A Precise and Scalable Post-Modification of Mesoporous Metal-Organic Framework NU-1000 Via Atomic Layer Deposition

• Published in: ECS transactions 2016-01, Vol.75 (6), p.93-99
• Main Authors: Kim, In Soo, Farha, Omar K., Hupp, Joseph T., Gagliardi, Laura, Chapman, Karena W, Cramer, Chris, Martinson, Alex B. F.
• Format: Article
• Language: English
• ISSN: 1938-5862; 1938-6737
• DOI: 10.1149/07506.0093ecst

The connectivity of NU-1000, a metal-organic framework, gives rise to Zr6 nodes with hydroxyl-containing functional groups pointing into the large 1D mesoporous hexagonal channels of the framework. These free and exposed -OH groups are ideal grafting sites, and they can be easily tailored to serve a specific function. Through atomic layer deposition in MOFs (AIM), we demonstrate the ability to form several oxides with atomic precision at the exposed -OH sites of NU-1000. Importantly, this process occurs without changing the overall structure of the framework. Recent progress in scaling AIM process of the ultrahigh surface area (2300 m2/g) framework as well as progress in pinpointing the location and mechanism of surface chemical reactions of catalytically relevant metals is discussed. Computational, synchrotron, and in-situ analytical methods including DFT, differential electron diffraction, and in situ FTIR are brought to bear on several new metal systems, many of which show remarkably self-limiting behavior.