CN111905766A - 一种0D/1D W18O49/CdS Z-型可见光催化剂的制备方法及应用 - Google Patents
一种0D/1D W18O49/CdS Z-型可见光催化剂的制备方法及应用 Download PDFInfo
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Abstract
本发明提供一种0D/1D W18O49/CdS Z‑型可见光催化剂的制备方法,包括以下步骤:(1)制备CdS前驱体(2)制备0D/1D W18O49/CdS异质结光催化剂。本发明同时公开了其可应用于催化光解水制氢。本发明所制得的0D/1D W18O49/CdS Z‑型可见光催化剂中W18O49量子点粒径较小,在载体表面分散均匀,充分保证W18O49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和稳定性。
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0D/1D W18O49/CdSZ-型可见光催化剂的制备方法及应用。
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。
构建Ⅱ型异质结构是一种常见的增强光吸收,促进电荷空间分离,提高光催化活性的有效方法,已经广泛应用于CdS基光催化材料的改性。例如专利CN 107890877B公开了一种Bi3O4Cl/CdS复合材料及制备方法和用途,该发明通过水热法制备了这一复合光催化剂,可见光照射下光催化降解污染物的性能得到一定的提升。虽然传统的Ⅱ型异质结构可以实现有效的电荷分离,但这需要以牺牲催化剂的氧化还原能力为代价。与之相比,Z-scheme型异质结构可以同时赋予光催化剂体系更高的电荷分离效率和更强的氧化还原能力,在促进光催化应用方面显示出更大的潜力和优势。例如,解士杰等报道了一种采用沉淀法制备的CdS/WO3 Z型光催化剂,该催化剂表现出较高的光催化制氢效率(ACS Catal.2014, 4, 10, 3724-3729)。大量研究表明,在Z-scheme体系的两组分之间构建紧密的界面接触或引入电子介质(如Au、Ag、Pt、还原氧化石墨烯等)有利于降低界面电子的传递阻抗,提高电子传递速率。例如,张金龙等结合光沉积法和沉积-沉淀法制备了CdS-Au-BiVO4 Z型光催化剂,表现出了较高的光催化降解有机污染物性能(Catal. Sci. Technol., 2017,7,124-132)。然而,这些界面优化策略虽然能有效提高表面电荷分离效率,但对CdS体相载流子分离过程的促进作用并不显著,从而导致Z-scheme体系的光催化效率仍远低于理论效率。与块体材料相比,低维纳米材料具有更独特的电子结构,更多的内部原子暴露于材料表面,从而暴露出更活跃的光催化和电催化位点。此外,低维纳米结构的光生载流子从体相到表面的扩散距离比块体材料短,这有利于降低电子-空穴对的复合概率,从而实现高的光催化效率。
发明内容
为了解决上述问题,本发明提供了一种0D/1D W18O49/CdS Z-型可见光催化剂的制备方法,将低维CdS与另一种低维材料进行整合,构建Z-scheme体系,可以同时实现体相和表面载流子的高效分离。
同时提供了该制备方法制备的光催化剂的应用。
本发明是通过以下技术方案实现的:
一种0D/1D W18O49/CdS Z-型可见光催化剂的制备方法,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180 ℃下反应24小时,所得产物自然冷却到室温,分别用无水乙醇、去离子水洗涤多次,离心收集沉淀,烘干,即得到CdS前驱体;
(2)制备0D/1D W18O49/CdS异质结光催化剂
将步骤(1)所得产物100mg超声分散于乙醇中,磁力搅拌下加入100-500 mg的六羰基钨(W(CO)6)或六氯化钨(WCl6),充分混合后继续搅拌30 min,在180 ℃下反应12小时,所得产物自然冷却到室温,经抽滤、洗涤和干燥,即得0D/1D W18O49/CdS光催化剂。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。
在本申请中钨源可以使用六羰基钨(W(CO)6)或六氯化钨(WCl6),均可以制成0D/1DW18O49/CdS光催化剂。钨源与前驱体的质量比不同,产氢速率不同,当钨源与前驱体的质量比为3:1时,制成的催化剂分散在纯水中的产氢速率可达到215.25 μmol h-1 g-1,分散在100 mL 20 vol.%的乳酸溶液中的产氢速率可达到81.57mmol h-1 g-1。
有益效果
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CdS基Z型异质结构光催化剂显著不同。由于本发明采用原位合成的方式,所得W18O49/CdS催化剂的两组分之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,成本较低,对环境友好。本发明所制得的0D/1D W18O49/CdS Z-型可见光催化剂中W18O49量子点粒径较小,在载体表面分散均匀,充分保证W18O49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和稳定性。本发明可应用于催化光解水制氢。
附图说明
图1. (a) 空白CdS纳米棒的TEM图,(b) 0D/1D W18O49/CdS光催化剂的TEM图,(c)是0D/1D W18O49/CdS光催化剂的HRTEM图;
图2为本发明所合成的光催化剂在乳酸溶液中的光催化产氢效果图;
图3为本发明所合成的光催化剂在纯水中的光催化产氢效果图;
图4为本发明所合成的0D/1D W18O49/CdS Z-型可见光催化剂的稳定性评价图。
具体实施方式
下面对本发明的实施例作详细说明,本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
实施例1
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180℃下反应24小时,所得产物自然冷却到室温,分别用去离子水、乙醇洗涤多次,离心收集沉淀,真空烘干,即得到CdS前驱体。
实施例2
将实施例1中制得的CdS 100mg超声分散于60 mL无水乙醇中,磁力搅拌下加入100 mg六羰基钨(W(CO)6),充分混合后继续搅拌30 min,在180 ℃下反应12小时,所得产物自然冷却到室温,经抽滤、洗涤和干燥,即得0D/1D W18O49/CdS Z-型可见光催化剂,标记为W-CS-100。
实施例3
将实施例1中制得的CdS 100mg超声分散于60 mL无水乙醇中,磁力搅拌下加入200 mg六羰基钨(W(CO)6),充分混合后继续搅拌30 min,在180 ℃下反应12小时,所得产物自然冷却到室温,经抽滤、洗涤和干燥,即得0D/1D W18O49/CdS Z-型可见光催化剂,标记为W-CS-200。
实施例4
将实施例1中制得的CdS 100mg超声分散于60 mL无水乙醇中,磁力搅拌下加入300 mg六羰基钨(W(CO)6),充分混合后继续搅拌30 min,在180 ℃下反应12小时,所得产物自然冷却到室温,经抽滤、洗涤和干燥,即得0D/1D W18O49/CdS Z-型可见光催化剂,标记为W-CS-300。
图1中a是空白CdS纳米棒的TEM图;图b是0D/1D W18O49/CdS光催化剂的TEM图,图c是0D/1D W18O49/CdS催化剂的HRTEM图。由图4可知,成功地制备了W18O49量子点修饰的CdS纳米棒复合材料(0D/1D W18O49/CdS光催化剂)。
实施例5
将实施例1中制得的CdS 100mg超声分散于60 mL无水乙醇中,磁力搅拌下加入400 mg六羰基钨(W(CO)6),充分混合后继续搅拌30 min,在180 ℃下反应12小时,所得产物自然冷却到室温,经抽滤、洗涤和干燥,即得0D/1D W18O49/CdS Z-型可见光催化剂,标记为W-CS-400。
实施例6
将400 mg六羰基钨(W(CO)6)加入到聚四氟乙烯反应釜中,加入无水乙醇至反应釜容积60%,磁力搅拌至完全溶解,将其在180℃下反应12小时,所得产物自然冷却到室温,用乙醇洗涤多次,离心收集沉淀,真空烘干,即得到W18O49。
实施例7
分别取实施例1、2、3、4、5和6中制得的催化剂各20 mg,分散在100 mL 20 vol.%的乳酸溶液中,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2。
由图2可知,W-CS-300可见光催化剂催化活性最高,其产氢速率为81.57mmol h-1g-1,是纯的CdS产氢速率的159.9倍。
实施例8
分别取实施例1、2、3、4、5和6中制得的催化剂各50 mg,分散在100 mL 超纯水中,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3。
由图3可知,W-CS-300可见光催化剂催化活性最高,其产氢速率为215.25 μmol h-1g-1,而纯的CdS和W18O49几乎不产生氢气。
实施例9
取实施例4中制得的催化剂20 mg,分散在100 mL 20 vol.%的乳酸溶液中,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30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。
由图4可知,所制备的0D/1D W18O49/CdS Z-型可见光催化剂具有较好的稳定性。
实施例10
将实施例1中制得的CdS 100mg超声分散于60 mL无水乙醇中,磁力搅拌下加入100mg、200mg、300mg、400mg六氯化钨(WCl6),充分混合后继续搅拌30 min,在180 ℃下反应12小时,所得产物自然冷却到室温,经抽滤、洗涤和干燥,均可以得到0D/1D W18O49/CdS Z-型可见光催化剂。
显然,本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样,倘若本发明的这些修改和变型属于本发明权利要求及其等同技术的范围之内,则本发明也意图包含这些改动和变型在内。
Claims (7)
1.一种0D/1D W18O49/CdS Z-型可见光催化剂的制备方法,其特征在于,包括以下步骤:
(1)制备CdS前驱体
以四水合硝酸镉和硫脲分别作为镉和硫源,反应制备CdS前驱体;
(2)制备0D/1D W18O49/CdS异质结光催化剂
将步骤(1)中所述的前驱体分散于乙醇中,加入钨源,搅拌均匀后反应制备催化剂。
2.根据权利要求1所述的制备方法,其特征在于,步骤(1)中四水合硝酸镉和硫脲摩尔比为1:3;步骤(2)中前驱体与钨源的质量比为1:1-5。
3.根据权利要求1所述的制备方法,其特征在于,步骤(2)中钨源为六羰基钨或六氯化钨。
4.根据权利要求1所述的制备方法,其特征在于,制备CdS前驱体的具体步骤为:
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180 ℃下反应24小时,所得产物自然冷却到室温,分别用无水乙醇、去离子水洗涤多次,离心收集沉淀,烘干,即得到CdS前驱体。
5.根据权利要求1所述的制备方法,其特征在于,制备0D/1D W18O49/CdS异质结光催化剂的具体步骤为:
将步骤(1)所得产物100mg超声分散于乙醇中,磁力搅拌下加入100-500 mg的六羰基钨或六氯化钨,充分混合后继续搅拌30 min,在180 ℃下反应12小时,所得产物自然冷却到室温,经抽滤、洗涤和干燥,即得0D/1D W18O49/CdS光催化剂。
6.一种权利要求1-5之一所述的制备方法制备的0D/1D W18O49/CdS光催化剂。
7.一种权利要求6所述的0D/1D W18O49/CdS光催化剂在催化光解水制氢中的应用。
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