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 strong adsorption energies 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.