Replication Data for: 2H-NMR as a practical tool for following MOF formation: a case study of UiO-66

Abstract: Deuterium-NMR spectroscopy is the optimal inter-lab methodology to understand in-situ kinetics of metal-organic framework (MOF) formation. This method is facile, affordable, and can be used to isolate and monitor one reagent at a time by using one deuterated component with the remaining components having no deuterium present. Developing a mechanistic basis for MOF formation is critical for rapid development of new materials. This work utilizes 2H-NMR, by means of the spectrometer’s lock channel, to demonstrate how UiO 66 forms as a function of different modulators (acetic acid, benzoic acid, and hydrochloric acid). Monitoring the concentration of deuterated linker and the chemical shift and peak width of deuterated water over time unravels key elements of MOF formation. Paradoxically, conditions that would cause ligand to be consumed more slowly results in MOFs to appear more quickly and with fewer defects. This is due to the dissociative mechanism associated with the ZrIV-containing node.