Democratizing the Assessment of Thermal Robustness of Metal–Organic Frameworks

Abstract

With the pressing need of having reliable materials for carbon dioxide capture, metal–organic frameworks (MOFs) have shown promising performance due to their flexible sign and tunable functionality by applying reticular chemistry principles. One of the main characteristics of practical MOFs is to design thermally robust candidates for sustainable functionality. Here, we introduce a comprehensive methodology for examining the thermal stability of MOFs by combining theoretical calculations and affordable experimental methods to fully describe their performance under thermal variations. We chose the prototypical MOF, HKUST-1, to assess the methodology by performing density functional theory and classical molecular dynamics simulations and validating with experiments such as in situ powder X-ray diffraction, differential scanning calorimetry, and thermogravimetric analysis. HKUST-1 shows thermal robustness until a temperature of 240 °C at different atmospheric gases with a reversible breathing trend with temperature. This methodology is affordable as it uses minimal experimental testing and can be applied to any MOF materials to explore its suitability for practical applications.

MOFs as Versatile Catalysts: Synthesis Strategies and Applications in Value-Added Compound Production

“…In the partial thermal decomposition of MOF, MOFs are decomposed along with the capturing of small metal or metal oxide particles inside hierarchical pores to create MOF derivatives by keeping the backbone and crystallinity of MOFs. 98 Meanwhile, in pyrolysis, MOFs are decomposed at a higher temperature to get the respective metal oxides, sulfides, carbides, phosphides, and nitrides embedded in a porous carbon matrix such as MOF. Recently, a review reported the experimental works of MOFs containing porous metal oxides.…”

Copper(ii)-MOFs for bio-applications

“…[29][30][31] For example, HKUST-1 (also known as MOF-199, Cu-BTC and Basolite C300), is one of the copper-based MOFs developed for the detection of biological signals, being the most reported and used for the detection of glucose, proteins and other biological molecules, 32 but it has also proven useful for the detection of environmental contaminants, separation and purification of chemical compounds, as well as the detection and removal of harmful gases, as well as drug delivery. [33][34][35][36][37] However, copper-based MOFs also have some disadvantages, the most important of which is stability under extreme conditions, that is, copper-based MOFs can be sensitive to certain extreme environments, such as high temperature, strong acids, and highly corrosive environments 38 This limits their use in some industrial applications and therefore their low contribution to these fields. Therefore, the main disadvantage is thermal stability, although this may vary depending on the specific structure of the MOFs due to the coordinated bonding of copper, in addition to the stability of the organic ligands that comprise them.…”

“…Specific studies have been reported to characterize the thermal stability of various copper-based MOFs, which allows identifying the maximum temperature they can withstand before decomposing. 38 Fig. 1 Recent advances in metal-organic framework-based electrochemical biosensing applications.…”

“…However, copper-based MOFs also have some disadvantages, the most important of which is stability under extreme conditions, that is, copper-based MOFs can be sensitive to certain extreme environments, such as high temperature, strong acids, and highly corrosive environments 38 This limits their use in some industrial applications and therefore their low contribution to these fields. Therefore, the main disadvantage is thermal stability, although this may vary depending on the specific structure of the MOFs due to the coordinated bonding of copper, in addition to the stability of the organic ligands that comprise them.…”

“…Specific studies have been reported to characterize the thermal stability of various copper-based MOFs, which allows identifying the maximum temperature they can withstand before decomposing. 38…”