Chemistry of Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 16, 2024
The
hangman
structure
plays
a
critical
role
in
determining
the
reaction
rates
of
molecular
CO2
electrocatalysis
through
constructing
pendant
functional
groups
secondary
coordination
spheres
metal
active
sites.
However,
achieving
structures
commonly
requires
complicated
asymmetric
synthesis.
It
is
necessary
to
search
for
simple
alternative
strategies
develop
with
realization
concept
green
chemistry.
In
this
work,
we
report
synthesis
electrocatalysts
based
on
noncovalent
π–π
interaction
between
cobalt
(Co)
phthalocyanine
nanotubes
and
1-aminopyrene.
promoted
kinetics
interfacial
inner
outer
sphere
electron
transfer
complex
chemisorption
*COOH
*CO
species
both
Co
sites
amine
bridge
geometry.
resultant
afforded
very
high
turnover
frequency
4.37
s–1
at
an
overpotential
0.29
V
electrochemical
CO
conversion
thus
industrial
interest
current
density
being
steady
350
mA
cm–2.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 10, 2025
The
electrochemical
coupling
of
CO2
and
NO3–
on
copper-based
catalysts
presents
a
sustainable
strategy
for
urea
production
while
simultaneously
addressing
wastewater
denitrification.
However,
the
inefficient
random
adsorption
copper
surface
limits
interaction
key
carbon
nitrogen
intermediates,
thereby
impeding
efficient
C–N
coupling.
In
this
study,
we
demonstrate
that
residual
lattice
oxygen
in
oxide-derived
nanosheets
(OL-Cu)
can
effectively
tune
electron
distribution,
thus
activating
neighboring
atoms
generating
electron-deficient
(Cuδ+)
sites.
These
Cuδ+
sites
enhance
stabilize
*CO
which
enables
directional
at
adjacent
This
mechanism
shortens
pathway
achieves
yield
up
to
298.67
mmol
h–1
g–1
−0.7
V
versus
RHE,
with
an
average
Faradaic
efficiency
31.71%
high
current
density
∼95
mA
cm–2.
situ
spectroscopic
measurements
confirmed
formation
tracked
evolution
intermediates
(i.e.,
*CO,
*NO,
*OCNO,
*NOCONO)
during
synthesis.
Density
functional
theory
calculations
revealed
promote
coadsorption
*NO3,
as
well
*OCNO
significantly
improving
kinetics.
study
underscores
critical
role
facilitating
selectivity.
Advanced Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 4, 2025
Electrocatalysts
can
efficiently
convert
earth-abundant
simple
molecules
into
high-value-added
products.
In
this
context,
heterostructures,
which
are
largely
determined
by
the
interface,
have
emerged
as
a
pivotal
architecture
for
enhancing
activity
of
electrocatalysts.
review,
atomistic
understanding
heterostructured
electrocatalysts
is
considered,
focusing
on
reaction
kinetic
rate
and
electron
configuration,
gained
from
both
empirical
studies
theoretical
models.
We
start
fundamentals
microkinetic
model,
adsorption
energy
theory,
electric
double
layer
model.
The
importance
heterostructures
to
accelerate
electrochemical
processes
via
modulating
configuration
interfacial
reactive
microenvironment
highlighted,
considering
rectification,
space
charge
region,
built-in
field,
synergistic
interactions,
lattice
strain,
geometric
effect.
conclude
review
summarizing
challenges
perspectives
in
field
electrocatalysts,
such
determination
transition
state
energy,
their
dynamic
evolution,
refinement
approaches,
use
machine
learning.
Advanced Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 25, 2025
Abstract
Electrochemically
converting
carbon
dioxide
(CO
2
)
and
nitrate
(NO
3
−
into
urea
via
the
C─N
coupling
route
offers
a
sustainable
alternative
to
traditional
industrial
production
technology,
but
it
is
still
limited
by
poor
yield
rate,
low
Faradaic
efficiency,
insufficient
kinetics.
Herein,
high‐density
Ga─Y
dual‐atom
catalyst
developed
with
loading
up
14.1
wt.%
of
Ga
Y
supported
on
N,
P‐co‐doped
substrate
(Ga/Y‐CNP)
for
electrosynthesis.
The
facilitates
efficient
through
co‐reduction
CO
NO
,
resulting
in
high
rate
41.9
mmol
h
−1
g
efficiency
22.1%
at
−1.4
V
versus
reversible
hydrogen
electrode.
In
situ
spectroscopy
theoretical
calculations
reveal
that
superior
performance
attributed
cross‐tuning
between
adjacent
pair
sites,
which
can
mutually
optimize
their
electronic
states
facilitating
reduction
*CO
sites
promoting
conversion
hydroxylamine
(*NH
OH)
followed
spontaneous
*NH
OH
intermediates
form
bonds.
This
work
pioneering
strategy
manipulate
pathways
active
produce
high‐value‐added
chemicals.
