Ultrafast room-temperature synthesis of hierarchically porous metal–organic frameworks by a versatile cooperative template strategy

Abstract

Hierarchically porous MOFs (HP-MOFs) are commonly prepared by means of hydrothermal synthesis. Nonetheless, its relatively long crystallization time and harsh synthesis conditions have strongly obstructed the enhancement of HP-MOFs space–time yields (STYs) and the decrease in energy consumption. Herein, a simple and versatile method for preparing various HP-MOFs at room temperature was demonstrated, which had introduced surfactant as the template, whereas zinc oxide (ZnO) has been used as an accelerant. The resulting HP-MOFs showed multimodal hierarchical porous structures and excellent thermal stability. More importantly, the synthesis time was reduced dramatically to 11 min, with a maximal HP-MOFs STY of as high as 2575 kg m−3 d−1. Furthermore, the rapid formation process of HP-MOFs was examined through quantum chemistry calculation, and a feasible synthesis mechanism was also proposed. Notably, our synthesis strategy had shown a versatility, since other surfactants could also be used as the templates for the rapid room-temperature fabrication of diverse stable HP-MOFs. Importantly, the porosity of the HP-MOFs could be readily tuned through controlling the type of template. Moreover, gas adsorption measurement of HP-MOFs revealed high CH4 uptake capacity at 298 K due to the increase in surface area and pore volume. Our findings suggest that such method is applicable for the rapid synthesis of a wide variety of HP-MOFs on an industrial scale.