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

Kim, I. S.; Farha, O. K.; Hupp, J. T.; Gagliardi, L.; Chapman, K. W.; Cramer, C. J.; Martinson, A. B. F.
ECS Trans. 2016, 75, 93 (doi:10.1149/07506.0093ecst).

The connectivity of NU-1000, a metal-organic framework, gives rise to Zr6 nodes with hydroxyl-containingfunctional 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.