CN105688939B - 基于能带调制的双重量子点敏化氧化物复合光催化材料 - Google Patents
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Abstract
本发明涉及一种基于能带调制的双重量子点敏化石墨烯/氧化物复合结构光催化材料的制备方法，属于半导体材料光催化领域。本发明在能带调制原理下，利用石墨烯与氧化物形成复合结构，通过能级位置的差别实现复合结构中光生载流子的有效分离，采用窄带隙半导体量子点对氧化锌进行敏化，采用金属量子点对石墨烯进行敏化，在进一步增加光生载流子的分离和传递的同时，还可以拓宽光谱响应范围。本发明的优势是在宽的光谱响应范围下，利用双重量子点敏化既可以实现载流子的分离，又能够促进光生电子和空穴的快速传递，减少复合几率。
Description
技术领域
本发明涉及一种基于能带调制的双重量子点敏化石墨烯/氧化物复合结构光催化材料的制备方法，属于半导体材料光催化领域。
背景技术
随着环境污染的不断加剧，对污染物的处理一直是各国科研人员的研究热点。半导体光催化材料是降解有机污染物的有效途径之一。目前，实现光生载流子有效分离和传递，减少复合几率；拓宽光谱响应范围，增加太阳光利用效率；增加比表面积，提高与被降解物的有效接触程度是高效率光催化材料研究中的主要内容。常用的方式是对半导体材料进行掺杂、表面修饰或构建半导体复合结构。通过将不同的半导体纳米材料，或者半导体纳米材料与金属量子点、半导体量子点组合在一起，形成新的双组分或者多组分异质结构复合材料，从而提高光催化性能。
目前常用的半导体光催化材料有二氧化钛(TiO2)，氧化锌(ZnO)等。氧化锌为直接带隙材料，具有高吸收系数和高量子效率等优点。石墨烯为零带隙材料，载流子迁移率高。因此，石墨烯与氧化锌形成的复合结构可将氧化锌中光生电子快速分离到石墨烯一侧，提高了光生载流子的分离和传递效率。同时利用窄带隙半导体量子点(CdSe、CdS等)和金属量子点(Pt、Au、Ag等)对石墨烯/氧化锌复合结构进行敏化，能够提高光谱响应范围，且进一步提高光生载流子的转移效率。
本发明从能带调制实现载流子有效分离的角度出发，选择石墨烯与氧化物形成复合结构，采用窄带隙半导体量子点对氧化物进行敏化，采用金属量子点对石墨烯进行敏化，本发明的优势是在宽的光谱响应范围下，利用双重量子点敏化既可以实现载流子的分离，又能够促进光生电子和空穴的快速传递，减少复合几率。
发明内容
本发明从能带调制实现载流子有效分离的角度出发，提出一种基于能带调制的双重量子点敏化石墨烯/氧化物复合结构光催化材料的制备方法。首先利用溅射或沉积等方法在衬底材料上生长金属量子点材料(Pt、Au、Ag等)；其次利用化学气相沉积(CVD)制备石墨烯并迁移至已沉积金属量子点的衬底材料表面；在此基础上采用原子层沉积(ALD)进一步生长氧化物薄膜；最后采用化学浴(CBD)方法在金属量子点敏化的石墨烯/氧化物复合结构上生长窄带隙半导体量子点(CdSe、CdS等)材料，得到双重量子点敏化的石墨烯/氧化物复合光催化材料。
本发明的技术效果在于利用窄带隙半导体量子点和金属量子点对石墨烯/氧化物进行双重量子点敏化处理，能够在宽的光谱响应范围下，即紫外-可见光范围内，实现载流子的高效分离，促进光生电子和空穴的快速传递，减少复合几率，最终提高半导体材料的光催化性能。
具体实施方式
实施例一：
步骤一：利用等离子体溅射仪在玻璃衬底表面生长Pt量子点材料，电流为15mA，溅射时间为10秒，延长溅射时间将影响Pt量子点的尺寸及密度；
步骤二：利用CVD在常压下用Ni膜作为催化剂生长石墨烯，生长温度为930℃。利用无胶迁移将所生长的石墨烯迁移至沉积Pt量子点的玻璃衬底表面，其中迁移用腐蚀液为FeCl3；
步骤三：利用ALD生长ZnO薄膜，Zn源采用Zn(C2H5)2，无需加热，用水(H2O)做氧（O）源，氮气(N2)作为载气，沉积温度120℃，脉冲间隔时间为0.02秒，沉积周期为500周期；
步骤四：利用CBD方法生长CdS量子点，将Pt量子点/石墨烯/氧化锌交替浸泡在0.2mol/L的Na2S和0.2mol/L的Cd(NO3)2溶液中5分钟，期间用去离子水反复冲洗，重复3周期即可。最后在60℃下放置2小时干燥，得到Pt/石墨烯/氧化锌/CdS的双重量子点敏化复合光催化材料。
实施例二：
步骤一：利用等离子体溅射仪在玻璃衬底表面生长Ag量子点材料，电流为15mA，溅射时间为10秒，延长溅射时间将影响Ag量子点的尺寸及密度；
步骤二：利用CVD在常压下用Ni膜作为催化剂生长石墨烯，生长温度为930℃。利用无胶迁移将所生长的石墨烯迁移至沉积Ag量子点的玻璃衬底表面，其中迁移用腐蚀液为FeCl3；
步骤三：利用ALD生长ZnO薄膜，Zn源采用Zn(C2H5)2，无需加热，用水(H2O)做氧（O）源，氮气(N2)作为载气，沉积温度150℃，脉冲间隔时间为0.02秒，沉积周期为500周期；
步骤四：利用CBD方法生长CdSe量子点，将Ag量子点/石墨烯/氧化锌交替浸泡在0.2mol/L的H2Se和0.2mol/L的Cd(NO3)2溶液中5分钟，期间用去离子水反复冲洗，重复3周期即可。最后在60℃下放置2小时干燥；得到Ag/石墨烯/氧化锌/CdSe的双重量子点敏化复合光催化材料。
实施例三：
步骤一：利用等离子体溅射仪在玻璃衬底表面生长Au量子点材料，电流为15mA，溅射时间为10秒，延长溅射时间将影响Au量子点的尺寸及密度；
步骤二：利用CVD在常压下用Ni膜作为催化剂生长石墨烯，生长温度为930℃。利用无胶迁移将所生长的石墨烯迁移至沉积Au量子点的玻璃衬底表面，其中迁移用腐蚀液为FeCl3；
步骤三：利用ALD生长TiO2薄膜，Ti反应源采用C8H24N4Ti，无需加热，用水(H2O)做氧（O）源，氮气(N2)作为载气，沉积温度200℃，脉冲间隔时间为0.02秒，沉积周期为500周期；
步骤四：利用CBD方法生长CdS量子点，将Au量子点/石墨烯/二氧化钛交替浸泡在0.2mol/L的Na2S和0.2mol/L的Cd(NO3)2溶液中5分钟，期间用去离子水反复冲洗，重复3周期即可。最后在60℃下放置2小时干燥；得到Au/石墨烯/二氧化钛/CdS的双重量子点敏化复合光催化材料。
Claims (4)
1.一种基于能带调制的双重量子点敏化石墨烯/氧化物复合结构光催化材料的制备方法，其特征在于，首先利用溅射或沉积的方法在衬底材料上生长金属量子点材料Pt、Au或Ag；其次利用化学气相沉积制备石墨烯并迁移至已沉积金属量子点的衬底材料表面；在此基础上采用原子层沉积进一步生长氧化物薄膜；最后采用化学浴方法在金属量子点敏化的石墨烯/氧化物复合结构上生长窄带隙半导体量子点材料CdSe或CdS，得到双重量子点敏化的石墨烯/氧化物复合光催化材料；所述的氧化物薄膜为ZnO或TiO2。
2.根据权利要求1所述的光催化材料的制备方法，其特征在于，利用窄带隙半导体量子点和金属量子点对石墨烯/氧化物进行双重量子点敏化处理，能够在宽的光谱响应范围下，即紫外-可见光范围内，实现载流子的高效分离，促进光生电子和空穴的快速传递，减少复合几率，提高半导体材料的光催化性能。
3.根据权利要求1所述的光催化材料的制备方法，其特征在于，衬底材料为硬质透明衬底或多孔结构。
4.根据权利要求3所述的光催化材料的制备方法，其特征在于，所述的硬质透明衬底为玻璃或石英，多孔结构为金属网或纤维。
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