Nanoporous Graphene and H-BN from BCN Precursors: First-Principles Calculations

Abstract

We propose, based on results of first-principles calculations, that nanoporous graphene and h-BN might be efficiently produced from B−C−N layers as precursors. In our calculations, we find that the removal of the h-BN islands that naturally occur in BN-doped graphene, forming nanoporous graphene, requires less energy than if pristine graphene is used as a precursor. The same reduction ΔE f in pore formation energy is found for nanoporous h-BN obtained from graphenedoped BN as a precursor. ΔE f is found to increase linearly as a function of the number of B−C and N−C bonds at the island boundary, with the slope being nearly the same for either porous graphene or porous h-BN. This is explained by an analytical bond-energy model. In the case of porous graphene, we find that the pore formation energy would be further reduced by passivation by pyridinic and quaternary remnant nitrogen atoms at the pore edges, a mechanism that is found to be more effective than the passivation by hydrogen atoms. Both mechanisms for pore formation energy reduction should lead to a possibly efficient method for nanoporous graphene production.

Recent progress in on-surface synthesis of nanoporous graphene materials

“…Zwaneveld et al first introduced B/O dopants into NPG to fabricate boroxine-linked and dioxaborole-linked covalent organic frameworks (COFs) via surface-assisted dehydration reactions, indicating the tunability of nanoporous sizes 118 . Graphene and BN sheets have commensurate parameters, making it feasible to introduce B and N atoms as co-dopants into graphene nanostructures, as extensively demonstrated in theories and experiments 119 – 122 . Sánchez-Sánchez et al obtained the NPG containing periodic B and N atoms via surface-assisted Ullmann coupling and subsequent cyclodehydrogenation (Fig.…”

Charge and Spin Current Rectification through Functionalized Boron Nitride Bilayers

“…Graphene possesses unique characteristics such as high mobility, resistance, and conductivity that have found a prominent position in the electronics, optoelectronics, spintronics, oil and gas industry, − and other fields. − The mechanical exfoliation technique, which is one of the most promising ways to achieve large-scale production at a low cost, , can produce other 2D materials besides graphene, contributing to the continuous expansion of the family of novel 2D materials. Single layers of boron nitride (BN), − silicon, , boron, Xenes, , germanium, phosphorus, , and transition-metal dichalcogenides − have been produced in the laboratory, , which have motivated further experimental and theoretical investigations, ,− leading to the observation of many interesting phenomena regarding structural/mechanical, electronic, and magnetic properties.…”