Thermal engineering of porphyrin-perylene COFs: a study on the structural behaviour and photocatalytic performance Kathryn McCarthy , Roberto Gonzalez Gomez, Pau Farràs Costa University of Galway, Ireland Covalent organic frameworks (COFs) are a burgeoning area of research due to their unique properties; they are crystalline, porous, easily functionalised, robust, chemically and thermally stable, and diverse in structure 1 . Due to these attractive characteristics, COFs have been designed for many applications, such as gas storage, sensing, drug delivery and water purification 2 . Furthermore, via the careful selection of photo-active building blocks, namely, porphyrin and perylene, COFs have shown high visible-light absorption capacity and fast charge-carrier mobility, expanding their applicability towards heterogeneous photocatalysis 3 . Despite significant achievements in COF chemistry in recent years, difficulties still arise when designing reproducible synthetic methods to make high quality COFs, which is a major hindrance to the advancement of this promising field 4 . Previous works have shown that even slight modifications to reaction parameters during COF synthesis can have profound impacts on their properties. Hence, understanding the effects caused by modifying these parameters will provide better knowledge on how to adapt these materials to suit specific applications, accelerating their advancement towards industrial-scale processes 5 . In this work, we show that by modifying reaction temperature, the properties of our designed porphyrin-perylene- based COF can be controlled to enhance their short-range order, porosity and photostability. The materials were synthesised at temperatures ranging from 140 °C to 200 °C, and extensively characterised to study differences in morphology, optical properties, crystallinity, thermal stability and surface area as a function of synthesis temperature. Furthermore, absorption-desorption studies and photodegradation of methylene blue dye were also performed. References 1. Xiao, J.; Chen, J.; Liu, J.; Ihara, H.; Qiu, H. Synthesis Strategies of Covalent Organic Frameworks: An Overview from Nonconventional Heating Methods and Reaction Media. Green Energy & Environment 2022 . https://doi.org/10.1016/J. GEE.2022.05.003. 2. Liu, R.; Tan, K. T.; Gong, Y.; Chen, Y.; Li, Z.; Xie, S.; He, T.; Lu, Z.; Yang, H.; Jiang, D. Covalent Organic Frameworks: An Ideal Platform for Designing Ordered Materials and Advanced Applications. Chemical Society Reviews . Royal Society of Chemistry January 7, 2021, pp 120–242. https://doi.org/10.1039/d0cs00620c. 3. Yang, Q.; Luo, M.; Liu, K.; Cao, H.; Yan, H. Covalent Organic Frameworks for Photocatalytic Applications. Applied Catalysis B: Environmental . Elsevier B.V. November 5, 2020. https://doi.org/10.1016/j.apcatb.2020.119174. 4. Li, Y.; Chen, W.; Xing, G.; Jiang, D.; Chen, L. New Synthetic Strategies toward Covalent Organic Frameworks. Chemical Society Reviews . Royal Society of Chemistry May 21, 2020, pp 2852–2868. https://doi.org/10.1039/d0cs00199f. 5. Karak, S.; Dey, K.; Banerjee, R.; Karak, S.; Dey, K.; Banerjee, R. 2202751 (1 of 18) Maneuvering Applications of Covalent Organic Frameworks via Framework-Morphology Modulation. 2022 . https://doi.org/10.1002/adma.202202751.
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