Effectively boosting selective ammonia synthesis on electron-deficient surface of MoB2

“Sabatier principle” of d electron number for describing the nitrogen reduction reaction performance of single-atom alloy catalysts

“…According to recent reports, NH * 3 can be easily desorbed from the active sites by further protonation under acid or alkalescent conditions to form NH 4 + , which is readily soluble in an electrolyte and releases the active sites for the next catalytic cycle. 15,48,49 Therefore, the above desorption process would not limit the NRR activity, while the PDS is the rst protonation step. The overpotential (h) on Re-Cu(553) computed using eqn (5) was just 0.17 V, which denotes excellent catalytic activity towards NRR.…”

“…10,13,14 Zhou et al designed an electron-deficient MoB 2 catalyst with empty Mo d z 2 orbitals for preferential N 2 adsorption by optimizing the acceptance mechanism. 15 Li et al strengthened the donation process by applying tensile strain on the bulk TiO 2 , which modified d orbital broadening to match well with the N 2 –π* orbitals. 16 Nevertheless, it is quite difficult to optimize both the acceptance and donation processes simultaneously.…”

Tailoring Electronic Structure of Copper Twin Boundaries Toward Highly Efficient Nitrogen Reduction Reaction

“…Recent studies have reported that the NH 3 * can desorb from the active sites by further protonation to form NH 4 + under acidic or alkaline conditions, which is readily soluble in electrolyte. [46,47] Therefore, the desorption of NH 3 * would not limit the NRR performance and is thus neglected. In this case, the first step of the distal mechanism is identified as the PDS, and the U L is À 0.27 V. The free energy diagrams of ReÀ Cu(111)-TBE along the alternating mechanism are shown in Figure 4d, where the PDS is the second protonation step with ΔG = 0.78 eV.…”

The development of catalysts for electrochemical nitrogen reduction toward ammonia: theoretical and experimental advances

“…5a). 76 The unique electronic structure of the B atom, with three valence electrons distributed across four orbitals, promotes valence electron transfer from Mo to B, inducing empty orbitals at Mo d+ sites, which is favourable for ''sacceptance''. Compared with an electron-neutral Mo site (Mo 0 ), Mo d+ sites are more favourable for the formation of stable Mo-N bonds with fewer filled antibonding orbitals (Fig.…”