AUTHOR=Choutipalli Venkata Surya Kumar , Esackraj Karthikraja , Subramanian Venkatesan 

TITLE=Nitrogen Fixation at the Edges of Boron Nitride Nanomaterials: Synergy of Doping

JOURNAL=Frontiers in Chemistry

VOLUME=Volume 9 - 2021

YEAR=2022

URL=https://www.frontiersin.org/journals/chemistry/articles/10.3389/fchem.2021.799903

DOI=10.3389/fchem.2021.799903

ISSN=2296-2646

ABSTRACT=Synthesis of ammonia at ambient conditions is very demanding yet challenging to achieve due to the production of ammonia fuel which is considered as future fuel for sustainable energy. In this context, computational studies on the catalytic activity of the edgesites of boron nitride nanomaterials for the possible nitrogen reduction into ammonia have been investigated. Geometrical and electronic properties of zigzag and armchair B-open edges of BN sheet (BOE) models have been unraveled to substantiate their catalytic nature. Results reveal that BOE sites exhibit very high potential determining steps (PDS) of 2.0 eV. Doping of carbon at the nitrogen center, which is vicinal to the BOE site reduces the PDS of N2 reduction reaction (NRR) (to 1.18-1.33 eV) due to the regulation of charge distribution around the active BOE site. Further, NRR at the C doped at various edge sites of boron nitride sheet (BNS) has also been studied in detail. Among the twelve new C-doped defective BNS models, nine model catalysts are useful for nitrogen activation through either chemisorption or physisorption. Amongst, ZCN, ACN, and ZCBV models are efficient in catalyzing NRR with lower PDS of 0.86, 0.88, and 0.86 eV, respectively. The effect of carbon doping in tuning the potential requirements of NRR has been analyzed by comparing the relative stability of intermediates on the catalyst with and without carbon doping. Results reveal that C-doping destabilizes the intermediates compared to non-doped systems, thereby reducing the possibility of catalyst poisoning. However, their interactions with catalysts are good enough so that the NRR activity of the catalyst do not decrease due to C-doping.