The Journal of Physical Chemistry Letters,
Journal Year:
2024,
Volume and Issue:
16(1), P. 294 - 307
Published: Dec. 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 Energy Materials,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 5, 2025
Abstract
Electrocatalytic
CO
2
reduction
(CO
RR)
is
rapidly
emerging
as
a
promising
sustainable
strategy
for
transforming
into
valuable
fuels
and
chemical
feedstocks,
crucial
step
toward
carbon‐neutral
society.
The
efficiency,
selectivity,
stability
of
RR
are
heavily
influenced
by
the
chosen
catalyst
operating
conditions
used.
Despite
substantial
advances
in
development
catalysts,
there
scarcity
comprehensive
reviews
focusing
on
influence
different
environments
performance.
This
review
offers
detailed
examination
internal
external
environmental
control
strategies
designed
to
enhance
efficiency.
fundamental
reaction
mechanisms
through
situ
operational
techniques,
paired
with
theoretical
analyses,
discussed
while
also
identifying
key
challenges
future
research
directions
technology.
By
delivering
overview
current
state
field,
this
highlights
critical
role
control,
mechanistic
insights,
practical
considerations
needed
successful
commercialization
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 2, 2025
Single-atom
Fe-N-C
catalysts
have
attracted
significant
attention
in
the
NOx
reduction
reaction
(NOxRR).
However,
origin
of
their
selectivity
NOxRR
remains
unclear,
impeding
further
advancements
application.
Herein,
we
investigate
potential-driven
competitive
mechanism
for
NH3
and
NH2OH
production
over
single-atom
pyridinic-FeN4
pyrrolic-FeN4
sites
using
constant-potential
density
functional
theory
calculations.
The
is
linked
to
switching
Fe
3d
orbitals
as
they
interact
with
intermediates.
between
determined
by
applied
potentials.
predominantly
generates
at
higher
potentials
(-0.6
-1.2
V,
vs
SHE),
while
favored
lower
(0.6
-0.6
V).
shows
a
similar
potential-dependent
product
distribution,
crossover
potential
-1.0
V.
selectivity-determining
intermediates
(SDIs)
are
*NH2OH
*NH2
+
*OH.
governed
interacting
SDIs,
from
dumbbell-shaped
3dz2
four-leaf
clover-like
3dxz,
3dyz,
3dx2-y2,
which
plays
crucial
role
controlling
distribution
based
on
These
findings
offer
new
insights
into
NOxRR.
The Journal of Physical Chemistry Letters,
Journal Year:
2025,
Volume and Issue:
unknown, P. 1470 - 1477
Published: Feb. 2, 2025
Modeling
electrified
interfaces
has
long
been
a
great
challenge
in
electrochemistry.
In
recent
years,
the
grand-canonical
treatment
for
electrons
gradually
developed,
and
its
combination
with
density
functional
theory
widely
used
to
simulate
electrochemical
processes
on
an
atomistic
scale.
this
Perspective,
we
aim
discuss
several
practical
applications
of
powerful
technique
after
short
review
necessary
fundamentals.
We
will
begin
capacitor-based
parametrization
method
calculated
results.
If
considering
electrodes
under
different
applied
potentials
as
materials,
can
be
viewed
kind
"quadratic
scaling
relation",
which
might
reduce
overall
computational
costs
by
data
postanalysis
rather
than
algorithm
development.
Following
example
abnormal
potential-independent
energetic
curve
within
bandgap
area,
turn
topic
semiconducting
electrodes.
Meanwhile,
specific
behaviors
also
indicate
that
besides
reaction
thermodynamics
kinetics,
detailed
electronic
structure
system
well
described
electrons.
Several
possibilities
further
are
proposed
correspondingly
summarized
at
end
paper.
believe
calculations
greatly
enrich
our
understanding
fundamental
mechanisms
environments.
Journal of Materials Chemistry A,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 17, 2024
The
relationship
between
support
properties
and
CO
2
electroreduction
performance
was
elucidated.
A
series
of
N-doped
porous
carbons
with
varying
structures
degrees
graphitization
were
prepared
to
single
atomic
Ni–N
4
sites.
Phthalocyanines
have
emerged
as
attractive
materials
for
electrocatalytic
carbon
dioxide
reduction.
However,
the
challenge
of
finding
a
support
that
is
stable
while
maintaining
catalytic
activity
and
loading
remains
elusive.
Porous
are
considered
reliable
substrates
supporting
molecular
catalysts.
Herein,
nitrogen-rich
nanosheet
(NiPc/NMCN)
with
multilayer
mesoporous
structure
synthesized
based
on
kinetically
controlled
self-assembly
strategy
used
phthalocyanine
loading.
The
composite
NMCN
guides
molecular-scale
dispersion
plays
crucial
role
in
its
process.
Moreover,
molecules
retain
their
metal-N4
after
impregnation.
Therefore,
remarkable
CO2
electroreduction
properties
fully
demonstrated.
At
−0.73
V
vs.
RHE,
NiPc/NMCN
achieves
highest
CO
faradaic
efficiency
(FECO)
96.0%.
Meanwhile,
current
densities
membrane
electrode
module
electrolyzers
can
reach
industrial
amperage
levels,
FEco
at
60%
880
mA
cm–2.
Density
functional
theory
(DFT)
indicates
high
performance
attributed
to
significant
reduction
CO2RR
energy
barrier.
restricted
by
porous
could
produce
intermediate
*COOH
more
rapidly,
determining
selectivity,
which
confirmed
situ
(FTIR)
spectroscopy.
Consequently,
constructing
confined
structures
provides
an
avenue
design
efficient
