Hetero-metallic metal-organic frameworks for room-temperature NO2 sensing. 2022

Muhammad Waqas Khan, and M Munir Sadiq, and Karuppasamy Gopalsamy, and Kai Xu, and Azmira Jannat, and Bao Yue Zhang, and Md Mohiuddin, and Muhammad Haris, and Rui Ou, and Sanjida Afrin, and Turki Alkathiri, and Suraj Loomba, and Xavier Mulet, and Nasir Mahmood, and Ravichandar Babarao, and Jian Zhen Ou
School of Engineering, RMIT University, Melbourne, VIC, Australia.

Metal-organic frameworks (MOFs) with exceptional features such as high structural diversity and surface area as well as controlled pore size has been considered a promising candidate for developing room temperature highly-sensitive gas sensors. In comparison, the hetero-metallic MOFs with redox-active open-metal sites and mixed metal nodes may create peculiar surface properties and synergetic effects for enhanced gas sensing performances. In this work, the Fe atoms in the Fe3 (Porous coordination network) PCN-250 MOFs are partially replaced by transition metal Co, Mn, and Zn through a facile hydrothermal approach, leading to the formation of hetero-metallic MOFs (Fe2IIIMII, M = Co, Mn, and Zn). While the PCN-250 framework is maintained, the morphological and electronic band structural properties are manipulated upon the partial metal replacement of Fe. More importantly, the room temperature NO2 sensing performances are significantly varied, in which Fe2Mn PCN-250 demonstrates the largest response magnitude for ppb-level NO2 gas compared to those of pure Fe3 PCN-250 and other hetero-metallic MOF structures mainly attributed to the highest binding energy of NO2 gas. This work demonstrates the strong potential of hetero-metallic MOFs with carefully engineered substituted metal clusters for power-saving and high-performance gas sensing applications.

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