Influence of Humidity and Heating Rate on the Continuous ZIF Coating during Hydrothermal Growth.

Abstract

Zeolitic imidazolate frameworks (ZIFs) have potential for various gas and ion separations due to their well-defined pore structure and relatively easy fabrication process compared to other metal-organic frameworks and zeolites. As a result, many reports have focused on preparing polycrystalline and continuous ZIF layers on porous supports with good separation performance in various target gases, such as hydrogen extraction and propane/propylene separation. To utilize the separation properties in industry, membrane is required to be prepared in large scale with high reproducibility. In this study, we investigated how humidity and chamber temperature influence the structure of a ZIF-8 layer prepared by the hydrothermal method. Many synthesis conditions can affect the morphology of polycrystalline ZIF membranes, and previous studies have mainly focused on reaction solutions, such as precursor molar ratio, concentration, temperature, and growth time. On the other hand, we found that the humidity of the chamber and the heating rate of the solution also lead to dramatic changes in the morphology of ZIF membranes. To analyze the trend between humidity and chamber temperature, we set up the chamber temperature (ranging from 50 °C to 70 °C) and relative humidity (ranging from 20% to 100%) using a thermo-hygrostat chamber. We found that as the chamber temperature increased, ZIF-8 preferentially grew into particles rather than forming a continuous polycrystalline layer. By measuring the temperature of the reacting solution based on chamber humidity, we discovered that the heating rate of the reacting solution varied with humidity, even at the same chamber temperature. At a higher humidity, the thermal energy transfer was accelerated as the water vapor delivered more energy to the reacting solution. Therefore, a continuous ZIF-8 layer could be formed more easily at low humidity ranges (ranging from 20% to 40%), while micron ZIF-8 particles were synthesized at a high heating rate. Similarly, under higher temperatures (above 50 °C), the thermal energy transfer was increased, leading to sporadic crystal growth. The observed results were obtained with a controlled molar ratio, in which zinc nitrate hexahydrate and 2-MIM were dissolved in DI water at a molar ratio of 1:45. While the results are limited to these specific growth conditions, our study suggests that controlling the heating rate of the reaction solution is critical for preparing a continuous and large-area ZIF-8 layer, particularly for the future scale-up of ZIF-8 membranes. Additionally, humidity is an important factor in forming the ZIF-8 layer, as the heating rate of the reaction solution can vary even at the same chamber temperature. Further research related to humidity will be necessary for the development of large-area ZIF-8 membranes.