Hydroxylation of a metal-supported hexagonal boron nitride monolayer by oxygen induced water dissociation

Abstract

Hydroxylated hexagonal boron nitride (h-BN) nanosheets exhibit potential application in nanocomposites and functional surface coating. Our first-principles calculations reveal possible hydroxylation of a h-BN monolayer on a Ni substrate by surface O adatom induced spontaneous dissociation of water molecules. Here one H atom is split from a water molecule by bonding with the O adatom on the B atom and the resulting O-H radical then bonds with an adjacent B atom, which leads to two hydroxyl groups formed on h-BN/Ni. Hydroxylation slightly influences the electronic properties of a Ni-supported h-BN layer. Similar water dissociation and hydroxylation can occur on the surface of O functionalized h-BN/Cu depending on the O adsorption configuration. Metal substrates play an important catalytic role in enhancing the chemical reactivity of O adatoms on h-BN with water molecules through transferring additional charges to them.

Oxygen‐Induced Dissociation of a Single Water Molecule in Confined 2‐D Layers: A Semiempirical Study

“…However, in the case of oxygen adsorption on a metal-supported h-BN monolayer, two stable sites were reported 1) "top B" and 2) "bridge". [29,45] From our semiempirical calculations on a free-standing h-BN monolayer, we found the "bridge" configuration as the most stable one, with an adsorption energy value of À 2.00 eV. A metastable configuration with an adsorption energy value of À 0.45 eV is also obtained from our semiempirical calculations.…”

“…A slight elongation of bond distances is observed between the B atom attached to the adatom and the three closest neighbouring nitrogen atoms [1.55, 1.55 and 1.56 Å]. Guo and Guo [29] studied the oxygen adsorption on a Ni (111) supported h-BN layer and reported the binding energy values for O adsorbed on B and BÀ N sites were À 5.57 and À 2.21 eV, respectively. According to their studies, the van der Waals interaction between the O-functionalized h-BN monolayer and the metal support layer provides additional stability to the complex.…”

h-BN Defective Layers as Giant N-Donor Macrocycles for Cu Adatom Trapping from the Underlying Metal Substrate

“…The h-BN/metal interface is an interesting platform for many applications including catalysis, electrocatalysis, and corrosion protection. − Both physical and chemical properties of bidimensional layers of h-BN were shown to be affected by the presence of an underlying substrate and of defects, , which may alter its insulating properties and chemical inertness. Cu is a very attractive substrate because of the possibility of using Cu foils and, thus, of moving toward large-scale preparations for commercial use .…”

Hydroxylated boron nitride materials: from structures to functional applications

“…Because of the reactivity of boron compounds, theoretical calculations are essential to gain an in-depth insight into the electronic and mechanical properties of layered BN [2]. Density functional theory (DFT) and molecular dynamics (MD) simulations provide valuable predictions and corroborations on the impact of hydroxyl chemical species on the BNNSs surfaces [99][100][101][102][103][104].…”