Advancing electrochemical nitrogen reduction: Efficacy of two-dimensional SiP layered structures with single-atom transition metal catalysts.
J Colloid Interface Sci
; 668: 399-411, 2024 Aug 15.
Article
em En
| MEDLINE
| ID: mdl-38685165
ABSTRACT
Researchers are interested in single-atom catalysts with atomically scattered metals relishing the enhanced electrocatalytic activity for nitrogen reduction and 100 % metal atom utilization. In this paper, we investigated 18 transition metals (TM) spanning 3d to 5d series as efficient nitrogen reduction reaction (NRR) catalysts on defective 2D SiPV layered structures through first-principles calculation. A systematic screening identified Mo@SiPV, Nb@SiPV, Ta@SiPV and W@SiPV as superior, demonstrating enhanced ammonia synthesis with significantly lower limiting potentials (-0.25, -0.45, -0.49 and -0.15 V, respectively), compared to the benchmark -0.87 eV for the defective SiP. In addition, the descriptor ΔG*N was introduced to establish the relationship between the different NRR intermediates, and the volcano plot of the limiting potentials were determined for their potential-determining steps (PDS). Remarkably, the limiting voltage of the NRR possesses a good linear relationship with the active center TM atom Æd, which is a reliable descriptor for predicting the limiting voltage. Furthermore, we verified the stability (using Ab Initio Molecular Dynamics - AIMD) and high selectivity (UL(NRR)-UL(HER) > -0.5 V) of these four catalysts in vacuum and solvent environments. This study systematically demonstrates the strong catalytic potential of 2D TM@SiPV(TM = Mo, Nb, Ta, W) single-atom catalysts for nitrogen reduction electrocatalysis.
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01-internacional
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MEDLINE
Idioma:
En
Ano de publicação:
2024
Tipo de documento:
Article