CN105498802A - 一种氧化锌-金-硫化镉三元复合型光催化剂 - Google Patents
一种氧化锌-金-硫化镉三元复合型光催化剂 Download PDFInfo
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Abstract
本发明公开了氧化锌-金-硫化镉三元纳米棒阵列型复合光催化剂的制备及其在模拟太阳光照射下光催化选择性还原芳香性硝基化合物的应用。通过简单的电化学沉积和光沉积过程,制备得到了具有一维纳米棒阵列结构的氧化锌-金-硫化镉(ZnO-Au-CdS)三元复合型光催化剂。所制备的ZnO-Au-CdS三元复合光催化剂具有比单独ZnO纳米棒阵列、ZnO-Au和ZnO-CdS复合材料更高的光催化选择性还原芳香性硝基化合物至相应的胺基化合物的性能。该法制备过程简单,反应条件温和,并且可以实现催化剂的有效回收与分离,对促进光催化技术在选择性有机合成领域中的应用具有重要的意义。
Description
技术领域
本发明属于光催化剂领域,具体涉及氧化锌-金-硫化镉三元纳米棒阵列的制备方法及其在模拟太阳光照射下光催化选择性还原芳香性硝基化合物至相应的胺基化合物的应用。
背景技术
随着世界经济的快速发展和化石燃料的不断消耗,由此引发的环境和能源问题日益凸显。光催化技术作为一项有望利用太阳能治理受污环境和制备化石燃料替代能源的绿色途径,得到了越来越多的关注。实现光催化技术在实际反应中的应用,光催化剂必须满足两个基本条件:一是高的太阳能利用率和高活性,二是便于分离回收。目前所研究的光催化剂通常存在光生载流子易复合,量子效率低的问题,且多以粉末形式存在,需要通过离心或过滤等方式回收,在很大程度上阻碍了其在太阳能转化方面的应用。
将两种或多种组分复合构建多元复合型光催化剂为实现高太阳能利用率和高活性这一目标利用提供了一条有效的方法和途径。例如将宽带隙的半导体组分(常用的有二氧化钛和氧化锌)与能带结构相匹配的窄带隙半导体(如硫化镉)复合,既可以更有效地利用太阳能,又有利于电子-空穴对的有效分离和转移,从而促进复合材料光催化活性的提高。另外,为了避免复杂且耗时耗力的催化剂回收过程,在实际应用中通常需要将光催化剂固定,同时还需保证所固定的催化剂与反应底物之间有充分的接触。将光催化剂制成膜材料为实现以上目标提供了可能性。从操作和成本的角度考虑,将催化剂直接以膜材料的形式制备在相应的基底材料上具有更为显著的优势。
发明内容
本发明的目的在于提供一种太阳能利用率高且工艺简单的氧化锌-金-硫化镉(ZnO-Au-CdS)三元纳米棒阵列的制备方法及其在光催化选择性有机合成中的应用。所制备的ZnO-Au-CdS三元复合光催化剂具有比单独ZnO纳米棒阵列、ZnO-Au和ZnO-CdS复合材料更高的光催化选择性还原芳香性硝基化合物至相应的胺基化合物的性能,并且光催化剂易于分离回收。
为实现上述目的,本发明采用如下技术方案:
一种氧化锌-金-硫化镉(ZnO-Au-CdS)三元复合型光催化剂为生长在掺杂氟的二氧化锡(FTO)透明导电玻璃上的一维纳米棒阵列;所述的氧化锌-金-硫化镉三元复合型光催化剂中氧化锌的质量分数为(58%~64%),金的质量分数为(2%~6%),硫化镉的质量分数为(30%~40%)。
制备如上所述的ZnO-Au-CdS三元复合型光催化剂的方法包括以下步骤:
(1)通过电化学沉积法制备氧化锌纳米棒阵列,采用Pt电极为对电极,Ag/AgCl电极为参比电极,FTO导电玻璃为工作电极,将三电极体系置于含有Zn(NO3)2和NaNO3的混合溶液中,溶液温度保持在85oC,加–1.3V的电压10s,然后将电压调为–1.0V保持1000~2000s,用去离子水冲洗工作电极后,氮气吹干,最后在空气中350oC煅烧2h,得到氧化锌纳米棒阵列;
(2)将步骤(1)制得的氧化锌纳米棒阵列置于预先除氧的甲醇水的混合溶液中,然后加入氯金酸(HAuCl4)溶液,混合均匀后,光沉积0.5~2h,用去离子水冲洗,氮气吹干,得到负载金的氧化锌纳米棒阵列;
(3)将步骤(2)制得的氧化锌-金纳米棒阵列置于预先除氧的无水甲醇溶液中,加入氯化镉和升华硫,混合均匀后,光沉积1h,用去离子水冲洗,氮气吹干,得到氧化锌-金-硫化镉三元纳米棒阵列复合型光催化剂。
步骤(1)中所述的Zn(NO3)2和NaNO3的混合溶液的pH=9。
步骤(2)中所述的甲醇水混合溶液,其中甲醇与水的体积比为2:3。
步骤(3)中所述的氯化镉和升华硫的摩尔比为1:1.4。
所述的氧化锌-金-硫化镉三元复合型光催化剂用于水相中在模拟太阳光照射下选择性还原芳香性硝基化合物至相应的胺基化合物。
所述的芳香性硝基化合物为下列结构:
中的任意一种。
光催化选择性还原芳香性硝基化合物至相应的胺基化合物具体步骤如下:
(1)取4mL浓度为10ppm的芳香性硝基化合物于反应器中,加入10mg甲酸铵,然后将生长有ZnO-Au-CdS光催化剂的导电玻璃片浸于反应溶液中,并通入氮气(60mL/min),在黑暗状态下吸附1h,使反应底物在光催化剂表面达到吸附-脱附平衡;
(2)在氮气保护下,对上述体系进行模拟太阳光光照,每隔一定时间后取出负载有催化剂的FTO玻璃片,对反应溶液进行紫外-可见吸收光谱分析和液相色谱分析。
本发明的有益效果在于:
(1)本发明首次结合电化学沉积和光沉积法制备得到了具有一维纳米棒阵列结构的氧化锌-金-硫化镉(ZnO-Au-CdS)三元复合型光催化剂;
(2)所制备的ZnO-Au-CdS三元纳米棒阵列型复合光催化剂表现出显著优于单独ZnO纳米棒阵列、ZnO-Au和ZnO-CdS复合材料的光催化活性,三元组分之间的协同作用更有利于对光的吸收和光生电子-空穴对的快速有效分离,从而使复合光催化材料具有更高的光催化性能,芳香性硝基化合物的转化率高达50%~97%,对目标产物芳香性胺基化合物的选择性高达98%以上;
(3)ZnO-Au-CdS复合型光催化剂的生产工艺简单且易于分离回收。
附图说明
图1是制备具有一维纳米棒阵列结构的ZnO-Au-CdS三元复合型光催化剂的流程示意图;
图2是(1)FTO玻璃、(2)ZnO、(3)ZnO-CdS、(4)ZnO-Au和(5)ZnO-Au-CdS纳米棒阵列复合光催化剂的光学图片;
图3是生长在FTO导电玻璃上的ZnO纳米棒阵列的SEM图;
图4是ZnO-Au-CdS三元复合型光催化剂在模拟太阳光照射下选择性还原一系列芳香性硝基化合物的活性图:(A)对硝基苯胺;(B)邻硝基苯胺;(C)间硝基苯胺;(D)对硝基苯酚;(E)邻硝基苯酚;(F)间硝基苯酚。
具体实施方式
本发明用下列实施例来进一步说明本发明,但本发明的保护范围并不限于下列实施例。
实施例1
将超声清洗干净的FTO导电玻璃作为工作电极,与Pt对电极和Ag/AgCl参比电极一起置于50mL浓度分别为5mM和50mM的Zn(NO3)2和NaNO3(pH=9)混合溶液中,溶液温度保持在85oC,加–1.3V的电压10s,然后将电压调为–1.0V保持1000s,用去离子水冲洗工作电极,氮气吹干,空气中350oC煅烧2h,得到ZnO纳米棒阵列。将所得的ZnO纳米棒阵列置于预先除氧的50mL甲醇水的混合溶液(体积比2:3)中,加入20μL浓度为40mM的氯金酸(HAuCl4)溶液,混合均匀后,光沉积0.5h,用去离子水冲洗,氮气吹干,得到ZnO-Au纳米棒阵列。将ZnO-Au纳米棒阵列置于预先除氧的无水甲醇溶液中,加入氯化镉和升华硫(摩尔比为1:1.4),混合均匀后,光沉积1h,用去离子水冲洗,氮气吹干,得到ZnO-Au-CdS三元纳米棒阵列复合型光催化剂。将生长有ZnO-Au-CdS纳米棒阵列光催化剂的导电玻璃片浸于含有4mL10ppm的对硝基苯胺溶液和10mg甲酸铵的混合溶液中,以60mL/min的流量向反应液中持续通入氮气,待吸脱附平衡后,置于模拟太阳光下光照14min,对硝基苯胺的转化率为92%,对目标产物对苯二胺的选择性达99%以上。
实施例2
将超声清洗干净的FTO导电玻璃作为工作电极,与Pt对电极和Ag/AgCl参比电极一起置于50mL浓度分别为5mM和50mM的Zn(NO3)2和NaNO3(pH=9)混合溶液中,溶液温度保持在85oC,加–1.3V的电压10s,然后将电压调为–1.0V保持1500s,用去离子水冲洗工作电极,氮气吹干,空气中350oC煅烧2h,得到ZnO纳米棒阵列。将所得的ZnO纳米棒阵列置于预先除氧的50mL甲醇水的混合溶液(体积比2:3)中,加入20μL浓度为40mM的氯金酸(HAuCl4)溶液,混合均匀后,光沉积2h,用去离子水冲洗,氮气吹干,得到ZnO-Au纳米棒阵列。将ZnO-Au纳米棒阵列置于预先除氧的无水甲醇溶液中,加入氯化镉和升华硫(摩尔比为1:1.4),混合均匀后,光沉积1h,用去离子水冲洗,氮气吹干,得到ZnO-Au-CdS三元纳米棒阵列复合型光催化剂。将生长有ZnO-Au-CdS纳米棒阵列光催化剂的导电玻璃片浸于含有4mL10ppm的邻硝基苯胺溶液和10mg甲酸铵的混合溶液中,以60mL/min的流量向反应液中持续通入氮气,待吸脱附平衡后,置于模拟太阳光下光照14min,邻硝基苯胺的转化率为97%,对目标产物邻苯二胺的选择性达98%以上。
实施例3
将超声清洗干净的FTO导电玻璃作为工作电极,与Pt对电极和Ag/AgCl参比电极一起置于50mL浓度分别为5mM和50mM的Zn(NO3)2和NaNO3(pH=9)混合溶液中,溶液温度保持在85oC,加–1.3V的电压10s,然后将电压调为–1.0V保持2000s,用去离子水冲洗工作电极,氮气吹干,空气中350oC煅烧2h,得到ZnO纳米棒阵列。将所得的ZnO纳米棒阵列置于预先除氧的50mL甲醇水的混合溶液(体积比2:3)中,加入20μL浓度为40mM的氯金酸(HAuCl4)溶液,混合均匀后,光沉积1h,用去离子水冲洗,氮气吹干,得到ZnO-Au纳米棒阵列。将ZnO-Au纳米棒阵列置于预先除氧的无水甲醇溶液中,加入氯化镉和升华硫(摩尔比为1:1.4),混合均匀后,光沉积1h,用去离子水冲洗,氮气吹干,得到ZnO-Au-CdS三元纳米棒阵列复合型光催化剂。将生长有ZnO-Au-CdS纳米棒阵列光催化剂的导电玻璃片浸于含有4mL10ppm的对硝基苯酚溶液和10mg甲酸铵的混合溶液中,以60mL/min的流量向反应液中持续通入氮气,待吸脱附平衡后,置于模拟太阳光下光照14min,对硝基苯酚的转化率为64%,对目标产物对氨基苯酚的选择性达99%以上。
从图4可以看出,与单独ZnO纳米棒阵列、ZnO-Au和ZnO-CdS复合材料相比,所制备的ZnO-Au-CdS三元纳米棒阵列型复合光催化剂表现出更加显著的光催化活性,对硝基苯胺、邻硝基苯胺、间硝基苯胺、对硝基苯酚、邻硝基苯酚、间硝基苯酚的转化率更高。
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 (7)
1.一种氧化锌-金-硫化镉三元复合型光催化剂,其特征在于:所述的氧化锌-金-硫化镉三元复合光催化剂为生长在掺杂氟的二氧化锡透明导电玻璃上的一维纳米棒阵列;所述的氧化锌-金-硫化镉三元复合型光催化剂中氧化锌的质量分数为(58%~64%),金的质量分数为(2%~6%),硫化镉的质量分数为(30%~40%)。
2.一种制备如权利要求1所述的氧化锌-金-硫化镉三元复合型光催化剂的方法,其特征在于:包括以下步骤:
(1)通过电化学沉积法制备氧化锌纳米棒阵列,采用Pt电极为对电极,Ag/AgCl电极为参比电极,掺杂氟的二氧化锡导电玻璃为工作电极,将三电极体系置于含有Zn(NO3)2和NaNO3的混合溶液中,溶液温度保持在85oC,加–1.3V的电压10s,然后将电压调为–1.0V保持1000~2000s,用去离子水冲洗工作电极后,氮气吹干,最后在空气中350oC煅烧2h,得到氧化锌纳米棒阵列;
(2)将步骤(1)制得的氧化锌纳米棒阵列置于预先除氧的甲醇水的混合溶液中,然后加入氯金酸溶液,混合均匀后,光沉积0.5~2h,用去离子水冲洗,氮气吹干,得到负载金的氧化锌纳米棒阵列;
(3)将步骤(2)制得的负载金的氧化锌纳米棒阵列置于预先除氧的无水甲醇溶液中,加入氯化镉和升华硫,混合均匀后,光沉积1h,用去离子水冲洗,氮气吹干,得到氧化锌-金-硫化镉三元纳米棒阵列复合型光催化剂。
3.根据权利要求2所述的方法,其特征在于:步骤(1)中所述的Zn(NO3)2和NaNO3的混合溶液的pH=9。
4.根据权利要求2所述的方法,其特征在于:步骤(2)中所述的甲醇水混合溶液,其中甲醇与水的体积比为2:3。
5.根据权利要求2所述的方法,其特征在于:步骤(3)中所述的氯化镉和升华硫的摩尔比为1:1.4。
6.一种如权利要求1所述的氧化锌-金-硫化镉三元复合型光催化剂的应用,其特征在于:所述的氧化锌-金-硫化镉三元复合型光催化剂用于水相中在模拟太阳光照射下选择性还原芳香性硝基化合物至相应的胺基化合物。
7.根据权利要求6所述的应用,其特征在于:所述的芳香性硝基化合物为下列结构:
中的任意一种。
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