Metal–organic frameworks (MOFs)
have received a great deal
of attention for their potential in atmospheric filtering, and recent
work has shown that catecholate linkers can bind metals, creating
MOFs with monocatecholate metal centers and abundant open coordination
sites. In this study, M–catecholate systems (with M = Mg2+, Sc2+, Ti2+, V2+, Cr2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, and Zn2+) were used as computational
models of metalated catecholate linkers in MOFs. Nitric oxide (NO)
is a radical molecule that is considered an environmental pollutant
and is toxic if inhaled in large quantities. Binding NO is of interest
in creating atmospheric filters, at both the industrial and personal
scale. The binding energies of NO to the metal–catecholate
systems were calculated using density functional theory (DFT) and
complete active space self-consistent field (CASSCF) followed by second-order
perturbation theory (CASPT2). Selectivity was studied by calculating
the binding energies of additional guests (CO, NH3, H2O, N2, and CO2). The toxic guests have
stronger binding than the benign guests for all metals studied, and
NO has significantly stronger binding than other guests for most of
the metals studied, suggesting that metal–catecholates are
worthy of further study for NO filtration. Certain metal–catecholates
also show potential for separation of N2 and CO2 via N2 activation, which could be relevant for carbon
capture or ammonia synthesis.
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