h-BN Monolayer on the Ni(111) Surface: A Potential Catalyst for Oxidation

Abstract

The hexagonal boron nitride (h-BN) is traditionally considered to be inert. In sharp contrast to the inert behavior of free-standing hexagonal boron nitride (h-BN), we propose the catalytic property of h-BN monolayer on Ni(111) substrate using first-principles density functional theory investigation. The interaction of O2 molecule with the h-BN/Ni(111) substrate results in nondissociative adsorption of the molecule along with elongation of the O-O bond. This can be considered as the activated state of the O2 molecule. Further interaction of this complex viz O2-h-BN/Ni(111) with an incoming CO molecule leads to the spontaneous formation of CO2. Interestingly, the CO adsorption on the h-BN/Ni(111) substrate was found to be unfavorable, thereby implying the oxidation of CO selectively through Eley-Rideal (ER) mechanism.

Doped h-BN monolayer as efficient noble metal-free catalysts for CO oxidation: the role of dopant and water in activity and catalytic de-poisoning

“…This makes the accurate calculation of the activation barrier difficult. A similar phenomenon was also observed by Wasey et al 21 on a h-BN monolayer on Ni (111) surface, where they have stated that the reaction takes place spontaneously without any activation barrier. In order to calculate the small activation barrier, we constructed constrained potential energy curves keeping the CO -O 2 distance fixed and relaxing the entire system.…”

“…It is 6 well known by now that pristine h-BN sheets are highly inactive and hence do not adsorb any reactant molecules. 21 Addition of the n-type dopant C makes the h-BN structure reactive and O 2 is adsorbed rather strongly in the B atom nearest to the C dopant with an adsorption energy of E ad = -1.77 eV. The adsorbate-surface distance is about 1.58 Å and the molecular bond length of oxygen is increased to about 1.34 Å, (free O 2 molecule in triplet state the bond length is 1.24 Å) indicating that the oxygen molecule is highly activated due to the electronic charge transfer from the BN sheet to the 2π* orbital of O 2 .…”

A Cu(111) supported h-BN nanosheet: a potential low-cost and high-performance catalyst for CO oxidation

“…16,[19][20][21][22][23][24][25][26] As indicated in the previous theories, h-BNNS can facilely bind to the metal substrate and the electronic properties of the h-BN monolayer are considerably modified, due to the mixing of orbitals between metal and h-BNNS. 19,[28][29][30] By both of experimental and theoretical proofs, Uosaki and the coworkers reported the ORR activity of h-BNNS supported on gold. 19,[28][29][30] By both of experimental and theoretical proofs, Uosaki and the coworkers reported the ORR activity of h-BNNS supported on gold.…”

An oxygen reduction catalytic process through superoxo adsorption states on n-type doped h-BN: A first-principles study

“…This type of overlayer can provide protection against CO poisoning and also retard the formation of H 2 O 2 [17]. This concept can be extended to a metal-free electrode, such as the complex of the C-doped h-BN on graphitic materials, as depicted in the Figure S4.…”

“…However, in addition to the high cost of Pt, neither its reaction efficiency nor its durability is fully satisfactory. In the search for alternatives, Pt alloys, Pt-free metal oxides, and metal-free catalysts have been evaluated [14][15][16][17][18][19][20]. In terms of the reaction type, four-electron ORR ( attractive [21][22][23][24].…”