CN102863005B

CN102863005B - Preparation method of multi-shell core-shell micro/nano structure Cu2O

Info

Publication number: CN102863005B
Application number: CN201210347293.1A
Authority: CN
Inventors: 徐海燕; 陈琛; 董金矿
Original assignee: Anhui University of Architecture
Current assignee: Anhui Jianzhu University; Anhui University of Architecture
Priority date: 2012-09-10
Filing date: 2012-09-10
Publication date: 2015-03-11
Anticipated expiration: 2032-09-10
Also published as: CN102863005A

Abstract

The invention relates to a preparation method of multi-shell core-shell micro/nano structure Cu2O, belonging to the field of semiconductors. The existing method has the defects of higher facility request, complex process and difficulty in control of cost, and seriously influences the application range of the Cu2O sample. The preparation method is characterized by comprising the following steps: adding a trisodium citrate solution into a copper sulfate solution to implement sufficient complexation, and adding a glucose solution, wherein the mol concentration ratio of copper sulfate to trisodium citrate is 12:4-12:18, and the mol concentration ratio of copper sulfate to glucose is 12:2-12:22; regulating the pH value of the solution to 12.3-14.0; reacting at 50-95 DEG C for 1.5-6.0 hours; and after the reaction finishes, flushing, and drying to obtain the required product. Compared with other liquid-phase methods for preparing the core-shell (multi-shell) micro/nano structure Cu2O (template or intermediate phase method), the method (chemical bath deposition method using glucose as a reducer) simplifies the preparation technique, lowers the production cost, and avoids introducing impure phases due to incomplete elimination of the template or intermediate phase; and the prepared product is high-purity multi-shell core-shell micro/nano structure Cu2O.

Description

A kind of many shell core-shell micro/nano structure Cu 2the preparation method of O

Technical field

A kind of many shell core-shell micro/nano structure Cu ₂the preparation method of O belongs to semiconductor applications.

Technical background

Recently, the solid material of nucleocapsid structure and hollow structure receives increasing concern, because they have important impact to the development of the association area of nanotechnology, such as, on the preparation of the delivery vehicles of energy storage system, medicine, composite catalyst, photonic crystal, isoionic generation, magnetic developer, low κ-ionogen, chemistry and optical pickocff and protective function material etc. and performance, there is important impact.The method preparing nucleocapsid structure and hollow structure at present can be divided into hard template method (such as polymkeric substance, pottery, metal ball body etc.), soft template method (such as emulsion droplets, tensio-active agent and bubble etc.) and based on Kirkendall effect, the physics of Ostwald ripening effect and chemical substance inductive effect etc. or chemical process, but, because the template or centre that will process introducing are equal, these preparation methods are too loaded down with trivial details when preparing nucleocapsid structure and hollow structure, even processing costs is higher, therefore, be badly in need of finding a kind of fast simple preparation method.

Red copper oxide (Cu ₂o) be one of semiconductor material of being found the earliest, it is cheap, material source is extensive and obtain the accreditation of more and more people.Cu ₂o is can by the P-type semiconductor of excited by visible light, and its energy gap is about 1.9 ~ 2.2eV.The Cu of polycrystalline state ₂o good stability, can utilization repeatedly and be not easy be oxidized to Cu (II) and be reduced into Cu; Secondly, Cu ₂o nontoxicity, good with the consistency of environment, and easily obtain.Therefore be the semiconductor material that a kind of application potential is very large, in superconductor, hydrogen manufacturing, solar cell, electrochromism and organic matter degradation etc., have potential application.In numerous pattern, wherein there is the Cu of nucleocapsid structure (zonal structure) pattern ₂o, owing to having larger specific surface area, has greater advantage in organic matter degradation.

At present at the Cu preparing nucleocapsid structure (zonal structure) pattern ₂can by template or mesophase spherule in O process, and then adopt relevant physics or chemical process to remove these templates or mesophase spherule, but these methods are comparatively loaded down with trivial details, and may cause there is dephasign in product, in addition, these preparation methods may have higher requirements to equipment, cause cost higher.Prepared the Cu of nucleocapsid structure (zonal structure) as reductive agent by glucose by chemical bath deposition method ₂o has fast, outside simple, low cost, high pure phase feature, be also applicable to the deposition of various abnormity, non-conductive or non-refractory substrate; And in multilayer film deposition process, the feature of damage can not be caused to the film that substrate has deposited.

Summary of the invention

The invention provides the softening method preparation that a kind of preparation technology is simple, the cycle is short, energy consumption is low and there is many shell core-shell micro/nano structure Cu ₂o, is specially adapted to film forming and the batch production of out-of-shape object.

Many shell core-shell micro/nano structure Cu provided by the invention ₂the preparation method of O sample, it comprises the following steps:

A) in copper-bath, flatly put into substrate, add citric acid three sodium solution, after abundant complexing, add glucose solution, and constant volume;

B) in the solution after constant volume, drip the pH value of NaOH solution regulator solution;

C) solution at a certain temperature after deposition reaction certain hour will adjusting pH value, takes out and rinses post-drying well.

Described step a) in the molar concentration rate scope of copper sulfate and trisodium citrate be 12: 4 ~ 12: 18; The molar concentration rate of copper sulfate and glucose is in 12: 2 ~ 12: 22 scopes;

Described step a) middle concentration of copper sulfate controls at 0.10mol/L ~ 0.50mol/L;

Described step b) in adjustment solution ph scope be 12.3 ~ 14.0;

Described step c) in the temperature range of solution control at 50 DEG C ~ 95 DEG C;

Described step c) reaction times controls at 1.5h ~ 6.0h.

The method and other liquid phase prepare the Cu of nucleocapsid structure (zonal structure) ₂o method (template and mesophase spherule) is compared, and not only greatly simplify preparation technology, and relatively low to the requirement of reaction conditions, is applicable to the production of mass-producing, reduces production cost, also shorten the production cycle; What is more important uses glucose that reductibility is comparatively gentle as reductive agent, Cu (II) can be prevented to be reduced into Ni metal, thus prepare the Cu of pure phase ₂o, utilizes by the gluconic acid of the oxidized generation of glucose simultaneously, participates in many shell core-shell micro/nano structure Cu ₂the formation of O, avoids because template and mesophase spherule process not exclusively introduce dephasign.

Employing Bruker Advance D8X ray powder diffractometer (Cu K α radiation, 2 θ=20-75 °) measure the structure of prepared material.Adopt the surface topography of material prepared by Sirion200 sem observation.

From Fig. 1 and Fig. 2, prepared Cu ₂o sample is pure cubic structure (JCPDS card No.74-1230), and wherein in Fig. 2, (111) crystallographic plane diffraction peak Strength Changes is obvious, shows that pH is more than or equal to 10.7 and all can prepares pure Cu ₂o sample, wherein pH 11.5 ~ 13.2 scope can prepare desirable, pure Cu ₂o sample.Product obtained as shown in Figure 3 is nucleocapsid structure and many shells micro-nano structure Cu ₂o sample; As shown in Figure 4, the Cu of nucleocapsid structure (zonal structure) only just can be prepared when pH is greater than 12.0 ₂o sample.

Accompanying drawing explanation

Fig. 1: when pH is 12.5, the X-ray diffractogram of the product that reaction 2h obtains;

Fig. 2: be in 10.5 ~ 13.2 scopes at pH, the X-ray diffractogram of the associated products that reaction 4h obtains;

Fig. 3: when pH is 12.5, the scanning electron microscope (SEM) photograph of the product that reaction 2h obtains;

Fig. 4: be in 10.5 ~ 13.2 scopes at pH, the scanning electron microscope (SEM) photograph of the associated products that reaction 4h obtains.

Embodiment

1. in the copper-bath of 0.3mol/L, the substrate of cleaning activation in advance is flatly put into according to concentration ratio 12: 9: 8, add the citric acid three sodium solution prepared, glucose solution is added after abundant complexing, stir and be settled to 50ml, the pH value of regulator solution is 12.5,80 DEG C of reactions 2 hours, take out after cleaning up and can obtain Cu ₂o sample (F).

2. in the copper-bath of 0.3mol/L, the substrate of cleaning activation in advance is flatly put into according to concentration ratio 12: 9: 8, add the citric acid three sodium solution prepared, glucose solution is added after abundant complexing, stir and be settled to 50ml, the pH value of regulator solution is 10.5,80 DEG C of reactions 4 hours, take out after cleaning up and can obtain Cu ₂o sample (a).

3. in the copper-bath of 0.3mol/L, the substrate of cleaning activation in advance is flatly put into according to concentration ratio 12: 9: 8, add the citric acid three sodium solution prepared, glucose solution is added after abundant complexing, stir and be settled to 50ml, the pH value of regulator solution is 10.7,80 DEG C of reactions 4 hours, take out after cleaning up and can obtain Cu ₂o sample (b).

4. in the copper-bath of 0.3mol/L, the substrate of cleaning activation in advance is flatly put into according to concentration ratio 12: 9: 8, add the citric acid three sodium solution prepared, glucose solution is added after abundant complexing, stir and be settled to 50ml, the pH value of regulator solution is 11.0,80 DEG C of reactions 4 hours, take out after cleaning up and can obtain Cu ₂o sample (c).

5. in the copper-bath of 0.3mol/L, the substrate of cleaning activation in advance is flatly put into according to concentration ratio 12: 9: 8, add the citric acid three sodium solution prepared, glucose solution is added after abundant complexing, stir and be settled to 50ml, the pH value of regulator solution is 11.5,80 DEG C of reactions 4 hours, take out after cleaning up and can obtain Cu ₂o sample (d).

6. in the copper-bath of 0.3mol/L, the substrate of cleaning activation in advance is flatly put into according to concentration ratio 12: 9: 8, add the citric acid three sodium solution prepared, glucose solution is added after abundant complexing, stir and be settled to 50ml, the pH value of regulator solution is 12.0,80 DEG C of reactions 4 hours, take out after cleaning up and can obtain Cu ₂o sample (e).

7. in the copper-bath of 0.3mol/L, the substrate of cleaning activation in advance is flatly put into according to concentration ratio 12: 9: 8, add the citric acid three sodium solution prepared, glucose solution is added after abundant complexing, stir and be settled to 50ml, the pH value of regulator solution is 12.5,80 DEG C of reactions 4 hours, take out after cleaning up and can obtain Cu ₂o sample (f).

8. in the copper-bath of 0.3mol/L, the substrate of cleaning activation in advance is flatly put into according to concentration ratio 12: 9: 8, add the citric acid three sodium solution prepared, glucose solution is added after abundant complexing, stir and be settled to 50ml, the pH value of regulator solution is 13.2,80 DEG C of reactions 4 hours, take out after cleaning up and can obtain Cu ₂o sample (g).

Claims

1. chemical bath deposition many shell core-shell micro/nano structure Cu ₂the preparation method of O, comprises the following steps:

A) in copper-bath, flatly substrate is put into, be the ratio of 12: 4 ~ 12: 18 according to the mol ratio of copper sulfate and trisodium citrate, add citric acid three sodium solution, after abundant complexing, be add glucose solution at 12: 2 ~ 12: 22 according to the mol ratio of copper sulfate and glucose, and constant volume make the concentration of copper-bath in 0.10mol/L ~ 0.50mol/L scope;

C) by adjust pH value the arbitrary temperature of solution between 50 DEG C ~ 95 DEG C under after isothermal reaction 1.5h ~ 6.0h, take out and rinse post-drying well.

2. preparation method according to claim 1, is characterized in that, described step b) in adjustment solution ph scope be 12.3 ~ 14.0.