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

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 11min, with a maximal HP-MOFs STY of as high as 2575kgm(-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 298K 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.