阅读说明：本技术 一种四氧化三钴掺杂碳酸氧铋催化剂的制备方法 (Preparation method of cobaltosic oxide-doped bismuthyl carbonate catalyst ) 是由 马红超 董清溪 付颖寰 王国文 董晓丽 于 2019-11-26 设计创作，主要内容包括：本发明提供一种四氧化三钴掺杂碳酸氧铋催化剂的制备方法,包括以下步骤：以硝酸铋和碳酸钠为原料,硝酸溶液为溶剂,CTAB为表面活性剂,制备纯相Bi<Sub>2</Sub>O<Sub>2</Sub>CO<Sub>3</Sub>,并溶解在乙醇中,加入醋酸钴后用氨水调节PH,洗涤后得到最后得到沉淀,经过洗涤烘干即得四氧化三钴掺杂碳酸氧铋催化剂。本发明制得的四氧化三钴掺杂碳酸氧铋催化剂,不仅扩展了碳酸氧铋在实际生产中的应用,而且与其他碳酸氧铋催化剂相比,也克服了激发电子-空穴对的迁移距离长和快速复合率、量子效率低、降低太阳能的利用率、限制其在光降解中的应用等缺点,其中掺杂0.6％四氧化三钴的碳酸氧铋降解效果是纯相碳酸氧铋的1.5倍。(The invention provides a preparation method of cobaltosic oxide doped bismuth oxycarbonate catalyst, which comprises the following steps: preparing pure-phase Bi by using bismuth nitrate and sodium carbonate as raw materials, using a nitric acid solution as a solvent and using CTAB as a surfactant 2 O 2 CO 3 Dissolving the cobaltous oxide in ethanol, adding the cobalt acetate, adjusting the pH value by using ammonia water, washing to obtain a precipitate, and washing and drying to obtain the cobaltosic oxide-doped bismuthyl carbonate catalyst. The cobaltosic oxide-doped bismuth oxycarbonate catalyst prepared by the invention not only expands the application of bismuth oxycarbonate in practical production, but also overcomes the defects of long migration distance, quick recombination rate, low quantum efficiency, reduction of solar energy utilization rate, limitation of the application of the catalyst in photodegradation and the like of excited electron-hole pairs compared with other bismuth oxycarbonate catalysts, wherein the degradation effect of the cobaltosic oxide-doped.)

1. A preparation method of cobaltosic oxide doped bismuth oxycarbonate catalyst is characterized by comprising the following preparation processes:

s1, dissolving 4.7-5 g of bismuth nitrate in 8-12 mL of HNO with the concentration of 0.8-1 mol/L₃Stirring the solution at room temperature for 25-35 min;

s2, dissolving 0.8-1.2 g of CTAB and 8.3-8.6 g of anhydrous sodium carbonate in 80-100 mL of deionized water, and stirring at room temperature for 25-35 min;

s3, dripping the solution prepared in the step S1 into the solution prepared in the step S2, and stirring at room temperature for 25-35 min to obtain a mixed solution;

s4, sequentially adding ethanol and the mixed solution obtained in the step S3 into the mixed solution respectivelyWashing with deionized water for 2-4 times, and drying the precipitate left after washing at 55-65 ℃ for 3-5 h to obtain pure-phase Bi₂O₂CO₃；

S5, taking the pure phase Bi obtained in the step S4₂O₂CO₃Adding the mixture into 15-25 mL of absolute ethyl alcohol, stirring for 60-70 min, adding cobalt acetate, continuously stirring for 20-40 min to obtain a suspension, adjusting the pH value of the suspension to 10-11 by using ammonia water, sealing, drying at 140-150 ℃ for 2-4 h, and cooling to room temperature;

s6, washing the product obtained in the step S5 with ethanol and deionized water for 2-4 times through centrifugation, and drying at 55-65 ℃ for 7-9 hours to obtain a product, namely Co₃O₄Doping with Bi₂O₂CO₃A catalyst.

2. The method for preparing a cobaltosic oxide-doped bismuth oxycarbonate catalyst according to claim 1, wherein the dropping speed in the step S3 is 1-2 drops/S.

3. The method of claim 1, wherein the cobalt acetate and the pure phase Bi are mixed in step S5₂O₂CO₃The weight percentage is 0.3-1.2%.

4. The method for preparing cobaltosic oxide-doped bismuth oxycarbonate catalyst according to claim 1, wherein the centrifugal rotation speed in step S6 is 8000 r/min.

Technical Field

The invention relates to the field of photocatalytic materials, in particular to a preparation method of a cobaltosic oxide-doped bismuth oxycarbonate catalyst.

Background

Current industrialization and rapid population growth have led to global energy shortages and environmental pollution. For the sustainable development of human society, the development of pollution-free technologies for environmental remediation and replacement of clean energy supply has attracted considerable attention.

Among various green earth and renewable energy projects, optical drive photocatalysts have become one of the most promising technologies. The technology of utilizing semiconductor metal oxide as photocatalyst to decompose water directly by sunlight to generate hydrogen and oxygen is called as 'dream of 21 century'. However, semiconductor metal oxide as a photocatalyst requires more electrons in the process of photocatalytic oxidation of water to produce oxygen, and is more difficult to produce hydrogen in kinetics than the process of water reduction with only 2 electrons. Compared with the process of producing hydrogen by photo-catalytic oxidation of water, the current research on photo-catalytic oxygen evolution reaction has not attracted much attention.

However, photocatalytic oxygen generation is one of the necessary steps for constructing semiconductors to completely split water into hydrogen and oxygen. Therefore, the seeking of a novel and efficient semiconductor material for photocatalytic oxidation of water to prepare oxygen is beneficial to promoting the development of a technology for efficiently preparing hydrogen by utilizing solar energy. Theoretically, the semiconductor forbidden band width is larger than 1.23eV, water can be photolyzed, energy loss is taken into consideration due to the existence of overpotential, and the most suitable forbidden band width is 2.0-2.2 eV. And Co₃O₄Because the narrow bandwidth of 2.1eV is the most suitable choice, the preparation method of the cobaltosic oxide doped bismuth oxycarbonate catalyst is urgent priority for photolysis of water to generate oxygen.

Disclosure of Invention

The invention provides a preparation method of cobaltosic oxide-doped bismuth subcarbonate catalyst, which aims to solve the problem that a novel and efficient semiconductor material for photocatalytic oxidation of water to prepare oxygen is lacked at present.

In order to achieve the purpose, the technical scheme of the invention is as follows:

s1, dissolving 4.7-5 g of bismuth nitrate in 8-12 mL of HNO with the concentration of 0.8-1 mol/L₃In solution, stirring at room temperature to 25 ℃35min；

S2, dissolving 0.8-1.2 g of CTAB and 8.3-8.6 g of anhydrous sodium carbonate in 80-100 mL of deionized water, and stirring at room temperature for 25-35 min;

s3, dripping the solution prepared in the step S1 into the solution prepared in the step S2, and stirring at room temperature for 25-35 min to obtain a mixed solution;

s4, washing the mixed solution obtained in the step S3 with ethanol and deionized water for 2-4 times respectively, and drying the precipitate left after washing at 55-65 ℃ for 3-5 hours to obtain pure-phase Bi₂O₂CO₃；

S5, taking the pure phase Bi obtained in the step S4₂O₂CO₃Adding the mixture into 15-25 mL of absolute ethyl alcohol, stirring for 60-70 min, adding cobalt acetate, continuously stirring for 20-40 min to obtain a suspension, adjusting the pH value of the suspension to 10-11 by using ammonia water, sealing, drying at 140-150 ℃ for 2-4 h, and cooling to room temperature;

s6, washing the product obtained in the step S5 with ethanol and deionized water for 2-4 times through centrifugation, and drying at 55-65 ℃ for 7-9 hours to obtain a product, namely Co₃O₄Doping with Bi₂O₂CO₃A catalyst.

Wherein the dropping speed in the step S3 is 1-2 drops/S.

Wherein the cobalt acetate and the pure phase Bi in step S5₂O₂CO₃The weight percentage is 0.3-1.2%.

Wherein, the centrifugal speed in the step S6 is 8000 r/min.

The cobaltosic oxide doped bismuth oxycarbonate catalyst prepared by the invention not only expands the application of bismuth oxycarbonate in actual production, but also overcomes the defects of long migration distance, quick recombination rate, low quantum efficiency, reduction of solar energy utilization rate, limitation of application of the catalyst in photodegradation and the like of excited electron-hole pairs compared with a pure bismuth oxycarbonate catalyst. Wherein the degradation effect of the bismuth subcarbonate doped with 0.6 percent of cobaltosic oxide is 1.5 times that of the pure-phase bismuth subcarbonate.

Drawings

FIG. 1 is a pure phaseBi₂O₂CO₃Scanning Electron Microscope (SEM) images;

FIG. 2 is a Scanning Electron Microscope (SEM) image of the 0.3% tricobalt tetroxide doping level;

FIG. 3 is a Scanning Electron Microscope (SEM) image of the 0.6% tricobalt tetroxide doping level;

FIG. 4 is a Scanning Electron Microscope (SEM) image of the 0.9% tricobalt tetroxide doping level;

FIG. 5 is a Scanning Electron Microscope (SEM) image of the doping level of 1.2% cobaltosic oxide;

FIG. 6 is a Scanning Electron Microscope (SEM) image of pure phase cobaltosic oxide;

FIG. 7 shows the pure phase Bi of the present invention₂O₂CO₃、Co₃O₄Doping with Bi₂O₂CO₃X-ray diffraction (XRD) patterns of cobaltosic oxide at different loadings and in pure phase;

FIG. 8 shows the pure phase Bi of the present invention₂O₂CO₃、Co₃O₄Doping with Bi₂O₂CO₃Photocatalytic degradation of different loading amounts.

Detailed Description

The present invention will be described in further detail with reference to the accompanying drawings and examples.

The following reagents and drugs were purchased from Mimi European chemical reagent Co., Ltd, Tianjin.