Ammonia (NH3) is a commonly used industrial gas, but
its corrosiveness and toxicity are hazardous to human health. Although
many adsorbents have been investigated for NH3 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 (Ca2+, Mn2+, and Sr2+) 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 (Qst) 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.