Single atom-doped arsenene as electrocatalyst for reducing nitrogen to ammonia: a DFT study

Due to the wide application of NH 3 in the energy and chemical industry, the rational design of a highly efficient and low-cost electrocatalyst for nitrogen fixation at moderate conditions is highly desirable to meet the increasing demand for sustainable energy production in the modern society. Herein, we have systematically studied the catalytic performance of transition metal (TM) atom ( i.e. , V, Cr, Fe, Co, Cu, Ru, Pd, Ag, Pt, Au)-doped arsenene nanosheet, a new two-dimensional (2D) nanomaterial in VA group, as a heterogeneous catalyst for nitrogen reduction reaction (NRR). By density functional theory (DFT) calculation and systematic theoretical screening, our study predicts that the systems of V-, Fe-, Co- and Ru-doped arsenene have promising potentials as NRR electrocatalysts with high-loading TM and highly stable adsorption of N 2 molecule. Particularly, the V-doped system exhibits two feasible configurations for N 2 adsorption and an ultralow overpotential (0.10 V) via the enzymatic pathway, which is very competitive among similar reported electrocatalysts. This theoretical study not only extends the electrocatalyst family for nitrogen fixation, but also further deepens our physical insights into catalytic improvement, which can be expected to guide the rational design of novel NRR catalysts. A single metal atom-doped 2D material, arsenene, presents potential properties of catalyzing gaseous N 2 to ammonia (NH 3 ) under ambient conditions.