CN103212708B - Hollow and echinoid nanometer material of copper oxide compounded with gold and preparing method thereof - Google Patents
Hollow and echinoid nanometer material of copper oxide compounded with gold and preparing method thereof Download PDFInfo
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Abstract
本发明公开了一种中空海胆状的铜氧化物与金复合的纳米材料及其制备方法，制备过程中利用环境友好，方便易得的氯化铜、氢氧化钠、抗坏血酸和氯金酸为原料，提供一种操作简单、产率高、成本低、绿色环保的多级结构铜氧化物与金复合纳米材料的水相合成制备方法。制得的材料是一种具有多级结构氧化铜与金复合的纳米材料，且形貌为中空海胆状、尺寸均一。经本发明方法制得的材料应用于气敏传感器上。
The invention discloses a hollow sea urchin-shaped nanometer material composited with copper oxide and gold and a preparation method thereof. In the preparation process, environment-friendly, convenient and easy-to-obtain copper chloride, sodium hydroxide, ascorbic acid and chloroauric acid are used as raw materials The invention provides an aqueous-phase synthesis preparation method of multi-level copper oxide and gold composite nanomaterials with simple operation, high yield, low cost, and environmental protection. The prepared material is a composite nano material of copper oxide and gold with a multi-level structure, and has a hollow sea urchin shape and uniform size. The material prepared by the method of the invention is applied to a gas sensor.
Description
技术领域technical field
本发明涉及一种用作半导体气体传感器的纳米材料的制备方法，更特别地说，是指一种中空海胆状的铜氧化物与金复合的纳米材料及其制备方法。The invention relates to a preparation method of a nanometer material used as a semiconductor gas sensor, more particularly, a hollow sea urchin-shaped copper oxide and gold composite nanometer material and a preparation method thereof.
背景技术Background technique
气敏传感器是一种将检测到的气体成分和浓度转换为电信号的传感器。它主要包括半导体气敏传感器、接触燃烧式气敏传感器和电化学气敏传感器等，其中用的最多的是半导体气敏传感器。该类传感器能够有效监控空气环境质量、控制各种有毒害及可燃性气体的排放。A gas sensor is a sensor that converts the detected gas composition and concentration into an electrical signal. It mainly includes semiconductor gas sensors, contact combustion gas sensors and electrochemical gas sensors, among which semiconductor gas sensors are the most used. This type of sensor can effectively monitor the quality of the air environment and control the emission of various toxic and flammable gases.
2007年10月第6卷第10期在《广东大学学报》自然科学版公开了题目为“金属氧化物气敏传感器”一文。文中介绍了多种制备金属氧化物半导粉体的方法。In October 2007, Volume 6, Issue 10 published a paper titled "Metal Oxide Gas Sensors" in the Natural Science Edition of "Journal of Guangdong University". A variety of methods for preparing metal oxide semiconductor powders are introduced in this paper.
理想的气敏传感器在性能上应该有如下的优点：灵敏度高，选择性好，功耗低、长期工作情况下稳定性好、成本低等。然而，实际的气敏传感器由于材料、制备工艺等各种因素的限制，往往不能很好的满足应用的需求。An ideal gas sensor should have the following advantages in terms of performance: high sensitivity, good selectivity, low power consumption, good stability under long-term working conditions, and low cost. However, due to the limitations of various factors such as materials and manufacturing processes, the actual gas sensor often cannot meet the requirements of the application well.
发明内容Contents of the invention
本发明的目的之一是提供一种中空海胆状的铜氧化物与金复合的纳米材料，该材料是一种具有多级结构氧化铜与金复合的纳米材料，且形貌为中空海胆状、尺寸均一、比表面积高。One of the purposes of the present invention is to provide a hollow sea urchin-shaped copper oxide and gold composite nanomaterial, which is a composite nanomaterial with a multi-level structure of copper oxide and gold, and has a hollow sea urchin shape, Uniform size and high specific surface area.
本发明的目的之二是提出一种制备中空海胆状的铜氧化物与金复合的纳米材料的方法，在本发明方法中利用环境友好，方便易得的氯化铜、氢氧化钠、抗坏血酸和氯金酸为原料，提供一种操作简单、产率高、成本低、绿色环保的多级结构铜氧化物与金复合纳米材料的水相合成制备方法。The second object of the present invention is to propose a method for preparing hollow sea urchin-shaped cupric oxide and gold composite nano-materials. In the inventive method, environment-friendly, easily available cupric chloride, sodium hydroxide, ascorbic acid and Chlorauric acid is used as a raw material, and an aqueous phase synthesis preparation method of multi-level copper oxide and gold composite nanomaterials with simple operation, high yield, low cost, and environmental protection is provided.
制备本发明的中空海胆状的铜氧化物与金复合的纳米材料的方法，包括有下列步骤：The method for preparing the hollow sea urchin-shaped copper oxide and gold composite nanomaterial of the present invention comprises the following steps:
第一步骤：在15℃～25℃温度下将二水合氯化铜（CuCl2·2H2O）溶解在去离子水中混合均匀后，得到氯化铜质量百分比浓度为1.5g/L～2.0g/L的第一溶液；Step 1: Dissolve copper chloride dihydrate (CuCl 2 2H 2 O) in deionized water at a temperature of 15°C to 25°C and mix well to obtain copper chloride with a mass percentage concentration of 1.5g/L to 2.0g /L of the first solution;
第二步骤：在45℃～60℃水浴温度中，在搅拌状态下缓慢向第一溶液中滴加氢氧化钠（NaOH）水溶液；滴加完氢氧化钠水溶液后继续搅拌10分钟～30分钟，得到第二溶液；The second step: slowly add sodium hydroxide (NaOH) aqueous solution dropwise to the first solution under stirring at a water bath temperature of 45°C-60°C; continue stirring for 10 minutes to 30 minutes after adding the aqueous sodium hydroxide solution dropwise, obtain the second solution;
滴加速度为50滴/分钟～80滴/分钟；The dropping rate is 50 drops/minute to 80 drops/minute;
搅拌速度为200转/分钟～400转/分钟；The stirring speed is 200 rpm to 400 rpm;
氢氧化钠水溶液的质量百分比浓度为80g/L；The mass percentage concentration of sodium hydroxide aqueous solution is 80g/L;
1L的第一溶液中加入0.088L～0.118L的氢氧化钠水溶液；Add 0.088L ~ 0.118L of sodium hydroxide aqueous solution to 1L of the first solution;
第三步骤：在45℃～60℃水浴温度中，在搅拌状态下缓慢向第二溶液中滴加抗坏血酸（C6H8O6）水溶液；滴加完抗坏血酸水溶液后继续搅拌150分钟～200分钟，得到第一悬浊液；Step 3: Slowly add ascorbic acid (C 6 H 8 O 6 ) aqueous solution to the second solution under stirring at a water bath temperature of 45°C-60°C; continue stirring for 150-200 minutes after adding the aqueous ascorbic acid solution , to obtain the first suspension;
滴加速度为10滴/分钟～30滴/分钟；The dropping rate is 10 drops/minute to 30 drops/minute;
搅拌速度为200转/分钟～400转/分钟；The stirring speed is 200 rpm to 400 rpm;
抗坏血酸水溶液的质量百分比浓度为105.7g/L；The mass percentage concentration of ascorbic acid aqueous solution is 105.7g/L;
1L的第一溶液中加入0.088L～0.118L的抗坏血酸水溶液；Add 0.088L to 0.118L of ascorbic acid aqueous solution to 1L of the first solution;
第四步骤：对第一悬浊液进行离心分离，得到第一沉淀物；The fourth step: centrifuging the first suspension to obtain the first precipitate;
将第一沉淀物先用去离子水进行离心洗涤1～3次，随后用无水乙醇进行离心洗涤1～3次，得到第二沉淀物；The first precipitate is first centrifuged and washed with deionized water for 1 to 3 times, and then centrifuged and washed with absolute ethanol for 1 to 3 times to obtain the second precipitate;
将第二沉淀物在干燥温度为40℃～50℃条件下干燥1小时～6小时后，得到第一固体粉末；drying the second precipitate at a drying temperature of 40° C. to 50° C. for 1 hour to 6 hours to obtain a first solid powder;
离心分离条件：4000转/分钟～5000转/分钟，离心时间3分钟～10分钟；Centrifugation conditions: 4000 rpm to 5000 rpm, centrifugation time 3 minutes to 10 minutes;
第五步骤：将第一固体粉末采用超声进行分散于乙醇水溶液中，得到第二悬浊液；The fifth step: dispersing the first solid powder in the ethanol aqueous solution by ultrasonic to obtain the second suspension;
乙醇水溶液的质量百分比浓度为10%；The mass percent concentration of ethanol aqueous solution is 10%;
用量：将1g的第一固体粉末加入0.8L～1.2L乙醇水溶液中；Dosage: Add 1g of the first solid powder into 0.8L~1.2L ethanol aqueous solution;
第六步骤：在15℃～25℃温度下、在搅拌状态下缓慢向第二悬浊液中滴加氯金酸（HAuCl4）水溶液；滴加完氯金酸水溶液后继续搅拌10分钟～30分钟，得到第三悬浊液；Step 6: Slowly add chloroauric acid (HAuCl 4 ) aqueous solution to the second suspension under stirring at a temperature of 15°C to 25°C; continue stirring for 10 minutes to 30 minutes after adding the aqueous chloroauric acid solution. Minutes to obtain the third suspension;
滴加速度为10滴/分钟～30滴/分钟；The dropping rate is 10 drops/minute to 30 drops/minute;
搅拌速度为200转/分钟～400转/分钟；The stirring speed is 200 rpm to 400 rpm;
氯金酸水溶液的质量百分比浓度为0.17g/L；The mass percentage concentration of chloroauric acid aqueous solution is 0.17g/L;
0.1L的第二悬浊液中加入0.015L～0.025L的氯金酸水溶液；Add 0.015L to 0.025L of chloroauric acid aqueous solution to 0.1L of the second suspension;
第七步骤：将第三悬浊液置于50℃～70℃的温度条件下，反应2～4小时后取出，冷却至15℃～25℃，得到第四悬浊液；The seventh step: place the third suspension at a temperature of 50°C to 70°C, take it out after reacting for 2 to 4 hours, and cool it to 15°C to 25°C to obtain the fourth suspension;
第八步骤：对第四悬浊液进行离心分离，得到第三沉淀物；The eighth step: centrifuging the fourth suspension to obtain the third precipitate;
将第三沉淀物先用去离子水进行离心洗涤1～3次，随后用无水乙醇进行离心洗涤1～3次，得到第四沉淀物；The third precipitate is first centrifuged and washed with deionized water for 1 to 3 times, and then centrifuged and washed with absolute ethanol for 1 to 3 times to obtain the fourth precipitate;
离心分离条件：4000转/分钟～5000转/分钟，离心时间3分钟～10分钟；Centrifugation conditions: 4000 rpm to 5000 rpm, centrifugation time 3 minutes to 10 minutes;
将第四沉淀物在干燥温度为40℃～50℃条件下干燥1小时～6小时后，得到铜氧化物与金复合的纳米材料。After drying the fourth precipitate at a drying temperature of 40° C. to 50° C. for 1 hour to 6 hours, a nanometer material composed of copper oxide and gold is obtained.
本发明制备方法的优点在于：The advantage of preparation method of the present invention is:
①本发明方法利用环境友好，方便易得的氯化铜、氢氧化钠、抗坏血酸和氯金酸为原料，提供一种操作简单、产率高、成本低、绿色环保的多级结构铜氧化物与金复合纳米材料的水相合成制备方法。1. The inventive method utilizes environment-friendly, convenient and easy-to-obtain copper chloride, sodium hydroxide, ascorbic acid and chloroauric acid as raw materials to provide a multi-level structure copper oxide with simple operation, high yield, low cost, and environmental protection Preparation method of aqueous phase synthesis of nanomaterials composited with gold.
②在制得高比表面积的中空复合结构的多级结构铜氧化物时无需模板，且贵金属（金元素）纳米颗粒的生成与复合一步完成，贵金属原料用量少，利用率高。简化了合成步骤与周期，废料少，适用于流水线批量生产，生产成本得以降低，具有市场应用价值。② No template is required to prepare multi-level structure copper oxide with hollow composite structure with high specific surface area, and the generation and compounding of noble metal (gold element) nanoparticles are completed in one step, the amount of precious metal raw materials is small, and the utilization rate is high. The synthesis steps and cycle are simplified, and the waste material is less, which is suitable for mass production in an assembly line, reduces the production cost, and has market application value.
③本发明是一种温和的溶液合成法，合成过程简单易操作，合成温度低，所需合成设备方便易得，得到的多级结构氧化铜与金复合纳米材料尺寸和形貌较为均一。③ The present invention is a mild solution synthesis method, the synthesis process is simple and easy to operate, the synthesis temperature is low, the required synthesis equipment is convenient and easy to obtain, and the size and shape of the obtained multi-level structure copper oxide and gold composite nanomaterial are relatively uniform.
④本发明选用价格低廉、环境无毒的氯化铜、氢氧化钠和抗坏血酸等为原料，且原料利用率高，具有绿色环保节能的优点。4. The present invention selects copper chloride, sodium hydroxide and ascorbic acid with low price and environmental nontoxicity as raw materials, and the utilization rate of raw materials is high, and has the advantages of environmental protection and energy saving.
附图说明Description of drawings
图1是本发明实施例1制备得到的第一固体粉末的XRD衍射图。FIG. 1 is an XRD diffraction pattern of the first solid powder prepared in Example 1 of the present invention.
图2是本发明实施例1制备得到的第一固体粉末的SEM图。FIG. 2 is an SEM image of the first solid powder prepared in Example 1 of the present invention.
图3A是本发明实施例1制备得到的铜氧化物与金复合的纳米材料的XRD衍射图。FIG. 3A is an XRD diffraction pattern of the copper oxide-gold composite nanomaterial prepared in Example 1 of the present invention.
图3B是是本发明实施例1制备得到的铜氧化物与金复合的纳米材料的X射线能量分析光谱。FIG. 3B is an X-ray energy analysis spectrum of the copper oxide-gold composite nanomaterial prepared in Example 1 of the present invention.
图4是本发明实施例1制备得到的铜氧化物与金复合的纳米材料的SEM图。Fig. 4 is an SEM image of the copper oxide and gold composite nanomaterial prepared in Example 1 of the present invention.
图5A是本发明实施例1制备得到的铜氧化物与金复合的纳米材料的TEM图。FIG. 5A is a TEM image of the copper oxide-gold composite nanomaterial prepared in Example 1 of the present invention.
图5B是图5A中部分放大的TEM图和高分辨率的透射电镜（HRTEM）图。Fig. 5B is a partially enlarged TEM image and a high-resolution transmission electron microscope (HRTEM) image of Fig. 5A.
具体实施方式Detailed ways
下面将结合附图和实施例对本发明做进一步的详细说明。The present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments.
制备本发明的一种中空海胆状的铜氧化物与金复合的纳米材料包括有下列步骤：Preparation of a hollow sea urchin-shaped copper oxide and gold composite nanomaterial comprises the following steps:
第一步骤：在15℃～25℃温度下将二水合氯化铜（CuCl2·2H2O）溶解在去离子水中混合均匀后，得到氯化铜质量百分比浓度为1.5g/L～2.0g/L的第一溶液；Step 1: Dissolve copper chloride dihydrate (CuCl 2 2H 2 O) in deionized water at a temperature of 15°C to 25°C and mix well to obtain copper chloride with a mass percentage concentration of 1.5g/L to 2.0g /L of the first solution;
第二步骤：在45℃～60℃水浴温度中，在搅拌状态下缓慢向第一溶液中滴加氢氧化钠（NaOH）水溶液；滴加完氢氧化钠水溶液后继续搅拌10分钟～30分钟，得到第二溶液；The second step: slowly add sodium hydroxide (NaOH) aqueous solution dropwise to the first solution under stirring at a water bath temperature of 45°C-60°C; continue stirring for 10 minutes to 30 minutes after adding the aqueous sodium hydroxide solution dropwise, obtain the second solution;
滴加速度为50滴/分钟～80滴/分钟；The dropping rate is 50 drops/minute to 80 drops/minute;
搅拌速度为200转/分钟～400转/分钟；The stirring speed is 200 rpm to 400 rpm;
氢氧化钠水溶液的质量百分比浓度为80g/L；The mass percentage concentration of sodium hydroxide aqueous solution is 80g/L;
1L的第一溶液中加入0.088L～0.118L的氢氧化钠水溶液；Add 0.088L ~ 0.118L of sodium hydroxide aqueous solution to 1L of the first solution;
第三步骤：在45℃～60℃水浴温度中，在搅拌状态下缓慢向第二溶液中滴加抗坏血酸（C6H8O6）水溶液；滴加完抗坏血酸水溶液后继续搅拌150分钟～200分钟，得到第一悬浊液；Step 3: Slowly add ascorbic acid (C 6 H 8 O 6 ) aqueous solution to the second solution under stirring at a water bath temperature of 45°C-60°C; continue stirring for 150-200 minutes after adding the aqueous ascorbic acid solution , to obtain the first suspension;
滴加速度为10滴/分钟～30滴/分钟；The dropping rate is 10 drops/minute to 30 drops/minute;
搅拌速度为200转/分钟～400转/分钟；The stirring speed is 200 rpm to 400 rpm;
抗坏血酸水溶液的质量百分比浓度为105.7g/L；The mass percentage concentration of ascorbic acid aqueous solution is 105.7g/L;
1L的第一溶液中加入0.088L～0.118L的抗坏血酸水溶液；Add 0.088L to 0.118L of ascorbic acid aqueous solution to 1L of the first solution;
第四步骤：对第一悬浊液进行离心分离，得到第一沉淀物；The fourth step: centrifuging the first suspension to obtain the first precipitate;
将第一沉淀物先用去离子水进行离心洗涤1～3次，随后用无水乙醇进行离心洗涤1～3次，得到第二沉淀物；The first precipitate is first centrifuged and washed with deionized water for 1 to 3 times, and then centrifuged and washed with absolute ethanol for 1 to 3 times to obtain the second precipitate;
将第二沉淀物在干燥温度为40℃～50℃条件下干燥1小时～6小时后，得到第一固体粉末；drying the second precipitate at a drying temperature of 40° C. to 50° C. for 1 hour to 6 hours to obtain a first solid powder;
离心分离条件：4000转/分钟～5000转/分钟，离心时间3分钟～10分钟；Centrifugation conditions: 4000 rpm to 5000 rpm, centrifugation time 3 minutes to 10 minutes;
第五步骤：将第一固体粉末采用超声进行分散于乙醇水溶液中，得到第二悬浊液；The fifth step: dispersing the first solid powder in the ethanol aqueous solution by ultrasonic to obtain the second suspension;
乙醇水溶液的质量百分比浓度为10%；The mass percent concentration of ethanol aqueous solution is 10%;
用量：将1g的第一固体粉末加入0.8L～1.2L乙醇水溶液中；Dosage: Add 1g of the first solid powder into 0.8L~1.2L ethanol aqueous solution;
第六步骤：在15℃～25℃温度下、在搅拌状态下缓慢向第二悬浊液中滴加氯金酸（HAuCl4）水溶液；滴加完氯金酸水溶液后继续搅拌10分钟～30分钟，得到第三悬浊液；Step 6: Slowly add chloroauric acid (HAuCl 4 ) aqueous solution to the second suspension under stirring at a temperature of 15°C to 25°C; continue stirring for 10 minutes to 30 minutes after adding the aqueous chloroauric acid solution. Minutes to obtain the third suspension;
滴加速度为10滴/分钟～30滴/分钟；The dropping rate is 10 drops/minute to 30 drops/minute;
搅拌速度为200转/分钟～400转/分钟；The stirring speed is 200 rpm to 400 rpm;
氯金酸水溶液的质量百分比浓度为0.17g/L；The mass percentage concentration of chloroauric acid aqueous solution is 0.17g/L;
0.1L的第二悬浊液中加入0.015L～0.025L的氯金酸水溶液；Add 0.015L to 0.025L of chloroauric acid aqueous solution to 0.1L of the second suspension;
第七步骤：将第三悬浊液置于50℃～70℃的温度条件下，反应2～4小时后取出，冷却至15℃～25℃，得到第四悬浊液；The seventh step: place the third suspension at a temperature of 50°C to 70°C, take it out after reacting for 2 to 4 hours, and cool it to 15°C to 25°C to obtain the fourth suspension;
第八步骤：对第四悬浊液进行离心分离，得到第三沉淀物；The eighth step: centrifuging the fourth suspension to obtain the third precipitate;
将第三沉淀物先用去离子水进行离心洗涤1～3次，随后用无水乙醇进行离心洗涤1～3次，得到第四沉淀物；The third precipitate is first centrifuged and washed with deionized water for 1 to 3 times, and then centrifuged and washed with absolute ethanol for 1 to 3 times to obtain the fourth precipitate;
离心分离条件：4000转/分钟～5000转/分钟，离心时间3分钟～10分钟；Centrifugation conditions: 4000 rpm to 5000 rpm, centrifugation time 3 minutes to 10 minutes;
将第四沉淀物在干燥温度为40℃～50℃条件下干燥1小时～6小时后，得到铜氧化物与金复合的纳米材料。After drying the fourth precipitate at a drying temperature of 40° C. to 50° C. for 1 hour to 6 hours, a nanometer material composed of copper oxide and gold is obtained.
实施例1Example 1
制备具有中空海胆状的Cu2O/Au/CuO复合纳米材料的步骤有：The steps for preparing the Cu 2 O/Au/CuO composite nanomaterial with a hollow sea urchin shape include:
第一步骤：在22℃温度下将二水合氯化铜（CuCl2·2H2O）溶解在去离子水中混合均匀后，得到氯化铜质量百分比浓度为1.7g/L的第一溶液；The first step: after dissolving copper chloride dihydrate (CuCl 2 ·2H 2 O) in deionized water at a temperature of 22°C and mixing them uniformly, a first solution with a mass percent concentration of copper chloride of 1.7 g/L was obtained;
在本发明中，色泽是以GSB05-1426-2001，国标色卡-漆膜颜色标准样卡对照获得。所述第一溶液的色泽为蛋壳绿色（26G07）。In the present invention, the color is obtained by comparing with GSB05-1426-2001, national standard color card-paint film color standard sample card. The color of the first solution is eggshell green (26G07).
第二步骤：在55℃水浴温度中，在搅拌状态下缓慢向第一溶液中滴加氢氧化钠（NaOH）水溶液；滴加完氢氧化钠水溶液后继续搅拌30分钟，得到第二溶液；The second step: Slowly add sodium hydroxide (NaOH) aqueous solution dropwise to the first solution under stirring at a water bath temperature of 55°C; continue stirring for 30 minutes after adding the aqueous sodium hydroxide solution to obtain the second solution;
滴加速度为50滴/分钟；The dropping rate is 50 drops/minute;
选用杭州谱仪科技有限公司生产的RET basic C IKA加热磁力搅拌器进行处理，搅拌速度为200转/分钟；The RET basic C IKA heating magnetic stirrer produced by Hangzhou Spectrometer Technology Co., Ltd. was selected for processing, and the stirring speed was 200 rpm;
氢氧化钠水溶液的质量百分比浓度为80g/L；The mass percentage concentration of sodium hydroxide aqueous solution is 80g/L;
1L的第一溶液中加入0.100L的氢氧化钠水溶液；Add 0.100L of sodium hydroxide aqueous solution to 1L of the first solution;
在本发明中，第一溶液在滴加氢氧化钠过程中，色泽由蛋壳绿色变成浑浊的景蓝色（20B14），随后变成棕色（57YR05），故第二溶液的色泽为棕色。In the present invention, the color of the first solution changes from eggshell green to cloudy blue (20B14) and then brown (57YR05) during the dropwise addition of sodium hydroxide, so the color of the second solution is brown.
第三步骤：在55℃水浴温度中，在搅拌状态下缓慢向第二溶液中滴加抗坏血酸（C6H8O6）水溶液；滴加完抗坏血酸水溶液后继续搅拌180分钟，得到第一悬浊液；The third step: Slowly add ascorbic acid (C 6 H 8 O 6 ) aqueous solution to the second solution under stirring in a water bath temperature of 55°C; after adding the aqueous ascorbic acid solution, continue stirring for 180 minutes to obtain the first suspension liquid;
滴加速度为20滴/分钟；The dropping rate is 20 drops/minute;
搅拌速度为200转/分钟；Stirring speed is 200 rpm;
抗坏血酸水溶液的质量百分比浓度为105.7g/L；The mass percentage concentration of ascorbic acid aqueous solution is 105.7g/L;
1L的第一溶液中加入0.100L的抗坏血酸水溶液；Add 0.100L of ascorbic acid aqueous solution to 1L of the first solution;
在本发明中，第二溶液在滴加抗坏血酸水溶液过程中，色泽由棕色逐渐变为深棕黄色（55YR07），故第一悬浊液的色泽为深棕黄色。In the present invention, the color of the second solution gradually changes from brown to dark brown-yellow (55YR07) during the process of adding the ascorbic acid aqueous solution dropwise, so the color of the first suspension is dark brown-yellow.
第四步骤：对第一悬浊液进行离心分离，得到第一沉淀物；The fourth step: centrifuging the first suspension to obtain the first precipitate;
将第一沉淀物先用去离子水进行离心洗涤2次，随后用无水乙醇进行离心洗涤2次，得到第二沉淀物；选用湘仪TG16-WS台式高速离心机进行离心处理，离心分离条件为5000转/分钟，离心时间5分钟；The first precipitate was first centrifuged and washed twice with deionized water, and then centrifuged twice with absolute ethanol to obtain the second precipitate; Xiangyi TG16-WS desktop high-speed centrifuge was selected for centrifugation, and the centrifugation conditions were: 5000 rpm, centrifugation time 5 minutes;
将第二沉淀物在干燥温度为40℃条件下干燥2小时后，得到第一固体粉末；第一固体粉末的色泽为铁红色（64R01）。选用上海博迅实业有限公司医疗设备厂，GZX-9140MBE数显鼓风干燥箱。After drying the second precipitate at a drying temperature of 40° C. for 2 hours, a first solid powder was obtained; the color of the first solid powder was iron red (64R01). Choose the GZX-9140MBE digital blast drying oven from Shanghai Boxun Industrial Co., Ltd. Medical Equipment Factory.
对第一固体粉末采用X射线衍射进行成分分析，如图1所示，图中的衍射谱线与标准PDF卡片Cu2O(JCPDS No.77-0199)的衍射峰较好符合。图中的衍射峰分别对应Cu2O的(1,1,1)，(2,0,0)，(2,2,0)和(3,1,1)面的衍射峰。没有其它杂质峰出现，表明第一固体粉末的纯度很好。The component analysis of the first solid powder was carried out by X-ray diffraction, as shown in Figure 1 , the diffraction lines in the figure are in good agreement with the diffraction peaks of the standard PDF card Cu 2 O (JCPDS No.77-0199). The diffraction peaks in the figure correspond to the diffraction peaks of (1,1,1), (2,0,0), (2,2,0) and (3,1,1) planes of Cu 2 O, respectively. No other impurity peaks appeared, indicating that the purity of the first solid powder was very good.
对第一固体粉末采用扫描电子显微镜进行形貌分析，如图2所示，图2中显示了产物的整体形貌为边长在400～600nm的立方体状颗粒，表面光滑，棱边与角分明。The morphology of the first solid powder was analyzed by scanning electron microscope, as shown in Figure 2. Figure 2 shows that the overall morphology of the product is a cube-shaped particle with a side length of 400-600 nm, with a smooth surface and distinct edges and corners. .
第五步骤：将第一固体粉末采用超声进行分散于乙醇水溶液中，得到第二悬浊液；The fifth step: dispersing the first solid powder in the ethanol aqueous solution by ultrasonic to obtain the second suspension;
乙醇水溶液的质量百分比浓度为10%；The mass percent concentration of ethanol aqueous solution is 10%;
用量：将0.1g的第一固体粉末加入0.1L乙醇水溶液中；Dosage: Add 0.1g of the first solid powder to 0.1L ethanol aqueous solution;
在本发明中，选用昆山禾创超声仪器有限公司，型号为kh3200e的超声清洗器，功率150W。In the present invention, Kunshan Hechuang Ultrasonic Instrument Co., Ltd., a model kh3200e ultrasonic cleaner with a power of 150W was selected.
第六步骤：在22℃温度下、在搅拌状态下缓慢向第二悬浊液中滴加氯金酸（HAuCl4）水溶液；滴加完氯金酸水溶液后继续搅拌30分钟，得到第三悬浊液；Step 6: Slowly add chloroauric acid (HAuCl 4 ) aqueous solution to the second suspension under stirring at 22°C; continue stirring for 30 minutes after adding the chloroauric acid aqueous solution to obtain the third suspension turbid liquid;
滴加速度为20滴/分钟；The dropping rate is 20 drops/minute;
搅拌速度为300转/分钟；Stirring speed is 300 rpm;
氯金酸水溶液的质量百分比浓度为0.17g/L；The mass percentage concentration of chloroauric acid aqueous solution is 0.17g/L;
0.1L的第二悬浊液中加入0.02L的氯金酸水溶液；Add 0.02L of chloroauric acid aqueous solution in the second suspension of 0.1L;
第七步骤：将第三悬浊液置于60℃的烘箱内，反应3小时后取出，冷却至25℃，得到第四悬浊液；The seventh step: put the third suspension in an oven at 60°C, take it out after reacting for 3 hours, and cool it to 25°C to obtain the fourth suspension;
第八步骤：对第四悬浊液进行离心分离，得到第三沉淀物；The eighth step: centrifuging the fourth suspension to obtain the third precipitate;
将第三沉淀物先用去离子水进行离心洗涤2次，随后用无水乙醇进行离心洗涤2次，得到第四沉淀物；选用湘仪TG16-WS台式高速离心机进行离心处理，离心分离条件为5000转/分钟，离心时间5分钟；The third precipitate was first centrifuged and washed twice with deionized water, and then centrifuged twice with absolute ethanol to obtain the fourth precipitate; Xiangyi TG16-WS desktop high-speed centrifuge was selected for centrifugation, and the centrifugation conditions were: 5000 rpm, centrifugation time 5 minutes;
将第四沉淀物在干燥温度为50℃条件下干燥3小时后，得到铜氧化物与金复合的纳米材料。After drying the fourth precipitate at a drying temperature of 50° C. for 3 hours, a composite nanomaterial of copper oxide and gold is obtained.
在本发明中，铜氧化物与金复合的纳米材料的色泽为紫棕色（58YR03）。In the present invention, the color of the copper oxide-gold composite nanomaterial is purple-brown (58YR03).
对铜氧化物与金复合的纳米材料采用X射线衍射进行成分分析，如图3A所示，图中的衍射谱线与标准PDF卡片Cu2O(JCPDS No.77-0199)和CuO(JCPDS48-1548)的衍射峰较好符合。图中的衍射峰分别对应Cu2O的(1,1,1)，(2,0,0)，(2,2,0)和(3,1,1)面的衍射峰和CuO的(1,1,0)，(0,0,2)，(1,1,1)，(2,0,2)，(2,0,2)，(1,1,3)，(3,1,1)，(1,1,3)，(3,1,1)，(0,0,4)和(2,2,2)面的衍射峰。金在复合结构中的含量较少，不能在XRD衍射谱图中体现出来，以X射线能量分析光谱结果如图3B所示。图中金（Au）在纳米复合材料中的质量百分比含量为3.7%。The nanomaterials composited with copper oxide and gold were analyzed by X-ray diffraction, as shown in Figure 3A, the diffraction lines in the figure are consistent with the standard PDF cards Cu 2 O (JCPDS No.77-0199) and CuO (JCPDS48- 1548) diffraction peaks are in good agreement. The diffraction peaks in the figure correspond to the (1,1,1), (2,0,0), (2,2,0) and (3,1,1) diffraction peaks of Cu 2 O and the ( 1,1,0), (0,0,2), (1,1,1), (2,0,2), (2,0,2), (1,1,3), (3, 1,1), (1,1,3), (3,1,1), (0,0,4) and (2,2,2) diffraction peaks. The content of gold in the composite structure is small, which cannot be reflected in the XRD diffraction spectrum, and the spectral results analyzed by X-ray energy are shown in Figure 3B. In the figure, the mass percentage content of gold (Au) in the nanocomposite material is 3.7%.
对铜氧化物与金复合的纳米材料采用扫描电子显微镜进行形貌分析，如图4所示，图中显示铜氧化物与金复合的纳米材料的整体形貌为边长在450～700nm的中空海胆状颗粒，这种多级结构表面粗糙，有许多毛刺结构，刺长为60～150nm。Scanning electron microscopy was used to analyze the morphology of the nanomaterials composited with copper oxide and gold. As shown in Figure 4, the overall morphology of the nanomaterials composited with copper oxide and gold is hollow with a side length of 450-700 nm. Sea urchin-like particles, this multi-level structure has a rough surface, with many burr structures, and the thorn length is 60-150nm.
对铜氧化物与金复合的纳米材料采用透射电子显微镜进行形貌分析，如图5A、图5B所示。图5A中显示铜氧化物与金复合的多级纳米材料具有明显的中空和毛刺结构。图5B中是图5A中部分放大的TEM图,显示铜氧化物与金复合的多级纳米材料的表面毛刺有序排列，且具有多晶特征。右上角的高分辨率的透射电镜（HRTEM）图是毛刺结构的局部放大，其中的晶格间距为0.25nm，对应CuO晶体的(0,0,2)晶面的间距，说明铜氧化物与金复合的多级纳米材料的毛刺结构是CuO成分。The morphology of the nanomaterials composited with copper oxide and gold was analyzed by transmission electron microscope, as shown in Fig. 5A and Fig. 5B. Figure 5A shows that the copper oxide and gold composite hierarchical nanomaterials have obvious hollow and burr structures. Figure 5B is a partially enlarged TEM image in Figure 5A, showing that the surface burrs of the multi-level nanomaterials composited with copper oxide and gold are arranged in an orderly manner and have polycrystalline characteristics. The high-resolution transmission electron microscope (HRTEM) image in the upper right corner is a partial enlargement of the burr structure, in which the lattice spacing is 0.25nm, which corresponds to the (0,0,2) crystal plane spacing of CuO crystals, indicating that copper oxide and The burr structure of gold-composite hierarchical nanomaterials is CuO composition.
实施例2Example 2
制备具有中空海胆状的Cu2O/Au/CuO复合纳米材料的步骤有：The steps for preparing the Cu 2 O/Au/CuO composite nanomaterial with a hollow sea urchin shape include:
第一步骤：在15℃温度下将二水合氯化铜（CuCl2·2H2O）溶解在去离子水中混合均匀后，得到氯化铜质量百分比浓度为1.5g/L的第一溶液；The first step: after dissolving copper chloride dihydrate (CuCl 2 ·2H 2 O) in deionized water at a temperature of 15°C and mixing them evenly, a first solution with a mass percentage concentration of copper chloride of 1.5 g/L was obtained;
在本发明中，所述第一溶液的色泽为蛋壳绿色。In the present invention, the color of the first solution is eggshell green.
第二步骤：在60℃水浴温度中，在搅拌状态下缓慢向第一溶液中滴加氢氧化钠（NaOH）水溶液；滴加完氢氧化钠水溶液后继续搅拌10分钟，得到第二溶液；The second step: slowly add sodium hydroxide (NaOH) aqueous solution dropwise to the first solution under stirring at a water bath temperature of 60°C; after adding the aqueous sodium hydroxide solution dropwise, continue stirring for 10 minutes to obtain the second solution;
滴加速度为60滴/分钟；The dropping rate is 60 drops/min;
搅拌速度为300转/分钟；Stirring speed is 300 rpm;
氢氧化钠水溶液的质量百分比浓度为80g/L；The mass percentage concentration of sodium hydroxide aqueous solution is 80g/L;
1L的第一溶液中加入0.088L的氢氧化钠水溶液；Add 0.088L of sodium hydroxide aqueous solution to 1L of the first solution;
在本发明中，第一溶液在滴加氢氧化钠过程中，色泽由蛋壳绿色变成浑浊的景蓝色，随后变成棕色，故第二溶液的色泽为棕色。In the present invention, during the dropwise addition of sodium hydroxide, the color of the first solution changes from eggshell green to turbid blue, and then turns brown, so the color of the second solution is brown.
第三步骤：在60℃水浴温度中，在搅拌状态下缓慢向第二溶液中滴加抗坏血酸（C6H8O6）水溶液；滴加完抗坏血酸水溶液后继续搅拌150分钟，得到第一悬浊液；The third step: Slowly add ascorbic acid (C 6 H 8 O 6 ) aqueous solution to the second solution under stirring in a water bath temperature of 60°C; after adding the aqueous ascorbic acid solution, continue stirring for 150 minutes to obtain the first suspension liquid;
滴加速度为30滴/分钟；The dropping rate is 30 drops/minute;
搅拌速度为300转/分钟；Stirring speed is 300 rpm;
抗坏血酸水溶液的质量百分比浓度为105.7g/L；The mass percentage concentration of ascorbic acid aqueous solution is 105.7g/L;
1L的第一溶液中加入0.088L的抗坏血酸水溶液；Add 0.088L of ascorbic acid aqueous solution to 1L of the first solution;
在本发明中，第二溶液在滴加抗坏血酸水溶液过程中，色泽由棕色逐渐变为深棕黄色，故第一悬浊液的色泽为深棕黄色。In the present invention, the color of the second solution gradually changes from brown to dark brown-yellow during the dropwise addition of the ascorbic acid aqueous solution, so the color of the first suspension is dark brown-yellow.
第四步骤：对第一悬浊液进行离心分离，得到第一沉淀物；The fourth step: centrifuging the first suspension to obtain the first precipitate;
将第一沉淀物先用去离子水进行离心洗涤1次，随后用无水乙醇进行离心洗涤1次，得到第二沉淀物；离心分离条件为4000转/分钟，离心时间10分钟；The first precipitate was first centrifuged and washed once with deionized water, and then centrifuged once with absolute ethanol to obtain the second precipitate; the centrifugation condition was 4000 rpm, and the centrifugation time was 10 minutes;
将第二沉淀物在干燥温度为50℃条件下干燥1小时后，得到第一固体粉末；drying the second precipitate at a drying temperature of 50° C. for 1 hour to obtain a first solid powder;
第五步骤：将第一固体粉末采用超声进行分散于乙醇水溶液中，得到第二悬浊液；The fifth step: dispersing the first solid powder in the ethanol aqueous solution by ultrasonic to obtain the second suspension;
乙醇水溶液的质量百分比浓度为10%；The mass percent concentration of ethanol aqueous solution is 10%;
用量：0.1g的第一固体粉末需要0.08L乙醇水溶液；Dosage: 0.1g of the first solid powder needs 0.08L ethanol aqueous solution;
第六步骤：在15℃温度下、在搅拌状态下缓慢向第二悬浊液中滴加氯金酸（HAuCl4）水溶液；滴加完氯金酸水溶液后继续搅拌10分钟，得到第三悬浊液；Step 6: Slowly add chloroauric acid (HAuCl 4 ) aqueous solution to the second suspension under stirring at 15°C; continue stirring for 10 minutes after adding the chloroauric acid aqueous solution to obtain the third suspension turbid liquid;
搅拌速度为200转/分钟；Stirring speed is 200 rpm;
氯金酸水溶液的质量百分比浓度为0.17g/L；The mass percentage concentration of chloroauric acid aqueous solution is 0.17g/L;
0.1L的第二悬浊液中加入0.025L的氯金酸水溶液；Add 0.025L of chloroauric acid aqueous solution in the second suspension of 0.1L;
第七步骤：将第三悬浊液置于70℃的温度条件下，反应2小时后取出，冷却至20℃，得到第四悬浊液；The seventh step: place the third suspension at a temperature of 70°C, take it out after reacting for 2 hours, and cool it to 20°C to obtain the fourth suspension;
第八步骤：对第四悬浊液进行离心分离，得到第三沉淀物；The eighth step: centrifuging the fourth suspension to obtain the third precipitate;
将第三沉淀物先用去离子水进行离心洗涤3次，随后用无水乙醇进行离心洗涤3次，得到第四沉淀物；离心分离条件为4000转/分钟，离心时间10分钟；The third precipitate was first centrifuged and washed 3 times with deionized water, and then centrifuged and washed 3 times with absolute ethanol to obtain the fourth precipitate; the centrifugation condition was 4000 rpm, and the centrifugation time was 10 minutes;
将第四沉淀物在干燥温度为40℃条件下干燥6小时后，得到铜氧化物与金复合的纳米材料。After drying the fourth precipitate at a drying temperature of 40° C. for 6 hours, a composite nanomaterial of copper oxide and gold is obtained.
在本发明中，铜氧化物与金复合的纳米材料的色泽为紫棕色。In the present invention, the color of the copper oxide-gold composite nanomaterial is purple-brown.
实施例3Example 3
制备具有中空海胆状的Cu2O/Au/CuO复合纳米材料的步骤有：The steps for preparing the Cu 2 O/Au/CuO composite nanomaterial with a hollow sea urchin shape include:
第一步骤：在25℃温度下将二水合氯化铜（CuCl2·2H2O）溶解在去离子水中混合均匀后，得到氯化铜质量百分比浓度为2.0g/L的第一溶液；The first step: after dissolving copper chloride dihydrate (CuCl 2 ·2H 2 O) in deionized water at a temperature of 25°C and mixing them uniformly, a first solution with a mass percent concentration of copper chloride of 2.0 g/L was obtained;
在本发明中，所述第一溶液的色泽为蛋壳绿色。In the present invention, the color of the first solution is eggshell green.
第二步骤：在45℃水浴温度中，在搅拌状态下缓慢向第一溶液中滴加氢氧化钠（NaOH）水溶液；滴加完氢氧化钠水溶液后继续搅拌25分钟，得到第二溶液；The second step: slowly add sodium hydroxide (NaOH) aqueous solution dropwise to the first solution under stirring at a water bath temperature of 45°C; continue stirring for 25 minutes after adding the aqueous sodium hydroxide solution to obtain the second solution;
滴加速度为80滴/分钟；The dropping rate is 80 drops/minute;
搅拌速度为400转/分钟；Stirring speed is 400 rpm;
氢氧化钠水溶液的质量百分比浓度为80g/L；The mass percentage concentration of sodium hydroxide aqueous solution is 80g/L;
1L的第一溶液中加入0.118L的氢氧化钠水溶液；Add 0.118L of sodium hydroxide aqueous solution to 1L of the first solution;
在本发明中，第一溶液在滴加氢氧化钠过程中，色泽由蛋壳绿色变成浑浊的景蓝色，随后变成棕色，故第二溶液的色泽为棕色。In the present invention, during the dropwise addition of sodium hydroxide, the color of the first solution changes from eggshell green to turbid blue, and then turns brown, so the color of the second solution is brown.
第三步骤：在60℃水浴温度中，在搅拌状态下缓慢向第二溶液中滴加抗坏血酸（C6H8O6）水溶液；滴加完抗坏血酸水溶液后继续搅拌200分钟，得到第一悬浊液；The third step: Slowly add ascorbic acid (C 6 H 8 O 6 ) aqueous solution to the second solution under stirring in a water bath temperature of 60°C; after adding the ascorbic acid aqueous solution, continue to stir for 200 minutes to obtain the first suspension liquid;
滴加速度为10滴/分钟；The dropping rate is 10 drops/minute;
搅拌速度为400转/分钟；Stirring speed is 400 rpm;
抗坏血酸水溶液的质量百分比浓度为105.7g/L；The mass percentage concentration of ascorbic acid aqueous solution is 105.7g/L;
1L的第一溶液中加入0.118L的抗坏血酸水溶液；Add 0.118L of ascorbic acid aqueous solution to 1L of the first solution;
在本发明中，第二溶液在滴加抗坏血酸水溶液过程中，色泽由棕色逐渐变为深棕黄色，故第一悬浊液的色泽为深棕黄色。In the present invention, the color of the second solution gradually changes from brown to dark brown-yellow during the dropwise addition of the ascorbic acid aqueous solution, so the color of the first suspension is dark brown-yellow.
第四步骤：对第一悬浊液进行离心分离，得到第一沉淀物；The fourth step: centrifuging the first suspension to obtain the first precipitate;
将第一沉淀物先用去离子水进行离心洗涤3次，随后用无水乙醇进行离心洗涤3次，得到第二沉淀物；离心分离条件为4500转/分钟，离心时间3分钟；The first precipitate was first centrifuged and washed 3 times with deionized water, and then centrifuged and washed 3 times with absolute ethanol to obtain the second precipitate; the centrifugation condition was 4500 rpm, and the centrifugation time was 3 minutes;
将第二沉淀物在干燥温度为45℃条件下干燥6小时后，得到第一固体粉末；drying the second precipitate at a drying temperature of 45° C. for 6 hours to obtain a first solid powder;
第五步骤：将第一固体粉末采用超声进行分散于乙醇水溶液中，得到第二悬浊液；The fifth step: dispersing the first solid powder in the ethanol aqueous solution by ultrasonic to obtain the second suspension;
乙醇水溶液的质量百分比浓度为10%；The mass percent concentration of ethanol aqueous solution is 10%;
用量：0.1g的第一固体粉末需要0.12L乙醇水溶液；Dosage: 0.1g of the first solid powder needs 0.12L ethanol aqueous solution;
第六步骤：在25℃温度下、在搅拌状态下缓慢向第二悬浊液中滴加氯金酸（HAuCl4）水溶液；滴加完氯金酸水溶液后继续搅拌25分钟，得到第三悬浊液；Step 6: Slowly add chloroauric acid (HAuCl 4 ) aqueous solution to the second suspension under stirring at 25°C; continue stirring for 25 minutes after adding the chloroauric acid aqueous solution to obtain the third suspension turbid liquid;
搅拌速度为400转/分钟；Stirring speed is 400 rpm;
氯金酸水溶液的质量百分比浓度为0.17g/L；The mass percentage concentration of chloroauric acid aqueous solution is 0.17g/L;
0.1L的第二悬浊液中加入0.015L的氯金酸水溶液；Add 0.015L of chloroauric acid aqueous solution in the second suspension of 0.1L;
第七步骤：将第三悬浊液置于50℃的温度条件下，反应4小时后取出，冷却至15℃，得到第四悬浊液；The seventh step: place the third suspension at a temperature of 50°C, take it out after reacting for 4 hours, and cool it to 15°C to obtain the fourth suspension;
第八步骤：对第四悬浊液进行离心分离，得到第三沉淀物；The eighth step: centrifuging the fourth suspension to obtain the third precipitate;
将第三沉淀物先用去离子水进行离心洗涤1次，随后用无水乙醇进行离心洗涤1次，得到第四沉淀物；离心分离条件为4500转/分钟，离心时间3分钟；The third precipitate was first centrifuged and washed once with deionized water, and then centrifuged once with absolute ethanol to obtain the fourth precipitate; the centrifugation condition was 4500 rpm, and the centrifugation time was 3 minutes;
将第四沉淀物在干燥温度为40℃条件下干燥6小时后，得到铜氧化物与金复合的纳米材料。After drying the fourth precipitate at a drying temperature of 40° C. for 6 hours, a composite nanomaterial of copper oxide and gold is obtained.
在本发明中，铜氧化物与金复合的纳米材料的色泽为紫棕色。In the present invention, the color of the copper oxide-gold composite nanomaterial is purple-brown.
在本发明中，如果没有特别地说明，所采用的装置、仪器、设备、材料、工艺、方法、步骤、制备条件等都是本领域常规采用的或者本领域普通技术人员按照本领域常规采用的技术可以容易地获得的。In the present invention, if not specifically stated, the devices, instruments, equipment, materials, processes, methods, steps, preparation conditions, etc. used are all conventionally used in the field or those of ordinary skill in the art according to the routinely used in the field Technology is readily available.
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