Single <i>p</i>-block atom doped boron nitride monolayer: versatile catalysts for nitrate reduction beyond transition metals

Abstract Electrochemical reduction of nitrate ( <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mrow> <mml:msubsup> <mml:mrow> <mml:mtext>NO</mml:mtext> </mml:mrow> <mml:mn>3</mml:mn> <mml:mo>−</mml:mo> </mml:msubsup> </mml:mrow> </mml:math> ) to ammonia is a sustainable strategy to convert the pollutant nitrate into high-valued chemicals. Currently, the nitrate reduction reaction (NO 3 RR) is mainly based on transition metal catalysts. Here, by using density functional theory calculations, we studied six p -block atoms doped in 2D boron nitride (BN) monolayers for the NO 3 RR. Our results reveal that the doped BN monolayers are thermodynamically stable, and that <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mrow> <mml:msubsup> <mml:mrow> <mml:mtext>NO</mml:mtext> </mml:mrow> <mml:mn>3</mml:mn> <mml:mo>−</mml:mo> </mml:msubsup> </mml:mrow> </mml:math> can be strongly absorbed and activated on the In@BN, Si@BN, Ge@BN and Sn@BN monolayers. BN is a promising substrate support for catalysts due to high stability and thermal resistance. Among the six doped BN monolayers, In@BN and Sn@BN exhibit exceptional NO 3 RR performance with a limiting potential of only −0.30 V. Additionally, the hydrogen evolution reaction can be completely suppressed due to the weak adsorption of protons on the catalyst surfaces. Our work provides a new avenue on designing p -block atom-based catalyst’s for efficient NO 3 RR.