Premium
Phosphorene‐Supported Transition‐Metal Dimer for Effective N 2 Electroreduction
Author(s) -
Tang Qing,
Jiang Deen
Publication year - 2019
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201900279
Subject(s) - overpotential , electrocatalyst , phosphorene , dimer , hydride , transition metal , chemistry , electrochemistry , density functional theory , catalysis , inorganic chemistry , photochemistry , hydrogen , materials science , electrode , computational chemistry , organic chemistry , biochemistry , monolayer
The electrochemical reduction of N 2 to NH 3 at ambient conditions is a promising alternative to the energy‐intensive, high‐temperature, high‐pressure Haber‐Bosch process. But it is extremely challenging to find an electrocatalyst that can effectively activate N 2 and reduce it to NH 3 . From first principles density functional theory, we found that the Ti dimer supported on single‐layer phosphorene can be used as a promising electrocatalyst for N 2 capture and conversion to NH 3 . The overpotential (relative to the standard hydrogen electrode) was found to be as low as 0.20, much lower than those predicted on the Ti surface (1 to 1.5 V) or their nitrides (0.5 to 1 V). In addition, we found that hydride is involved in the N 2 reduction on the Ti dimer catalyst via formation of Ti 2 ‐H species, and the hydride would favorably transfer onto the adsorbed N 2 * to form *NNH intermediate and further reduced to NH 3 . Moreover, we also examined other first‐row transition metal dimers, and found that Sc and Fe dimer to be potential catalysts which could catalyze N 2 reduction at a low overpotential of about 0.21 and 0.45 V, respectively. Our predictions hence suggest Ti, Sc and Fe dimer clusters supported on phosphorene as promising electrocatalysts for N 2 reduction to NH 3 .