CN108975381B - Preparation method of monodisperse cuprous oxide nanospheres with uniform morphology - Google Patents

Preparation method of monodisperse cuprous oxide nanospheres with uniform morphology Download PDF

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CN108975381B
CN108975381B CN201810994064.6A CN201810994064A CN108975381B CN 108975381 B CN108975381 B CN 108975381B CN 201810994064 A CN201810994064 A CN 201810994064A CN 108975381 B CN108975381 B CN 108975381B
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cuprous oxide
monodisperse
cuso
oxide nanospheres
uniform
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CN108975381A (en
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程志鹏
褚效中
周翔
仲慧
殷竟洲
戴本林
赵伟
徐继明
张莉莉
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Hefei Longzhi Electromechanical Technology Co ltd
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Huaiyin Normal University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/02—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
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • 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

Abstract

The invention discloses a monodispersed uniform morphologyA preparation method of cuprous oxide nanospheres belongs to the field of nano material preparation. Adding a certain amount of copper source CuSO4Dissolving the cuprous oxide nanospheres and the alkali source NaF in deionized water to form a mixed solution, then adding a proper amount of reducing agent ascorbic acid, reacting for a period of time, centrifuging, washing and drying the product to obtain the monodisperse cuprous oxide nanospheres with uniform morphology. The synthesis method of the invention does not need to add strong base, organic alkaline solvent and any surfactant, does not need a high-temperature reaction kettle, has the characteristics of low cost, simplicity, easy operation and the like, and the prepared cuprous oxide nanospheres have uniform appearance and good dispersibility.

Description

Preparation method of monodisperse cuprous oxide nanospheres with uniform morphology
Technical Field
The invention relates to the field of nano material preparation, in particular to a method for reducing CuSO by using ascorbic acid and using NaF as an alkali source4The method for obtaining the cuprous oxide nanospheres with monodispersed uniform shapes.
Background
Cuprous oxide is an important p-type transition metal oxide, and shows excellent physical and chemical properties in the fields of catalysis, gas sensitivity, electricity and the like, so the cuprous oxide is widely applied to important fields of photocatalysts, gas-sensitive sensing elements, solar cells and the like.
The application performance of the cuprous oxide is closely related to the shape and the structure of the cuprous oxide. The cuprous oxide nanospheres with uniform shapes are paid much attention by researchers due to better shape integrity and higher performance repeatability. The preparation of cuprous oxide nanospheres with uniform morphology becomes a hot point of research in recent years. For example, the method comprises the steps of slowly dripping a sodium hydroxide solution into a copper sulfate solution containing histidine polypeptide by using Wang Queen (CN 105692679B), standing for reaction, adding an ascorbic acid solution, and obtaining cuprous oxide nanoparticles after the reaction is finished. The Zhaoweije (CN 105621473B) is prepared by using copper salt, strong base and a reducing agent as raw materials, adding the strong base solution and the reducing agent solution into the copper salt solution in sequence, controlling the molar ratio of copper ions, hydroxyl ions and the reducing agent, the adding rate of the hydroxyl ions and the adding rate of the reducing agent, and obtaining the nano cuprous oxide with uniform particle size and regular shape. What is (CN 104591256B) discloses a method for preparing cuprous oxide in a copper chloride system, which comprises the steps of firstly adjusting the concentration and the pH value of a copper chloride solution, then preparing a sulfite and chloride mixed solution with a certain concentration, preheating the copper chloride solution and a mixed solution, then slowly adding the mixed solution into the copper chloride solution for reaction, dropwise adding alkali liquor to control the pH value of the reaction solution, and obtaining cuprous oxide powder after the reaction. Wuling (CN 104477969A) adopts copper acetate as a raw material, N-N dimethylformamide as a solvent, polyvinylpyrrolidone as a dispersing agent and sodium borohydride as a reducing agent, and the reaction temperature is regulated and controlled to prepare the sphere-like cuprous oxide nano-particles.
It can be seen that, in the prior art, reports have been made on the preparation of monodisperse cuprous oxide nanospheres with uniform morphology, but the alkali source added in the reports is mostly strong alkali or high-temperature-dependent organic alkaline solvent, and a certain amount of surfactant needs to be added.
Disclosure of Invention
The invention aims to: aiming at the technical current situation of the monodisperse cuprous oxide nanospheres with uniform morphology, the preparation method of the monodisperse cuprous oxide nanospheres with uniform morphology is provided, and has the advantages of simple method, easy operation, low production cost, no need of adding strong base, organic alkaline solvent and surfactant, and no need of a high-temperature reaction kettle.
The technical solution of the invention is as follows: NaF is used as an alkali source, and CuSO is reduced by ascorbic acid4The method obtains the monodisperse cuprous oxide nanospheres with uniform shapes.
The preparation method of the monodisperse cuprous oxide nanospheres with uniform morphology comprises the following specific steps:
(1) preparing CuSO with a certain concentration at room temperature4An aqueous solution; according to the preset NaF, ascorbic acid and CuSO4To CuSO in a molar ratio of4Adding NaF and ascorbic acid into the aqueous solution, and stirring to obtain a clear mixed solution, wherein the stirring speed is set to be 300 revolutions per minute;
(2) and heating the mixed solution to a certain reaction temperature, keeping the reaction temperature for a period of time, and centrifuging, washing and drying the obtained product to obtain the monodisperse cuprous oxide nanospheres with uniform shapes.
Wherein, in the step (1), the CuSO4The concentration of the aqueous solution is 0.005-0.015 mol/L.
Wherein, in the step (1), the preset NaF, ascorbic acid and CuSO4The molar ratio of (3-6) to (2.5: 1).
Wherein in the step (2), the reaction temperature is 30-70 ℃.
Wherein in the step (2), the reaction time is 0.5-2 h.
The principle of the invention is as follows: NaF, ascorbic acid and CuSO at room temperature4After the solution is mixed, the ascorbic acid does not contain CuSO due to the lack of alkalinity in the system4The capacity of reducing the cuprous oxide into cuprous oxide, so that a clear mixed solution is formed after the cuprous oxide, the cuprous oxide and the cuprous oxide are mixed; under the heating condition, F in NaF is increased along with the increase of the reaction temperature-Slow hydrolysis to form OH-Gradually increasing the alkalinity of the mixed solution, and forming initial cuprous oxide crystal nuclei which are reduced in the solution when the alkalinity exceeds a certain critical value; due to the slow hydrolysis rate of NaF, OH formed by subsequent hydrolysis-With CuSO4After the combination, the reduced cuprous oxide atoms are deposited on the surface of the initial cuprous oxide crystal nucleus; with the prolonging of the reaction time, the initial cuprous oxide crystal nucleus grows up gradually, and finally the monodisperse cuprous oxide nanospheres with uniform morphology are formed.
The invention has the beneficial effects that:
1. the cuprous oxide nanospheres with the monodisperse and uniform appearance are obtained in one step by using NaF as an alkali source and adopting a simple ascorbic acid reduction process, the particle size is uniform and is about 800 nm, and the product has high purity and good dispersibility.
2. The synthesis method simplifies production conditions, does not need to add strong alkali, organic alkaline solvent and any surfactant, does not need a high-temperature reaction kettle, has low production cost and easy operation, and realizes the large-scale industrial production of the monodisperse cuprous oxide nanospheres with uniform morphology.
Drawings
FIG. 1 is a scanning electron microscope picture of monodisperse cuprous oxide nanospheres with uniform morphology.
Detailed Description
The technical solution of the present invention is further illustrated below with reference to examples, but it should not be construed as being limited thereto.
Example 1: the monodisperse cuprous oxide nanospheres with uniform morphology are prepared according to the following steps
(1) Preparing CuSO with the concentration of 0.005 mol/L at room temperature4An aqueous solution; according to the preset NaF, ascorbic acid and CuSO4In a molar ratio of 3:2.5:1 to CuSO4Adding NaF and ascorbic acid into the aqueous solution, and stirring to obtain a clear mixed solution, wherein the stirring speed is set to be 300 revolutions per minute;
(2) and heating the mixed solution to the reaction temperature of 30 ℃, keeping the reaction for 2 hours, and centrifuging, washing and drying the obtained product to obtain the monodisperse cuprous oxide nanospheres with uniform morphology.
Example 2: the monodisperse cuprous oxide nanospheres with uniform morphology are prepared according to the following steps
(1) Preparing CuSO with the concentration of 0.01mol/L at room temperature4An aqueous solution; according to the preset NaF, ascorbic acid and CuSO4In a molar ratio of 4.5:2.5:1 to CuSO4Adding NaF and ascorbic acid into the aqueous solution, and stirring to obtain a clear mixed solution, wherein the stirring speed is set to be 300 revolutions per minute;
(2) and heating the mixed solution to the reaction temperature of 50 ℃, keeping the reaction for 1.25 h, and centrifuging, washing and drying the obtained product to obtain the monodisperse cuprous oxide nanospheres with uniform morphology.
Example 3: the monodisperse cuprous oxide nanospheres with uniform morphology are prepared according to the following steps
(1) Preparing CuSO with the concentration of 0.015 mol/L at room temperature4An aqueous solution; according to the preset NaF, ascorbic acid and CuSO4In a molar ratio of 6:2.5:1 to CuSO4Adding NaF and ascorbic acid into the aqueous solution, and stirring to obtain a clear mixed solution, wherein the stirring speed is set to be 300 revolutions per minute;
(2) and heating the mixed solution to a reaction temperature of 70 ℃, keeping the reaction for 0.5h, and centrifuging, washing and drying the obtained product to obtain the monodisperse cuprous oxide nanospheres with uniform morphology.
The scanning electron microscope pictures of the monodisperse cuprous oxide nanospheres with uniform morphology obtained in examples 1-3 are shown in fig. 1.

Claims (2)

1. The preparation method of the monodisperse cuprous oxide nanospheres with uniform morphology is characterized by comprising the following steps of: NaF is used as an alkali source, and CuSO is reduced by ascorbic acid4The method obtains the cuprous oxide nanospheres with monodispersed uniform appearance; the method comprises the following specific steps:
(1) preparing CuSO with a certain concentration at room temperature4An aqueous solution; according to NaF, ascorbic acid and CuSO4In a molar ratio of (3-6) to (2.5: 1) to CuSO4Adding NaF and ascorbic acid into the aqueous solution, and stirring to obtain a clear mixed solution, wherein the stirring speed is 300 revolutions per minute;
(2) and heating the mixed solution to the reaction temperature of 30-70 ℃, keeping the reaction time for 0.5-2 h, and centrifuging, washing and drying the obtained product to obtain the monodisperse cuprous oxide nanospheres with uniform morphology.
2. The preparation method of the monodisperse cuprous oxide nanospheres with uniform morphology as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (1), the CuSO4The concentration of the aqueous solution is 0.005-0.015 mol/L.
CN201810994064.6A 2018-08-29 2018-08-29 Preparation method of monodisperse cuprous oxide nanospheres with uniform morphology Active CN108975381B (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018119543A1 (en) * 2016-12-29 2018-07-05 Pontificia Universidad Catolica De Chile Method for producing a cu2o/tio2 nanoparticle catalyst, and cu2o/tio2 nanoparticle catalyst

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KR100869026B1 (en) * 2007-07-25 2008-11-17 주식회사 엘지화학 Spherical assembly particle composition of cuprous oxide and preparation method thereof
CN101805010A (en) * 2010-04-02 2010-08-18 青岛科技大学 Method for preparing hollow sphere made from cuprous oxide
CN107473257B (en) * 2016-06-07 2019-08-16 中国科学院化学研究所 The controllable cuprous nano crystalline substance and its preparation method and application of a kind of pattern, size

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018119543A1 (en) * 2016-12-29 2018-07-05 Pontificia Universidad Catolica De Chile Method for producing a cu2o/tio2 nanoparticle catalyst, and cu2o/tio2 nanoparticle catalyst

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