CAREER: Tuning Photoredox Properties of Carbazolic Porous Organic Frameworks for Visible-Light-Mediated Catalysis

职业：调整咔唑多孔有机框架的光氧化还原性质以实现可见光介导的催化

• 批准号: 1554918
• 负责人: Jian Zhang
• 金额: $ 52.72万
• 依托单位: University of Nebraska-Lincoln
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-03-01 至 2020-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1554918&HistoricalAwards=false
• 关键词: CAREER; Tuning; Photoredox; Properties; Carbazolic

Non-technical AbstractWith 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.Technical AbstractThe 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.

在材料研究部固态与材料化学项目的支持下，研究小组提出开发一类新的有机多孔材料。咔唑多孔有机骨架（Cz-POFs）。扩展π共轭、三维聚咔唑网络以及可定制的电子和光学性质的独特组合使Cz-POFs在太阳能收集、转换和利用方面具有重要的潜在应用。这些基础研究工作与一系列教育活动相结合，包括对研究生和本科生进行材料研究方面的培训和指导，创建易于使用、适应性强、价格低廉的多孔材料模型工具包，以支持多种推广活动，并向不同年龄和知识水平的受众传达对材料化学的基本理解。以及在内布拉斯加大学林肯分校建立化学大使项目，以提高公众对材料化学在日常生活中所起作用的认识和赞赏。技术摘要：本研究解决了将Cz-POFs作为新一代太阳能收集、转换和利用的光活性材料的关键知识空白。研究小组已经证明，与线性材料相比，原型Cz-POFs具有较大的表面积，增强的介孔率和高稳定性，以及强大的还原能力和可回收性，使其非常适合许多光电应用。本研究的具体目标集中在开发合成方法(1)通过理论指导的化学修饰进一步提高Cz-POFs的氧化能力；(2)通过调节分子内D-A相互作用来开发具有增强光氧化还原性能的供体-受体Cz-POFs；(3)增强Cz-POFs的光氧化还原催化活性。这项研究为更好地理解控制Cz-POFs和其他pi-共轭聚合物网络的电子和光学性质、光诱导能量和电子转移以及光氧化还原催化活性的合成因素提供了基础。这项研究还有助于将POFs用于从二氧化碳中光化学生产清洁有机燃料以及太阳能水分解。此外，多孔有机框架资源（Porous Organic Framework Resource）在线综合数据库的建立，促进了多孔材料的跨学科研究。