CN102357659A - Preparation method of Cu-Cu2O heterogenous junction - Google Patents

Preparation method of Cu-Cu2O heterogenous junction Download PDF

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Publication number
CN102357659A
CN102357659A CN2011102125968A CN201110212596A CN102357659A CN 102357659 A CN102357659 A CN 102357659A CN 2011102125968 A CN2011102125968 A CN 2011102125968A CN 201110212596 A CN201110212596 A CN 201110212596A CN 102357659 A CN102357659 A CN 102357659A
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junctions
hetero
powder
deionized water
preparation
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CN2011102125968A
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CN102357659B (en
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孙少东
孔春才
杨志懋
宋晓平
丁秉钧
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Yangzhou Love New Mstar Technology Ltd
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Xian Jiaotong University
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Abstract

The invention discloses a preparation method of a Cu-Cu2O heterogenous junction. The preparation method comprises the following steps of: adding Cu2O powder into deionized water and stirring to obtain a suspension solution of the Cu2O powder and the deionized water; adding 5 to 35 mass percent of hydrazine hydrate into the suspension solution to obtain a suspension solution in which Cu particles are grown on the surface of the Cu2O; performing heat preservation for 1 to 120 minutes at the temperature of between 50 and 85 DEG C to obtain a primary product of the Cu-Cu2O heterogenous junction; and washing and drying the primary product, and thus obtaining the Cu-Cu2O metal-semiconductor heterogenous junction material with good photocatalysis performance. The preparation method is simple in process and low in cost, can be used for synthesizing the Cu-Cu2O metal-semiconductor heterogenous junction material with good dispersibility and good photocatalysis performance, and is suitable for large-scale production and industrial application.

Description

A kind of Cu-Cu 2The preparation method of O hetero-junctions
Technical field
The present invention relates to the preparation method of hetero-junctions, particularly a kind of Cu-Cu 2The preparation method of O hetero-junctions.
Background technology
Be accompanied by the development of interface science, the research worker recognizes and can utilize different materials to be combined into the material of heterojunction structure that the surface and interface that contact produced between the dissimilar materials can make that the material that is synthesized has special functional characteristic.Can be used for preparing novel material and device by this functional characteristic of hetero-junctions.Along with reducing of material size, some character of material can change, and when the size of material was reduced to micron or nanometer, surface or interface were very significant to the influence of material.The design of surface and interface and control are the key factors of research material thus; Heterojunction material is by material different be combined in some way; Formed interface can change the original performance of material between the different materials, can be used for constructing functional material or device.
Heterojunction material has hetero-junctions between semiconductor, metal-semiconductor hetero-junctions, material with carbon element-heterojunction semiconductor and inorganic semiconductor-kinds such as organic matter hetero-junctions, and these different types of heterojunction materials show excellent performance and huge application potential at aspects such as photocatalysis, electrical conductivity.The Cu-Cu that the present invention is prepared 2The O hetero-junctions belongs to a kind of of metal-semiconductor hetero-junctions.The metal-semiconductor hetero-junctions is called schottky junction again, and the space charge layer of this material is present in the semiconductor, has only semiconductor energy by optical excitation; When optical excitation; The photic electronics of crossing entering metal in interface from semiconductor does not accumulate, but directly forms electric current, and the metal-semiconductor hetero-junctions not only has the quantity of photogenerated charge separating power thus; Can also walk the photic electron transfer that separates fast, it is favourable that light-catalyzed reaction is participated in the hole.The metal-semiconductor hetero-junctions has the heterogeneous AuPbS of having of metal-semiconductor, AuZnS, AuCdS, AuAg2S, the AuCu of bibliographical information at present because excellent photocatalysis characteristic has been subjected to increasing concern 2O, Ag-ZnO and Au-ZnO etc. can see that these materials mainly combine with semi-conductive round precious metal material, though the material that finally obtains has performances such as good photocatalysis, have improved cost greatly.
Cuprous oxide Cu 2The O crystal is as a kind of nontoxic low energy gap p type semiconductor; Owing to self unique physical chemical property, obtained important use in solar cell, photocatalytic degradation, gas sensor, lithium ion battery negative material, chemical template, metal-insulator-metal type electric impedance memory field.Therefore adopt a kind of simple method at Cu 2The O superficial growth goes out deposition and goes up Cu particle, the Cu-Cu cheaply for preparing 2O metal semiconductor heterojunction material is very to be necessary.The Cu-Cu that does not also have a kind of simple method to prepare cheaply, have good catalytic in the prior art 2The O heterojunction material.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide a kind of Cu-Cu 2The preparation method of O hetero-junctions, preparation method's technology of the present invention is simple, with low cost, can synthesize the Cu-Cu that monodispersity is good, have the good light catalytic performance 2O metal-semiconductor heterojunction material.
To achieve these goals, the technical scheme of the present invention's employing is:
A kind of Cu-Cu 2The preparation method of O hetero-junctions may further comprise the steps:
Step 1: with Cu 2The O powder adds in the deionized water, add Cu 2The mass ratio of O powder and deionized water is 1: 10～1: 1000, and continues down to stir 5～10min at 15～35 ℃, obtains Cu 2The aaerosol solution of O powder and deionized water;
Step 2: be 5%～35% hydrazine hydrate (N with mass percent 2H 4H 2O) join the Cu that step 1 obtains 2In the aaerosol solution of O powder and deionized water, add the deionized water that adds in hydrazine hydrate and the step (1) volume ratio be 1: 1～1: 500, and continue to stir 1～5min down at 15-35 ℃, obtain Cu 2The O superficial growth goes out the aaerosol solution of Cu particle;
Step 3: with step 2 gained Cu 2The aaerosol solution that the O superficial growth goes out the Cu particle is heated to 50～85 ℃ under stirring, and under this temperature, is incubated 1～120min, obtains Cu-Cu 2The elementary product of O hetero-junctions;
Step 4: with step 3 gained Cu-Cu 2The elementary product of O hetero-junctions is earlier with absolute ethyl alcohol centrifuge washing 2～5 times under the 6000rpm rotating speed, and centrifuge washing 1～5min at every turn is then with the Cu-Cu behind the centrifuge washing 2The O hetero-junctions places the dry 2～5h of vacuum drying chamber, and baking temperature is 45～60 ℃, promptly obtains Cu-Cu 2The O hetero-junctions.
The described Cu of step 1 2The O powder shape is cube, octahedron, the tetrakaidecahedron, 20 hexahedrons, five decahedrons or seven tetrakaidecahedrons.
The described Cu of step 1 2The particle diameter of O powder is 0.05～5 μ m.
Preparation method's technology of the present invention is simple, with low cost, can synthesize the Cu-Cu that monodispersity is good, have the good light catalytic performance 2O metal-semiconductor heterojunction material is fit to large-scale production and commercial Application.
The specific embodiment
With embodiment the present invention is explained further details below.
Embodiment one
Present embodiment Cu-Cu 2The preparation method of O hetero-junctions may further comprise the steps:
Step 1: will be shaped as 20 hexahedrons, particle diameter is that 3 μ m, quality are the Cu of 0.1g 2The O powder joins in the 60ml deionized water, and continues down to stir 5min at 35 ℃, obtains Cu 2The aaerosol solution of O powder and deionized water;
Step 2: be 35% hydrazine hydrate (N with 0.6ml, mass percent 2H 4H 2O) join Cu in the step 1 2In the aaerosol solution of O powder and deionized water, and, obtain Cu at 35 ℃ of lasting down 3min that stir 2The O superficial growth goes out the aaerosol solution of Cu particle;
Step 3: with step 2 gained Cu 2The aaerosol solution that the O superficial growth goes out the Cu particle is heated to 65 ℃ under stirring, and under this temperature, is incubated 1min, obtains Cu-Cu 2The elementary product of O hetero-junctions;
Step 4: with step 3 gained Cu-Cu 2The elementary product of O hetero-junctions is with absolute ethyl alcohol centrifuge washing 3 times under the 6000rpm rotating speed, and each centrifuge washing 2min is with the Cu-Cu behind the centrifuge washing 2The O hetero-junctions places the dry 5h of vacuum drying chamber, and baking temperature is 60 ℃, can obtain 20 hexahedron Cu-Cu of superficial growth Cu particle 2The O hetero-junctions.
Embodiment two
Present embodiment Cu-Cu 2The preparation method of O hetero-junctions may further comprise the steps:
Step 1: will be shaped as five decahedrons, particle diameter is that 5 μ m, quality are the Cu of 2.0g 2The O powder joins in the 20ml deionized water, and continues down to stir 10min at 25 ℃, obtains Cu 2The aaerosol solution of O powder and deionized water;
Step 2: be 5% hydrazine hydrate (N with 20ml, mass percent 2H 4H 2O) join Cu in the step 1 2In the aaerosol solution of O powder and deionized water, and, obtain Cu at 25 ℃ of lasting down 5min that stir 2The O superficial growth goes out the aaerosol solution of Cu particle;
Step 3: with step 2 gained Cu 2The aaerosol solution that the O superficial growth goes out the Cu particle is heated to 50 ℃ under stirring, and under this temperature, is incubated 120min, obtains Cu-Cu 2The elementary product of O hetero-junctions;
Step 4: with step 3 gained Cu-Cu 2The elementary product of O hetero-junctions is with absolute ethyl alcohol centrifuge washing 5 times under the 6000rpm rotating speed, and each centrifuge washing 1min is with the Cu-Cu behind the centrifuge washing 2The O hetero-junctions places the dry 3h of vacuum drying chamber, and baking temperature is 45 ℃, can obtain five decahedron Cu-Cu of superficial growth Cu particle 2The O hetero-junctions.
Embodiment three
Present embodiment Cu-Cu 2The preparation method of O hetero-junctions may further comprise the steps:
Step 1: will be shaped as 20 hexahedrons, particle diameter is that 3 μ m, quality are the Cu of 0.2g 2The O powder joins in the 200ml deionized water, and continues down to stir 8min at 15 ℃, obtains Cu 2The aaerosol solution of O powder and deionized water;
Step 2: be 25% hydrazine hydrate (N with 0.4ml, mass percent 2H 4H 2O) join Cu in the step 1 2In the aaerosol solution of O powder and deionized water, and, obtain Cu at 15 ℃ of lasting down 1min that stir 2The O superficial growth goes out the aaerosol solution of Cu particle;
Step 3: with step 2 gained Cu 2The aaerosol solution that the O superficial growth goes out the Cu particle is heated to 85 ℃ under stirring, and under this temperature, is incubated 30min, obtains Cu-Cu 2The elementary product of O hetero-junctions;
Step 4: with step 3 gained Cu-Cu 2The elementary product of O hetero-junctions is with absolute ethyl alcohol centrifuge washing 4 times under the 6000rpm rotating speed, and each centrifuge washing 2.5min is with the Cu-Cu behind the centrifuge washing 2The O hetero-junctions places the dry 2h of vacuum drying chamber, and baking temperature is 60 ℃, can obtain 20 hexahedron Cu-Cu of superficial growth Cu particle 2The O hetero-junctions.
Embodiment four
Present embodiment Cu-Cu 2The preparation method of O hetero-junctions may further comprise the steps:
Step 1: will be shaped as octahedron, particle diameter is that 0.05 μ m, quality are the Cu of 2.0g 2The O powder joins in the 100ml deionized water, and continues down to stir 5min at 20 ℃, obtains Cu 2The aaerosol solution of O powder and deionized water;
Step 2: be 35% hydrazine hydrate (N with 3.0ml, mass percent 2H 4H 2O) join Cu in the step 1 2In the aaerosol solution of O powder and deionized water, and, obtain Cu at 20 ℃ of lasting down 3min that stir 2The O superficial growth goes out the aaerosol solution of Cu particle;
Step 3: with step 2 gained Cu 2The aaerosol solution that the O superficial growth goes out the Cu particle is heated to 68 ℃ under stirring, and under this temperature, is incubated 5min, obtains Cu-Cu 2The elementary product of O hetero-junctions;
Step 4: with step 3 gained Cu-Cu 2The elementary product of O hetero-junctions is with absolute ethyl alcohol centrifuge washing 3 times under the 6000rpm rotating speed, and each centrifuge washing 3min is with the Cu-Cu behind the centrifuge washing 2The O hetero-junctions places the dry 3h of vacuum drying chamber, and baking temperature is 50 ℃, can obtain the octahedra Cu-Cu of superficial growth Cu particle 2The O hetero-junctions.
Embodiment five
Present embodiment Cu-Cu 2The preparation method of O hetero-junctions may further comprise the steps:
Step 1: will be shaped as octahedron, particle diameter is that 1.5 μ m, quality are the Cu of 3.0g 2The O powder joins in the 300ml deionized water, and continues down to stir 6min at 25 ℃, obtains Cu 2The aaerosol solution of O powder and deionized water;
Step 2: be 20% hydrazine hydrate (N with 6.0ml, mass percent 2H 4H 2O) join Cu in the step 1 2In the aaerosol solution of O powder and deionized water, and, obtain Cu at 25 ℃ of lasting down 4min that stir 2The O superficial growth goes out the aaerosol solution of Cu particle;
Step 3: with step 2 gained Cu 2The aaerosol solution that the O superficial growth goes out the Cu particle is heated to 73 ℃ under stirring, and under this temperature, is incubated 5min, obtains Cu-Cu 2The elementary product of O hetero-junctions;
Step 4: with step 3 gained Cu-Cu 2The elementary product of O hetero-junctions is with absolute ethyl alcohol centrifuge washing 2 times under the 6000rpm rotating speed, and each centrifuge washing 3min is with the Cu-Cu behind the centrifuge washing 2The O hetero-junctions places the dry 3h of vacuum drying chamber, and baking temperature is 50 ℃, can obtain the octahedra Cu-Cu of superficial growth Cu particle 2The O hetero-junctions.

Claims (3)

1. Cu-Cu 2The preparation method of O hetero-junctions may further comprise the steps:
Step 1: with Cu 2The O powder adds in the deionized water, add Cu 2The mass ratio of O powder and deionized water is 1: 10～1: 1000, and continues down to stir 5～10min at 15～35 ℃, obtains Cu 2The aaerosol solution of O powder and deionized water;
Step 2: be 5%～35% hydrazine hydrate (N with mass percent 2H 4H 2O) join the Cu that step 1 obtains 2In the aaerosol solution of O powder and deionized water, add in hydrazine hydrate and the step 1 deionized water that adds volume ratio be 1: 1～1: 500, and continue to stir 1～5min down at 15-35 ℃, obtain Cu 2The O superficial growth goes out the aaerosol solution of Cu particle;
Step 3: with step 2 gained Cu 2The aaerosol solution that the O superficial growth goes out the Cu particle is heated to 50～85 ℃ under stirring, and under this temperature, is incubated 1～120min, obtains Cu-Cu 2The elementary product of O hetero-junctions;
Step 4: with step 3 gained Cu-Cu 2The elementary product of O hetero-junctions is earlier with absolute ethyl alcohol centrifuge washing 2～5 times under the 6000rpm rotating speed, and centrifuge washing 1～5min at every turn is then with the Cu-Cu behind the centrifuge washing 2The O hetero-junctions places the dry 2～5h of vacuum drying chamber, and baking temperature is 45～60 ℃, promptly obtains Cu-Cu 2The O hetero-junctions.
2. Cu-Cu according to claim 1 2The preparation method of O hetero-junctions is characterized in that: the described Cu of step 1 2The O powder shape is cube, octahedron, the tetrakaidecahedron, 20 hexahedrons, five decahedrons or seven tetrakaidecahedrons.
3. Cu-Cu according to claim 1 2The preparation method of O hetero-junctions is characterized in that: the described Cu of step 1 2The particle diameter of O powder is 0.05～5 μ m.
CN 201110212596 2011-07-27 2011-07-27 Preparation method of Cu-Cu2O heterogenous junction Expired - Fee Related CN102357659B (en)

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CN103212708A (en) * 2013-04-13 2013-07-24 北京航空航天大学 Hollow and echinoid nanometer material of copper oxide compounded with gold and preparing method thereof
CN104651790A (en) * 2015-02-12 2015-05-27 常州大学 Metallic resistance Cu/Cu2O semiconductor dispersion composite membrane and preparation method thereof
CN106215824A (en) * 2016-09-07 2016-12-14 南京理工大学 A kind of Cu2the preparation method of O/Cu composite
CN107051459A (en) * 2017-03-30 2017-08-18 常州大学 A kind of preparation method of hud typed cupric oxide/bronzing catalyst
CN107857583A (en) * 2017-11-08 2018-03-30 陕西航空电气有限责任公司 A kind of cuprous oxide semiconductor ceramic material and preparation method thereof
CN111482175A (en) * 2020-05-09 2020-08-04 中国科学技术大学 Preparation method of copper/cuprous oxide heterojunction nanosheet catalyst
CN111595918A (en) * 2020-05-26 2020-08-28 信阳师范学院 Octahedron Cu-Cu2Preparation method of O composite material
CN115779931A (en) * 2022-12-07 2023-03-14 云南师范大学 Heterojunction photocatalytic material based on cubic cuprous oxide and preparation method thereof

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103212708A (en) * 2013-04-13 2013-07-24 北京航空航天大学 Hollow and echinoid nanometer material of copper oxide compounded with gold and preparing method thereof
CN103212708B (en) * 2013-04-13 2014-12-10 北京航空航天大学 Hollow and echinoid nanometer material of copper oxide compounded with gold and preparing method thereof
CN104651790A (en) * 2015-02-12 2015-05-27 常州大学 Metallic resistance Cu/Cu2O semiconductor dispersion composite membrane and preparation method thereof
CN104651790B (en) * 2015-02-12 2017-10-20 常州大学 A kind of metallic resistance rate Cu/Cu2O semiconductor disperse laminated films and preparation method thereof
CN106215824A (en) * 2016-09-07 2016-12-14 南京理工大学 A kind of Cu2the preparation method of O/Cu composite
CN106215824B (en) * 2016-09-07 2019-01-18 南京理工大学 A kind of Cu2The preparation method of O/Cu composite material
CN107051459A (en) * 2017-03-30 2017-08-18 常州大学 A kind of preparation method of hud typed cupric oxide/bronzing catalyst
CN107857583A (en) * 2017-11-08 2018-03-30 陕西航空电气有限责任公司 A kind of cuprous oxide semiconductor ceramic material and preparation method thereof
CN107857583B (en) * 2017-11-08 2020-11-13 陕西航空电气有限责任公司 Cuprous oxide semiconductor ceramic material and preparation method thereof
CN111482175A (en) * 2020-05-09 2020-08-04 中国科学技术大学 Preparation method of copper/cuprous oxide heterojunction nanosheet catalyst
CN111595918A (en) * 2020-05-26 2020-08-28 信阳师范学院 Octahedron Cu-Cu2Preparation method of O composite material
CN115779931A (en) * 2022-12-07 2023-03-14 云南师范大学 Heterojunction photocatalytic material based on cubic cuprous oxide and preparation method thereof

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