Rules of Boron–Nitrogen Doping in Defect Graphene Sheets: A First‐Principles Investigation of Band‐Gap Tuning and Oxygen Reduction Reaction Catalysis Capabilities

Abstract

Introduction of defects and nitrogen doping are two of the most pursued methods to tailor the properties of graphene for better suitability to applications such as catalysis and energy conversion. Doping nitrogen atoms at defect sites of graphene and codoping them along with boron atoms can further increase the efficiency of such systems due to better stability of nitrogen at defect sites and stabilization provided by B-N bonding. Systematic exploration of the possible doping/codoping configurations reflecting defect regions of graphene presents a prevalent doping site for nitrogen-rich BN clusters and they are also highly suitable for modulating (0.2-0.9 eV) the band gap of defect graphene. Such codoped systems perform significantly better than the platinum surface, undoped defect graphene, and the single nitrogen or boron atom doped defect graphene system for dioxygen adsorption. Significant stretching of the O-O bond indicates a lowering of the bond breakage barrier, which is advantageous for applications in the oxygen reduction reaction.

Tuning dissociation using isoelectronically doped graphene and hexagonal boron nitride: Water and other small molecules

“…Various theoretical studies on band gap engineering using h-BN and graphene mixtures, [15][16][17][18][19][20][21][22][23] have revealed the tuneability of these materials through the mixture of atoms. Other studies have focused on exploiting this tuneability for catalysis of oxygen reduction reactions, [24][25][26][27][28][29][30][31][32][33] water transport, 34 and H 2 adsorption. [35][36][37] An important aspect to consider, if using graphene and h-BN based materials as catalysts, is their degree of selectivity.…”

Theoretical investigation of structures and energetics of sodium adatom and its dimer on graphene: DFT study

“…First-principles investigation of oxygen reduction reaction catalysis capabilities of As decorated defect graphene has shown that As adatoms adsorbed on double vacancy graphene system are very efficient and highly stable as an alternate Pt free oxygen reduction reaction(ORR) electrocatalyst [21]. Doping nitrogen atoms at defect sites of graphene and codoping them along with boron atoms can further increase the efficiency of such systems due to better stability of nitrogen at defect sites and stabilization provided by B-N bonding [22]. Recently sodium-ion batteries (SIBs) have drawn much attention over lithium ion batteries (LIBs) because of inexhaustible resources of sodium distributed evenly across the globe [23][24][25].…”

Computational chemistry for graphene-based energy applications: progress and challenges

“…In one recent report 210 a large part of their work was devoted to an exhaustive study of boron, nitrogen, and B/N co-dopants on the double-vacancy (555-777) graphene surface. Their data indicate that a dopant structure with three boron atoms and seven nitrogen atoms, at the centre of the defect, was the most favourable in terms of formation energy.…”

“…The influence of dopants on graphene surfaces with defects has been investigated by quantum chemical approaches 202,[207][208][209][210][211] . In one recent report 210 a large part of their work was devoted to an exhaustive study of boron, nitrogen, and B/N co-dopants on the double-vacancy (555-777) graphene surface.…”

“…Having used PW-DFT PBE calculations to identify plausible sites in their study of boron-nitrogen codopants in graphene substrates with defects, Sen et al 210 calculated adsorption energies of O 2 and related these to activated ORR processes. The presence of sulfur dopants in graphene and their impact on binding of ORR intermediates was explored by Zhang et al 207 .…”