Metal−organic frameworks (MOFs) have been heavily researched due to their porous and crystalline nature. Because of this, MOFs are enticing materials for fields as diverse as gas separation and purification, water harvesting, and heterogeneous catalysis. Within most potential applications, it is critical for the material to remain unchanged when operating over prolonged periods and/or at elevated temperatures. Therefore, thermal stability is crucial in order to utilize MOFs industrially. In this article, we present a method to thermally stabilize MOF-808 by employing post-synthetic functionalization to incorporate benzoate moieties into its framework. We further describe how this incorporation changes the MOFs' physicochemical properties (i.e., surface area, gas-adsorptive behavior, and crystallographic structure). The materials described herein are well characterized and provide novel options for the design of stable catalysts and adsorbents for future technologies.
Metal–organic frameworks (MOFs) are nanoporous materials composed of organic linkers and inorganic nodes. The large variety of linkers and nodes and the multiple ways to combine them make MOFs highly tunable materials, which are thoroughly studied for their use in, e.g., catalysis, gas capture, and separation. The chemistry of MOFs is further enriched by defects, e.g., missing linker defects, which provide active sites for catalysis or anchoring sites for introducing new functionalities. A commonly reported method to quantify linker defects assumes the presence of one type of linker and the complete removal of capping agents, solvents, and other impurities upon activation at high temperature, e.g., 400 °C (M-400). However, attempts to use this method for MOFs containing different types of linkers, also called multivariate MOFs (MTV-MOFs), or capping agents that are not completely removed at 400 °C, give inaccurate results and hamper comparing results from different publications. In this work, we have developed a new procedure to compute missing linker defects in Zr-based MOFs using standard analytical techniques to quantify the capping agents that remain in the MOF upon activation at 200 °C (M-200). This method, which has been tested in UiO-66/67 based MOFs, should be applicable to any MOF that (1) has known decomposition products, (2) has no missing cluster defects, (3) has empty pores or contain species that can be quantified after activation, and (4) has a known node composition at 200 °C.
A spectroscopic and computational insight in the defective nature of the acetylene dicarboxylic acid based Ce-MOF, having UiO-66 topology and denoted as Ce-UiO-66-ADC MOF.
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