Advanced Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 25, 2025
Abstract
To
overcome
the
challenges
of
low
catalytic
activity
and
instability,
a
molecular
weight
engineering
strategy
coupled
with
oxidative
ammonolysis
is
developed
to
synthesize
CoRu‐based
alloy
catalysts
distinct
morphologies
properties
from
biorefinery
lignin.
This
approach
effectively
modulates
intrinsic
active
sites
exposes
unsaturated
nitrogen‐oxygen
structures,
thereby
tailoring
morphology
defect
structure
carbon
layers
in
catalysts.
The
as‐synthesized
CoRu
lignin
precursors
varying
weights
are
designated
as
CoRu@OALC‐EtOAC,
CoRu@OALC‐EtOH,
CoRu@OALC‐Residual.
featuring
defect‐rich
graphitic
carbon‐coated
structure,
exhibited
exceptional
overall
water‐splitting
performance
(1.48
V
at
10
mA
cm
−2
),
significantly
surpassing
Pt/C
||
Ru/C
(1.58
).
In
contrast,
CoRu@OALC‐Residual,
its
amorphous
demonstrated
remarkable
stability
(350
h
100
vastly
outperforming
(6
In‐situ
Raman
spectroscopy
DFT
calculations
revealed
that
adsorb
*
H
intermediates,
accelerating
process.
strong
adsorption
also
induces
layer
rearrangement,
leading
dissolution
oxidation
metal
particles.
provides
universal
method
for
biomass‐derived
catalysts,
establishing
direct
relationship
between
weight,
catalyst
morphology,
electrocatalytic
performance.
Abstract
Modulating
electronic
structure
to
balance
the
requirement
of
both
hydrogen
evolution
reaction
(HER)
and
oxygen
(OER)
is
crucial
for
developing
bifunctional
catalysts.
Herein,
phase
transformation
engineering
utilized
separately
regulate
catalyst
structure,
designed
NiFe@Ni/Fe‐MnOOH
schottky
heterojunction
exhibits
remarkable
electrocatalytic
activity
with
low
overpotentials
19
230
mV
at
10
mA
cm
−2
HER
OER
in
1M
KOH,
respectively.
Meanwhile,
an
anion‐exchange
membrane
water
electrolyzer
employing
as
electrodes
shows
voltages
1.487/1.953
V
10/1000
,
operating
over
200
h
1000
.
Combining
theoretical
calculations
experiments
reveal
that
can
differentially
active
phases
HER/OER.
In
HER,
Ni/Fe‐MnOOH
metallic
NiFe
act
*OH
*H
acceptors
respectively
accelerates
dissociation
subsequent
Heyrovsky/Tafel
step.
While
OER,
significant
Jahn‐Teller
effect
Mn
3+
induces
surface
reconstruction
from
Ni/Fe‐MnO
2
The
formative
high
value
4+
modify
M‐O
hybridization
activate
lattice
mechanism,
which
pivotal
breaking
restriction
volcanic
relationship
reducing
overpotential.
These
findings
provide
valuable
design
guidelines
high‐performance
multi‐functional
electrocatalysts
via
engineering.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 24, 2025
Earth-abundant
3d-orbital
late
transition
metals
are
the
most
used
and
highly
desired
catalysts
for
oxygen
evolution
reaction
(OER)
but
prone
to
quick
oxidative
dissolution,
leading
poor
durability.
We
first
report
that
FeCoNiCu
multielemental
alloy
nanoparticles
(MEA
NPs)
can
be
stabilized
with
only
0.3
at.
%
Pd,
a
4d-orbital
element.
Although
pure
Pd
is
known
extremely
OER
activity
durability,
Pd-FeCoNiCu
sustains
1000
h
at
10
mA
cm-2.
In
an
accelerating
durability
test
(ADT)
100
cm-2,
it
exhibits
mere
8.9
mV
increase
over
25
degradation
rate
of
0.356
h-1,
which
1/350th
(125
h-1)
among
stable
reported
so
far.
Aberration-corrected
HAADF-STEM
X-ray
absorption
fine
structure
(XAFS)
reveal
atomically
dispersed
atoms,
surrounded
by
Fe,
Co,
Ni,
Cu
contributed
more
delocalized
electronic
stronger
bonding
via
strong
d-d/sp
hybridization
vibronic
coupling
induced
atomic
displacement.
The
altered
local
density
states
(LDOS)
mitigates
oxidation
in
50%,
quantified
hard
photoelectron
spectroscopy
(HAXPES),
making
combination
these
five
dissoluble
elements
durable
catalyst.
Advanced Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 25, 2025
Abstract
To
overcome
the
challenges
of
low
catalytic
activity
and
instability,
a
molecular
weight
engineering
strategy
coupled
with
oxidative
ammonolysis
is
developed
to
synthesize
CoRu‐based
alloy
catalysts
distinct
morphologies
properties
from
biorefinery
lignin.
This
approach
effectively
modulates
intrinsic
active
sites
exposes
unsaturated
nitrogen‐oxygen
structures,
thereby
tailoring
morphology
defect
structure
carbon
layers
in
catalysts.
The
as‐synthesized
CoRu
lignin
precursors
varying
weights
are
designated
as
CoRu@OALC‐EtOAC,
CoRu@OALC‐EtOH,
CoRu@OALC‐Residual.
featuring
defect‐rich
graphitic
carbon‐coated
structure,
exhibited
exceptional
overall
water‐splitting
performance
(1.48
V
at
10
mA
cm
−2
),
significantly
surpassing
Pt/C
||
Ru/C
(1.58
).
In
contrast,
CoRu@OALC‐Residual,
its
amorphous
demonstrated
remarkable
stability
(350
h
100
vastly
outperforming
(6
In‐situ
Raman
spectroscopy
DFT
calculations
revealed
that
adsorb
*
H
intermediates,
accelerating
process.
strong
adsorption
also
induces
layer
rearrangement,
leading
dissolution
oxidation
metal
particles.
provides
universal
method
for
biomass‐derived
catalysts,
establishing
direct
relationship
between
weight,
catalyst
morphology,
electrocatalytic
performance.
