Surface Pore Engineering of Covalent Organic Frameworks for Ammonia Capture through Synergistic Multivariate and Open Metal Site Approaches

Abstract

High Resolution Image Download MS PowerPoint Slide Ammonia (NH 3 ) is a commonly used industrial gas, but its corrosiveness and toxicity are hazardous to human health. Although many adsorbents have been investigated for NH 3 sorption, limited ammonia uptake remains an urgent issue yet to be solved. In this article, a series of multivariate covalent organic frameworks (COFs) are explored which are densely functionalized with various active groups, such as —N—H, —C═O, and carboxyl group. Then, a metal ion (Ca 2+, Mn 2+, and Sr 2+ ) is integrated into the carboxylated structure achieving the first case of an open metal site in COF architecture. X-ray photoelectron spectroscopy reveals conclusive evidence for the multiple binding interactions with ammonia in the modified COF materials. Infrared spectroscopy indicates a general trend of binding capability from weak to strong along with —N—H, —C═O, carboxyl group, and metal ion. Through the synergistic multivariate and open metal site, the COF materials show excellent adsorption capacities (14.3 and 19.8 mmol g –1 at 298 and 283 K, respectively) and isosteric heat ( Q st ) of 91.2 kJ mol –1 for ammonia molecules. This novel approach enables the development of tailor-made porous materials with tunable pore-engineered surface for ammonia uptake.