CN102897723A

CN102897723A - Hydrothermal method for preparing selenium-copper-based nano-crystals

Info

Publication number: CN102897723A
Application number: CN2012103121155A
Authority: CN
Inventors: 施伟东; 石佳奇; 范伟强; 刘裴
Original assignee: Jiangsu University
Current assignee: Jiangsu University
Priority date: 2012-08-29
Filing date: 2012-08-29
Publication date: 2013-01-30

Abstract

The invention belongs to the technical field of environment-friendly nano-grade material preparation, and relates to a method for preparing selenium-copper-based nano-crystals. The invention especially relates to a hydrothermal method used for preparing selenium-copper-based nano-crystals. According to the invention, copper nitrate is mixed with inorganic metal salt; tartaric acid is adopted as a complexing agent; ammonia water is used in alkalization; sodium selenite is added; hydrazine hydrate is adopted as a reducing agent; a hydrothermal reaction is carried out; and centrifugal washing is carried out, such that the selenium-copper-based nano-crystals are obtained. According to the invention, the hydrothermal method is adopted as a synthesizing means, and selenium-copper-based nano-crystal large-scale preparation can be realized. The method has the advantages that the synthesizing method is simple, environment-friendly, and highly efficient.

Description

A kind of hydrothermal method prepares the method for copper selenide base nanometer crystal

Technical field

The invention belongs to environmental friendliness nano material preparing technical field, relate to a kind of method for preparing the copper selenide base nanometer crystal, relate in particular to the method that a kind of hydrothermal method prepares the copper selenide base nanometer crystal.

Background technology

In recent years, the correlative study problem is used in preparations of nanomaterials and assembling thereof has become research emphasis in the nature subject.Within the scope that nano material refers to have at least a dimension to be in nano-scale on the three dimension scale of material (1-100nm), perhaps with its material that is consisted of as the essentially consist unit.Generally speaking, the relation of the size of material character and crystal is very close, after the size of material enters nanometer scale, the minimizing of material granule size can cause the destruction of material boundary condition, so that the energy band structure of material and relevant energy level thereof and the size of material had larger dependency.Along with reducing of crystalline size, generally speaking, continuous energy level can split gradually and be divided into discrete energy levels, and energy gap reducing and increase with particle size.And when energy gap greater than the heat energy of material itself, or during electrostatic energy, it is comparatively obvious that quantum effect becomes, thereby so that nano material at light, electricity, the aspects such as magnetic present the character that is different from its macroscopic material.For example, the metal that itself belongs to conductor can become isolator at the nano-scale degree, and its absorption spectrum can change with particle size and gathering behavior.Material shows on nanoscale, the physico-chemical property that is different from its bulk material has caused people and has studied greatly interest, so that people are regulating and control synthetic technology to nano material, large quantity research has been carried out in the aspects such as assembling of manually cutting out aspect and device of nanotopography structure and corresponding properties thereof.

In the research and development of nanotechnology, relate generally to the content aspect two: material preparation and application and development.Nanotechnology has obtained important progress in process nearly two development about ten years, and aspect the nanometer synthetic technology, the preparation of some systems has the synthetic of nano material of specific morphology and sets up gradually.But because under nanoscale, the factor that affects the crystal growth is a lot, in addition compound this in form and crystalline structure on difference, set up the preparations of nanomaterials method of universality and be not easy, in order to satisfy the Application of micron requirement, it is still significant to develop the synthetic method for preparing the nano material with ad hoc structure and pattern under the simple mild conditions simultaneously.The application and development of nanotechnology is the final purpose of Nano-technology Development, and some unique physicochemical property that nano material shows provide numerous possibilities for its application in different field.

VI main group nano material is being played the part of important role in day by day flourish inorganic nanometer functional material and device, this class material has shown the performances such as optics, electricity, magnetics, catalysis and air-sensitive different from its body phase material, can be widely used in various important researchs and production field.The selenide nano material has good photoelectric properties and diamagnetic character as Typical Representative wherein, has broad application prospects in fields such as nonlinear optics, electromagnetism, photoelectronics.For example, the selenide nano material has been applied to the fields such as solar cell, sensor, biomedicine, electrodes selective, rectifier, so the selenide nano material is one of the study hotspot in the outer material field of Present Domestic.

Summary of the invention

The present invention can prepare the copper selenide base nanometer crystal on a large scale take hydrothermal method as synthesizing mean, and its advantage is simple synthetic method, and environmental protection is efficient.

The present invention mixes cupric nitrate with inorganic metal salt, take tartrate as complexing agent, liquid ammonia alkalinization adds Sodium Selenite again, and through hydro-thermal reaction, centrifuge washing makes take hydrazine hydrate as reductive agent.

A preferred embodiment of the present invention, described inorganic metal salt is zinc salt, pink salt, indium salt, be specially a kind of in zinc nitrate, tin tetrachloride, the Indium-111 chloride or with atoms metal equimolar ratio example mix several.

A preferred embodiment of the present invention, the applied amount of described cupric nitrate, inorganic metal salt and Sodium Selenite are that the molar ratio according to each atoms metal in the final copper selenide based products is applied in the hydrothermal reaction kettle.

A preferred embodiment of the present invention, the temperature of described hydro-thermal reaction is 180 ℃, reaction 3h.

Description of drawings

Fig. 1 Cu ₂SnSe ₃X-ray diffraction analysis figure (XRD);

Fig. 2 Cu ₂ZnSnSe ₄X-ray diffraction analysis figure (XRD);

Fig. 3 Cu ₂SnSe ₃Scanning electron microscope (SEM) photograph;

Fig. 4 Cu ₂SnSe ₃Scanning transmission electron micrograph (STEM);

Fig. 5 Cu ₂ZnSnSe ₄Scanning transmission electron micrograph (STEM).

Embodiment

The present invention is described in detail below in conjunction with embodiment, so that those skilled in the art understand the present invention better, but the present invention is not limited to following examples.

Embodiment 1

Cu ₂SnSe ₃Synthetic concrete steps: get cupric nitrate and tin tetrachloride and join in the reactor of 20ml with the ratio of 0.4mmol:0.2mmol, add 0.1g tartrate, the dissolved in distilled water that adds 3 milliliters, the ammoniacal liquor that then adds 7ml, and then the Sodium Selenite of adding 0.6mmol, add at last 180 ℃ of reactions of hydrazine hydrate dress still 3h of 8ml, the taking-up naturally cooling is at last centrifugal can to obtain Cu ₂SnSe ₃Nanocrystalline.

Embodiment 2

CuInSe ₂Synthesis step: get cupric nitrate and Indium-111 chloride and join in the reactor of 20ml with the ratio of 0.2mmol:0.2mmol, add 0.1g tartrate, the dissolved in distilled water that adds 3 milliliters, the ammoniacal liquor that then adds 7ml, and then the Sodium Selenite of adding 0.4mmol, add at last 180 ℃ of reactions of hydrazine hydrate dress still 3h of 8ml, the taking-up naturally cooling is at last centrifugal can to obtain CuInSe ₂Nanocrystalline.

Embodiment 3

Cu ₂ZnSnSe ₄Synthesis step: get cupric nitrate, zinc nitrate and tin tetrachloride join in the reactor of 20ml with the ratio of 0.4mmol:0.2mmol:0.2mmol, add 0.1g tartrate, the dissolved in distilled water that adds 3 milliliters, the ammoniacal liquor that then adds 7ml, and then the Sodium Selenite of adding 0.8mmol, the hydrazine hydrate that adds at last 8ml fills 180 ℃ of reactions of still 3h, and the taking-up naturally cooling is at last centrifugal can to obtain Cu ₂ZnSnSe ₄Nanocrystalline.

Embodiment 4

Cu ₂Se synthesis step: get in the reactor that cupric nitrate 0.4mmol joins 20mol, add 0.1g tartrate, the dissolved in distilled water that adds 3 milliliters, the ammoniacal liquor that then adds 7ml, and then the Sodium Selenite of adding 0.2mmol, add at last 180 ℃ of reactions of hydrazine hydrate dress still 3h of 8ml, the taking-up naturally cooling is at last centrifugal can to obtain Cu ₂Se is nanocrystalline.

Embodiment 5

Cu ₂ZnSnSe ₄Synthesis step: get zinc nitrate and tin tetrachloride and join in the reactor of 50ml with the ratio of 4mmol:2mmol:2mmol, add 0.1g tartrate, the dissolved in distilled water that adds 3 milliliters, the ammoniacal liquor that then adds 7ml, and then the Sodium Selenite of adding 8mmol, add at last 180 ℃ of reactions of hydrazine hydrate dress still 3h of 8ml, the taking-up naturally cooling is at last centrifugal can to obtain a large amount of Cu ₂ZnSnSe ₄Nanocrystalline.

Embodiment 6

Cu ₂SnSe ₃Synthesis step: get cupric nitrate and tin tetrachloride and join in the reactor of 50ml with the ratio of 4mmol:2mmol, add 0.1g tartrate, the dissolved in distilled water that adds 3 milliliters, the ammoniacal liquor that then adds 7ml, and then the Sodium Selenite of adding 0.6mmol, add at last 180 ℃ of reactions of hydrazine hydrate dress still 3h of 8ml, the taking-up naturally cooling is at last centrifugal can to obtain a large amount of Cu ₂SnSe ₃Nanocrystalline.

Figure one and figure two are respectively Cu ₂SnSe ₃And Cu ₂ZnSnSe ₄XRD figure, as can be seen from the figure different sample XRD diffraction peaks all appear at 2 θ=27.2 °, 45.1 °, 52.6 °, 65.2 °, 72.0 ° and locate, and all meet XRD figure spectrum signature peak separately.

Figure three is Cu ₂SnSe ₃Scanning electron microscope (SEM) photograph, can observe resulting product pattern by picture is Cu ₂SnSe ₃Nanocrystalline.

Figure four and figure five are respectively Cu ₂SnSe ₃And Cu ₂ZnSnSe ₄STEM figure because the XRD characteristic peak of copper selenide base nanometer crystal is identical, so need to usually distinguish by the concrete unit of measuring them, can find sample Cu by its Mapping ₂SnSe ₃Cu, Sn, Se element evenly distribute wherein sample Cu ₂ZnSnSe ₄Cu, Sn, Zn, Se element also evenly distribute wherein.

Claims

1. a hydrothermal method prepares the method for copper selenide base nanometer crystal, is that cupric nitrate is mixed with inorganic metal salt, and take tartrate as complexing agent, liquid ammonia alkalinization adds Sodium Selenite again, and through hydro-thermal reaction, centrifuge washing makes take hydrazine hydrate as reductive agent.

2. hydrothermal method according to claim 1 prepares the method for copper selenide base nanometer crystal, it is characterized in that, described inorganic metal salt is zinc salt, pink salt, indium salt, be specially a kind of in zinc nitrate, tin tetrachloride, the Indium-111 chloride or with atoms metal equimolar ratio example mix several.

3. hydrothermal method according to claim 1 prepares the method for copper selenide base nanometer crystal, it is characterized in that the applied amount of described cupric nitrate, inorganic metal salt and Sodium Selenite is that the molar ratio according to each atoms metal in the final copper selenide based products is applied in the hydrothermal reaction kettle.

4. hydrothermal method according to claim 1 prepares the method for copper selenide base nanometer crystal, it is characterized in that, the temperature of described hydro-thermal reaction is 180 ℃, reaction 3h.