The Journal of Physical Chemistry Letters,
Год журнала:
2024,
Номер
15(4), С. 1121 - 1129
Опубликована: Янв. 24, 2024
Using
first-principles
calculations
combined
with
a
constant-potential
implicit
solvent
model,
we
comprehensively
studied
the
activity
of
oxygen
electrode
reactions
catalyzed
by
electride-supported
FeN4-embedded
graphene
(FeN4Cx).
The
physical
quantities
in
FeN4Cx/electrides,
i.e.,
work
function
electrides,
interlayer
spacing,
stability
heterostructures,
charge
transferred
to
Fe,
d-band
center
and
adsorption
free
energy
O,
are
highly
intercorrelated,
resulting
being
fully
expressed
nature
electrides
themselves,
thereby
achieving
precise
modulation
selecting
different
electrides.
Strikingly,
FeN4PDCx/Ca2N
FeN4PDCx/Y2C
systems
maintain
high
evolution
reaction
(OER)
reduction
(ORR)
overpotential
less
than
0.46
0.62
V
wide
pH
range.
This
provides
an
effective
strategy
for
rational
design
efficient
bifunctional
catalysts
as
well
model
system
simple
activity-descriptor,
helping
realize
significant
advances
devices.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(8), С. 5532 - 5542
Опубликована: Фев. 16, 2024
The
electrochemical
carbon
dioxide
reduction
reaction
(CO2RR)
toward
C2
products
is
a
promising
way
for
the
clean
energy
economy.
Modulating
structure
of
electric
double
layer
(EDL),
especially
interfacial
water
and
cation
type,
useful
strategy
to
promote
C–C
coupling,
but
atomic
understanding
lags
far
behind
experimental
observations.
Herein,
we
investigate
combined
effect
alkali
metal
cations
on
coupling
at
Cu(100)
electrode/electrolyte
interface
using
ab
initio
molecular
dynamics
(AIMD)
simulations
with
constrained
MD
slow-growth
approach.
We
observe
linear
correlation
between
water-adsorbate
stabilization
effect,
which
manifests
as
hydrogen
bonds,
corresponding
alleviation
in
free
energy.
role
larger
cation,
compared
smaller
(e.g.,
K+
vs
Li+),
lies
its
ability
approach
through
desolvation
coordinates
*CO+*CO
moiety,
partially
substituting
hydrogen-bonding
stabilizing
water.
Although
this
only
results
marginal
barrier
it
creates
local
hydrophobic
environment
scarcity
bonds
owing
great
ionic
radius,
impeding
surrounding
oxygen
adsorbed
*CO.
This
skillfully
circumvents
further
hydrogenation
*CO
C1
pathway,
serving
predominant
factor
facilitates
coupling.
study
unveils
comprehensive
mechanism
cation–water–adsorbate
interactions
that
can
facilitate
optimization
electrolyte
EDL
efficient
CO2RR.
Advanced Functional Materials,
Год журнала:
2024,
Номер
34(32)
Опубликована: Март 25, 2024
Abstract
Understanding
of
fundamental
mechanism
and
kinetics
the
oxygen
evolution
reaction
(OER)
is
pivotal
for
designing
efficient
OER
electrocatalysts
owing
to
its
key
role
in
electrochemical
energy
conversion
devices.
In
past
few
years,
lattice
oxidation
(LOM)
arising
from
anodic
redox
chemistry
has
attracted
significant
attention
as
it
involves
a
direct
O─O
coupling
thus
bypasses
thermodynamic
limitations
traditional
adsorbate
(AEM).
Transition
metal‐based
oxyhydroxides
are
generally
acknowledged
real
catalytic
phase
alkaline
media.
particular,
their
low‐dimensional
layered
structures
offer
sufficient
structural
flexibility
trigger
LOM.
Herein,
comprehensive
overview
provided
recent
advances
anion
LOM‐based
electrocatalysts.
Based
on
analyses
electronic
structure
LOM,
strategy
proposed
activate
Possible
identification
techniques
corroboration
also
reviewed.
addition,
reconstruction
process
induced
by
LOM
focused
importance
multiple
situ/operando
characterizations
highlighted
unveil
chemical
origins
To
conclude,
prospect
remaining
challenges
future
opportunities
presented.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(22), С. 15640 - 15647
Опубликована: Май 21, 2024
Single-atom
catalysts
(SACs)
have
been
widely
investigated
and
emerged
as
a
transformative
approach
in
electrocatalysis.
Despite
their
clear
structure,
the
origin
of
exceptional
activity
remains
elusive.
Herein,
we
elucidate
common
phenomenon
hybridization
state
transition
metal
centers,
which
is
responsible
for
across
various
SACs
different
reactions.
Focusing
on
N-doped
carbon-supported
Ni
SAC
(NiN4
SAC)
CO2
reduction
reaction
(CO2RR),
our
comprehensive
computations
successfully
clarify
under
working
conditions
its
relation
with
activity.
This
transition,
triggered
by
intermediates
applied
potential,
converts
center
from
inert
dsp2
to
active
d2sp3
state.
Importantly,
calculated
selectivity
CO2RR
over
d2sp3-hybridized
are
consistent
experimental
results,
offering
strong
support
proposed
hypothesis.
work
suggests
universal
principle
electronic
structure
evolution
that
could
revolutionize
catalyst
design,
also
introduces
new
paradigm
manipulating
states
enhance
catalytic
performance,
implications
reactions
platforms.
Accounts of Chemical Research,
Год журнала:
2024,
Номер
57(2), С. 198 - 207
Опубликована: Янв. 3, 2024
ConspectusSingle
atom
electrocatalysts,
with
noble
metal-free
composition,
maximal
efficiency,
and
exceptional
reactivity
toward
various
energy
environmental
applications,
have
become
a
research
hot
spot
in
the
recent
decade.
Their
simplicity
isolated
nature
of
atomic
structure
their
active
site
also
made
them
an
ideal
model
catalyst
system
for
studying
reaction
mechanisms
activity
trends.
However,
state
single
sites
during
electrochemical
reactions
may
not
be
as
simple
is
usually
assumed.
To
contrary,
electrocatalysts
been
reported
to
under
greater
influence
from
interfacial
dynamics,
solvent
electrolyte
ions
perpetually
interacting
electrified
center
applied
electrode
potential.
These
complexities
render
trends
derived
simplistic
models
dubious.In
this
Account,
few
popular
electrocatalysis
systems,
we
show
how
change
potential
induces
nontrivial
variation
free
profile
elemental
steps,
demonstrate
centers
different
electronic
features
can
induce
solvation
structures
at
interface
even
same
intermediate
simplest
reaction,
discuss
implication
on
kinetics
thermodynamics
better
address
selectivity
We
venture
into
more
intriguing
phenomena,
such
alternative
pathways
intermediates
that
are
favored
stabilized
by
polarization
effects,
long-range
dynamics
across
region
far
beyond
contact
layer,
dynamic
activation
or
deactivation
operation
conditions.
necessity
including
realistic
aspects
(explicit
solvent,
electrolyte,
potential)
correctly
capture
physics
chemistry
understand
design
principles
fail
they
revised
factors
model.
All
these
rich
would
remain
hidden
overlooked
otherwise.
believe
complexity
curse
but
blessing
it
enables
deeper
understanding
finer
control
potential-dependent
landscape
reactions,
which
opens
up
new
dimensions
further
optimization
beyond.
Limitations
current
methods
challenges
faced
theoretical
experimental
communities
discussed,
along
possible
solutions
awaiting
development
future.
Chemical Reviews,
Год журнала:
2024,
Номер
124(14), С. 8620 - 8656
Опубликована: Июль 11, 2024
Heterogeneous
electrocatalysis
lies
at
the
center
of
various
technologies
that
could
help
enable
a
sustainable
future.
However,
its
complexity
makes
it
challenging
to
accurately
and
efficiently
model
an
atomic
level.
Here,
we
review
emerging
atomistic
methods
simulate
electrocatalytic
interface
with
special
attention
devoted
components/effects
have
been
model,
such
as
solvation,
electrolyte
ions,
electrode
potential,
reaction
kinetics,
pH.
Additionally,
relevant
computational
spectroscopy
methods.
Then,
showcase
several
examples
applying
these
understand
design
catalysts
green
hydrogen.
We
also
offer
experimental
views
on
how
bridge
gap
between
theory
experiments.
Finally,
provide
some
perspectives
opportunities
advance
field.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(24), С. 16499 - 16510
Опубликована: Июнь 11, 2024
Reducing
iridium
(Ir)
catalyst
loading
for
acidic
oxygen
evolution
reaction
(OER)
is
a
critical
strategy
large-scale
hydrogen
production
via
proton
exchange
membrane
(PEM)
water
electrolysis.
However,
simultaneously
achieving
high
activity,
long-term
stability,
and
reduced
material
cost
remains
challenging.
To
address
this
challenge,
we
develop
framework
by
combining
density
functional
theory
(DFT)
prediction
using
model
surfaces
proof-of-concept
experimental
verification
thin
films
nanoparticles.
DFT
results
predict
that
oxidized
Ir
monolayers
over
titanium
nitride
(IrOx/TiN)
should
display
higher
OER
activity
than
IrOx
while
reducing
loading.
This
verified
depositing
TiN
physical
vapor
deposition.
The
promising
film
are
then
extended
to
commercially
viable
powder
IrOx/TiN
catalysts,
which
demonstrate
lower
overpotential
mass
commercial
IrO2
stability
of
250
h
maintain
current
10
mA
cm–2.
superior
performance
further
confirmed
electrolyzer
(PEMWE),
shows
cell
voltage
achieve
1
A
Both
in
situ
X-ray
absorption
spectroscopy
reveal
the
strongly
depends
on
IrOx-TiN
interaction
direct
Ir–Ti
bonding.
study
highlights
importance
close
between
theoretical
based
mechanistic
understanding
catalysts
facilitate
development
more
practical
with
OER.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 9, 2025
Single-atom
catalysts
(SACs)
with
metal–nitrogen–carbon
(M–N–C)
structures
are
widely
recognized
as
promising
candidates
in
oxygen
reduction
reactions
(ORR).
According
to
the
classical
Sabatier
principle,
optimal
3d
metal
catalysts,
such
Fe/Co–N–C,
achieve
superior
catalytic
performance
due
moderate
binding
strength.
However,
substantial
ORR
activity
demonstrated
by
weakly
M–N–C
Ni/Cu–N–C
challenges
current
understandings,
emphasizing
need
explore
new
underlying
mechanisms.
In
this
work,
we
integrated
a
pH-field
coupled
microkinetic
model
detailed
experimental
electron
state
analyses
verify
novel
key
step
reaction
pathway
of
weak-binding
SACs─the
adsorption
at
metal–nitrogen
bridge
site.
This
significantly
altered
scaling
relations,
electric
field
responses,
and
solvation
effects,
further
impacting
kinetic
barrier
from
HOO*
O*
pH-dependent
performance.
Synchrotron
spectra
analysis
provides
evidence
for
model,
showing
an
increase
density
on
antibonding
π
orbitals
N
atoms
confirming
presence
N–O
bonds.
These
findings
redefine
understanding
catalyst
behavior,
opening
up
perspectives
their
application
clean
energy.
Chemical Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 16, 2025
The
application
of
external
electric
fields
to
influence
chemical
reactions
at
electrode
interfaces
has
attracted
considerable
interest
in
recent
years.
However,
the
design
achieve
highly
efficient
and
selective
catalytic
systems,
akin
optimized
found
enzyme
active
sites,
remains
a
significant
challenge.
Consequently,
there
been
substantial
effort
probing
understanding
interfacial
electrode/electrolyte
their
effect
on
adsorbates.
In
this
review,
we
examine
advances
experimental,
computational,
theoretical
studies
field,
origin
vibrational
Stark
adsorbates
surfaces,
effects
interfaces.
We
also
discuss
control
charge
transfer
using
magnetic
fields.
Finally,
outline
perspectives
key
areas
for
future
studies.
Advanced Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 3, 2025
The
controlled
formation
of
a
functional
adlayer
at
the
catalyst-water
interface
is
highly
challenging
yet
potentially
powerful
strategy
to
accelerate
proton
transfer
and
deprotonation
for
ultimately
improving
performance
proton-exchange
membrane
water
electrolysis
(PEMWE).
In
this
study,
synthesis
robust
vinylene-linked
covalent
organic
frameworks
(COFs)
possessing
high
conductivities
reported,
which
are
subsequently
hybridized
with
ruthenium
dioxide
yielding
high-performance
anodic
catalysts
acidic
oxygen
evolution
reaction
(OER).
situ
spectroscopic
measurements
corroborated
by
theoretical
calculations
reveal
that
assembled
hydrogen
bonds
formed
between
COFs
adsorbed
oxo-intermediates
effectively
orient
interfacial
molecules,
stabilizing
transition
states
intermediate
OER.
This
determines
decrease
in
energy
barriers
deprotonation,
resulting
exceptional
OER
performance.
When
integrated
into
PEMWE
device,
system
achieves
record
current
density
1.0
A
cm-2
only
1.54
V
cell
voltage,
long-term
stability
exceeding
180
h
industrial-level
200
mA
cm-2.
approach
relying
on
self-assembly
an
oriented
hydrogen-bonded
highlights
disruptive
potential
customizable
structures
multifunctional
sites
advancing
technologies.