CN101412530B - Preparation with organic addition for controlling external morphology of cuprous oxide crystal - Google Patents

Abstract

The invention discloses a preparation method for controlling the external form of a cuprous oxide crystal by utilizing an organic additive. The method is as follows: bluestone is dissolved in water and stirred; sodium lactate the mol number of which is 8 to 10 times of that of the bluestone is added into the solution and continuously stirred; the pH value of the solution is adjusted to 7.0 by utilizing sodium hydroxide the molar concentration of which is 4.0 mol/L; 5 to 15 ml of organic additive is added into the solution; the finally prepared solution is put into an autoclave and subjected to hydrothermal treatment for 4 to 8 hours at a temperature of between 150 and 180 DEG C; and finally, the treated solution is centrifugated and dried to obtain the cubic-phase cuprous oxide powder with different forms. The preparation method for controlling the external form of the cuprous oxide crystal by utilizing the organic additive controls the relative growth rate of a surface (100) and a surface (111) in the cuprous oxide crystal by controlling the variety and the dosage of the organic additive, so as to prepare the cubic-phase cuprous oxide powder with different forms.

Description

Preparation method for controlling external morphology of cuprous oxide crystals by using organic additives

technical field

The invention relates to a preparation method for controlling the external morphology of cuprous oxide crystals by using organic additives.

Background technique

Cuprous oxide (Cu ₂ O) is a very important oxide semiconductor material with a bandgap of 2.1eV, can be excited by visible light with a wavelength of 400-800nm, and has low preparation cost and high theoretical utilization efficiency. There are important applications in fields such as solar cells, catalysts, fuel cells, gas sensors, and superconducting materials. In recent years, with the wide application of cuprous oxide in the field of scientific research and production, the growth mechanism of cuprous oxide crystals has received more and more attention. The cuprous oxide crystal belongs to the cubic crystal system, and its crystal structure and internal point defects have an important influence on the mechanical, electrical, thermal, magnetic, optical and other properties of the material. Therefore, realizing the controllable crystal structure and external shape of cuprous oxide is not only of great significance for studying the growth mechanism of cuprous oxide crystal, but also can adjust various properties of the crystal to meet the specific requirements of different devices and achieve the optimal performance of the device. Purpose.

The hydrothermal method is an important method for preparing cuprous oxide crystals (Ming-Guo Ma, et al., Journal of Alloys and Compounds, 455, L15-L18, (2008)). The hydrothermal method is characterized in that the reaction is carried out in a closed container (reactor), so that some reactions that are difficult to occur at normal temperature and pressure occur at high temperature and high pressure. The hydrothermal method can directly obtain dispersed and well-crystallized powders, avoiding the possible hard agglomeration of powders, and in the hydrothermal process, the crystal structure, particle size, crystal form and crystal structure of the product can be controlled by adjusting the experimental conditions. grain purity. Using sodium lactate as the complexing agent and reducing agent of copper salt, compared with the traditional hydrothermal synthesis process using ethylenediaminetetraacetic acid (EDTA) and glucose as complexing agents to synthesize cuprous oxide crystals, the time can be greatly shortened. The invention utilizes organic additives: ethanol, acetone and isopropanol to control the relative growth rates of different crystal planes in the cuprous oxide crystal: (100) plane and (111) plane, so as to achieve the purpose of controlling the external shape of the cuprous oxide crystal.

Contents of the invention

The object of the present invention is to provide a preparation method for realizing the controllable shape of cuprous oxide crystals, using sodium lactate and copper salt (copper sulfate) to form a complex, and controlling the cubic crystals of cuprous oxide by controlling the type and dosage of organic additives The relative growth rate of the (100) plane and the (111) plane in order to prepare cuprous oxide powders with different external morphologies.

The technical solution adopted in the present invention is that the steps of the method are as follows:

1) dissolving the soluble copper salt in water, controlling the molar concentration of copper ions in the solution to be 0.02 to 0.04 mol/liter, and stirring;

2) adding sodium lactate whose molar concentration is 8 to 10 times the molar concentration of copper ions in the above solution, and continue stirring;

3) Utilize 4.0 mol/liter of sodium hydroxide to adjust the pH value of the solution to 7.0;

4) Add 5 to 15 milliliters of organic additives in the solution;

5) Put the prepared solution into an autoclave, and perform hydrothermal treatment in the temperature range of 150-180°C for 4-8 hours;

6) centrifuging and drying the hydrothermally treated solution to obtain cubic phase cuprous oxide powder.

The copper sulfate is used as a soluble copper salt, and the sodium lactate is used as a complexing agent and a reducing agent to control the relative relationship between the (100) plane and the (111) plane in the cuprous oxide cubic crystal by controlling the type and dosage of the organic additive. Growth rate, thereby preparing cuprous oxide powders with different external morphologies.

The organic additive is ethanol, acetone or isopropanol.

The beneficial effects that the present invention has are:

The traditional hydrothermal synthesis process for synthesizing cuprous oxide crystals generally uses ethylenediaminetetraacetic acid (EDTA) and glucose as complexing agents. Copper crystals have a shorter time. A simple method of controlling the type and dosage of the organic additive is used to control the relative growth rate of the (100) plane and the (111) plane in the cuprous oxide crystal, so as to realize the controllable shape of the cuprous oxide crystal.

Description of drawings

Fig. 1 is the XRD spectrum of the cuprous oxide crystal obtained in the comparative example.

Fig. 2 is a scanning electron micrograph of the cuprous oxide crystal obtained in the comparative example.

Fig. 3 is the XRD spectrum of the cuprous oxide crystal obtained in Example 1.

4 is a scanning electron micrograph of the cuprous oxide crystal obtained in Example 1.

Fig. 5 is the XRD spectrum of the cuprous oxide crystal obtained in Example 2.

6 is a scanning electron micrograph of the cuprous oxide crystal obtained in Example 2.

Fig. 7 is the XRD spectrum of the cuprous oxide crystal obtained in Example 3.

Fig. 8 is a scanning electron micrograph of the cuprous oxide crystal obtained in Example 3.

Detailed ways

Comparative example:

Dissolve 0.3995 grams of copper sulfate (CuSO ₄ 5H ₂ O) in 75.0 milliliters of deionized water, stir for 5 minutes, then add 2.5 milliliters of 60% sodium lactate (C ₃ H ₅ NaO ₃ ), the molar concentration of sodium lactate is 0.2 molar / liter, after stirring for 5 minutes, utilize 4.0 mol/liter of sodium hydroxide to adjust the pH value of the solution to 7.0, without adding any organic additives, and stir for 5 minutes. The final solution volume was adjusted to 80.0 ml with deionized water, and the molar concentration of copper ions in the solution was 0.02 mol/liter. Put the prepared solution above into the polytetrafluoroethylene lining of the autoclave. The solution was treated at 150° C. for 8 hours, and the treated solution was centrifuged and dried to obtain a cuprous oxide powder whose external morphology was shown in the scanning electron microscope photo in FIG. 1 . Figure 2 is the XRD pattern of the cuprous oxide crystal, which is completely consistent with the standard card (JCPDS No.65-3288) of cubic phase cuprous oxide.

Example 1:

Dissolve 0.3995 grams of copper sulfate (CuSO ₄ 5H ₂ O) in 65.0 milliliters of deionized water, stir for 5 minutes, then add 2.5 milliliters of 60% sodium lactate (C ₃ H ₅ NaO ₃ ), the molar concentration of sodium lactate is 0.2 molar / liter, after stirring for 5 minutes, utilize 4.0 mol/liter of sodium hydroxide to adjust the pH value of the solution to 7.0. Add 10.0 mL of ethanol and stir for 5 minutes. The final solution volume was adjusted to 80.0 ml with deionized water, and the molar concentration of copper ions in the solution was 0.02 mol/liter. Put the prepared solution above into the polytetrafluoroethylene lining of the autoclave. The solution was treated at 150° C. for 8 hours, and the treated solution was centrifuged and dried to obtain a cuprous oxide powder whose external morphology was shown in the scanning electron microscope photo in FIG. 3 . Figure 4 is the XRD pattern of the cuprous oxide crystal, which is completely consistent with the standard card (JCPDS No.65-3288) of cubic phase cuprous oxide.

Example 2:

Dissolve 0.7990 g of copper sulfate (CuSO ₄ 5H ₂ O) in 60.0 ml of deionized water, stir for 5 minutes, then add 4.0 ml of 60% sodium lactate (C ₃ H ₅ NaO ₃ ), the molar concentration of sodium lactate is 0.32 molar / liter, after stirring for 5 minutes, utilize 4.0 mol/liter of sodium hydroxide to adjust the pH value of the solution to 7.0. Add 15.0 mL of isopropanol and stir for 5 minutes. The final solution volume was adjusted to 80.0 ml with deionized water, and the molar concentration of copper ions in the solution was 0.04 mol/liter. Put the prepared solution above into the polytetrafluoroethylene lining of the autoclave. The solution was treated at 150° C. for 8 hours, and the treated solution was centrifuged and dried to obtain the cuprous oxide powder whose external morphology is shown in the scanning electron microscope photo in FIG. 5 . Figure 6 is the XRD pattern of the cuprous oxide crystal, which is completely consistent with the standard card (JCPDS No. 65-3288) of cubic phase cuprous oxide.

Example 3:

Dissolve 0.3995 grams of copper sulfate (CuSO ₄ 5H ₂ O) in 70 milliliters of deionized water, stir for 5 minutes, then add 2.5 milliliters of 60% sodium lactate (C ₃ H ₅ NaO ₃ ), the molar concentration of sodium lactate is 0.2 molar / liter, after stirring for 5 minutes, utilize 4.0 mol/liter of sodium hydroxide to adjust the pH value of the solution to 7.0. Add 5.0 ml of acetone and stir for 5 minutes. The final solution volume was adjusted to 80.0 ml with deionized water, and the molar concentration of copper ions in the solution was 0.02 mol/liter. Put the prepared solution above into the polytetrafluoroethylene lining of the autoclave. The solution was treated at 150° C. for 8 hours, and the treated solution was centrifuged and dried to obtain cuprous oxide powder whose external morphology was shown in the scanning electron microscope photo in FIG. 7 . Figure 8 is the XRD spectrum of the cuprous oxide crystal, which is completely consistent with the standard card of cubic phase cuprous oxide (JCPDS No.65-3288).

Claims (2)

1. method of utilizing organic addition for controlling external morphology of cuprous oxide crystal is characterized in that the step of this method is as follows:

1) soluble copper salt is soluble in water, the volumetric molar concentration of cupric ion is 0.02～0.04 mol in the control solution, stirs;

2) in above-mentioned solution, add the Sodium.alpha.-hydroxypropionate that volumetric molar concentration is 8～10 times of the volumetric molar concentrations of cupric ion again, continue to stir;

3) utilizing the pH value of the sodium hydrate regulator solution of 4.0 mol is 7.0;

4) in solution, add 5～15 milliliters organic additive; Described organic additive is ethanol, acetone or Virahol;

5) solution for preparing is put into autoclave, hydrothermal treatment consists is 4～8 hours in 150～180 ℃ of temperature ranges;

6), just obtained the cuprous powder of cubic phase oxygenization with the solution centrifugal after the hydrothermal treatment consists, drying.

2. a kind of method of utilizing organic addition for controlling external morphology of cuprous oxide crystal according to claim 1, it is characterized in that: employing copper sulfate is soluble copper salt, described Sodium.alpha.-hydroxypropionate is as complexing agent and reductive agent, kind and dosage by the control organic additive, come the relative growth rate of (100) face and (111) face in the cuprous cubic system of controlled oxidation, thus the Red copper oxide powder that preparation has different formalnesses.

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