An X-ray Photoelectron Spectroscopy Study of Postsynthetic Exchange in UiO-66.

Postsynthetic exchange (PSE) is a method that is widely used to change the composition of metal-organic frameworks (MOFs) by replacing connecting linkers or metal nodes after the framework has been synthesized. However, few techniques can probe the nature and distribution of exchanged species following PSE. Herein, we show that X-ray photoelectron spectroscopy can be used to compare the relative concentrations of exchanged ligands at the surface and interior regions of MOF particles. Specifically, PSE of iodobenzene dicarboxylate ligands results in a gradient distribution from surface to bulk in UiO-66 nanoparticles that depends on PSE time. X-ray photoelectron spectroscopy also reveals differences between the surface chemistry of the PSE product and that of the direct synthesis product.