CN114768835A - 一种多级纳米结构复合光催化剂及其制备方法和用途 - Google Patents
一种多级纳米结构复合光催化剂及其制备方法和用途 Download PDFInfo
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Abstract
本发明属于催化剂制备技术领域,具体公开了一种多级纳米结构复合光催化剂及其制备方法及应用,其制备方法为通过低温热还原法将单原子Pt纳米颗粒负载到MoO3纳米片表面得到Pt@MoO3,然后将Pt@MoO3与CaIn2O4纳米棒均匀混合,在硫的气氛中还原,得到Pt@MoS2@CaIn2S4多级纳米结构复合光催化剂。其中,单原子Pt负载在层状半导体态的2H‑MoS2表面,而Pt@MoS2又负载在单斜相CaIn2S4表面。这种多级纳米结构的合理设计可以有效抑制光生载流子的复合,同时单原子Pt的负载可以降低光催化反应的活化能、提高Pt原子的利用率。本发明所制备的多级纳米结构复合光催化剂Pt@MoS2@CaIn2S4在可见光下表现出优异的光催化制氢性能和光催化制氢稳定性,是一种极具有潜力的新型光催化制氢材料。
Description
技术领域
本发明属于光催化技术领域,涉及一种多级纳米结构复合光催化剂及其制备方法和用途。
背景技术
氢能具有环境友好、热值高、无毒无污染等优点,是替代化石能源实现碳中和、碳达峰目标的重要选择,在21世纪世界能源舞台上将成为一种举足轻重的二次能源。利用太阳能光催化分解水制氢是目前最有前途的无污染、可再生的太阳能转换途经,也是全球能源科学技术的研究热点和战略方向。该技术可以将低密度的太阳能转化为高密度的化学能、电能,同时可以直接利用低密度的太阳能分解水制氢,降解和矿化水和空气中的各种有机污染物,甚至还原重金属离子。该技术具有在室温下反应、可直接利用太阳能、无二次污染等优点,对于从根本上解决环境污染和能源短缺问题具有不可估量的意义。
硫化物光催化剂,因具有较窄的禁带宽度、合适的价带导带电位,是一类很好的可见光响应型光催化剂。其中,具有单斜相结构的CaIn2S4光催化剂,在可见光下比立方相CaIn2S4表现出更好的光催化制氢性能,其产氢活性为30.2μmol/h(0.5wt%Pt的负载)(Journal of Physical Chemistry C,2014,118,27690)。但是,对于单组份CaIn2S4光催化剂,因较高的光生载流子复合几率,使得其光催化性能偏低,限制了其应用。
发明内容
本发明目的之一是提供一种基于单斜相CaIn2S4的多级纳米结构复合光催化剂,用于解决单斜相CaIn2S4光催化性能低的不足问题。
为实现上述目的,本发明采用了以下技术方案:
一种多级纳米结构复合光催化剂,由分级结构的单原子Pt、层状半导体态的MoS2和单斜相的CaIn2S4组成,所述单原子Pt负载在层状半导体态的MoS2表面形成Pt@MoS2,所述Pt@MoS2负载在单斜相CaIn2S4表面。
作为上述多级纳米结构复合光催化剂进一步的改进:
优选的,所述单原子Pt的粒径在0.1-0.2纳米,其在Pt@MoS2中的负载量为0.1-10wt%。
优选的,所述Pt@MoS2在单斜相CaIn2S4上的负载量为0.5-10wt%。
本发明的目的之二是提供一种上述多级纳米结构复合光催化剂的制备方法,其包括如下步骤:
(1)将MoO3纳米片加入到含有金属Pt前驱体的水溶液中,搅拌反应后,经过过滤、洗涤、干燥,得到单原子Pt负载的Pt@MoO3粉体。
(2)将步骤1得到的Pt@MoO3粉体与CaIn2O4纳米棒粉体均匀混合,然后置于管式炉中,在硫源的条件下进行退火反应,即可得到Pt@MoS2@CaIn2S4多级纳米结构复合光催化剂。
作为上述多级纳米结构复合光催化剂的制备方法进一步的改进:
优选的,步骤(1)中所述搅拌反应的温度为50-160℃,反应时间为0.5-24小时。
优选的,步骤(1)中所述的金属Pt前驱体为金属Pt的氯化物、硝酸盐和/或金属Pt的其他水溶性盐。
优选的,步骤(1)中所述的金属Pt前驱体为如H2PtCl6、K2PtCl6、Na2PtCl4、K2PtCl4、N2H8PtCl6中的一种或两种以上。
优选的,所述步骤(2)中所述的硫源为H2S、硫粉、硫脲、硫代乙酰胺中的一种或两种以上。
优选的,步骤(2)中所述退火反应的设备为管式炉,温度为600-1000℃,反应时间为0.5-24小时。
本发明的目的之二是提供一种上述多级纳米结构复合光催化剂在光催化制氢领域的用途。
本发明相比现有技术的有益效果在于:
本发明提供了一种由贵金属Pt和二维层状材料MoS2协同负载单斜相CaIn2S4的多级纳米结构复合光催化剂。本发明复合光催化剂的特色在于:二维层状材料MoS2负载于单斜相CaIn2S4表面,单原子Pt纳米颗粒负载于二维层状材料MoS2表面,Pt、MoS2和CaIn2S4形成多级纳米复合结构。该多级纳米结构复合光催化剂通过界面工程,能有效促进光生载流子的分离和传输,降低光催化制氢反应的表观活化能,同时还能最大限度发挥贵金属助催化剂的利用率,从而能大幅增强单斜相CaIn2S4的光催化制氢性能。
在可见光照射下,在单斜相CaIn2S4价带和导带分别生成光生空穴和光生电子。由于MoS2的费米能级低于单斜相CaIn2S4的导带电位,单斜相CaIn2S4表面的光生电子会迁移到MoS2表面,促进光生电荷的分离;由于金属Pt的费米能级低于MoS2的费米能级,迁移到MoS2表面的光生电子会进一步迁移至Pt表面,从而大幅降低光生电荷的复合几率。同时,MoS2表面的单原子Pt,不仅能降低光催化制氢反应的活化能,还能最大限度发挥贵金属Pt的利用率。因此,多级纳米结构复合光催化剂Pt@MoS2@CaIn2S4在可见光下表现出优异的光催化制氢性能,贵金属Pt发挥助催化剂的作用,整体的催化性能远优于单斜相CaIn2S4,是一种非常具有潜力的新型光催化制氢材料。
本发明提供了一种Pt@MoS2@CaIn2S4多级纳米复合结构光催化剂的制备方法,通过低温热还原法将单原子Pt纳米颗粒负载到MoO3纳米片表面得到Pt@MoO3,然后将Pt@MoO3与CaIn2O4纳米棒均匀混合,在硫的气氛中还原,得到Pt@MoS2@CaIn2S4多级纳米结构复合光催化剂。
附图说明
图1所示为实施例1制备的单斜相CaIn2S4和多级纳米结构复合光催化剂Pt@MoS2@CaIn2S4的X射线衍射谱图。
图2所示为实施例2制备的CaIn2S4、MoS2@CaIn2S4、Pt@CaIn2S4和Pt@MoS2@CaIn2S4在可见光下光催化制氢的性能。
图3所示为实施例2制备的多级纳米结构复合光催化剂Pt@MoS2@CaIn2S4在可见光下光催化制氢的稳定性。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明,基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
称取0.1克的MoO3纳米片粉末,加入到含有100毫升去离子水的烧杯中,再加入0.015克的氯铂酸粉末,搅拌30分钟。然后将烧杯放入70℃的水浴锅中,搅拌4小时。反应结束后,将悬浮液过滤、洗涤、干燥,得到单原子Pt负载的Pt@MoO3。通过电感耦合等离子体原子发射光谱仪,测出Pt@MoO3中Pt的含量为5.9wt%。
取上述Pt@MoO3粉末0.045克,加入到0.1克的CaIn2O4纳米棒(制备方法参考ZL200510039255.X)粉末中,研磨1小时,使得Pt@MoO3与CaIn2O4纳米棒混合均匀。然后将混合后的粉末置入管式炉中,通入15%H2S+85%N2混合气氛,在700℃下退火6小时。在退火过程中,MoO3和CaIn2O4纳米棒中的O原子全部被S原子取代,从而分别被还原为MoS2和单斜相CaIn2S4。同时,单原子Pt负载于MoS2表面,而MoS2负载于单斜相CaIn2S4表面,生成多级纳米结构复合光催化剂Pt@MoS2@CaIn2S4,其中Pt、MoS2和CaIn2S4的质量比为0.003:0.05:1。
对上述制得的单斜相CaIn2S4和Pt@MoS2@CaIn2S4的晶体结构进行X射线衍射分析,结果如图1所示。对于单斜相CaIn2S4而言,其XRD谱图与标准卡片#72-0875完全一致。对于Pt@MoS2@CaIn2S4,其XRD谱图与单斜相CaIn2S4完全一致,表明单原子Pt和MoS2的负载并未改变单斜相CaIn2S4的晶体结构,同时也未观察到单原子Pt和MoS2的衍射峰。
实施例2
称取0.15克的MoO3纳米片粉末,加入到含有120毫升去离子水的烧杯中,再加入0.0025克的氯铂酸钾粉末,搅拌45分钟。然后将烧杯放入60℃的水浴锅中,搅拌6小时。反应结束后,将悬浮液过滤、洗涤、干燥,得到单原子Pt负载的Pt@MoO3。通过电感耦合等离子体原子发射光谱仪,测出Pt@MoO3中Pt的含量为0.38wt%。
取上述Pt@MoO3粉末0.036克,加入到0.2克的CaIn2O4纳米棒粉末中,研磨2小时,使得Pt@MoO3与CaIn2O4纳米棒混合均匀。然后将混合后的粉末置入管式炉中,并加入0.4克的硫粉,在600℃下退火9小时。硫化反应结束后,得到多级纳米结构复合光催化剂Pt@MoS2@CaIn2S4,其中Pt、MoS2和CaIn2S4的质量比为0.000076:0.02:1。同时,采用类似的方法,分别合成Pt@CaIn2S4和MoS2@CaIn2S4复合光催化剂。
以光催化分解水制氢反应来评估上述制得的复合光催化剂在可见光下的光催化性能。具体的光催化制氢反应过程如下:(1)称取10毫克的光催化剂粉末,加入到含有100毫升去离子水的光催化反应器中,再加入3.15克亚硫酸钠和6克硫化钠,搅拌30分钟。光源为PLS-SXE300D型氙灯和UV420型滤光片(北京泊菲莱科技有限公司);(2)搅拌均匀后,密封光催化反应器。通入高纯氮气,以50毫升每分钟的流速吹扫反应器,以消除反应器内残留的氧气。然后开始光催化反应;(3)每隔一段时间,采用气相色谱仪(科晓GC 1690C,分子筛填充柱,高纯氮气为载气)在线检测反应过程中氢气的产量。图2为5小时反应后的平均产氢速率。对于单斜相CaIn2S4,在可见光下的产氢速率为5.9μmol/h。对于MoS2@CaIn2S4和Pt@CaIn2S4复合光催化剂,其产氢速率分别为9.6和76.5μmol/h,表明MoS2在单斜相CaIn2S4表面的负载可以小幅增强CaIn2S4光催化制氢的活性,而单原子Pt在单斜相CaIn2S4表面的负载可以显著增强CaIn2S4光催化制氢的活性,这是因为与MoS2相比,Pt是一种更好的产氢助催化剂。特别是当Pt以单原子形态存在时,可以最大限度地发挥Pt的催化作用。对于多级纳米结构复合光催化剂Pt@MoS2@CaIn2S4,在可见光下的产氢速率可以达到1083.5μmol/h,分别是单斜相CaIn2S4、MoS2@CaIn2S4和Pt@CaIn2S4的183.6、112.8和14.2倍。这是因为在多级纳米结构复合光催化剂Pt@MoS2@CaIn2S4中,光生电子会先从单斜相CaIn2S4表面迁移至MoS2表面,然后再迁移至Pt表面,有效降低了光生载流子的复合几率;同时,单原子Pt的负载可以降低光催化制氢反应的活化能并提高Pt的原子利用率。因此,多级纳米结构复合光催化剂Pt@MoS2@CaIn2S4在可见光下表现出优异的光催化制氢性能,是一种非常具有潜力的新型光催化制氢材料。
图3是多级纳米结构复合光催化剂Pt@MoS2@CaIn2S4光催化制氢的稳定性。经过5轮反应,氢气的生成总量分别是5417、5460、5421、5467和5341μmol,表明本发明合成的多级纳米结构复合光催化剂Pt@MoS2@CaIn2S4具有良好的光催化稳定性。
实施例3
称取0.2克的MoO3纳米片粉末,加入到含有80毫升去离子水的烧杯中,再加入0.012克的氯铂酸铵粉末,搅拌60分钟。然后将烧杯放入80℃的水浴锅中,搅拌5小时。反应结束后,将悬浮液过滤、洗涤、干燥,得到单原子Pt负载的Pt@MoO3。通过电感耦合等离子体原子发射光谱仪,测出Pt@MoO3中Pt的含量为2.7wt%。
取上述Pt@MoO3粉末0.09克,加入到0.1克的CaIn2O4纳米棒粉末中,研磨3小时,使得Pt@MoO3与CaIn2O4纳米棒混合均匀。然后将混合后的粉末置入管式炉中,并加入0.96克的硫脲粉末,在700℃下退火6小时。硫化反应结束后,得到多级纳米结构复合光催化剂Pt@MoS2@CaIn2S4,其中Pt、MoS2和CaIn2S4的质量比为0.0027:0.1:1。
本领域的技术人员应理解,以上所述仅为本发明的若干个具体实施方式,而不是全部实施例。应当指出,对于本领域的普通技术人员来说,还可以做出许多变形和改进,所有未超出权利要求所述的变形或改进均应视为本发明的保护范围。
Claims (10)
1.一种多级纳米结构复合光催化剂,其特征在于,由分级结构的单原子Pt、层状半导体态的MoS2和单斜相的CaIn2S4组成,所述单原子Pt负载在层状半导体态的MoS2表面形成Pt@MoS2,所述Pt@MoS2负载在单斜相CaIn2S4表面。
2.根据权利要求1所述的多级纳米结构复合光催化剂,其特征在于,所述单原子Pt的粒径在0.1-0.2纳米,其在MoS2上的负载量为0.1-10wt%。
3.根据权利要求1或2所述的多级纳米结构复合光催化剂,其特征在于,所述Pt@MoS2在单斜相CaIn2S4上的负载量为0.5-10wt%。
4.一种权利要求1-3任意一项所述多级纳米结构复合光催化剂的制备方法,其特征在于,包括如下步骤:
(1)将MoO3纳米片加入到含有金属Pt前驱体的水溶液中,搅拌反应后,经过过滤、洗涤、干燥,得到单原子Pt负载的Pt@MoO3粉体。
(2)将步骤1得到的Pt@MoO3粉体与CaIn2O4纳米棒粉体均匀混合,然后在硫源的条件下进行退火反应,即可得到Pt@MoS2@CaIn2S4的多级纳米结构复合光催化剂。
5.根据权利要求4所述的多级纳米结构复合光催化剂的制备方法,其特征在于,步骤(1)中所述搅拌反应的温度为50-160℃,反应时间为0.5-24小时。
6.根据权利要求4所述的多级纳米结构复合光催化剂的制备方法,其特征在于,步骤(1)中所述的金属Pt前驱体为金属Pt的氯化物、硝酸盐和/或金属Pt的其他水溶性盐。
7.根据权利要求6所述的多级纳米结构复合光催化剂的制备方法,其特征在于,步骤(1)中所述的金属Pt前驱体为H2PtCl6、K2PtCl6、Na2PtCl4、K2PtCl4、N2H8PtCl6中的一种或两种以上。
8.根据权利要求4所述的多级纳米结构复合光催化剂的制备方法,其特征在于,所述步骤(2)中所述的硫源为H2S、硫粉、硫脲、硫代乙酰胺中的一种或两种以上。
9.根据权利要求4所述的多级纳米结构复合光催化剂的制备方法,其特征在于,步骤(2)中所述退火反应的设备为管式炉,温度为600-1000℃,反应时间为0.5-24小时。
10.一种权利要求1-3任意一项所述多级纳米结构复合光催化剂在光催化制氢领域的用途。
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