CN102863005A

CN102863005A - Preparation method of multi-shell core-shell micro/nano structure Cu2O

Info

Publication number: CN102863005A
Application number: CN2012103472931A
Authority: CN
Inventors: 徐海燕; 陈琛; 董金矿
Original assignee: Anhui University of Architecture
Current assignee: Anhui University of Architecture
Priority date: 2012-09-10
Filing date: 2012-09-10
Publication date: 2013-01-09
Anticipated expiration: 2032-09-10
Also published as: CN102863005B

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 shells nucleocapsid micro-nano structure Cu 2The preparation method of O

Technical field

A kind of many shells nucleocapsid 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, preparation and the performance 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. had important impact.At present the method for each nucleocapsid structure of system and hollow structure can be divided into hard template method (polymkeric substance for example, pottery, metal ball body etc.), soft template method (emulsion droplets for example, tensio-active agent and bubble etc.) and based on Kirkendall effect, physics or the chemical process of Ostwald ripening effect and chemical substance inductive effect etc., yet, owing to will process template or middle the equating of introducing, it is too loaded down with trivial details when preparation nucleocapsid structure and hollow structure that these make each method, 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 found semiconductor material the earliest, it is cheap, material source is extensive and obtain more and more people's approval.Cu ₂O is can be 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 ₂The O good stability, utilization that can be repeatedly and be not easy to be oxidized to Cu (II) and be reduced into Cu; Secondly, Cu ₂The O nontoxicity, good with the consistency of environment, and obtain easily.Therefore be the very large semiconductor material of a kind of application potential, at aspects such as superconductor, hydrogen manufacturing, solar cell, electrochromism and organic matter degradations potential application arranged.In numerous patterns, wherein has the Cu of nucleocapsid structure (zonal structure) pattern ₂O owing to have larger specific surface area, has greater advantage aspect organic matter degradation.

At present at the Cu for preparing nucleocapsid structure (zonal structure) pattern ₂Can be by template or middle phase in the O process, and then adopt relevant physics or chemical process to remove these templates or middle phase, but these methods are comparatively loaded down with trivial details, and may cause existing in the product dephasign, in addition, these preparation methods may have higher requirements to equipment, cause cost higher.The Cu for preparing nucleocapsid structure (zonal structure) by chemical bath deposition method by glucose as reductive agent ₂O has fast, outside simple, low-cost, the high pure phase characteristics, also be applicable to the deposition of various abnormity, non-conductive or non-refractory substrate; And in the multilayer film deposition process, can be to the characteristics of the film injury that deposited on the substrate.

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 have many shells nucleocapsid micro-nano structure Cu ₂O is specially adapted to film forming and the batch production of out-of-shape object.

Many shells nucleocapsid micro-nano structure Cu provided by the invention ₂The preparation method of O sample, it may further comprise the steps:

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

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

C) solution that will adjust the pH value takes out and rinses post-drying well behind specified temp deposit reaction certain hour.

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 is controlled at 0.10mol/L～0.50mol/L;

Described step b) adjusting the pH scope in is 12.3～14.0;

Described step c) temperature range of solution is controlled at 50 ℃～95 ℃ in;

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

The method and other liquid phase prepare the Cu of nucleocapsid structure (zonal structure) ₂O method (template and middle phase) is compared, and has not only simplified greatly preparation technology, and to reaction conditions require relatively lowly, be fit to the production of mass-producing, reduced production cost, also shortened the production cycle; What is more important uses the comparatively gentle glucose of reductibility as reductive agent, can prevent from Cu (II) is reduced into metal Cu, thereby prepare the Cu of pure phase ₂O utilizes the gluconic acid by the oxidized generation of glucose simultaneously, participates in many shells nucleocapsid micro-nano structure Cu ₂The formation of O has been avoided processing mutually the incomplete dephasign of introducing because of template and centre.

Employing Bruker Advance D8X ray powder diffraction instrument (Cu K α radiation,

2 θ=20-75 °) measure the structure of prepared material.Adopt the surface topography of the prepared material of Sirion200 sem observation.

By Fig. 1 and Fig. 2 as can be known, prepared Cu ₂The O sample is pure cubic structure (JCPDS card No.74-1230), and wherein (111) crystal face diffraction peak intensity changes obviously among Fig. 2, shows that pH all can prepare pure Cu more than or equal to 10.7 ₂The O sample wherein can be prepared desirable, pure Cu at pH in 11.5～13.2 scope ₂The O sample.Resulting product is nucleocapsid structure and many shells micro-nano structure Cu as shown in Figure 3 ₂The O sample; As shown in Figure 4, only could make the Cu that respectively goes out nucleocapsid structure (zonal structure) at pH greater than 12.0 o'clock ₂The O sample.

Description of drawings

Fig. 1: be 12.5 o'clock at pH, the X-ray diffractogram of the product that reaction 2h obtains;

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

Fig. 3: be 12.5 o'clock at pH, the scanning electron microscope (SEM) photograph of the product that reaction 2h obtains;

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

Embodiment

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

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

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

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

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

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

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

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

Claims

1. many shells of chemical bath deposition nucleocapsid micro-nano structure Cu ₂The preparation method of O may further comprise the steps:

C) solution that will adjust the pH value behind the isothermal reaction certain hour, takes out and rinses post-drying well under specified temp.

2. preparation method according to claim 1 is characterized in that, described step a) in the molar ratio range of copper sulfate and trisodium citrate be 12: 4～12: 18, the mol ratio of copper sulfate and glucose is in 12: 2～12: 22 scopes.

3. each method of system according to claim 1 is characterized in that, described step a) middle concentration of copper sulfate is controlled at 0.10mol/L～0.50mol/L.

4. preparation method according to claim 1 is characterized in that, described step b) in to adjust the pH scope be 12.3～14.0.

5. preparation method according to claim 1 is characterized in that, described step c) in the temperature range of solution be controlled at 50 ℃～95 ℃.

6. preparation method according to claim 1 is characterized in that, described step c) reaction times is controlled at 1.5h～6.0h.