Electrocatalytic Reduction of N₂ Using Metal-Doped Borophene

Abstract

Ammonia synthesis is an essential process in chemistry and industry. However, it is limited by the lack of efficient catalysts and high energy costs. Developing highly efficient systems for ammonia synthesis is an important and long-standing challenge. In this paper, a large class of metal atoms (including 3d/4d transition metals and main group metals) anchored onto borophene have been studied as single atom catalysts for ammonia synthesis. After comprehensive computational screening and systematic evaluation, four candidates stand out. We predict that Mo, Mn, Tc, and Cr@BM-β 12 will have superior performance for catalytic reduction of N 2 to NH 3 with low limiting potentials of −0.26, −0.32, −0.38, and −0.48 V, respectively. Furthermore, we studied the activity of the competitive HER on M@BM-β 12 . The results implied that the two materials Mo@BM-β 12 and Mn@BMβ 12 showed HER suppression. These properties exceed most currently reported nitrogen reduction reaction electrocatalysts. Our results suggest the possibility of efficient electrochemical reduction of N 2 to NH 3 in a lower energy process.

Density Functional Theory for Electrocatalysis

“…For instance, Yang et al performed the DFT highthroughput screening of catalysts for NRR among a series of transition metal atoms supported on phthalocyanine or borophene monolayer, which provided insights to rational design and explore the efficient and stable NRR catalysts. [403,406] In particular, the NRR reaction (N 2 + 6H + + 6e − → 2NH 3 ) involves several intermediates (*N 2 H, *N 2 H 2 , *N 2 H 3 , *NH 2 , and *N) with two potential reaction pathways (Figure 11b). One is the dissociative pathway, in which the first step is N 2 dissociates into two separate N atoms before the hydrogenation.…”

2D boron nanosheet architectonics: opening new territories by smart functionalization

“…6(c)]. [101][102][103] Xu et al studied the catalytic activity of metal doped borophene towards the CO 2 reduction reaction (CO 2 RR). 104 The results showed that the CO 2 RR was energetically more favorable than the HER on Co-and Pd-doped a-borophene nanosheets because of moderate adsorption energy [Fig.…”

Elemental 2D Materials: Solution‐Processed Synthesis and Applications in Electrochemical Ammonia Production

“…On the basis of these recent excellent studies, it is clear that 2D boron deserves further research efforts in N 2 fixation and a lot remains to be studied. Very recently, in a theoretical study by Xu et al, [291] the effects of various metal atoms (including 3d/4d transition metals and main group metals) as single atom dopants on 2D borophene Step numbers for the reaction sequences should be referred to (e). Reproduced with permission.…”