Theoretical Evaluation of Electrochemical Nitrate Reduction Reaction on Graphdiyne-Supported Transition Metal Single-Atom Catalysts.

The electrochemical reaction can be applied as a powerful method to eliminate the pollution of nitrate (NO 3 - ) and as a feasible synthesis to enable the conversion of nitrate into ammonia (NH 3 ) at room temperature. Herein, density functional theory calculations are applied to comprehensively analyze the electrochemical nitrate reduction reaction (NO 3 RR) on graphdiyne-supported transition metal single-atom catalysts (TM@GDY SACs) for the first time. It can be found that the vanadium-anchored graphdiyne (V@GDY) displays the lowest limiting potential of -0.63 V versus a reversible hydrogen electrode among the investigated systems in this work. Notably, the competing hydrogen evolution reaction is relatively restrained due to the comparatively weak adsorption of the H proton on the TM@GDY SACs. Moreover, higher energy intake is needed to overcome the energy barrier during the formation of byproducts (NO 2 , NO, N 2 O, and N 2 ) on V@GDY without applying extra electrode potential, showing the selectivity of NH 3 in the NO 3 RR process. The ab initio molecular dynamics simulation denotes that the V@GDY possesses excellent structure stability at the temperature of 600 K without much distortion, compared with the initial shape, indicating the promise for synthesis. This study not only offers a feasible NO 3 RR electrocatalyst but also paves the way for the development of the NO 3 RR process.