CN106040216B - 一种双层ZnO空心球光催化材料及其制备方法 - Google Patents
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Abstract
本发明光催化材料及其制备技术领域,具体涉及一种双层ZnO空心球光催化材料,其由内外两个ZnO空心球构成,内层空心球直径为1.0~2.5μm,外层空心球直径1.5~4.5μm。本发明还涉及该双层ZnO空心球光催化材料的制备方法:将可溶性锌盐溶解于一元醇和乙二醇的混合物中制成溶液,然后将该溶液在密闭条件下进行溶剂热反应,制得所述双层ZnO空心球光催化材料。
Description
技术领域
本发明属于光催化材料及其制备技术领域,具体涉及一种双层ZnO空心球光催化材料及其制备方法。
背景技术
能源与环境问题是21世纪人类可持续发展面临的两大挑战。太阳能具有廉价、清洁、可再生等优点,因此,高效快捷的利用、转化和储存太阳能是各国研究者努力的目标。半导体光催化技术具有处理效率高,不存在二次污染等优点,能有效降解有毒有害污染物,在解决环境问题中具有广阔的应用前景。
氧化锌(ZnO)是一种禁带宽度为3.2eV的半导体材料,在紫外光照射下,ZnO可以被激发并产生光生电子-空穴对,从而进一步发生氧化还原反应。相比于常用的TiO2光催化剂,ZnO具有高的电子传输速率和长的光生载流子寿命,使其在光催化降解有机污染物、太阳能电池等领域具有广泛应用前景。此外,研究表明,多孔和空心结构对于提高光催化材料的活性有重要作用,一方面该结构可提供更多的活性位点,另一方面,空心结构也有利于光的反复折射和散射,提高光的利用率。
为了制备空心结构ZnO颗粒,在其制备过程中,一般会加入炭球或硅球等模板剂来得到空心结构,然后经过高温煅烧除去模板,获得空心结构。但是以上方法比较繁琐,无法通过一步法直接合成ZnO空心球。此外,高温焙烧也可能导致空心结构破裂和颗粒团聚。
双层ZnO空心球结构及其合成方法,之前从未有人报道过。
发明内容
本发明的目的在于提供一种在温和条件下一步合成双层ZnO空心球的方法。这种方法通过溶剂热法实现双层ZnO空心球的可控合成,制备工艺简单,条件温和,且对环境无污染。得到的双层ZnO空心球在光催化降解有机污染物方面具有很好的应用前景。
本发明的第一方面涉及一种双层ZnO空心球光催化材料,其由内外两个ZnO空心球构成,内层空心球直径为1.0~2.5μm,外层空心球直径1.5~4.5μm。
本发明的第二方面涉及一种双层ZnO空心球光催化材料的制备方法,过程如下,将可溶性锌盐溶解于一元醇和乙二醇的混合物中制成溶液,然后将该溶液在密闭条件下进行溶剂热反应,制得所述双层ZnO空心球光催化材料。
其中“溶剂热反应”一词源自于“水热反应”。水热反应是指以水为溶剂的反应母液在密闭条件下在受热所产生的自生压力下进行的反应。当将反应溶剂由水改为其他溶剂时,反应母液在密闭条件下在受热所产生的自生压力下进行的反应,被称为“溶剂热反应”。
本发明中,一元醇作为溶剂,乙二醇作为形貌控制剂,乙二醇质量为一元醇质量的5%~15%。
优选地,所述可溶性锌盐为醋酸锌或硝酸锌或硫酸锌,其质量为一元醇质量的0.5%~2.5%。
优选地,溶剂热反应的温度范围为150~200℃,反应时间范围为1~24h。
优选地,所述一元醇为乙醇。
具体制备方法包括如下步骤:
步骤1:在一元醇(选无水乙醇)中加入形貌控制剂制成溶剂,形貌控制剂与溶剂的质量比例为5%~15%,搅拌一定时间后,将反应原料醋酸锌(Zn(CH3COO)2·2H2O)、硝酸锌(Zn(NO3)2·6H2O)或硫酸锌(ZnSO4)溶解在上述溶剂中制成溶液。
步骤2:将步骤1中配好的溶液移入水热釜内,密封后放入150~200℃烘箱中加热1~24小时后冷却至室温。
步骤3:步骤2结束后,将得到的产物离心,并将离心得到的产物用无水乙醇洗涤数次,然后在60℃下干燥12小时,得到双层ZnO空心球。
本发明具有以下优点:
1、本发明首次用一步法制备了双层ZnO空心球,双层空心结构可以提高ZnO光催化材料的比表面积,从而增加了光催化反应的活性位点;双层空心结构还可以提高光在双层空心球中的折射/反射次数,提高光的利用效率。这使得该双层ZnO空心球光催化材料在降解有机污染物方面具有很好的光催化性能,可以广泛用于环境净化。
2、本发明制备的双层ZnO空心球制备方法简单,容易操作,不需要加入模板剂再后处理等繁琐操作,产品制备成本低,制备条件温和,具有明显的经济效益,易于实现工业化生产,且对环境无污染。
附图说明:
图1为本发明实施例1制备的双层ZnO空心球的(a)SEM图像(b)TEM图像。
图2为本发明实施例1制备的双层ZnO空心球的XRD谱图。
图3为本发明实施例1和对比实施例制备的ZnO光催化降解苯酚效果图。
图4为对比实施例制备的ZnO的SEM图像。
图5为本发明实施例2所制备的双层ZnO空心球的高分辨率TEM图像。
具体实施方式:
下面结合附图对本发明的技术方案作进一步的说明,但并不局限于此,凡是对本发明技术方案进行修改或者等同替换,而不脱离本发明技术方案的精神和范围,均应涵盖在本发明的保护范围中。
实施例1
以150ml无水乙醇-乙二醇(乙二醇体积分数10%)混合溶液作为溶剂,室温下磁力搅拌半小时后,加入1.8g醋酸锌,搅拌半小时,待醋酸锌完全溶解后,将溶液移入水热釜中,放入烘箱中180℃下加热12小时,之后将产物离心,用离子水和无水乙醇洗涤数次,60℃下干燥12小时后得到ZnO双层空心球。
实施例2
以150ml无水乙醇-乙二醇(乙二醇体积分数10%)混合溶液作为溶剂,室温下磁力搅拌半小时后,加入1.8g硝酸锌,搅拌半小时,待硝酸锌完全溶解后,将溶液移入水热釜中,放入烘箱中180℃下加热12小时,之后将产物离心,并用去离子水和无水乙醇洗涤数次。60℃下干燥12小时后得到双层ZnO空心球。
实施例3
以150ml无水乙醇-乙二醇(乙二醇体积分数10%)混合溶液作为溶剂,室温下磁力搅拌半小时后,加入1.8g硫酸锌,搅拌半小时,待硫酸锌完全溶解后,将溶液移入水热釜中,放入烘箱中180℃下加热12小时,之后将产物离心,并用去离子水和无水乙醇洗涤数次。60℃下干燥12小时后得到双层ZnO空心球。
对比实施例
作为对照例,以150ml纯无水乙醇作为溶剂,加入1.8g醋酸锌,搅拌半小时,待醋酸锌完全溶解后,将溶液移入水热釜中,放入烘箱中180℃下加热12小时,之后将产物离心,并用去离子水和无水乙醇洗涤数次。60℃下干燥12小时后得到ZnO。图1为得到对比实施例产品的SEM图像,可以看出,纯乙醇下得到的ZnO产品没有规则形貌。
实施例4
该实施例中,对实施例1和对比实施例所得的产品进行形貌表征和活性测试。其中以SEM和TEM观察产品形貌,以XRD来鉴别产品组成和晶型。图1为实施例1所得产品的SEM图像和TEM图像,可以看出,得到的ZnO为双层空心球结构。图2为实施例1所得双层空心球的XRD谱图,可以观测到明显的ZnO衍射峰。
光催化性能测试程序如下:在带有水冷夹套的反应器中加入100ml 40ppm的苯酚溶液,并加入20mg催化剂,超声30分钟后在黑暗条件下搅拌吸附20分钟达到吸附平衡。然后进行光照,光源为高压氙灯,水平放置于反应器上方,并控制反应液温度在25℃左右。每隔一段时间取样,离心分离后取上层清液用紫外-可见分光光度计分析降解前后的苯酚浓度,以C/C0来表示,其中C为某时刻的苯酚浓度,C0为苯酚的起始浓度,从而计算光照后溶液中苯酚的降解率。
图3为实施例1所得ZnO双层空心球和对照例制备的ZnO光催化降解苯酚效果图,与对比实施例相比,同等反应时间下,实施例1所制备的双层ZnO空心球所得的C/C0更低,说明其光催化性能更优异。
Claims (1)
1.一种双层ZnO空心球光催化材料的制备方法,其特征在于,所述双层ZnO空心球光催化材料由内外两个ZnO空心球构成,内层空心球直径为1.0~2.5μm,外层空心球直径1.5~4.5μm;制备方法为:将可溶性锌盐溶解于乙醇和乙二醇的混合物中制成溶液,然后将该溶液在密闭条件下进行溶剂热反应,制得所述双层ZnO空心球光催化材料;其中乙醇作为溶剂,乙二醇作为形貌控制剂,乙二醇占乙醇和乙二醇总体积的体积分数为10%;所述可溶性锌盐为醋酸锌或硝酸锌或硫酸锌,其质量为乙醇质量的0.5%~2.5%;溶剂热反应的温度为180℃,反应时间范围为1~24h。
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