Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 2, 2025
Developing
cost-effective
electrocatalysts
for
efficient
seawater
splitting
requires
a
fundamental
understanding
of
the
oxygen
evolution
reaction
(OER)
mechanism.
Herein,
iron-doped
nickel
phosphide
(Fe-Ni2P)
is
synthesized
via
hydrothermal-impregnation-phosphidation
strategy
to
investigate
role
Fe
incorporation
in
modulating
electronic
structure
and
OER
pathways.
Mechanistic
investigations
demonstrate
that
doping
triggers
shift
from
adsorbate
mechanism
(AEM)
lattice
oxygen-mediated
(LOM)
pathways,
evidenced
by
pH-dependent
kinetics,
tetramethylammonium
cation
probing,
situ
electrochemical
impedance
spectroscopy
(EIS).
The
LOM
involves
nonconcerted
proton-electron
transfers,
facilitated
accelerated
hydroxide
adsorption
(ks
=
0.275
s-1)
dynamic
surface
reconstruction
into
amorphous
NiOOH.
reduced
activation
energy
(27.1
kJ
mol-1)
lower
charge-transfer
resistance
Fe-Ni2P
underscore
its
superior
thermodynamics
kinetics.
X-ray
photoelectron
EIS
further
validate
vacancy
accumulation
during
process.
Electrochemical
studies
reveal
exhibits
low
overpotential
220
mV
at
10
mA
cm-2
remarkable
stability
through
phosphate-mediated
Cl-
repulsion
involving
alkaline
seawater.
This
work
establishes
Fe-induced
modulation
as
critical
activating
LOM-dominated
catalysis
transition
metal
phosphides.
Advanced Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 15, 2025
Abstract
Oxygen
evolution
reaction
(OER)
is
a
cornerstone
of
various
electrochemical
energy
conversion
and
storage
systems,
including
water
splitting,
CO
2
/N
reduction,
reversible
fuel
cells,
rechargeable
metal‐air
batteries.
OER
typically
proceeds
through
three
primary
mechanisms:
adsorbate
mechanism
(AEM),
lattice
oxygen
oxidation
(LOM),
oxide
path
(OPM).
Unlike
AEM
LOM,
the
OPM
via
direct
oxygen–oxygen
radical
coupling
that
can
bypass
linear
scaling
relationships
intermediates
in
avoid
catalyst
structural
collapse
thereby
enabling
enhanced
catalytic
activity
stability.
Despite
its
unique
advantage,
electrocatalysts
drive
remain
nascent
are
increasingly
recognized
as
critical.
This
review
discusses
recent
advances
OPM‐based
electrocatalysts.
It
starts
by
analyzing
mechanisms
guide
design
Then,
several
types
novel
materials,
atomic
ensembles,
metal
oxides,
perovskite
molecular
complexes,
highlighted.
Afterward,
operando
characterization
techniques
used
to
monitor
dynamic
active
sites
examined.
The
concludes
discussing
research
directions
advance
toward
practical
applications.
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 29, 2025
Efficient
and
stable
nonprecious
metal-based
oxygen
evolution
reaction
(OER)
electrocatalysts
are
pivotal
for
water
electrolysis
technology.
Herein,
we
reporting
an
effective
strategy
fabricating
efficient
Co-based
OER
by
low-level
Fe
doping
in
CoMoO4
to
boost
surface
reconstruction
electronic
modulation,
which
resulted
excellent
electroactivity
consequently.
Our
findings
reveal
that
a
mere
5.30%
(wt
%)
of
can
raise
the
O
2p
band
center
energy
nearer
Fermi
level,
reduce
barrier
vacancy
(VO)
formation,
significantly
enhance
electrocatalytic
activity.
Additionally,
fast
dissolution
Mo
initial
facilitated
form
active
oxyhydroxide
species
stabilized
Co
from
leaching.
As
result,
optimized
catalyst
Fe-CoMoO4-0.2
exhibited
low
overpotential
276
mV
at
10
mA
cm-2
1
M
KOH
operate
stably
current
density
20
least
24
h
under
splitting
conditions.
This
work
provides
example
regulating
structure
properties
catalysts.
ACS Applied Materials & Interfaces,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 1, 2025
Rare-earth
elements
include
15
kinds
of
lanthanides
as
well
Sc
and
Y
elements.
Interestingly,
the
special
electronic
configuration
a
lanthanide
rare
earth
is
[Xe]4fn5d0–16s2
(n
=
0–14),
which
results
in
rare-earth
materials'
unique
activity
such
areas
thermal
catalysis,
electrocatalysis,
photocatalysis,
etc.
It
worth
noting
that
class
materials
with
spatial
confinement
effects
are
playing
an
increasingly
important
role
catalytic
performance;
especially,
construction
hollow
multishelled
structures
(HoMSs)
can
further
enhance
materials.
In
this
review,
we
discuss
depth
roles
4f5d
structure.
Subsequently,
review
systematically
summarizes
synthesis
methods
HoMSs
their
research
progress
field
catalysis
specifically
introduces
advanced
characterization
analysis
HoMSs.
Finally,
directions,
application
prospects,
challenges
need
to
be
focused
on
future
rare-earth-based
discussed
anticipated.
We
believe
will
not
only
inspire
more
creativity
optimizing
local
structure
design
catalysts
but
also
provide
valuable
insights
for
designing
other
types
catalysts.
Advanced Functional Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 26, 2025
Abstract
As
a
key
reaction
in
water
electrolysis
and
fuel
cells,
the
oxygen
evolution
(OER)
involves
sluggish
four‐electron
proton
transfer
process.
Understanding
OER
pathways
kinetics
is
critical
for
designing
efficient
electrocatalysts.
In
this
study,
through
density
functional
theory
(DFT)
calculations,
it
demonstrated
that
incorporation
of
Gd
into
Fe‐doped
NiO
elevates
O
2
p
band
center
generates
more
unoccupied
states.
Furthermore,
promotes
formation
vacancies,
which,
together,
enhance
lattice
oxidation
mechanism
(LOM)
pathway
OER.
The
adsorption‐free
energy
diagrams
confirm
doping
significantly
lowers
theoretical
overpotentials
at
both
Fe
Ni
sites
NiO,
thereby
improving
activity.
Based
on
these
findings,
co‐doped
ultrathin
nanosheets
are
synthesized
via
spray
combustion.
an
catalyst,
material
exhibited
low
overpotential
227
mV,
which
40
mV
lower
than
long‐term
catalytic
stability
over
150
h.
anion
exchange
membrane
system,
stable
performance
120
h
current
20
mA
cm
−2
.
