Locally Spontaneous Dynamic Oxygen Migration on Biphenylene: A DFT Study

Abstract

The dynamic oxygen migration on the interface of carbon materials, such as graphene and carbon nanotube, has opened up a new avenue to realizing the dynamic covalent materials. However, the understanding of dynamic behaviors of oxygen groups on the non-honeycomb structure, such as the biphenylene sheet, is still limited. Using both density functional theory calculations and ab initio molecular dynamics simulations, we demonstrate that the oxygen groups on the biphenylene, which is an allotrope of graphene and composed of four-, six-and eight-membered rings with unequal C-C bonds, can exhibit locally spontaneous dynamic oxygen migration through the breaking/reforming of the C-O bond. The density of state analyses show that the p-band center of the oxygen atom is closer to the Fermi energy level on biphenylene, compared to that of the oxygen atom adsorbed on graphene. This contrast confirms the locally spontaneous dynamic activity of the oxygen atom on biphenylene. This work provides scientific guidance for the exploration of the locally/globally spontaneous dynamic covalent materials and adds a new member to the 2D dynamic covalent material family.

Remarkable enhancement in catechol sensing by the decoration of selective transition metals in biphenylene sheet: A systematic first-principles study

“…The structure of BP comprises 4, 6, and 8 atoms of carbon rings, as presented in figure 1(a). The optimized lattice constants of the BP unit cell are a = 4.52 Å, and b = 3.75 Å, matching excellently with the reported literature values of 4.52 Å, and 3.76 Å [35]. We have obtained four different C-C bond lengths in the BP sheet, which have values of 1.452 Å, 1.446 Å, 1.459 Å, and 1.405 Å, consistent with the literature [35].…”

“…A 2 × 2 × 1 supercell of BP containing 24 carbon atoms is considered, and the vacuum of 30 Å is taken perpendicular to the sheet to avoid interaction between periodic layers. Grimme's dispersion correction DFT-D3 [34,35] is applied with GGA-PBE to include weak van der Waals (vdW) interactions. The AIMD simulations [40] are performed to investigate the thermal stability of the system at room temperature.…”

“…In the structure of BP, a large number of possible sites are presented for the decoration of metal atoms so that we can get the desired electrochemical properties [2,32]. Because of the presence of a large number of adsorption sites in the BP structure, it possesses outstanding behavior in various fields such as energy storage [33], gas sensing [2], Li-ion batteries [34], and so forth [35]. Recently, a theoretical study on catechol sensing has been performed in a similar type of 2D nanomaterial holey graphyne (hGY) decorated with an Sc atom [36].…”