The Journal of Physical Chemistry Letters,
Год журнала:
2024,
Номер
16(1), С. 294 - 307
Опубликована: Дек. 26, 2024
Heterogeneous
cobalt
phthalocyanine
has
emerged
as
a
promising
molecular
catalyst
for
electrochemical
reduction
of
CO2
to
methanol.
Boosting
both
electrocatalytic
durability
and
selectivity
remains
great
challenge,
which
is
more
difficult
with
unknown
regulation
factors
the
HER
side
reaction.
Herein,
discover
key
balancing
selectivity,
well
regulation,
we
carried
out
GC-DFT
calculations,
based
on
dynamic
product
distribution
modeling
was
conducted
visually
present
variation
within
applied
voltage
range.
The
strongly
electron-donating
NMe2-substituted
CoPc
found
be
an
excellent
candidate.
reveals
that
balance
regulate
potential
highest
methanol
Faradaic
efficiency
corresponding
energy
barrier
selectivity-determining
step
hydrogenated
CoPc.
pivotal
factor
in
stems
from
hindered
H
adsorption
due
ligand
hydrogenation,
arising
decreased
Co-to-H
charge
transfer.
analysis
provides
intuitive
theoretical
guidance
highly
selective
durable
electroreduction.
Advanced Functional Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 15, 2025
Abstract
Atomic‐level
metal
sites
at
the
edges
of
graphene‐like
carbon
supports
are
considered
more
active
for
CO
2
electrocatalysis
than
those
in‐plane.
However,
creating
high‐density
edge‐dominating
sites,
particularly
in
a
simple,
scalable,
and
self‐templated
fashion,
presents
significant
challenge.
Herein,
MOF‐mediated
self‐exfoliation
strategy
is
reported
to
preferentially
integrate
edge‐type
FeN
4
onto
ultrathin
edge‐rich
N‐doped
graphene
nanomesh
(e‐Fe‐NGM).
Theoretical
calculations,
finite
element
method
(FEM)
simulations,
together
with
series
situ
spectro‐electrochemical
experiments
corroborate
that
can
not
only
optimize
electronic
structure
catalysts,
facilitating
formation
*
COOH
desorption
CO,
but
also
effectively
induce
strong
local
electrostatic
field,
promoting
interfacial
H
O
supply
thereby
accelerating
protonation
process
.
Thus‐prepared
e‐Fe‐NGM
delivers
remarkable
Faraday
efficiency
(FE)
above
98%
over
an
ultra‐wide
potential
window
500
mV
high
turnover
frequency
6648
h
−1
,
much
superior
controlled
sample
dominant
plane‐type
sites.
Moreover,
this
self‐exfoliated,
non‐catalyzed
approach
readily
scalable
be
used
produce
large‐size
industrial
levels.
The Journal of Physical Chemistry Letters,
Год журнала:
2024,
Номер
16(1), С. 294 - 307
Опубликована: Дек. 26, 2024
Heterogeneous
cobalt
phthalocyanine
has
emerged
as
a
promising
molecular
catalyst
for
electrochemical
reduction
of
CO2
to
methanol.
Boosting
both
electrocatalytic
durability
and
selectivity
remains
great
challenge,
which
is
more
difficult
with
unknown
regulation
factors
the
HER
side
reaction.
Herein,
discover
key
balancing
selectivity,
well
regulation,
we
carried
out
GC-DFT
calculations,
based
on
dynamic
product
distribution
modeling
was
conducted
visually
present
variation
within
applied
voltage
range.
The
strongly
electron-donating
NMe2-substituted
CoPc
found
be
an
excellent
candidate.
reveals
that
balance
regulate
potential
highest
methanol
Faradaic
efficiency
corresponding
energy
barrier
selectivity-determining
step
hydrogenated
CoPc.
pivotal
factor
in
stems
from
hindered
H
adsorption
due
ligand
hydrogenation,
arising
decreased
Co-to-H
charge
transfer.
analysis
provides
intuitive
theoretical
guidance
highly
selective
durable
electroreduction.
