低温原位掺杂TiO2纳米管阵列及其可见光光催化性能研究

High energy ion implantation is one of the most effective doping methods for the TiO2 nanotubes without damage their 1D nanostructures. However, this approach requires high standard technologies and is hard to maintain with low cost. Finding out an alternative approach, which should be cheap enough, easy to operate, and industrial scale, is still a worldwide challenge. To this end, this proposal is presented based on our newly discovered “low-temperature crystallization” phenomenon, aiming to build up a novel, low cost, high efficiency, and non-ion-implantation doping method. This research program will further explore new phenomenon when the TiO2 nanotube arrays are exposed to transition-metal ions aqueous solutions (like Fe, Cu, Cr, Mn etc), and study the distribution, occupation, crystalline parameters and impurity level of the doping metal ions inside the TiO2 nanotube arrays. Meanwhile, the visible-light photocatalytic activities and mechanisms of the doping TiO2 nanotube arrays will be also systematically investigated. The success of this project would provide a good solution doping transition metal ions into TiO2 nanotubes arrays with low cost, which will benefits their applications in photocatalytic degradation of organic pollutants, and water splitting, and therefore it is of great importance for science and engineering communities.

高能离子注入是对TiO2纳米管进行金属离子掺杂而不破坏其一维纳米结构最行之有效的方法之一，却存在技术门槛高，运行维护成本大等缺点。如何找到一种低成本、易操作、可大规模生产的备选方法是当前面临的难题。为此，本项目拟以我们最近率先报道的“低温结晶”现象为技术基础，探索TiO2纳米管阵列在金属离子复杂水溶液环境中（包括Fe, Cu, Cr, Mn等过渡元素）低温原位掺杂新现象，研究掺杂金属离子在纳米管中的分布、离子占位、晶胞参数、杂质能级形成等新规律；同时，对掺杂TiO2纳米管阵列的可见光光催化性能和机理进行系统研究，并最终提炼出一种高效易行的TiO2纳米管低温原位掺杂方法。本项目的成功实施将有效解决TiO2纳米管阵列低成本金属离子掺杂问题，进而推进其在光催化降解有机物、分解水制氢等领域的研究和应用，具有重要的理论意义和实用价值。

该项目研究了一种高效易行的TiO2纳米管低温原位掺杂方法以及其相应的物理化学影响规律。在该项目的支持下，利用高度有序TiO2纳米管阵列自组织生长技术：阳极氧化法，率先发现了TiO2的“低温结晶”现象,以此为基础创新的提出“低温原位掺杂”技术，通过含有金属离子的水溶液对TiO2完成金属掺杂。系统研究了金属离子掺杂对TiO2纳米管阵列的晶型转变，以及杂质能级的引入对TiO2纳米管阵列的光催化活性影响作用。揭示出不同金属离子种类对其可见光光催化活性的影响规律和内在机制，同时探究了金属氧化物修饰以及金纳米颗粒修饰对TiO2纳米管的影响。研究了在光激发条件下，影响掺杂TiO2纳米管阵列光催化效率和光谱响应范围的因素，系统研究了过渡金属掺杂TiO2纳米管阵列光催化降解机理；基于本项目研究工作的开展，发表了SCI论文22篇，申请国家发明专利5项。