Density functional theory (DFT) calculations have been carried out to study the capacity of the B[Formula: see text]N[Formula: see text] nanocage encapsulated with alkali metals (Li, Na, K) for the CO2 adsorption and activation. It is found that after encapsulating alkali metals, the alkali metal atoms are closer to one side of clusters instead of exactly lying at the center, and a considerable charge transfers from the inner alkali metal atoms to the B[Formula: see text]N[Formula: see text] cage. Besides, the HOMO–LUMO gap (HLG) values of Li@B[Formula: see text]N[Formula: see text], Na@B[Formula: see text]N[Formula: see text] and K@B[Formula: see text]N[Formula: see text] are decreased to about 6[Formula: see text]eV, being much smaller than that of the pristine B[Formula: see text]N[Formula: see text]. Although the geometry structure parameters and the energy differences of M06-2X are slightly different from the ones of [Formula: see text]B97X-D, some identical results of two kinds of functional can be obtained. CO2 can be adsorbed chemically and physically on majority bonds of all the clusters, except for some bonds with large change in bond length and bond indices. The encapsulation of alkali-metal atoms may enhance the physical and chemical adsorption of CO2 on the surface of the clusters, in which Na@B[Formula: see text]N[Formula: see text] and K@B[Formula: see text]N[Formula: see text] are the most powerful physical and chemical adsorbent for CO2, respectively.
Density functional study of alkali-metal atoms and monolayers on graphite (0001)
