Advanced Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 14, 2024
Abstract
Electrocatalytic
water
splitting
is
long
constrained
by
the
sluggish
kinetics
of
anodic
oxygen
evolution
reaction
(OER),
and
rational
spin‐state
manipulation
holds
great
promise
to
break
through
this
bottleneck.
Low‐spin
Fe
3+
(LS,
t
2g
5
e
g
0
)
species
are
identified
as
highly
active
sites
for
OER
in
theory,
whereas
it
still
a
formidable
challenge
construct
experimentally.
Herein,
new
strategy
demonstrated
effective
construction
LS
NiFe‐layered
double
hydroxide
(NiFe‐LDH)
introducing
multiple
defects,
which
induce
coordination
unsaturation
over
thus
enlarge
their
d
orbital
energy.
The
as‐obtained
catalyst
exhibits
extraordinary
performance
with
an
ultra‐low
overpotential
244
mV
at
industrially
required
current
density
500
mA
cm
−2
,
110
lower
than
that
conventional
NiFe‐LDH
high‐spin
(HS,
3
2
superior
most
previously
reported
NiFe‐based
catalysts.
Comprehensive
experimental
theoretical
studies
reveal
configuration
effectively
reduces
adsorption
strength
O*
intermediate
compared
HS
case,
thereby
altering
rate‐determining
step
from
(O*
→
OOH*)
(OH*
O*)
lowering
its
energy
barrier.
This
work
paves
avenue
developing
efficient
spin‐dependent
electrocatalysts
beyond.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Фев. 15, 2024
Abstract
Cobalt
oxyhydroxide
(CoOOH)
is
a
promising
catalytic
material
for
oxygen
evolution
reaction
(OER).
In
the
traditional
CoOOH
structure,
Co
3+
exhibits
low-spin
state
configuration
(
$${t}_{2{{{{{\rm{g}}}}}}}^{6}{e}_{{{{{{\rm{g}}}}}}}^{0}$$
t2g6e0
),
with
electron
transfer
occurring
in
face-to-face
$${t}_{2{{{{{\rm{g}}}}}}}^{*}$$
*
orbitals.
this
work,
we
report
successful
synthesis
of
high-spin
by
introducing
coordinatively
unsaturated
atoms.
As
compared
to
CoOOH,
occurs
apex-to-apex
$${e}_{{{{{{\rm{g}}}}}}}^{*}$$
orbitals,
which
faster
ability.
result,
performs
superior
OER
activity
an
overpotential
226
mV
at
10
mA
cm
−2
,
148
lower
than
that
CoOOH.
This
work
emphasizes
effect
spin
on
based
electrocatalysts
water
splitting,
and
thus
provides
new
strategy
designing
highly
efficient
electrocatalysts.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Фев. 26, 2024
Abstract
Efficient
oxygen
evolution
reaction
electrocatalysts
are
essential
for
sustainable
clean
energy
conversion.
However,
catalytic
materials
followed
the
conventional
adsorbate
mechanism
(AEM)
with
inherent
scaling
relationship
between
key
intermediates
*OOH
and
*OH,
or
lattice-oxygen-mediated
(LOM)
possible
lattice
migration
structural
reconstruction,
which
not
favorable
to
balance
high
activity
stability.
Herein,
we
propose
an
unconventional
Co-Fe
dual-site
segmentally
synergistic
(DSSM)
single-domain
ferromagnetic
catalyst
CoFeS
x
nanoclusters
on
carbon
nanotubes
(CNT)
(CFS-ACs/CNT),
can
effectively
break
without
sacrificing
Co
3+
(L.S,
t
2g
6
e
g
0
)
supplies
strongest
OH*
adsorption
energy,
while
Fe
(M.S,
4
1
exposes
strong
O*
adsorption.
These
dual-sites
synergistically
produce
of
Co-O-O-Fe
intermediates,
thereby
accelerating
release
triplet-state
(
↑
O
=
).
As
predicted,
prepared
CFS-ACs/CNT
exhibits
less
overpotential
than
that
commercial
IrO
2
,
as
well
approximately
633
h
stability
significant
potential
loss.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(49)
Опубликована: Окт. 21, 2023
The
electrolyte
cations-dependent
kinetics
have
been
widely
observed
in
many
fields
of
electrocatalysis,
however,
the
exact
mechanism
influence
on
catalytic
performance
is
still
a
controversial
topic
considerable
discussion.
Herein,
combined
with
operando
X-ray
diffraction
(XRD)
and
high-resolution
transmission
electron
microscopy
(HRTEM),
we
verify
that
cations
could
intercalate
into
layer
pristine
CoOOH
catalyst
during
oxygen
evolution
reaction
(OER)
process,
while
bigger
lead
to
enlarged
interlayer
spacing
increased
OER
activity,
following
order
Cs+
>K+
>Na+
>Li+
.
absorption
spectroscopy
(XAS),
situ
Raman,
Ultraviolet-visible
(UV/Vis)
spectroscopy,
XAS
cyclic
voltammetry
(CV),
theoretical
calculations
reveal
intercalation
efficiently
modify
oxidation
states
Co
by
enlarging
Co-O
bonds,
which
turn
enhance
d-band
center
Co,
optimize
adsorption
strength
intermediates,
facilitate
formation
active
Co(IV)
species,
reduce
energy
barrier
rate-determing
step
(RDS),
thereby
enhancing
activity.
This
work
not
only
provides
an
informative
picture
understand
complicated
dependence
cations,
but
also
sheds
light
understanding
other
cation-targeted
electrocatalysis.
Advanced Materials,
Год журнала:
2023,
Номер
36(13)
Опубликована: Окт. 12, 2023
The
air
electrode
is
an
essential
component
of
air-demanding
energy
storage/conversion
devices,
such
as
zinc-air
batteries
(ZABs)
and
hydrogen
fuel
cells
(HFCs),
which
determines
the
output
power
stability
devices.
Despite
atom-level
modulation
in
catalyst
design
being
recently
achieved,
electrodes
have
received
much
less
attention,
causing
a
stagnation
development
equipment.
Herein,
evolution
for
ZABs
HFCs
from
early
stages
to
current
requirements
reviewed.
In
addition,
operation
mechanism
corresponding
electrocatalytic
mechanisms
are
summarized.
particular,
by
clarifying
interfaces
at
different
scales,
several
approaches
improve
rechargeable
reviewed,
including
innovative
structures
bifunctional
oxygen
catalysts.
Afterward,
operating
proton-exchange-membrane
(PEMFCs)
anion-exchange-membrane
(AEMFCs)
explained.
Subsequently,
strategies
employed
enhance
efficiency
membrane
assembly
(MEA)
PEMFCs
AEMFCs,
respectively,
highlighted
discussed
detail.
Last,
prospects
considered
discussing
main
challenges.
aim
this
review
facilitate
industrialization
HFCs.
Abstract
Ammonia,
a
vital
component
in
the
synthesis
of
fertilizers,
plastics,
and
explosives,
is
traditionally
produced
via
energy‐intensive
environmentally
detrimental
Haber–Bosch
process.
Given
its
considerable
energy
consumption
significant
greenhouse
gas
emissions,
there
growing
shift
toward
electrocatalytic
ammonia
as
an
eco‐friendly
alternative.
However,
developing
efficient
electrocatalysts
capable
achieving
high
selectivity,
Faraday
efficiency,
yield
under
ambient
conditions
remains
challenge.
This
review
delves
into
decades‐long
research
synthesis,
highlighting
evolution
fundamental
principles,
theoretical
descriptors,
reaction
mechanisms.
An
in‐depth
analysis
nitrogen
reduction
(NRR)
nitrate
(NitRR)
provided,
with
focus
on
their
electrocatalysts.
Additionally,
theories
behind
electrocatalyst
design
for
are
examined,
including
Gibbs
free
approach,
Sabatier
principle,
d
‐band
center
theory,
orbital
spin
states.
The
culminates
comprehensive
overview
current
challenges
prospective
future
directions
development
NRR
NitRR,
paving
way
more
sustainable
methods
production.
Chemical Society Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
This
review
systematically
summarizes
recent
advanced
strategies
for
manipulating
electron
spin
to
optimize
photocatalysis.
It
provides
valuable
insights
guide
future
research
on
control
enhancing
photocatalytic
applications.
