阅读说明：本技术 一种八面体Cu-Cu2O复合材料的制备方法 (Octahedron Cu-Cu2Preparation method of O composite material ) 是由 刘会俏 曹康哲 张航 曹纬琪 于 2020-05-26 设计创作，主要内容包括：本发明属于纳米材料制备技术领域,具体涉及一种八面体Cu-Cu<Sub>2</Sub>O复合材料的制备方法：将Cu(NO<Sub>3</Sub>)<Sub>2</Sub>溶于PVP溶液,冰水浴下边搅拌边加入NaOH溶液和水合肼,反应至溶液颜色不再变化后继续搅拌,离心分离沉淀物质,得到Cu-Cu<Sub>2</Sub>O前驱体材料；将上述所得Cu-Cu<Sub>2</Sub>O前驱体材料经真空干燥后得到棕色粉末,然后在氩气气氛中、200～450℃下煅烧,得到所述Cu-Cu<Sub>2</Sub>O复合材料。本发明在整个过程中无需复杂的设备,在普通的反应容器中即可完成,工艺步骤简单、制备时间短、安全可靠,无有毒或污染气体产生,低能耗,便于扩大生产,并且本发明制备的复合材料中Cu的量可以通过控制煅烧条件来调控,操作简单。(The invention belongs to the technical field of nano material preparation, and particularly relates to octahedral Cu-Cu 2 The preparation method of the O composite material comprises the following steps: adding Cu (NO) 3 ) 2 Dissolving in PVP solution, adding NaOH solution and hydrazine hydrate while stirring in ice water bath, reacting until the color of the solution is not changed, continuing stirring, centrifuging to separate precipitate to obtain Cu-Cu 2 An O precursor material; the obtained Cu-Cu 2 Carrying out vacuum drying on the O precursor material to obtain brown powder, and then calcining at 200-450 ℃ in an argon atmosphere to obtain the Cu-Cu 2 And (3) an O composite material.The method can be completed in a common reaction vessel without complex equipment in the whole process, has simple process steps, short preparation time, safety, reliability, no generation of toxic or polluted gas, low energy consumption and convenient expanded production, and the amount of Cu in the composite material prepared by the method can be regulated and controlled by controlling the calcination conditions, so the method is simple to operate.)

1. Octahedron Cu-Cu₂The preparation method of the O composite material is characterized by comprising the following steps:

step A. adding Cu (NO)₃)₂Dissolving in PVP solution to obtain mixed solution, adding NaOH solution and hydrazine hydrate into the mixed solution while stirring in ice water bath, reacting until the solution color does not change, continuing stirring, and centrifuging to separate precipitate to obtain Cu-Cu₂An O precursor material;

step B. mixingStep A obtaining Cu-Cu₂Carrying out vacuum drying on the O precursor material to obtain brown powder, and then calcining at 200-450 ℃ in an argon atmosphere to obtain the Cu-Cu₂And (3) an O composite material.

2. An octahedral Cu-Cu according to claim 1 or 2, of the type₂The preparation method of the O composite material is characterized in that the mass fraction of the PVP solution is 2-5%, and the relative molecular mass of PVP is 58000.

3. The octahedral Cu-Cu of claim 1, wherein₂A method for producing an O composite material, characterized in that the Cu (NO) is₃)₂The molar ratio of hydrazine hydrate to hydrazine hydrate is 1: 5.

4. the octahedral Cu-Cu of claim 1, wherein₂The preparation method of the O composite material is characterized in that Cu (NO) in the step A₃)₂The molar ratio of the NaOH to the NaOH is (100-200): 1.

5. the octahedral Cu-Cu of claim 1, wherein₂The preparation method of the O composite material is characterized in that the continuous stirring time in the step A is 0.5-2 hours.

6. The octahedral Cu-Cu of claim 1, wherein₂The preparation method of the O composite material is characterized in that the temperature of vacuum drying in the step B is 40-60 ℃, and the time is 10-12 h.

7. The octahedral Cu-Cu of claim 1, wherein₂The preparation method of the O composite material is characterized in that the calcination time in the step B is 1-2 h.

Technical Field

The invention belongs to the technical field of nano material preparation, and particularly relates to octahedral Cu-Cu₂A preparation method of an O composite material.

Background

In recent years, nanomaterials have received increasing attention. The nano material has a large specific surface area and good electron transfer capacity, and the nano material such as platinum, gold, silver, carbon nano tube, graphene and the like is widely used for electrochemical biosensing. The electrocatalytic performance of the nano material depends not only on the size and the elemental composition of the material, but also on the morphology of the material, and the crystal face with high surface energy often shows higher electrocatalytic activity than the crystal with low surface energy. Therefore, the rational design and controllable preparation of nanomaterials have become a hot spot of recent research.

Cu₂O is a novel P-type semiconductor material, has active electron-hole pairs, can show good catalytic activity, and has potential application value in the aspects of electrode materials, solar cells, sensors, photocatalysis and the like. Cu₂The common structures of O include cubic, octahedral, nanorod, nanotube, etc. Wherein (111) crystal face is dominant Cu₂The O catalytic performance is better than that of the material with the dominant crystal faces of (100) and (110). However, Cu₂The poor conductivity of O limits its further use in electrochemical sensing. Control Cu in reasonable design₂When the O crystal face is simultaneously added, Cu can be improved₂O quantum efficiency, increasing its conductivity.

At present Cu₂The preparation methods of O and its compound mainly include electrochemical deposition, microwave synthesis, solvothermal method, liquid phase synthesis, seed regulation and control method and microemulsion method, for example, Chinese patent CN102357659A discloses a Cu-Cu₂Preparation of O heterojunctions, i.e. using Cu₂Adding hydrazine hydrate into suspension solution of O powder and water to obtain Cu₂And growing a suspension solution of Cu particles on the surface of the O. Cu with different sizes and appearances can be obtained by the methods₂And O. However, Cu in these processes₂The synthesis process of O is relatively complicatedThe time is long, and some devices need high-temperature heating equipment. Next, Cu-Cu was prepared by the above-mentioned method₂The O compound is complicated in steps, and the content of Cu in the compound cannot be accurately regulated and controlled.

Disclosure of Invention

For solving the problem of the existing preparation of Cu-Cu₂The O compound preparation method has the problems of long time consumption, complicated steps and incapability of regulating and controlling the Cu content, and the invention provides octahedral Cu-Cu₂A preparation method of an O composite material.

In order to achieve the purpose, the invention adopts the following technical scheme:

octahedron Cu-Cu₂The preparation method of the O composite material comprises the following steps:

step A. adding Cu (NO)₃)₂Dissolving in PVP solution to obtain mixed solution, adding NaOH solution and hydrazine hydrate into the mixed solution while stirring in ice water bath, reacting until the solution color does not change, continuing stirring, and centrifuging to separate precipitate to obtain Cu-Cu₂An O precursor material;

step B, the Cu-Cu obtained in the step A₂Carrying out vacuum drying on the O precursor material to obtain brown powder, and then calcining at 200-450 ℃ in an argon atmosphere to obtain the Cu-Cu₂And (3) an O composite material.

Further, the mass fraction of the PVP solution is 2-5%, and the relative molecular mass of the PVP is 58000.

Further, the Cu (NO)₃)₂The molar ratio of hydrazine hydrate to hydrazine hydrate is 1: 5.

further, Cu (NO) in the step A₃)₂The molar ratio of the NaOH to the NaOH is (100-200): 1.

further, the continuous stirring time in the step A is 0.5-2 h.

Further, the temperature of vacuum drying in the step B is 40-60 ℃, and the time is 10-12 hours.

Further, the calcination time in the step B is 1-2 h.

The reaction principle of the invention is as follows: cu (NO) in the present invention₃)₂As a substrate, PVP solution as a surfaceThe activator guides the growth of crystal faces in the crystal growth process, when the mass fraction of the PVP solution in the reaction mixed solution is lower than 2%, the product is in a non-octahedral structure, the appearance and the structure are not affected by excessive PVP solution, and the redundant PVP solution can be removed through a subsequent centrifugation step. NaOH solution regulates the reaction mixture to be alkaline, when the sodium hydroxide is too little, the product is in a sheet shape, and when the sodium hydroxide is too little, the product is in a tetrahedral or spherical shape, because Cu₂The morphology of O mainly depends on the growth rates of the (100) crystal plane and the (111) crystal plane, the plane with the lower growth rate can finally form an exposed plane, and the plane with the high growth rate can finally disappear. When OH is in the reaction solution^-When the concentration is lower, the (100) crystal face grows faster, the final growth morphology is mainly flaky or dendritic, and OH^-The concentration is increased, the growth speed of the (100) crystal face is slowed down, the appearance is mainly octahedron, and OH^-The concentration is further increased, the growth of (111) crystal face is accelerated, the appearance approaches to cube, OH^-At higher concentrations, the (100) and (111) growth rates are close, and the morphology becomes spherical. Hydrazine hydrate is used as reducing agent, and Cu can be added²⁺Reduction to Cu₂Too little O will cause insufficient reaction, while too much will cause further Cu²⁺Reducing the alloy into Cu. In the step B, 200-450 ℃ is selected as the calcining temperature, because PVP can be carbonized to different degrees when calcined at different temperatures, and the carbonized PVP can be used for carbonizing Cu₂O is reduced to Cu. The higher the temperature, the more PVP carbonizes, reducing Cu₂The more Cu is obtained by O, but when the temperature is raised to 450 ℃, the octahedral structure of the calcined product is partially destroyed.

Compared with the prior art, the invention has the following advantages:

the invention utilizes a low-temperature reduction method to rapidly prepare Cu under the ice-water bath condition₂O nano material, exposing the (111) surface with higher catalytic performance, and reducing partial Cu by high-temperature calcination₂O, preparing to obtain octahedral Cu-Cu₂The O composite material can be finished in a common reaction vessel without complex equipment in the whole process, the reaction is carried out in an ice-water bath for controlling the reaction speed, the reaction speed is reduced, the nucleation is facilitated, and therefore a ruler is formedEven octahedral structure. The invention has the advantages of simple process steps, short preparation time, safety, reliability, no generation of toxic or polluted gas, low energy consumption and convenience for expanding production. And the amount of Cu in the composite material prepared by the method can be regulated and controlled by controlling the calcining condition, so that the operation is simple. The octahedron Cu-Cu obtained by preparation₂When the O composite material is used for electrochemical sensing, the Cu in the composite material can effectively improve the conductivity of the material, and has excellent electrocatalytic performance.

Drawings

FIG. 1 shows Cu-Cu prepared in example 1₂XRD pattern of the precursor of the O composite material;

FIG. 2 shows Cu-Cu prepared in example 1₂SEM image of O composite material precursor;

FIG. 3 shows Cu-Cu prepared in example 4₂SEM image of O composite material precursor;

FIG. 4 shows Cu-Cu obtained by calcination at different temperatures₂XRD pattern of O composite;

FIG. 5 shows Cu-Cu obtained by calcination at different temperatures₂SEM image of O composite;

FIG. 6 shows the Cu-Cu obtained by calcining the precursor at different temperatures₂An alternating current impedance plot of the O-composite;

FIG. 7 shows Cu-Cu₂And the O composite material modified electrode has current response curve to glucose NaOH solution with different concentrations.

Detailed Description

The present invention will now be described more fully hereinafter with reference to the accompanying drawings.