Constructing Ultraporous Covalent Organic Frameworks in Seconds via an Organic Terracotta Process

Abstract

Research on covalent organic frameworks (COFs) has recently gathered significant momentum by the virtue of their predictive design, controllable porosity, and long-range ordering. However, the lack of solvent-free and easy-to-perform synthesis processes appears to be the bottleneck toward their greener fabrication, thereby limiting their possible potential applications. To alleviate such shortcomings, we demonstrate a simple route toward the rapid synthesis of highly crystalline and ultraporous COFs in seconds using a novel salt-mediated crystallization approach. A high degree of synthetic control in interlayer stacking and layer planarity renders an ordered network with a surface area as high as 3000 m g. Further, this approach has been extrapolated for the continuous synthesis of COFs by means of a twin screw extruder and in situ processes of COFs into different shapes mimicking the ancient terracotta process. Finally, the regular COF beads are shown to outperform the leading zeolites in water sorption performance, with notably facile regeneration ability and structural integrity.

Design Principles for Covalent Organic Frameworks in Energy Storage Applications

“…Continuous-flow methods [93] and mechanochemical solid-states yntheses [91,92,94] have recently been reported for severalt ypes of COFs. The use of any new materiali no ur expansive energy infrastructure first requires that it be available in large quantities.…”

Opportunities of Covalent Organic Frameworks for Advanced Applications

“…[113] Specifically, the diamine linker was ground with p-toluenesulfonic acid and subsequent addition of 1,3,5-triformylphloroglucinol (Tp) and water, the ketoenamine COFs were obtained in high quality (BET surface area up to 3100 m 2 g −1 ) after heating to 170 °C for 1 min. [113] Specifically, the diamine linker was ground with p-toluenesulfonic acid and subsequent addition of 1,3,5-triformylphloroglucinol (Tp) and water, the ketoenamine COFs were obtained in high quality (BET surface area up to 3100 m 2 g −1 ) after heating to 170 °C for 1 min.…”

“…[115] Fang and co-workers successfully synthesized a series of 3D COFs under ambient conditions using ionic liquids as media within 12 h, which is substantially shorter than those from the traditional solvothermal method (3-7 days). [113] Copyright 2017, American Chemical Society. Figure 28.…”

Tailoring Covalent Organic Frameworks To Capture Water Contaminants

“…Although COFs can feature fascinating properties, these crystalline materials need to be further engineered to harness their full potential for practical applications . COF powders can be transformed or molded into specific geometric shapes, such as pellets, beads, and cylinders, improving their mechanical strength, durability, and permeability for adsorption applications. Banerjee and co‐workers developed a co‐agent based solid‐state synthetic methodology for molding the Tp‐series of COFs into the desired geometric shapes .…”