CN109174123B - 一种Z型CdS-Ag-TiO2复合光催化材料及其制备方法和应用 - Google Patents
一种Z型CdS-Ag-TiO2复合光催化材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种Z型CdS‑Ag‑TiO2复合光催化材料以及制备方法和应用,先以乙二胺和十二硫醇的混合溶液为溶剂,并添加隔源和硫源,通过溶剂热法制备得到CdS纳米线;再以硝酸银为原料,CdS纳米线为基底,光还原合成得到CdS‑Ag;最后再以CdS‑Ag为基体,在油酸和油胺的环境中,注入四异丙醇钛,通过第二次溶剂热法制备得到Z型CdS‑Ag‑TiO2复合光催化材料。通过将CdS与Ag、TiO2三者结合形成三元Z型结构,改变电子传输方向,使氢离子还原反应的场所发生转移,光生空穴也随之转向TiO2,而TiO2本身并不会发生光腐蚀的现象,有利于保持CdS的化学稳定性。能够减少CdS的光腐蚀现象,提高CdS与TiO2之间的复合材料之间的光催化制氢能力。
Description
技术领域
本发明涉及光催化剂技术领域,更具体地,涉及一种Z型CdS-Ag-TiO2复合光催化材料及其制备方法和应用。
背景技术
半导体光催化技术是现如今社会解决能源危机的重要的有前途的途径之一。TiO2是一种传统的光催化材料,但是它的吸收范围只限于低于400 nm的紫外光,大大限制了它的发展。除了金属氧化物之外,硫化物也是一大类,例如CdS就是一种可见光响应的光催化剂,其吸收边延长至520nm左右,但是其S2-非常容易在光照过程中被光生空穴进行自身氧化,发生光腐蚀现象。一般为了提高光催化制氢,现有通常采取两种不同能带结构的半导体材料形成传统Ⅱ型异质结,从而达到光催化提升的效果。但是这样的异质结的形成会导致氧化还原的能力产生一定的下降。
与植物光合作用相似,Z型光催化材料体系是由电子传输介质、光还原剂和光氧化剂组成的双光子体系,其应用于光催化反应具有很大的优势:借助双光子激发过程,在不同光催化剂上分别完成氧化反应和还原反应,有效促进了光生电荷的分离和迁移。Z型反应体系中的光催化剂只需分别满足各自的光激发过程和对应的半反应,为光催化材料的选择和设计提供了很大的空间。光催化还原位点和氧化位点分别在两个光催化半导体上,还原和氧化过程相互分离,可以有效抑制逆反应的发生。同时,催化材料光还原剂中的光生空穴被来自光氧化剂中的光生电子复合,光催化体系的稳定性随之增强。Z型光催化材料体系,表现出了宽光谱响应,高稳定性,高光生载流子的分离效率,强氧化还原能力,具有广阔的应用前景。
由于CdS和TiO2传统的Ⅱ型异质结虽然能够提高光催化的效果,但是其氧化还原能力有所降低,而且没能彻底解决光腐蚀的缺陷。
发明内容
本发明所要解决的技术问题是克服上述现有的光催化材料CdS和TiO2存在的缺陷和不足,为了能够减少CdS的光腐蚀现象,提高CdS与TiO2之间的复合材料之间的光催化制氢能力,提供一种新的Z型CdS-Ag-TiO2复合光催化材料,通过将CdS与Ag、TiO2三者结合形成三元Z型结构,改变电子传输方向,使氢离子还原反应的场所发生转移,光生空穴也随之转向TiO2,而TiO2本身并不会发生光腐蚀的现象,有利于保持CdS的化学稳定性。
本发明的第一个目的是提供一种Z型CdS-Ag-TiO2复合光催化材料的制备方法。
本发明的第二个目的是提供上述制备方法制备得到的Z型CdS-Ag-TiO2复合光催化材料。
本发明的第三个目的是提供所述Z型CdS-Ag-TiO2复合光催化材料的应用。
本发明的上述目的是通过以下技术方案给予实现的:
一种Z型CdS-Ag-TiO2复合光催化材料的制备方法,包括如下步骤:
S1.制备CdS纳米线:向乙二胺和十二硫醇的混合溶液中加入镉源和硫源,充分混匀、溶解后于180℃水热反应24~48h,反应产物经洗脱后即得CdS纳米线;
S2.制备CdS-Ag:将S1的CdS纳米线溶于超纯水中,然后加入硝酸银溶液,搅拌混匀后用氙灯照射20~40min,光还原反应得到CdS-Ag;
S3.制备CdS-Ag-TiO2:将CdS-Ag溶于95%的乙醇中,然后加入油胺、油酸和四异丙醇钛,于180℃水热反应20h,反应产物经洗脱后即得CdS-Ag-TiO2复合光催化材料。
本发明先以乙二胺和十二硫醇的混合溶液为溶剂,并添加隔源和硫源,通过溶剂热法制备得到CdS纳米线;再以硝酸银为原料,CdS纳米线为基底,光还原合成得到CdS-Ag;最后再以CdS-Ag为基体,在油酸和油胺的环境中,注入四异丙醇钛,通过第二次溶剂热法制备得到Z型CdS-Ag-TiO2复合光催化材料。通过将CdS与Ag、TiO2三者结合形成三元Z型结构,改变电子传输方向,使氢离子还原反应的场所发生转移,光生空穴也随之转向TiO2,而TiO2本身并不会发生光腐蚀的现象,有利于保持CdS的化学稳定性。能够减少CdS的光腐蚀现象,提高CdS与TiO2之间的复合材料之间的光催化制氢能力。
优选地,S1所述混合溶液中乙二胺与十二硫醇的体积比为18~19:1~2。
优选地,S1所述镉源为乙酸镉,所述硫源为硫化钠。
优选地,所述乙酸镉与硫化钠的摩尔比为1:1。
优选地,S2所述油酸、油胺与四异丙醇钛的体积比为3:1:0.3。
本发明还同时保护上述任一所述的制备方法制备得到的Z型CdS-Ag-TiO2复合光催化材料。
本发明制备得到的Z型CdS-Ag-TiO2复合光催化材料通过将CdS与Ag、TiO2三者结合形成三元Z型结构,改变电子传输方向,使氢离子还原反应的场所发生转移,光生空穴也随之转向TiO2,而TiO2本身并不会发生光腐蚀的现象,有利于保持CdS的化学稳定性。能够减少CdS的光腐蚀现象,提高CdS与TiO2之间的复合材料之间的光催化制氢能力。
因此,所述Z型CdS-Ag-TiO2复合光催化材料在光催制氢中的应用也在本发明保护范围内。
与现有技术相比,本发明具有以下有益效果:
本发明制备得到了一种新的Z型CdS-Ag-TiO2复合光催化材料,通过将CdS与Ag、TiO2三者结合形成三元Z型结构,改变电子传输方向,使氢离子还原反应的场所发生转移,光生空穴也随之转向TiO2,而TiO2本身并不会发生光腐蚀的现象,有利于保持CdS的化学稳定性。能够减少CdS纳米材料的本身光生空穴的光腐蚀现象,提高CdS与TiO2之间的复合材料之间的光催化制氢能力。
附图说明
图1为本发明Z型CdS-Ag-TiO2复合光催化材料的制备示意图。
图2为CdS纳米线与Z型CdS-Ag-TiO2复合光催化材料的TEM图像;a为CdS纳米线;b为CdS-Ag-TiO2。
图3为CdS纳米线与Z型CdS-Ag-TiO2复合光催化材料的UV-via谱图。
图4为CdS纳米线与Z型CdS-Ag-TiO2复合光催化材料的光催化制氢的效果比较图。
图5为CdS纳米线与Z型CdS-Ag-TiO2复合光催化材料光催化制氢的循环实验结果。
具体实施方式
以下结合说明书附图和具体实施例来进一步说明本发明,但实施例并不对本发明做任何形式的限定。除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
除非特别说明,以下实施例所用试剂和材料均为市购。
实施例1
一种Z型CdS-Ag-TiO2复合光催化材料的制备方法,包括如下步骤:
1、CdS纳米线的合成
将2 mL正十二硫醇加入到18 mL乙二胺溶液,超声融合之后,再加入1 mmol的前驱体乙酸镉,超声分散至透明溶液。然后,加入1mmol的硫化钠,在聚四氟乙烯反应釜中180℃反应24~48小时;冷却至室温后,直接用丙酮和无水乙醇洗涤沉淀,即得CdS纳米线。
2、CdS-Ag的光还原合成
将20 mg硝酸银加入到3 mL水中,之后将步骤1制备得到的CdS纳米线溶于97mL超纯水中;再将硝酸银溶液逐滴加入到CdS纳米线中,搅拌5min;接着,利用氙灯照射其混合溶液30min,使其达到光还原的目的,制备得到CdS-Ag。
3、CdS-Ag-TiO2的合成反应
将步骤2制备得到的CdS-Ag溶于20mL的95%的乙醇中,超声混匀,之后再加入1mL油胺、1mL油酸和1mL四异丙醇钛,在聚四氟乙烯反应釜中180℃,反应20h;冷却至室温后,直接用丙酮和无水乙醇洗涤沉淀,即得Z型CdS-Ag-TiO2复合光催化材料。
试样表征及性能测试
(1)步骤1制备得到的CdS纳米线以及步骤3的Z型CdS-Ag-TiO2复合光催化材料的透射电子显微像(TEM)如图2所示,(a)显示其纯CdS纳米线的状态,表面没有掺杂其他物质;(b)结果显示,TiO2以纳米球的状态负载在Ag纳米颗粒表面,Ag纳米颗粒以电子传输介质的身份处于CdS纳米线和TiO2纳米球之间。
(2)步骤1制备得到的CdS纳米线以及步骤3的Z型CdS-Ag-TiO2复合光催化材料的UV-via谱图如图3所示,结果显示,Z型CdS-Ag-TiO2与纯CdS线相比,其在可见光区域具有良好的吸收性能。
(3)步骤1制备得到的CdS纳米线以及步骤3的CdS-Ag-TiO2纳米异质结光催化材料的光催化制氢的效果比较图如图4所示,结果显示,Z型CdS-Ag-TiO2在同等条件下,其光催化制氢性能是纯CdS的光催化制氢的2.5倍。循环实验如图5所示,结果显示,Z型CdS-Ag-TiO2具有良好的抗光腐蚀的能力。
实施例2
一种Z型CdS-Ag-TiO2复合光催化材料的制备方法,包括如下步骤:
1、CdS纳米线的合成
将1 mL正十二硫醇加入到19 mL乙二胺溶液,超声融合之后,再加入1 mmol的前驱体乙酸镉,超声分散至透明溶液。然后,加入2mmol的硫化钠,在聚四氟乙烯反应釜中180℃反应24~48小时;冷却至室温后,直接用丙酮和无水乙醇洗涤沉淀,即得CdS纳米线。
2、CdS-Ag的光还原合成
将20 mg硝酸银加入到4 mL水中,之后将步骤1制备得到的CdS纳米线溶于96mL超纯水中;再将硝酸银溶液逐滴加入到CdS纳米线中,搅拌5min;接着,利用氙灯照射其混合溶液30min,使其达到光还原的目的,制备得到CdS-Ag。
3、CdS-Ag-TiO2的合成反应
将步骤2制备得到的CdS-Ag溶于20mL的95%的乙醇中,超声混匀,之后再加入1mL油胺、3mL油酸和1mL四异丙醇钛,在聚四氟乙烯反应釜中180℃,反应20h;冷却至室温后,直接用丙酮和无水乙醇洗涤沉淀,即得Z型CdS-Ag-TiO2复合光催化材料。
实施例3
一种Z型CdS-Ag-TiO2复合光催化材料的制备方法,包括如下步骤:
1、CdS纳米线的合成
将2 mL正十二硫醇加入到18 mL乙二胺溶液,超声融合之后,再加入1 mmol的前驱体乙酸镉,超声分散至透明溶液。然后,加入2mmol的硫化钠,在聚四氟乙烯反应釜中180℃反应24~48小时;冷却至室温后,直接用丙酮和无水乙醇洗涤沉淀,即得CdS纳米线。
2、CdS-Ag的光还原合成
将20 mg硝酸银加入到5 mL水中,之后将步骤1制备得到的CdS纳米线溶于95mL超纯水中;再将硝酸银溶液逐滴加入到CdS纳米线中,搅拌5min;接着,利用氙灯照射其混合溶液30min,使其达到光还原的目的,制备得到CdS-Ag。
3、CdS-Ag-TiO2的合成反应
将步骤2制备得到的CdS-Ag溶于20mL的95%的乙醇中,超声混匀,之后再加入1mL油胺、2mL油酸和1mL四异丙醇钛,在聚四氟乙烯反应釜中180℃,反应20h;冷却至室温后,直接用丙酮和无水乙醇洗涤沉淀,即得Z型CdS-Ag-TiO2复合光催化材料。
Claims (7)
1.一种Z型CdS-Ag-TiO2复合光催化材料的制备方法,其特征在于,包括如下步骤:
S1.制备CdS纳米线:向乙二胺和十二硫醇的混合溶液中加入镉源和硫源,充分混匀、溶解后于180℃水热反应24~48h,反应产物经洗脱后即得CdS纳米线;
S2.制备CdS-Ag:将S1的CdS纳米线溶于超纯水中,然后加入硝酸银溶液,搅拌混匀后用氙灯照射20~40min,光还原反应得到CdS-Ag;
S3.制备CdS-Ag-TiO2:将CdS-Ag溶于体积分数为95%的乙醇水溶液中,然后加入油胺、油酸和四异丙醇钛,于180℃水热反应20h,反应产物经洗脱后即得CdS-Ag-TiO2复合光催化材料。
2.根据权利要求1所述的制备方法,其特征在于,S1所述混合溶液中乙二胺与十二硫醇的体积比为18~19:1~2。
3.根据权利要求1所述的制备方法,其特征在于,S1所述镉源为乙酸镉,所述硫源为硫化钠。
4.根据权利要求3所述的制备方法,其特征在于,所述乙酸镉与硫化钠的摩尔比为1:1。
5.根据权利要求1所述的制备方法,其特征在于,S3所述油酸、油胺与四异丙醇钛的体积比为3:1:0.3。
6.权利要求1~5任一项所述的制备方法制备得到的Z型CdS-Ag-TiO2复合光催化材料。
7.权利要求6所述的Z型CdS-Ag-TiO2复合光催化材料在光催化制氢中的应用。
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