Modelling strategies for the covalent functionalization of 2D phosphorene

Abstract

This paper is a comparative outline of the potential acid–base adducts formed by an unsaturated main group or transition metal species and P atoms of phosphorene (Pn), which derives from black phosphorus exfoliation.

Nitrogen-based gas molecule adsorption of monolayer phosphorene under metal functionalization

“…For the bP-Ca, bP-Ca and bP-La systems, on the other hand, the lowest conduction bands of phosphorenes are pushed down relative to the other conduction bands due to the repulsive interaction of metal states. The spacings between the lowest and the second lowest conduction bands are of different degrees of increasing, especially for the AEM and La decorations cases 42 . When the Fermi levels shift upward and are located in the large spacings between the lowest and the second lowest conduction bands, the bP-Ca, bP-Ca and bP-La systems exhibit small indirect bandgaps.…”

“…Additionally, there are two O peaks near VBM, which is responsible for the large adsorption energy. The charge transfer quantity of 0.3 e from phosphorene to NO 2 molecule reduces the lone pair electrons and thus reduces repulsive interaction between the facing lone pairs at the ditch, which leads to the larger bandgap of 0.899 eV 42 .…”

“…The bandgaps of NO 2 adsorbed bP-Li and bP-Na are 0.921 and 0.902 eV, respectively, which are slightly larger than that of pristine phosphorene. This may be ascribed to decrease of repulsive interaction between the facing lone pair electrons at channel due to the wider channel 42 . For bP-AEM systems, as shown in Figs 8(f–h) and S9(f–h), the separations between the lowest and the second lowest conduction bands significantly decrease due to that the adsorptions of NO 2 molecules weaken the repulsive interaction between the Ni atom states and the lowest conduction band of phosphorene 42 .…”

“…This may be ascribed to decrease of repulsive interaction between the facing lone pair electrons at channel due to the wider channel 42 . For bP-AEM systems, as shown in Figs 8(f–h) and S9(f–h), the separations between the lowest and the second lowest conduction bands significantly decrease due to that the adsorptions of NO 2 molecules weaken the repulsive interaction between the Ni atom states and the lowest conduction band of phosphorene 42 . This leads to the lowest conduction bands shifting upward, and the Fermi levels cross through the lowest conduction bands.…”

Catalysis Mediated by 2D Black Phosphorus Either Pristine or Decorated with Transition Metals Species

“…The sp 3 hybridization of phosphorus atoms in BP is also responsible for the presence of a lone pair on each atom. Theoretical calculations have shown how the Lewis-basicity of black phosphorus is less than that of molecular phosphines, owing to an unfavorable combination of steric and electronic effects [26]; nonetheless, the naïve description of 2D BP as an extended polydentate ligand is irresistibly fascinating for a chemist and it provides a useful conceptual model toward its chemical functionalization, especially with metal units. Furthermore, the ability of 2D BP to form coordinative bonds with transition metals with bond-lengths that are even close to those found in some phosphine complexes has already been experimentally demonstrated in a 2D BP/Pd system (see Section 5.3).…”