Facile conversion of CO2 into useful multicarbon products
is of broad interest in the field of energy storage and controllable
carbon emission. However, electrochemical CO2 reduction
to ethanol on the Cu(111) surface is limited to the high applied potential
and low selectivity. Herein, we demonstrate that the Cu-based electrocatalysts
modified by boron (B) single-atom greatly reduce the thermodynamic
energy barrier and improve selectivity relative to pristine Cu(111)
in the hydrogenation of CO2 to ethanol. Electronic structure
analysis reveals that the doped B atom, as a charge transfer medium,
not only works in supplying electrons to stabilize the intermediates
but also undergoes distinct reaction paths compared with pristine
Cu(111) to improve the selectivity of ethanol. Moreover, the formation
of the robust B–C bond and the unique isomerization step keep
the C atoms of the intermediates in an opposite-charged state, which
makes C–C coupling facile to generate ethanol. These findings
would be very useful to guide the search for a new catalyst for electrochemical
CO2 reduction with high ethanol selectivity based on the
abundant Cu-based materials.
Pd-catalyzed borylation of fluorobenzene was theoretically studied. DFT calculations revealed that the reaction occurs through an unprecedented 3 + 6-membered ring transition state, in which one LiHMDS (HMDS = hexamethyldisilazane) acts as a ligand and another LiHMDS is essential to provide Li•••N and Li•••F interactions, overcoming the large destabilization of the strong phenyl−F bond distortion. The characteristic feature of LiHMDS was elucidated by comparing it with HMDS and NaHMDS analogues.
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