Abstract
Metal–organic frameworks (MOFs) are well suited as nanoporous materials for applications such as gas storage, catalysis and in medical devices. Literature predominantly covers information on the batch synthesis of MOF-5, however, for an industrially viable product to be formed, bridging the gap to scalable continuous processing is essential. Here, we show that crystals of MOF-5 can be formed in a scalable solvothermal continuous process with a maximum space time yield of nearly 1000kgm−3day−1. Analysis of the solid output as a function of time, in conjunction with variation of concentration of the feed supply, shows high purity MOF-5 is produced using a continuous system, with potentially high throughput on scale up. We also show that the output can be increased by increasing the concentration of reactants in the system, albeit resulting in a reduced surface area. The two most common solvents currently used for MOF-5 production are also compared to identify a more economically viable process.
Highlights
Metal–organic framework (MOF) materials [1] are of considerable interest due to the unique properties granted by the nature of their supramolecular construction [2,3]
Reaction time and temperature are known to have considerable effects upon the final product within MOF-5 synthesis, with lower temperature and slower reactions resulting in higher surface areas than the considerably faster reactions performed at higher temperatures [28]
This simplified formation pathway, with a reduced number of intermediate metastable crystalline phases present, results in the product forming in a relatively short period (t = 2 h) compared to many MOF-5 syntheses reported to date
Summary
Metal–organic framework (MOF) materials [1] are of considerable interest due to the unique properties granted by the nature of their supramolecular construction [2,3]. Microfluidic reactors have been used, and with promising results for many materials, including HKUST-1, MOF-5 and MIL53, three prototypical MOFs. Microfluidic reactions rely upon formation of nanoliter scale droplets which results in efficient heat and mass transfer, while providing a very high surface area to volume ratio [18]. Kim et al [18] reported continuous production of HKUST-1, showing the capability of producing high yields of high quality crystals in reaction times as short as 5 min with considerably less harsh operating conditions than Gimeno-Fabra et al, though still operating at 100 bar. Increasing the temperature and pressure for MOF synthesis has been shown to provide thermodynamic conditions that result in the formation of the framework in considerably shorter times than previously reported in the literature [26], operating at elevated temperatures and pressures is likely to increase the overall cost of the process significantly. Understanding of the effects of synthesis parameters on MOF-5 product quality gained here will be of value in development of continuous large-scale manufacture of MOFs
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