date: 2019-10-18
Filing date: 2019-10-18
Publication date: 2022-04-26
Anticipated expiration: 2039-10-18
Also published as: CN110576191A

Abstract

The invention belongs to the technical field of alloy nano materials, and particularly relates to a method for preparing a copper-nickel alloy nano material with a bevel bipyramid shape characteristic in a hydrophobic phase. The preparation method realizes the preparation of the copper-nickel alloy nano material with the single twin bevel bipyramid with special appearance in the hydrophobic phase for the first time, and expands the limitation of the appearance of the material; the method has the advantages of simple process and easily obtained raw materials, only needs to mix the organic solvent, the copper-nickel precursor and the complexing agent, and can carry out heating reaction without reaction means such as oscillation, ultrasound and the like.

Description

Method for preparing copper-nickel alloy nano material with bevel bipyramid morphology characteristics in hydrophobic phase

Technical Field

The invention belongs to the technical field of alloy nano materials, and particularly relates to a method for preparing a copper-nickel alloy nano material with a bevel bipyramid shape characteristic in a hydrophobic phase.

Background

Alloy nano materials have been receiving much attention among various metal nano materials. Because the single alloy nano material contains two or more metals and can play a synergistic role, the nano material has important application in the fields of catalysis, environmental science, biomedicine, energy, information technology, military equipment, aerospace and the like. The copper-nickel nano alloy is one of important conductive metal materials, is widely applied to various fields such as electricity, magnetism, catalysis and the like, has good catalytic performance (synthesis of carbon nano tube loaded nano copper-nickel alloy, Wangshanmin, Heilongjiang university, Master [ D ],2013), and is always the research focus on the preparation method of the copper-nickel nano alloy.

CN200810209721.8 discloses a method for preparing a nano copper-nickel alloy by a liquid phase method, which comprises the steps of reducing divalent copper and nickel salt in an alkaline environment by using propylene glycol as a reducing agent to synthesize copper-nickel alloy nano crystal particles by using 1, 2-propylene glycol as a solvent, and dropwise adding NaOH solution during reaction to prepare the nano copper-nickel alloy, wherein the reaction needs to be carried out in a hydrophilic phase, the surface groups need to be replaced during the reaction in the hydrophilic phase, the steps are complex, and agglomeration is easy to occur during the replacement process;

CN201410153158.2 discloses an ultralong copper-nickel alloy nanowire and a preparation method thereof, namely, a cationic surfactant is dissolved in an organic reducing agent; b) adding copper salt as a copper source into the organic reducing agent obtained in the step a), adding noble metal nano particles as a catalyst, and reacting at a first specified temperature; c) adding nickel salt into the reducing agent reacted in the step b) as a nickel source, reacting at a second specified temperature, cleaning and drying the obtained product to obtain the copper-nickel alloy nanowire.

Disclosure of Invention

Aiming at the technical problems, the invention aims to provide a method for preparing a copper-nickel alloy nano material with the appearance characteristics of a chamfered double cone in a hydrophobic phase.

The method for preparing the copper-nickel alloy nano material with the appearance characteristics of the bevel bipyramid in the hydrophobic phase comprises the steps of mixing copper salt, nickel salt, a complexing agent and an organic solvent to obtain a mixed solution, heating the mixed solution, carrying out heat preservation reaction, cooling to room temperature after reaction to obtain a reaction solution, and washing the reaction solution to obtain a finished product.

The copper salt is one of cupric chloride, cupric sulfate, cupric nitrate, cupric bromide, cupric hydroxide and copper acetylacetonate.

The nickel salt is one of nickel chloride, nickel sulfate, nickel nitrate, nickel bromide, nickel hydroxide and nickel acetylacetonate.

The organic solvent is one or more of oleylamine, oleic acid, octadecene and hexadecylamine;

preferably, the organic solvent is oleylamine, the oleylamine is low in price, is liquid at normal temperature, does not need to be heated in shape, is low in viscosity, has certain reducibility while being used as the solvent, and can be coordinated with metal to protect and disperse the metal nano material.

The complexing agent is one of triphenylphosphine, trioctylphosphine and tri-n-octylphosphine oxide;

preferably, the complexing agent is tri-n-octylphosphine oxide, the molecular structure of the tri-n-octylphosphine oxide is provided with a plurality of linear alkyl chains, the metal nano material can be effectively dispersed, the oxygen-containing group is easily coordinated/complexed with the metal surface, and the stability of the metal nano material in a reaction system is improved.

The mass ratio of the organic solvent to the copper salt is 200: 1-20: 1.

The molar ratio of the copper salt to the complexing agent is 1: 100-1: 0.01.

The temperature of the heat preservation reaction is 150-200 ℃, and the heat preservation time is 0.5-3 h.

According to the invention, through accurate regulation and control of kinetic and thermodynamic parameters, in a nucleation stage, a copper-nickel precursor is reduced to form a seed with a single twin crystal structure, atoms at twin crystal faces are arranged in a mirror surface mode, and subsequent copper-nickel atoms are symmetrically deposited according to the mode to form a biconical structure, and meanwhile, all crystal faces of a product are {100} faces due to the coating effect of complexing agent amino groups and other groups on the {100} faces to form a chamfered biconical structure.

The method is carried out in a hydrophobic phase, the hydrophobic phase is influenced by a reaction solvent compared with a hydrophilic phase, the reaction can be carried out at the temperature higher than 100 ℃, the alloying temperature point generally requires higher than 100 ℃, and therefore the method can be prepared by a one-step method, and the product in the hydrophilic phase can obtain a good alloying effect only through subsequent annealing treatment.

Compared with the prior art, the method has the following beneficial effects.

(1) The preparation method realizes the preparation of the copper-nickel alloy nano material with the single twin bevel bipyramid with special appearance in the hydrophobic phase for the first time, and expands the limitation of the appearance of the material;

(2) the method has simple process and easily obtained raw materials, only needs to mix the organic solvent, the copper-nickel precursor and the complexing agent, and can carry out heating reaction without reaction means such as oscillation, ultrasound and the like;

(3) the single-twin-crystal-cutting-angle bipyramid copper-nickel alloy nano material with the special morphology can be used as a catalyst, compared with other morphologies, the exposed crystal face of the morphology is a 100 crystal face, the surface energy is high, meanwhile, each particle also comprises a twin crystal face, the coordination number of atoms at the position is low, the catalytic reaction activity is high, and the single-twin-crystal-cutting-angle bipyramid copper-nickel alloy nano material can be used as a catalyst for coupling reaction and redox reaction.

Drawings

FIG. 1 is a Scanning Electron Microscope (SEM) image of a Cu-Ni alloy nanomaterial with a chamfered bipyramid morphology prepared in example 1;

FIG. 2 is an X-ray diffraction pattern of the Cu-Ni alloy nanomaterial with chamfered bipyramid morphology prepared in the example.

Detailed Description

The invention is described in detail below with reference to specific embodiments and the attached drawings.

Example 1

Mixing and stirring 1mmol of copper acetylacetonate, 1mmol of nickel acetylacetonate, 0.1mmol of tri-n-octylphosphine oxide and 50mL of oleylamine, preserving the temperature of the mixture at 170 ℃ for 1h, cooling to room temperature, and washing reaction liquid to obtain a product of the copper-nickel alloy nano material with the bevel bipyramid morphology feature.

Referring to fig. 1, the copper-nickel alloy nanomaterial prepared in this example has a truncated-angle biconical morphology, that is, an upper vertex and a lower vertex are cut on the basis of a triangular biconical structure. The vertex angle of each triangular surface of the cone is 90 degrees;

as shown in FIG. 2, the characteristic diffraction peaks in the X-ray diffraction pattern of the product obtained in this example were located between the corresponding characteristic diffraction peaks of Cu and Ni, which confirmed the Cu-Ni alloying characteristics of the product

Example 2

Mixing and stirring 1mmol of copper chloride, 1mmol of nickel acetylacetonate, 0.1mmol of trioctylphosphine and 30mL of oleylamine, preserving the temperature of the mixture at 200 ℃ for 1h, cooling to room temperature, and washing reaction liquid to obtain a product of the copper-nickel alloy nano material with the appearance characteristic of the bevel bipyramid.

Example 3

Mixing and stirring 10mmol of copper sulfate, 1mmol of nickel acetylacetonate, 0.1mmol of trioctylphosphine and 40mL of oleylamine, preserving the temperature of the mixture at 150 ℃ for 1.5h, cooling to room temperature, and washing reaction liquid to obtain a product of the copper-nickel alloy nano material with the appearance characteristic of the bevel bipyramid.

Example 4

1mmol of copper acetylacetonate, 1mmol of nickel chloride, 0.1mmol of tri-n-octylphosphine oxide and 65mL of oleylamine are mixed and stirred, the mixture is kept at 170 ℃ for 0.5h, and is cooled to room temperature, and reaction liquid is washed to obtain a product of the copper-nickel alloy nano material with the appearance characteristic of the bevel bipyramid.

Example 5

Mixing and stirring 1mmol of copper acetylacetonate, 1mmol of nickel sulfate, 0.1mmol of trioctylphosphine and 50mL of oleylamine, preserving the temperature of the mixture at 200 ℃ for 1h, cooling to room temperature, and washing reaction liquid to obtain a product of the copper-nickel alloy nano material with the appearance characteristic of the bevel bipyramid.

Example 6

1mmol of copper bromide, 1mmol of nickel acetylacetonate, 0.1mmol of tri-n-octylphosphine oxide and 27mL of oleylamine are mixed and stirred, the mixture is kept at 170 ℃ for 3h, and is cooled to room temperature, and reaction liquid is washed to obtain a product of the copper-nickel alloy nano material with the appearance characteristic of the bevel bipyramid.

Example 7

Mixing and stirring 1mmol of copper acetylacetonate, 1mmol of nickel acetylacetonate, 10mmol of triphenylphosphine and 65mL of oleylamine, preserving the temperature of the mixture at 160 ℃ for 2h, cooling to room temperature, and washing reaction liquid to obtain a product of the copper-nickel alloy nano material with the appearance characteristic of the chamfered bipyramid.

Example 8

Mixing and stirring 1mmol of copper acetylacetonate, 1mmol of nickel acetylacetonate, 0.1mmol of tri-n-octylphosphine oxide and 50mL of oleic acid, preserving the temperature of the mixture at 170 ℃ for 1h, cooling to room temperature, and washing reaction liquid to obtain a product of the copper-nickel alloy nano material with the bevel bipyramid morphology feature.

Example 9

Mixing and stirring 1mmol of copper acetylacetonate, 1mmol of nickel acetylacetonate, 0.1mmol of tri-n-octylphosphine oxide and 50mL of octadecene, preserving the temperature of the mixture at 170 ℃ for 1h, cooling to room temperature, and washing reaction liquid to obtain a product of the copper-nickel alloy nano material with the bevel bipyramid morphology feature.

Example 10

Mixing and stirring 1mmol of copper acetylacetonate, 1.5mmol of nickel acetylacetonate, 0.1mmol of tri-n-octylphosphine oxide and 50mL of oleylamine, preserving the temperature of the mixture at 150 ℃ for 1h, cooling to room temperature, and washing reaction liquid to obtain a product of the copper-nickel alloy nano material with the appearance characteristic of the bevel bipyramid.

Claims

1. A method for preparing a copper-nickel alloy nano material with the appearance characteristics of a chamfered bipyramid in a hydrophobic phase is characterized by comprising the following steps of: mixing copper salt, nickel salt, a complexing agent and an organic solvent to obtain a mixed solution, heating the mixed solution, keeping the temperature for reaction, cooling to room temperature after reaction to obtain a reaction solution, and washing the reaction solution to obtain a finished product; the organic solvent is one or more of oleylamine, oleic acid, octadecene and hexadecylamine; the complexing agent is one of triphenylphosphine, trioctylphosphine and tri-n-octylphosphine oxide; the temperature of the heat preservation reaction is 150 ℃, and the heat preservation time is 0.5-3 h.

2. The method for preparing the copper-nickel alloy nano material with the chamfered biconical morphology in the hydrophobic phase according to claim 1, wherein the method comprises the following steps: the copper salt is one of cupric chloride, cupric sulfate, cupric nitrate, cupric bromide, cupric hydroxide and copper acetylacetonate.

3. The method for preparing the copper-nickel alloy nano material with the chamfered biconical morphology in the hydrophobic phase according to claim 1 or 2, wherein the method comprises the following steps: the molar ratio of the copper salt to the complexing agent is 0.01-100: 1.

4. the method for preparing the copper-nickel alloy nano material with the chamfered biconical morphology in the hydrophobic phase according to claim 1, wherein the method comprises the following steps: the nickel salt is one of nickel chloride, nickel sulfate, nickel nitrate, nickel bromide, nickel hydroxide and nickel acetylacetonate.

5. The method for preparing the copper-nickel alloy nano material with the chamfered biconical morphology in the hydrophobic phase according to claim 1, wherein the method comprises the following steps: the mass ratio of the organic solvent to the copper salt is 200-20: 1.

6. the method for preparing the copper-nickel alloy nano material with the chamfered biconical morphology in the hydrophobic phase according to claim 1, wherein the method comprises the following steps: the organic solvent is oleylamine.

7. The method for preparing the copper-nickel alloy nano material with the chamfered biconical morphology in the hydrophobic phase according to claim 1, wherein the method comprises the following steps: the complexing agent is tri-n-octyl phosphine oxide.