CN112547125A - 一种可用于光解水的CdS/NiPc光催化剂及其制备方法 - Google Patents
一种可用于光解水的CdS/NiPc光催化剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种可用于光解水的CdS/NiPc光催化剂及其制备方法,属于光催化技术领域。本发明通过在二乙烯三胺(DETA)溶剂中形成硫化镉种子,再加入不同含量的酞菁镍(NiPc),有效分散NiPc,利用溶剂热法原位合成CdS/NiPc光催化剂,NiPc的引入不仅有利于拓宽可见光响应范围,而且有利于光生电荷的分离和转移,从而提高光催化活性。该合成方法工艺简单,易操作,成本低廉。所制备的CdS/NiPc光催化剂具有优异的光解水制氢性能。
Description
技术领域
本发明属于光催化技术领域,具体涉及一种可用于光解水的CdS/NiPc光催化剂及其制备方法。
背景技术
随着世界经济的快速发展,人们对石油等化工燃料的过度开发利用导致了严重的环境和能源危机,这就使得开发和利用可持续的清洁能源来替代化石燃料,成为人类社会面临的最重大的挑战之一。氢气作为燃料具有能量密度高、可再生性和环境友好等优点,被认为是化石能源的理想替代品。光催化分解水制氢是最有前途的获取氢能的技术之一。目前,人们开发各种半导体作为高效的光催化剂,特别是能够利用可见光(λ≥420nm)的光催化剂。其中硫化镉(CdS)由于其相对窄的带隙(通常为2.4eV)而成为高效的硫化物可见光催化剂之一。然而,纯CdS也存在光生载流子的强复合和有限的吸收边缘限制了对太阳能的有效利用等缺点,极大的限制了CdS的广泛应用,因此CdS光解水制氢活性有待进一步提高。
光敏化作为扩大半导体光谱响应范围的重要方法之一,已被广泛用于提高光催化剂对可见光的利用效率和光催化活性。常用的染料大部分只能吸收可见光中波长较短的部分(λ=400-600nm)。而金属酞菁具有平面π-π共轭体系、优异的化学稳定性和高消光系数的优点,并可以吸收太阳光的远可见光区(λ=600-800nm),因此被认为是宽带隙半导体敏化最有吸引力的染料。到目前为止,金属酞菁在光催化技术中得到了广泛的应用,如有机污染物的去除、水的分解和二氧化碳的还原等。虽然金属酞菁可以通过拓宽半导体光吸收范围和增强对可见光的吸收强度来优化光催化性能,但其在溶液中和半导体表面上都容易出现聚集,从而不利于与半导体光催化剂的充分接触,阻碍电荷的分离和削弱对可见光的利用效率。
发明内容
针对以上问题,本发明通过种子原位合成法制备CdS/NiPc光催化剂,通过在二乙烯三胺(DETA)溶剂中形成硫化镉种子,再加入不同含量的酞菁镍(NiPc),从而有效分散NiPc,利用溶剂热法原位合成CdS/NiPc光催化剂,NiPc的引入不仅有利于拓宽可见光响应范围,而且有利于光生电荷的转移和分离,从而提高光催化活性。该光催化剂不仅具有优异的可见光吸收特性,还具有很好的光解水制氢活性,该方法工艺简单、成本低廉,易于大规模生产。
本发明的目的是通过以下技术方案实现的:首先,一种可用于光解水的CdS/NiPc光催化剂的制备方法,所述方法包括如下步骤:
步骤一:先将镉源和升华硫混合,然后加入二乙烯三胺,混合搅拌得到硫化镉前驱液;;
步骤二:将酞菁镍(NiPc)加入到硫化镉前驱液中,搅拌均匀后加入到高压反应釜中,80~100℃下反应40-60h;
步骤三:反应结束后,洗涤产物、固液分离、干燥即可制备得到CdS/NiPc光催化剂。
进一步的,所述镉源和升华硫的摩尔比为12:50~75。
进一步的,所述镉源和二乙烯三胺摩尔体积比为(3~5)mmol:(25~40)mL。
进一步的,所述步骤一中的镉源可以是氯化镉、硝酸镉中的一种。
进一步的,所述步骤二中的NiPc的质量分数为硫化镉理论质量的1~15%。
进一步的,所述步骤三中,洗涤优选为用去离子水和乙醇洗涤。
进一步的,所述步骤三中,干燥为60~70℃烘干6~12h。
其次,本发明还提供了上述制备方法制备得到的CdS/NiPc光催化剂。
再者,本发明提供了上述CdS/NiPc光催化剂在光解水领域中的应用。
最后,本发明提供了一种光解水制氢的方法,所述方法利用上述CdS/NiPc光催化剂作为光催化剂。
本发明与现有技术相比,具有以下显著优点:
(1)本发明中通过引入钛菁镍(NiPc)能够拓宽半导体材料硫化镉(CdS)的可见光吸收范围,同时光照过程中产生的光生电子-空穴能被有效地激发、分离和迁移,从而提高材料的可见光催化活性。
(2)本发明制备的CdS/NiPc光催化剂,与其他贵金属催化剂,以及传统的光催化剂相比,其具有2D片层结构,CdS纳米片与钛菁镍有效的结合起来,从而获得更大比表面积,同时酞菁镍中的二价镍能有效的分离和转移光生电子-空穴对,提高光催化分解水制氢活性。
(3)本发明通过在二乙烯三胺(DETA)溶剂中形成硫化镉(CdS)种子,利用形成的CdS种子来分散钛菁镍(NiPc)从而解决NiPc容易团聚的问题,且含不同含量NiPc的光催化剂表现出不同程度的可见光催化活性。该合成方法工艺简单,易操作,成本低廉。
(4)本发明制备的CdS/NiPc光催化剂,可应用于光解水制氢,氢气产率高,推广应用有很大优势。
附图说明
图1为实施例2和对比例1制备得到的光催化剂的X-射线衍花样。
图2实施例1~3所制备光催化剂以及CdS、NiPc的紫外-可见光漫反射光谱。
图3所制备光催化剂的光解水制氢性能;其中(1)CdS;(2)NiPc;(3)CdS-5%NiPc;(4)CdS-10%NiPc;(5)CdS-15%NiPc;(6)对比例2得到的CdS-10%NiPc。
图4实施例1~3所制备光催化剂以及CdS的荧光发射光谱。
具体实施方式
下面结合实施例对本发明作进一步的描述,但本发明的实施方式不限于此。
实施例1
一种可用于光解水的CdS/NiPc光催化剂,其包括如下步骤:
步骤一:称取4.8mmol的氯化镉、30mmol的升华硫加入烧杯中,然后向烧杯加入30mL的二乙烯三胺(DETA)并搅拌30min,使其形成均匀的悬浮液,得到硫化镉前驱液;
步骤二:加入占硫化镉理论质量5%的酞菁镍(NiPc)到上述硫化镉前驱液中,并搅拌30min使其形成均匀的悬浮液,再将悬浮液转入50mL的含聚四氟乙烯内胆的不锈钢高压反应釜中,80℃下反应48h;
步骤三:反应后所得产物用去离子水和乙醇洗涤并离心分离,再将固体转移到烘箱70℃烘干12h,得到CdS/NiPc光催化剂。
实施例2
本实施例中的制备方法与实施例1相同,区别仅在于本实施例的步骤二加入的NiPc的质量是CdS理论质量的10%,其余条件不变。
实施例3
本实施例中的制备方法与实施例1相同,区别仅在于本实施例的步骤二加入的NiPc的质量是CdS理论质量的15%,其余条件不变。
对比例1
本实施例中的制备方法与实施例1相同,区别仅在于本实施例的步骤一不加入NiPc,其余条件不变。
对比例2
本实施例中的制备方法与实施例2相同,区别仅在于本实施例的步骤一先称取4.8mmol的氯化镉溶解于30mL的二乙烯三胺(DETA)中,再加入30mmol的升华硫,充分搅拌30min,其余条件不变。
对对比例1制备得到的纯CdS以及实施例2制备得到的酞菁镍含量为10%的CdS/NiPc光催化剂进行了X-射线衍射花样表征,如图1所示,NiPc加入未使CdS光催化剂的物相和结晶性发生明显变化。
通过紫外-可见光漫反射光谱对不同酞菁镍含量的CdS/NiPc光催化剂的光吸收强度和范围进行测试,如图2所示,发现添加NiPc后能明显拓宽催化剂的光吸收范围,提高光催化剂对可见光的吸收和利用。
为了研究光催化剂的光催化性能,将制备的光催化剂用于光解水制氢,具体的实验过程如下:称取5mg光催化剂加入20mL去离子水中,并加入2mL的乳酸溶液,作为空穴牺牲剂;将配好的溶液转移到离线制氢反应器中并封闭,通入氮气30min除去反应器中的氧气,然后使其进行光催化反应,3h后测试氢气产率;不同钛菁镍含量的CdS-xNiPc(x为质量分数)光催化剂的光催化性能如图3所示,其中(1)CdS;(2)NiPc;(3)CdS-5%NiPc;(4)CdS-10%NiPc;(5)CdS-15%NiPc;(6)对比例2得到的CdS-10%NiPc。可以看到添加NiPc之后,复合催化剂的氢气产率增大,当添加的质量分数达到10%时,氢气的产量达到最大值为17.74mmol g-1h-1,是纯CdS的19.1倍。当添加的质量分数为15%时,氢气的产量反而下降,这可能是由于过量的NiPc会抑制光生电子-空穴的分离,并成为新的电子-空穴的复合中心,从而降低光催化活性。此外,原料的加料顺序对样品的性能也有显著影响,对比例2中先将镉源溶于溶剂二乙烯三胺中,再加升华硫对最终样品的性能影响显著,从图3中(6)的结果可以看出,所得到的样品光解水性能下降到12.11mmol g-1h-1,可能是由于溶剂对镉源的强配位作用,限制了硫化镉种子前驱体的生成。
利用荧光光谱探究了催化剂的光生电子-空穴的分离效果,结果如图4所示,可以看到添加NiPc后,荧光光谱的发射峰强度下降,这表示光生电子-空穴的分离效果变好,降低了光生电荷的复合几率,且其结果与光催化性能相一致。
实施例4
一种可用于光解水的CdS/NiPc光催化剂,其包括如下步骤:
步骤一:称取4.8mmol的氯化镉、25mmol的升华硫加入烧杯中,然后向烧杯加入30mL的二乙烯三胺(DETA)并搅拌30min,使其形成均匀的悬浮液,得到硫化镉前驱液;
步骤二:加入占硫化镉理论质量8%的酞菁镍(NiPc)到上述硫化镉前驱液中,并搅拌30min使其形成均匀的悬浮液,再将悬浮液转入50mL的含聚四氟乙烯内胆的不锈钢高压反应釜中,90℃下反应45h;
步骤三:反应后所得产物用去离子水和乙醇洗涤并离心分离,再将固体转移到烘箱60℃烘干10h,得到CdS/NiPc光催化剂。
虽然本发明已以较佳实施例公开如上,但其并非用以限定本发明,任何熟悉此技术的人,在不脱离本发明的精神和范围内,都可做各种的改动与修饰,因此本发明的保护范围应该以权利要求书所界定的为准。
Claims (10)
1.一种可用于光解水的CdS/NiPc光催化剂的制备方法,其特征在于,所述方法包括如下步骤:
步骤一:先将镉源和升华硫混合,然后加入二乙烯三胺,混合搅拌得到硫化镉前驱液;
步骤二:将酞菁镍NiPc加入到硫化镉前驱液中,搅拌均匀后加入到高压反应釜中,80~100℃下反应40-60h;
步骤三:反应结束后,洗涤产物、固液分离、干燥即可制备得到CdS/NiPc光催化剂。
2.根据权利要求1所述的一种可用于光解水的CdS/NiPc光催化剂的制备方法,其特征在于,所述镉源和升华硫的摩尔比为12:50~75。
3.根据权利要求1或2所述的一种可用于光解水的CdS/NiPc光催化剂的制备方法,其特征在于,所述镉源和二乙烯三胺摩尔体积比为(3~5)mmol:(25~40)mL。
4.根据权利要求1~3任一所述的一种可用于光解水的CdS/NiPc光催化剂的制备方法,其特征在于,所述步骤一中的镉源包括氯化镉、硝酸镉中的一种。
5.根据权利要求1~4任一所述的一种可用于光解水的CdS/NiPc光催化剂的制备方法,其特征在于,所述步骤二中的NiPc的质量分数为硫化镉理论质量的1~15%。
6.根据权利要求1~5任一所述的一种可用于光解水的CdS/NiPc光催化剂的制备方法,其特征在于,所述步骤三中,干燥为60~70℃烘干6~12h。
7.根据权利要求1~6任一所述的一种可用于光解水的CdS/NiPc光催化剂的制备方法制备得到的CdS/NiPc光催化剂。
8.权利要求7所述的CdS/NiPc光催化剂在光解水领域中的应用。
9.根据权利要求8所述的应用,其特征在于,所述光解水为光解水制氢。
10.一种光解水制氢的方法,其特征在于,所述方法利用权利要求7所述的CdS/NiPc光催化剂作为光催化剂。
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