Non-technical Abstract With support from the Solid State and Materials Chemistry program in the Division of Materials Research, the research team proposes to develop a new class of organic porous material?carbazolic porous organic frameworks (Cz-POFs). The unique combination of extended pi-conjugation, three-dimensional polycarbazole networks, and tailorable electronic and optical properties of Cz-POFs enables their significant potential applications in solar energy harvesting, conversion, and utilization. These basic research efforts are integrated with a series of educational activities including the training and mentoring of graduate and undergraduate students in materials research, the creation of accessible, adaptable, and inexpensive model kits of porous materials to support multiple outreach activities and to convey a basic understanding of materials chemistry to audiences of different ages and knowledge levels, and the establishment of a Chemistry Ambassador program at the University of Nebraska-Lincoln to improve awareness of and public appreciation for the role of materials chemistry in everyday lives.
The proposed research addresses critical knowledge gaps for establishing Cz-POFs as a new generation of photoactive materials for solar-energy harvesting, conversion, and utilization. The research team have demonstrated that, compared to their linear counterparts, prototypic Cz-POFs exhibit large surface area, enhanced mesoporosity, and high stability, which, along with strong reductive ability and recyclability, make them well suited for many optoelectronic applications. The specific aims of this research are centered on developing synthetic approaches (1) to further increase the oxidative ability of Cz-POFs through theory-guided chemical modification, (2) to develop donor-acceptor Cz-POFs with enhanced photoredox properties by adjusting intramolecular D-A interactions, and (3) to enhance photoredox catalytic activities of Cz-POFs. This research provides a better understanding of synthetic factors that control the electronic and optical properties, photoinduced energy and electron transfer, and photoredox catalytic activities associated with Cz-POFs and other pi-conjugated polymer networks in general. This research also contributes to the use of POFs for photochemical production of clean organic fuels from carbon dioxide as well as solar water splitting. Further, the building of a comprehensive online database Porous Organic Framework Resource facilitates interdisciplinary research on porous materials.
