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

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 m(2)/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 insitu 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.