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

• Published in: Chemphyschem Vol. 15; no. 12; pp. 2542 - 2549
• Main Authors: Sen, Dipayan, Thapa, Ranjit, Chattopadhyay, Kalyan Kumar
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 25.08.2014; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Subjects: ab initio calculations; Boron; carbon; Catalysis; Chemistry; Defects; doping; Exact sciences and technology; General and physical chemistry; graphene; Graphite; Principles; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; Oxygen; Catalytic reaction; Doping; Nitrogen; Carbon; Chemical reduction; Heterogeneous catalysis; Boron; ab initio calculations; Graphene; Defect; Calculation; Catalyst; Modified material; doping; boron; carbon; graphene
• ISSN: 1439-4235; 1439-7641
• DOI: 10.1002/cphc.201402147

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. Who needs to be replaced? Various boron and nitrogen doping/codoping schemes on double‐vacancy defect graphene sheets are systematically explored by the means of first‐principles calculations. The oxygen reduction reaction capabilities of such structures are investigated in detail (see picture).