CN107649150B - 一种富含硫空位的Cd/CdS异质结可见光催化剂的制备方法及其应用 - Google Patents
一种富含硫空位的Cd/CdS异质结可见光催化剂的制备方法及其应用 Download PDFInfo
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Abstract
本发明公开了一种富含硫空位的Cd/CdS异质结可见光催化剂的制备方法及其应用。以溶剂热法制备的CdS为前驱体,通过热处理法合成中间体CdO/CdS复合材料,并利用硼氢化钠原位化学还原方法直接获得。本发明制备出的Cd/CdS复合可见光催化剂,由于含有大量的硫空位,大大提高了催化剂对可见光的吸收利用,且高导电性的Cd与CdS之间具有更加紧密的接触,从而光生电子‑空穴能更好分离,光催化效率更高。该异质结光催化剂具有较高的稳定性,在可见光照射下,表现出优良的光催化活性,可用于催化光解水制氢。本发明制备条件要求低,操作简单,原材料廉价易得。对环境友好,可见光催化效率高。在光催化领域具有广阔的应用前景。
Description
技术领域
本发明属于材料制备及可见光光催化技术领域,具体涉及一种富含硫空位的Cd/CdS异质结可见光催化剂的制备方法及其应用。
背景技术
随着经济的快速发展,环境污染与能源紧缺问题日益凸显,成为21世纪人类社会发展道路上面临的两大挑战。半导体光催化技术是以太阳能转化与储存为核心,以光能驱动光催化反应。将太阳能转化成化学能被认为是解决能源与环境这两个问题的一种理想的途径。但是,目前光催化剂技术在实际生产中的应用仍然面临着一些问题。例如,量子效率低,光催化剂光响应范围窄,稳定性差等。因此,寻找和制备高效、稳定的可见光光催化材料是实现光催化技术实际应用的先决条件,也是光催化材料研究者所需要解决的首要任务之一。
CdS作为一种重要的可见光光催化剂,由于它独特的电学、光学、磁学及其发光性能,在光催化反应中得到广泛的研究。然而,CdS的光生电子和空穴快速复合以及严重的光腐蚀仍然是限制其广泛应用的主要壁垒。因此,如何促进其载流子有效分离对于提高半导体金属硫化物光催化性能至关重要。界面调控是促进载流子有效分离,从而提高光催化活性最为有效的方法之一。
对于硫化物半导体,硫空位缺陷在物理化学过程中起到至关重要的作用。与普通硫位点相比,硫空位表现出与结合物更强的结合力,更有利于将吸附物分解为高活性的基团,因此,在许多化学反应中,硫空位通常是硫化物表面最主要的活性位点。更重要的是,在光催化反应中,硫空位还与优化电子结构和载流子分离有关。硫空位态作为杂质能级位于价带和导带之间,可以窄化半导体的带隙,从而促进可见光下光子的吸收和电子激发。硫空位带电的性质也有利于电子传递,从而促进电子空穴对分离,进而表现出优异的可见光光催化活性。
近年来,在半导体表面负载金属(如金(Au)、银(Ag)、铂(Pt)、钯(Pd)、铑(Rh)等)已经引起了众多研究者的兴趣。当金属沉积到光催化材料的表面时,就会在金属和光催化材料的界面处形成肖特基能垒,引起光催化材料表界面性质的改变。肖特基能垒可以作为电子陷阱能够有效地捕获光生载流子,提高光生电子-空穴的分离效率并延长其寿命,从而提高光催化效率。金属/CdS复合材料可以降低光生电子-空穴对的复合率,有利于光催化活性的提高。例如专利CN 104923264A公开了一种贵金属修饰的CdS纳米棒光催化剂的制备方法,该发明中的光催化剂由贵金属Pt、Pd或Ru和纳米棒状CdS构成,通过一锅的溶剂热法实现纳米棒状CdS的形成和贵金属的沉积修饰。所得样品具有高效、稳定的可见光催化活性。专利CN 105413712A公开了一种金纳米棒-CdS-金纳米粒子复合光催化剂。该发明采用简单的静电自组装方法制得的光催化剂具有高催化效率和高选择性。上述专利所利用的助催化剂均为贵金属,考虑到贵金属资源稀缺,价格昂贵,严重限制了实际的工业应用。考虑到廉价,低毒,传递性质及低的有效电荷质量等优势,金属镉成为一个理想的候选者。另外,金属Cd易与CdS的紧密结合也有利于光生载流子的传递。
目前,还未见到关于富含硫空位的Cd/CdS异质结可见光催化剂的相关报道。CN103316693A公开了一种含有助催化剂Cd的光催化剂Cd/CdS及其制备和在光催化产氢反应中的应用,该光催化剂通过超声,微波,光还原等技术实现了Cd/CdS光催化剂的合成,具有太阳光解水制氢性能,有较高的太阳光制氢效率。但该专利技术受其制备方法的限制,无法灵活地调控CdS基体的形貌和产生丰富的硫空位,也就无法利用形貌调控和缺陷工程的优势,难以实现高效地优化CdS的光吸收和光催化特性。张铁锐小组(L. Shang, B. Tong, H.Yu, G.I.N. Waterhouse, C. Zhou, Y. Zhao, M. Tahir, L.-Z. Wu, C.-H. Tung, T.Zhang, Advanced Energy Materials 6 (2016) 1501241)报道了一种Cd纳米片修饰的CdS纳米颗粒并应用于光催化产氢,该报道指出,他们先利用化学还原法制备出Cd纳米片,再将其硫化从而得到Cd纳米片与CdS的复合催化剂,该催化剂具有较高的光解水制氢性能,但同样面临上述问题的制约,无法充分发挥形貌调控和缺陷工程的优势,严重限制了CdS光催化剂的应用研究。上述专利与论文提及的制备方法和材料形貌结构与本专利有本质差别,更重要的是缺乏起关键作用的丰富S空位缺陷。
发明内容
本发明的目的在于针对现有技术中存在的问题,提供一种富含硫空位的Cd/CdS异质结可见光催化剂的制备方法及其应用。本发明制备条件要求低,操作简单,原材料廉价易得,对环境友好,所得异质结催化剂含有大量硫空位且两组分间具有更紧密的接触,具有优良的光解水活性及稳定性,且CdS基底的形貌可以灵活调控,可充分发挥形貌调控和缺陷工程的优势,为高效CdS光催化剂的开发应用提供重要的技术支持。
为实现上述目的,本发明采用如下技术方案:
一种富含硫空位的Cd/CdS异质结可见光催化剂的制备方法,以溶剂热法制备的CdS为前驱体,通过热处理法合成中间体CdO/CdS复合材料,并利用硼氢化钠原位化学还原方法直接获得,其中Cd颗粒的尺寸为10-50纳米,Cd和CdS的质量比为1:50-2:5。所得Cd/CdS异质结可见光催化剂中Cd与CdS的质量比可通过改变热处理的温度或时间调整。
制备方法包括以下步骤:
(1)制备CdS前驱体
将四水合硝酸镉和硫脲按摩尔比1:3溶解于乙二胺中,磁力搅拌1-2小时,在200℃下反应24小时,所得产物自然冷却到室温,分别用去离子水、乙醇洗涤3-5次,离心收集沉淀,烘干,即得到CdS前驱体;
(2)制备富含硫空位的Cd/CdS异质结光催化剂
将步骤(1)所得产物置于马弗炉中350-500℃热处理0.5-4h,即得中间体CdO/CdS复合材料,将其缓慢加入到1mol/L NaBH4溶液中,室温下搅拌4小时,经抽滤、洗涤和干燥,即得富含硫空位的Cd/CdS异质结可见光催化剂。
上述CdS前驱体为六方相和立方相中的一种或两种晶相的混相,其形貌为纳米颗粒、纳米球、纳米棒(线)、纳米片中的一种或几种。
本发明所述的可见光催化剂的应用是将催化剂用于催化光解水制氢。
本发明的显著优点在于:本发明所述的复合可见光催化剂在结构组成、制备方法和催化性能方面与现有的金属/CdS催化剂显著不同。由于本发明采用原位合成的方式,没有外部引入其他金属,所得Cd/CdS催化剂含有大量的硫空位且两组分间具有更紧密的接触,光吸收和可见光催化效率高。本发明制备条件要求低,操作简单,原材料廉价易得,对环境友好。本发明所制得的催化剂在负载量很高的情况下Cd颗粒粒径较小,在载体表面分散均匀,充分保证Cd纳米颗粒具有较高的比表面积,提供更多的活性位点,有效提高光生载流子分离效率,从而使所制备的催化剂具有优良的可见光光催化性能。
附图说明
图1为本发明纯CdS、Cd/CdS异质结可见光催化剂的XRD图;
图2为本发明所合成的Cd/CdS异质结可见光催化剂的室温EPR谱图;
图3为本发明所合成的Cd/CdS异质结可见光催化剂的紫外-可见漫反射图;
图4为本发明所合成的Cd/CdS异质结可见光催化剂光催化产氢效果图及稳定性评价图。
具体实施方式
以下结合具体实施例对本发明做进一步说明,但本发明不仅仅限于这些实施例。
CdS前驱体的制备:
将四水合硝酸镉和硫脲按摩尔比1:3加入到聚四氟乙烯反应釜中,加入乙二胺至反应釜容积60%,磁力搅拌至完全溶解,将其在200℃下反应24小时,所得产物自然冷却到室温,分别用去离子水、乙醇洗涤4次,离心收集沉淀,真空烘干,即得到CdS前驱体。
实施例1
将制得的CdS 500mg置于马弗炉中400℃热处理1h,即得中间体CdO/CdS复合材料,将其缓慢加入到50mL 1mol/L NaBH4溶液中,室温下搅拌4小时,经抽滤、洗涤和干燥,即得富含硫空位的Cd/CdS异质结可见光催化剂,标记为Cd-CdS-1h。
实施例2
将制得的CdS 500mg置于马弗炉中400℃热处理2h,即得中间体CdO/CdS复合材料,将其缓慢加入到50mL 1mol/L NaBH4溶液中,室温下搅拌4小时,经抽滤、洗涤和干燥,即得富含硫空位的Cd/CdS异质结可见光催化剂,标记为Cd-CdS-2h。
实施例3
将制得的CdS 500mg置于马弗炉中400℃热处理3h,即得中间体CdO/CdS复合材料,将其缓慢加入到50mL 1mol/L NaBH4溶液中,室温下搅拌4小时,经抽滤、洗涤和干燥,即得富含硫空位的Cd/CdS异质结可见光催化剂,标记为Cd-CdS-3h。
实施例4
将制得的CdS 500mg置于马弗炉中400℃热处理4h,即得中间体CdO/CdS复合材料,将其缓慢加入到50mL 1mol/L NaBH4溶液中,室温下搅拌4小时,经抽滤、洗涤和干燥,即得富含硫空位的Cd/CdS异质结可见光催化剂,标记为Cd-CdS-4h。
样品表征与性能测试:
按实施例1-4方法合成的催化剂与纯CdS,经X射线粉末衍射仪表征,结果表明,所合成的催化剂为Cd/CdS异质结可见光催化剂,参见附图1。
按实施例3方法合成的催化剂与纯CdS,经室温电子顺磁共振EPR表征,结果表明,所合成的Cd/CdS异质结可见光催化剂含有大量硫空位,其S空位浓度为0.01-0.09,参见附图2。
按实施例1-4方法分别合成的催化剂与纯CdS,经紫外-可见漫反射分析,结果表明通过硫空位和Cd纳米颗粒的原位修饰,可以显著改善Cd/CdS复合材料的可见光吸收,参见附图3。
分别取实施例1-4中制得的催化剂各30 mg,分散在100 mL 0.1M Na2S和0.1MNa2SO3混合溶液中,将其加入反应器中,5℃恒温条件下对反应体系进行脱气,用波长大于420 nm的可见光照射下,观察其每小时的产氢量变化,利用气相色谱进行分析,采用求取平均值的方法计算平均产氢速率,参见附图4中的(A)。
由附图4中的(A)可知,热处理温度为400℃,热处理时间为3h所制备富含硫空位的Cd/CdS异质结可见光催化剂催化活性最高,其产氢速率为2.08 mmol h-1 g-1,是纯的CdS产氢速率的8.8倍。
分别取实施例3中制得的催化剂30 mg,分散在100 mL 0.1M Na2S和0.1M Na2SO3混合溶液中,将其加入反应器中,5℃恒温条件下对反应体系进行脱气,用波长大于420 nm的可见光连续照射15小时,观察其每小时的产氢量变化,利用气相色谱进行分析,参见附图4中的(B)。
由附图4中的(B)可知,所制备富含硫空位的Cd/CdS异质结可见光催化剂具有较好的稳定性。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (5)
1.一种富含硫空位的Cd/CdS异质结可见光催化剂的制备方法,其特征在于:以溶剂热法制备的CdS为前驱体,通过热处理法合成中间体CdO/CdS复合材料,并在此基础上利用硼氢化钠原位化学还原方法制备而成;其中Cd颗粒的尺寸为10-50纳米,Cd和CdS的质量比为1:50-2:5;具体包括以下步骤:
(1)制备CdS前驱体
将四水合硝酸镉和硫脲按摩尔比1:3溶解于乙二胺中,磁力搅拌1-2小时,在200℃下反应24小时,所得产物自然冷却到室温,分别用去离子水和乙醇洗涤3-5次,离心收集沉淀,烘干,即得到CdS前驱体;
(2)制备Cd/CdS异质结光催化剂
将步骤(1)所得CdS前驱体置于马弗炉中进行热处理,即得中间体CdO/CdS复合材料,将其缓慢加入到NaBH4溶液中,室温下搅拌4小时,经抽滤、洗涤和干燥,即得富含硫空位的Cd/CdS异质结可见光催化剂;
上述步骤(2)中所述热处理的工艺参数为:热处理温度为350-500℃,热处理时间为0.5-4h。
2.根据权利要求1所述的一种富含硫空位的Cd/CdS异质结可见光催化剂的制备方法,其特征在于:所述CdS前驱体为六方相和立方相中的一种或两种晶相的混相。
3.根据权利要求1所述的一种富含硫空位的Cd/CdS异质结可见光催化剂的制备方法,其特征在于:所述CdS前驱体的形貌为纳米颗粒、纳米球、纳米棒、纳米线和纳米片中的一种或几种。
4.根据权利要求1所述的一种富含硫空位的Cd/CdS异质结可见光催化剂的制备方法,其特征在于:步骤(2)中所述的NaBH4溶液的浓度为1mol/L。
5.一种如权利要求1所述的方法制得的富含硫空位的Cd/CdS异质结可见光催化剂的应用,其特征在于:所述的光催化剂用于催化光解水制氢反应。
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