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

Abstract

Motivated by the recent successful synthesis of biphenylene structure [Science 372, (2021), 852], we have explored the sensing properties of this material towards the catechol biomolecule by performing the first-principles density functional theory and molecular dynamics simulations. Pristine biphenylene sheet adsorbs catechol molecule with a binding energy of -0.35 eV, which can be systematically improved by decorating the transition metals (Ag, Au, Pd, and Ti) at various possible sites of biphenylene. It is observed that the catechol molecule is adsorbed on Pd and Ti-decorated biphenylene sheets with a strong adsorption energy of -1.00 eV and -2.54 eV, respectively. The interaction of the catechol molecule with biphenylene and metal-decorated biphenylene is due to the charge transfer from the O-2p orbitals of the catechol molecule, to the C-2p orbitals of biphenylene and d-orbitals of metals in metal-decorated biphenylene, respectively. From the Bader charge calculation, we found that 0.05e amount of charge is transferred from the catechol molecule to pristine biphenylene, which gets almost double (~0.1e) for the Ti-decorated biphenylene sheet. The diffusion energy barrier for the clustering of the Pd and Ti atoms comes out to be 2.39 eV and 4.29 eV, computed by performing the climbing-image nudged elastic band calculations. We found that the catechol molecule gets desorbed from the pristine biphenylene sheet even at 100 K but remains attached to metal (Pd, Ti) decorated biphenylene sheets at room temperature by performing the ab-initio molecular dynamics simulations. The Ti-decorated biphenylene sheet has more sensitivity toward catechol adsorption while the Pd-decorated biphenylene sheet has a suitable recovery time at 500 K. The results suggest that the Pd and Ti-decorated biphenylene sheets are promising materials for catechol detection.

Locally spontaneous dynamic oxygen migration on biphenylene: a DFT study

“…Unlike the primitive hexagonal structure of graphene with a C-C bond length of 1.426 Å, 36 the biphenylene monolayer is composed of C 4 , C 6 and C 8 rings and shows different C-C bond lengths ranging from 1.408 Å to 1.461 Å, well matching the reported results. 34…”

“…Beyond graphene dominated by the periodic hexagonal rings, several carbon allotropes composed of hybrid carbon rings have been recently predicted by first-principles calculations or synthesized experimentally. [22][23][24][25][26][27][28] Biphenylene, as a novel 2D carbon material consisting of four-(C 4 ), six-(C 6 ) and eight-membered (C 8 ) carbon rings, shows great potential in applications such as catalysis, 29,30 batteries, 31 sensors, [32][33][34] etc. The hybrid carbon rings at the biphenylene monolayer surface introduce non-equivalent carbon sites and improve the interfacial activity, such that the biphenylene monolayer can be easily oxidized and shows more active carbon sites for chemical reactions.…”

Catechol Sensing Performance of Pd-Functionalized Two-Dimensional Polyaramid: A DFT Investigation

“…For example, the previous study shows small Cc adsorption energy on the pristine TM dichalcogenides (TMDCs) like MoS 2 and VSe 2 . , The TM functionalization has increased the conductivity and helped to increase the interaction of Cc. Graphene-like carbon 2D materials like gamma graphyne, hole graphyne (hGY), and biphenylene (Bp) were also predicted to be excellent Cc sensors. − The significant adsorption energy for Cc on the hGY system was due to the charge transfer between the 2p orbitals of Cc and the 3d orbitals of the decorated Sc atom on the hGY system. In the Bp system, though Ti decorations show higher sensitivity toward the Cc molecule than the Pd decorated system, the Pd + Bp system is the best due to the short recovery at 500 K.…”

An ab initio study of catechol sensing in pristine and transition metal decorated γ-graphyne

“…[33] investigated the TM (Ag, Au, Pd) decorated 2D VSe 2 as an effective and reversible CCdetecting material. Mahamiya et al [34] have reported the excellent sensing behavior of recently synthesized biphenylene sheet decorated with TMs towards CC biomolecule.…”