Cooperative Single-Atom Active Centers for Attenuating the Linear Scaling Effect in the Nitrogen Reduction Reaction

Abstract

Cooperative effects of adjacent active centers are critical for single-atom catalysts (SACs) as active site density matters. Yet how it affects scaling relationships in many important reactions like nitrogen reduction reaction (NRR) is underexplored. Herein we elucidate how the cooperation of two active centers can attenuate the linear scaling effect in NRR, through the first-principle study on 39 SACs comprised of two adjacent (~4 Å apart) four N-coordinated metal centers (MN4 duo) embedded in graphene. Bridge-on adsorption of dinitrogen-containing species appreciably tilts the balance of adsorption of N2H and NH2 towards N2H and thus substantially loosens the restraint of scaling relations in NRR, achieving low onset potential (V) and direct N≡N cleavage (Mo, Re) at room temperature, respectively. The potential of MN4 duo in NRR casts new insight into circumventing limitations of scaling relations in heterogeneous catalysis.

“Capture-Backdonation-Recapture” Mechanism for Promoting N2 Reduction by Heteronuclear Metal-Free Double-Atom Catalysts

“…However, it is difficult to improve the yield and Faraday efficiency of NRR simultaneously with that of a single-atom catalyst, mainly because NRR involves multiple protonation processes and many intermediates. To solve these problems, homonuclear metal double-atom catalysts for nitrogen fixation have been proposed, namely, Mn 2 @ g -C 2 N, Mo 2 @ g -C 2 N, Fe 2 N 4 @G, bi-Ti 3+ @TiO 2 , ReB 2 , and VN 4 duo@G . Unfortunately, the enhancement of catalytic performance by homonuclear metal double-atom catalysts is relatively limited.…”

Atomically Dispersed Cu Anchored on Nitrogen and Boron Codoped Carbon Nanosheets for Enhancing Catalytic Performance

“…The difference in charge on the Cu single atom was ascribed to the greater electrophilicity of the N atom relative to the B atom. Moreover, to further reveal the influence of the Cu–N 2 B 1 and Cu–N 3 interfaces on the adsorption energy of the adsorbate, we calculated the bonding strength between the adsorbate (O) and the Cu active center using the integrated crystal orbital Hamilton population (ICOHP) values. − The ICOHP values were calculated using the energy integral up to the highest occupied orbital (below the Fermi level), which fundamentally indicates the interaction change between reactants and active sites. The negative shift of the ICOHP value indicated the strengthened bonding.…”

Nitrogen reduction reaction energy and pathways in metal-zeolites: deep learning and explainable machine learning with local acidity and hydrogen bonding features

“…NH 3 * is facile to form NH 4 + in aqueous electrolytes under strong acidic conditions, as mentioned in the literature. 11,12,60,61 In Table S12, † some catalysts have realized ammonia production and achieved high Faraday efficiency (FE) for the conversion from N 2 to NH 3 in experiment, although the desorption step (NH 3 * to NH 3 ) required 0.94-1.73 eV energy inputs. [62][63][64][65][66] In metal-zeolites studied in this work, the NH 3 desorption step free energies were 2.12, 1.65, and 1.46 eV for Ti-, Co-, and Nb-zeolites, respectively.…”