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.
Interdisciplinary materials,
Год журнала:
2023,
Номер
2(3), С. 390 - 415
Опубликована: Май 1, 2023
Abstract
The
chief
culprit
impeding
the
commercialization
of
lithium–sulfur
(Li–S)
batteries
is
parasitic
shuttle
effect
and
restricted
redox
kinetics
lithium
polysulfides
(LiPSs).
To
circumvent
these
key
stumbling
blocks,
incorporating
electrocatalysts
with
rational
electronic
structure
modulation
into
sulfur
cathode
plays
a
decisive
role
in
vitalizing
higher
electrocatalytic
activity
to
promote
utilization
efficiency.
Breaking
stereotype
contemporary
electrocatalyst
design
kept
on
pretreatment,
field‐assisted
offer
strategic
advantages
dynamically
controllable
electrochemical
reactions
that
might
be
thorny
regulate
conventional
processes.
However,
highly
interdisciplinary
electrochemistry
puzzles
researchers
for
fundamental
understanding
ambiguous
correlations
among
structure,
surface
adsorption
properties,
catalytic
performance.
In
this
review,
mechanisms,
functionality
explorations,
including
electric,
magnetic,
light,
thermal,
strain
fields
Li–S
have
been
summarized.
By
demonstrating
pioneering
work
customized
geometric
configuration,
energy
band
engineering,
optimal
microenvironment
arrangement
response
decreased
activation
enriched
reactant
concentration
accelerated
kinetics,
cutting‐edge
insights
holistic
periscope
charge‐spin‐orbital‐lattice
interplay
between
LiPSs
are
scrutinized,
which
aspires
advance
comprehensive
complex
batteries.
Finally,
future
perspectives
provided
inspire
innovations
capable
defeating
existing
restrictions.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(47)
Опубликована: Авг. 23, 2024
Abstract
Although
the
electronic
state
of
catalysts
is
strongly
corrected
with
their
oxygen
evolution
reaction
(OER)
performances,
understanding
role
spin
in
dynamic
structure
during
OER
process
still
challenging.
Herein,
we
developed
a
regulation
strategy
to
boost
performance
CoOOH
through
elemental
doping
(CoMOOH,
M=V,
Cr,
Mn,
Co
and
Cu).
Experimental
results
including
magnetic
characterization,
situ
X‐ray
absorption
spectroscopy,
Raman
density
functional
theory
calculations
unveil
that
Mn
could
successfully
increase
sites
from
low
intermediate
state,
leading
largest
lattice
distortion
smallest
energy
gap
between
d
xy
z
2
orbitals
among
obtained
CoMOOH
electrocatalysts.
Benefiting
promoted
electron
transfer
orbital,
facilitated
formation
active
high‐valent
*O−Co
(IV)
species
at
applied
potential,
reduced
barrier
rate‐determining
step,
CoMnOOH
exhibits
highest
performance.
Our
work
provides
significant
insight
into
correction
by
metal
oxyhydroxides,
paving
new
avenue
for
rational
design
high‐activity
Advanced Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 17, 2024
Abstract
Understanding
the
spin‐dependent
activity
of
nitrogen‐coordinated
single
metal
atom
(M‐N‐C)
electrocatalysts
for
oxygen
reduction
and
evolution
reactions
(ORR
OER)
remains
challenging
due
to
lack
structure‐defined
catalysts
effective
spin
manipulation
tools.
Herein,
both
challenges
using
a
magnetic
field
integrated
heterogeneous
molecular
electrocatalyst
prepared
by
anchoring
cobalt
phthalocyanine
(CoPc)
deposited
carbon
black
on
polymer‐protected
magnet
nanoparticles,
are
addressed.
The
built‐in
can
shift
Co
center
from
low‐
high‐spin
(HS)
state
without
atomic
structure
modification,
affording
one‐order
higher
turnover
frequency,
50%
increased
H
2
O
selectivity
ORR,
≈4000%
magnetocurrent
enhancement
OER.
This
catalyst
significantly
minimize
usage,
enabling
safe
continuous
production
pure
solution
100
h
cm
electrolyzer.
new
strategy
demonstrated
here
also
applies
other
phthalocyanine‐based
catalysts,
offering
universal
platform
studying
spin‐related
electrochemical
processes.
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.
