To rationally design electrocatalysts with high promising performance is essential for the nitrogen reduction reaction (NRR). Using the first principle density functional theory and ab initio molecular dynamic calculations, we systematically explored the activity, selectivity, and thermodynamic stability of the single-atom or tetra-nuclear metal clusters of Fe and Ru supported on Nb 2 C MXene modified by oxygen (fluorine) functional groups, resulting in one excellent electrocatalyst (labeling as Ru/Nb 2 CO 2 ) for NRR. The obtained Ru/Nb 2 CO 2 catalyst mainly undergoes electroreduction of nitrogen that proceeds via an enzymatic hybrid mechanism due to high selectivity (99.9%) and low ΔG PDS (ΔG PDS = 0.59 eV), and the catalyst also has superior stability at 500 K, suggesting Ru/Nb 2 CO 2 has high promising performance for electrocatalytic synthesis of ammonia.
The design of high-performance single-atom
catalysts (SACs) for
two-electron oxygen reduction reaction (2e– ORR)
is of great importance for the large-scale commercial application
of H2O2 electrosynthesis. Herein, utilizing
the combination of density functional theory (DFT) calculation and
ab initio molecular dynamic (AIMD) simulation, an effective computational
framework was built to identify the critical role of coordination
fields and hydrosolvents in the 2e– ORR catalytic
properties of SAC-based two substrates [pristine γ-type graphyne
(γ-GY) and B-doped γ-GY]. The screening calculations of
168 TM@(B-doped) γ-GY (TM = transition metal) revealed that
both Co@B1-2-γ-GY and Pd@B3-2-γ-GY
feature outstanding catalytic properties with low overpotentials (0.06,
0.02 V) and excellent stability. The electronic structure results
uncovered that viewing from the coordination field, electron-deficient
boron atoms can manipulate the electron back-donation effect (d → π2p
*) of the TM–O bond to mediate the H2O2 property. Solvent effect calculations revealed
that the hydrogen-bond (H-bond) framework plays an important role
in the high selectivity of H2O2 by facilitating
the H transfer from water (>99.9 and 98.6% for Co@B1-2-γ-GY
and Pd@B3-2-γ-GY), shedding light on the higher accuracy
of an explicit solvent than that of an implicit one. This work will
provide one way to better design high-selectivity SACs for H2O2 synthesis effectively.
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