Tunable coordinative defects in UHM-3 surface-mounted MOFs for gas adsorption and separation: A combined experimental and theoretical study

Abstract The metal organic framework (MOF) UHM-3, constructed with Cu(II)-paddle wheel-type nodes and a new tetracarboxylic acid linker, 5,5′-(dimethylsilanediyl)diisophthalate, has a close-packed alignment of open Cu(II) sites which are of interest for applications in gas storage and separation. Here, we first report on the growth of oriented, homogeneous and virtually defect-free (below 1%) UHM-3 MOF thin films on a solid substrate using a room-temperature liquid phase epitaxy (LPE) method. Thermal postsynthetic treatment allowed to induce Cu(I) defect sites in a controlled fashion. The interaction of CO and CO 2 with the Cu(II) and Cu(I) sites was then studied using X-ray photoelectron spectroscopy (XPS) and IR-spectroscopy. The binding energy of these two species was determined using temperature-induced desorption. The interaction between the guest molecules and the Cu(I) and Cu(II) sites were also analyzed using density-functional theory (DFT). Surprisingly, both experiment and theory show that the binding energy of CO 2 to Cu(I) and Cu(II) sites are essentially identical, in pronounced contrast to CO, which binds much stronger to Cu(I).