基于n-型有机半导体的多酸主-客体材料的构筑及其光致变色性、光催化性能研究

Visible photocatalytic organic reactions has the advantages of low energy consumption and the use of solar energy, which is an extremely challenging and attractive research topic. Improving the activity and efficiency of photocatalyst is a key scientific problem to realize low energy excitation. Naphthalene or perylene bisimide derivatives is an typical n-type organic semiconductor which has unique photophysical and chemical properties, and has important applications in the field of light-harvesting, photochromic and photovoltaic materials. However, there are some problems such as easy aggregation, low utilization rate of visible light, difficult separation and recovery of catalyst, and single type of photocatalytic organic reactions. To realize the high efficiency and high photocatalytic activity of catalyst, it can introduce the organic semiconductors into the polyoxometalate-based host-guest system. Thus, the combination of light-harvesting materials as building unit and multifunctional polyoxometalates as guests, by using coordination-driven self-assembly and anion–π interaction, may obtain the light-stimuli responsive materials and high-efficiency photocatalytic materials. Investigate the structure activity relationships of composite structure with photochromism and visible photocatalytic activity, and provide the experimental basis and theoretical guidance for the design and synthesis of the efficient light responsive and photocatalytic materials.

可见光催化有机反应具有能耗低、可直接利用太阳能等优点，是极具挑战和诱惑力的研究方向。提高光催化剂的活性和效率、实现低能激发是可见光催化的关键科学问题。萘/苝二酰亚胺衍生物是n-型有机半导体，具有独特的光物理化学特性，在光捕获、光致变色和光伏材料等方面具有重要的应用。然而，其作为催化剂存在易聚集、可见光利用率低、催化剂难分离回收、光催化有机反应类型单一等问题。将其引入多酸主-客体系统中，有望解决上述问题，实现高效高活性、可见光利用率高的光催化过程。为此，本项目拟将这类光捕获材料作为构筑单元与多功能的多酸复合，利用配位导向和功能性相关的阴离子-π相互作用，自组装形成可见光利用率高的光响应材料和光催化材料。探究该类复合材料结构与光致变色性、可见光催化性能之间的构效关系，为设计合成新型高效的光响应材料和光催化材料提供实验依据和理论指导。

可见光催化有机反应具有能耗低、可直接利用太阳能等优点，是极具挑战和诱惑力的研究方向。提高光催化剂的活性和效率、实现低能激发是可见光催化的关键科学问题。本项目中，我们拟采用n-型有机半导体萘/苝二酰亚胺衍生物作为配体，与多功能性多酸阴离子自组装，来构建高效、高活性的基于多酸的主-客体光催化材料。由于合成、分离以及结构的复杂性等不可控因素，未获得结构稳定且可见光催化性能较好的多酸主-客体材料。然而，光捕获材料萘/苝二酰亚胺衍生物作为构筑单元与金属离子自组装，利用配位导向和功能性相关的阴离子-π、孤对电子-π等弱相互作用，获得了一系列活性有机自由基掺杂的功能材料，如在可见光区具有强吸收的光响应材料、抗菌材料和可见光催化材料等。探究了该类自由基掺杂材料结构与光致变色性、抗菌活性、可见光催化活性以及室温磷光之间的构效关系，不仅为设计合成新型高效的光响应材料和光催化材料提供实验依据和理论指导，而且为设计合成活性有机自由基掺杂的多功能材料提供了新策略。