Advanced Functional Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 21, 2025
Abstract
Advancing
energy
conversion
technologies
requires
cost‐efficient
electrocatalysts
for
the
oxygen
reduction
reaction
(ORR).
Iron
phthalocyanine
(FePc)
emerges
as
a
scalable
and
economical
ORR
electrocatalyst.
However,
Fe–N
4
configuration
in
FePc
still
falls
short
of
satisfied
activity
stability
under
electrocatalytic
conditions.
Here,
an
effective
f‐p‐d
(Eu–O–Fe)
gradient
orbital
coupling
strategy
is
introduced
by
integrating
with
Eu
2
O
3
(FePc/Eu
)
to
enhance
spin
state
performance
Fe
center
through
precisely
designed,
synthetic
approach.
The
Eu─O
bond
promotes
electron
delocalization
shifts
from
low‐spin
intermediate‐spin,
increasing
e
g
occupancy.
This
modification
optimizes
adsorption
oxygen‐containing
intermediates
lowers
barrier.
Notably,
increased
accelerates
charge
transfer
releasing
more
unpaired
electrons,
improving
kinetics.
Furthermore,
f‐band
serves
buffer
layer
compensation
during
ORR,
further
stabilizing
covalency
electronic
atomic
boosting
durability.
one‐batch
synthesis
produces
exceeding
300
g
FePc/Eu
,
achieving
half‐wave
potential
0.931
V
(vs
RHE)
at
cost
less
than
1/15
commercial
Pt/C.
It
demonstrates
exceptional
aluminum–air
batteries,
highlighting
its
significant
application
potential.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Июнь 4, 2024
Abstract
The
heteroatom
substitution
is
considered
as
a
promising
strategy
for
boosting
the
redox
kinetics
of
transition
metal
compounds
in
hybrid
supercapacitors
(HSCs)
although
dissimilar
identification
and
essential
mechanism
that
dominate
remain
unclear.
It
presented
d‐p
orbital
hybridization
between
electrolyte
ions
can
be
utilized
descriptor
understanding
kinetics.
Herein,
series
Co,
Fe
Cu
heteroatoms
are
respectively
introduced
into
Ni
3
Se
4
cathodes,
among
them,
only
moderate
Co‐substituted
hold
optimal
resulted
from
formed
more
unoccupied
antibonding
states
π*.
inevitably
enhances
interfacial
charge
transfer
ensures
balanced
OH
−
adsorption‐desorption
to
accelerate
validated
by
lowest
reaction
barrier
(0.59
eV,
matching
well
with
theoretical
calculations).
Coupling
lower
diffusion
energy
barrier,
prepared
cathode
delivers
ultrahigh
rate
capability
(~68.7
%
capacity
retention
even
current
density
increases
200
times),
an
assembled
HSC
also
presents
high
energy/power
density.
This
work
establishes
principles
determining
deciphers
underlying
effects
on
improving
performance
battery‐type
electrodes
novel
perspective
orbital‐scale
manipulation.
Advanced Energy Materials,
Год журнала:
2024,
Номер
14(12)
Опубликована: Янв. 8, 2024
Abstract
Fe─N─C
materials
with
Fe─N
4
sites
are
considered
as
most
promising
non‐precious
metal‐based
electrocatalysts
for
low‐cost
proton‐exchange‐membrane
fuel
cells
(PEMFCs).
Breaking
the
trade‐off
between
activity
and
stability
has
been
a
long‐standing
challenge
in
field
of
acidic
oxygen
reduction
reaction
(ORR).
Herein,
“top‐down”
thermally‐driven
strategy
is
developed
to
achieve
highly
active
pyrrolic
N‐coordinated
Fe
high
spin
state
atomic
cluster
(Fe
n
@Fe─N
pyrr
─C)
discover
that
neighboring
can
synergistically
stabilize
such
vulnerable
by
inhibiting
their
protonation.
Consequently,
─C
catalysts
exhibit
much
enhanced
ORR
stability,
endowing
PEMFCs
power
density
804.6
mW
cm
−2
(testing
conditions:
80
°C,
100%
RH,
2.0
bar)
over
100
h
durability
(at
0.5
V).
These
findings
open
up
opportunities
exploration
durable
other
applications.
Advanced Functional Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 21, 2025
Abstract
Advancing
energy
conversion
technologies
requires
cost‐efficient
electrocatalysts
for
the
oxygen
reduction
reaction
(ORR).
Iron
phthalocyanine
(FePc)
emerges
as
a
scalable
and
economical
ORR
electrocatalyst.
However,
Fe–N
4
configuration
in
FePc
still
falls
short
of
satisfied
activity
stability
under
electrocatalytic
conditions.
Here,
an
effective
f‐p‐d
(Eu–O–Fe)
gradient
orbital
coupling
strategy
is
introduced
by
integrating
with
Eu
2
O
3
(FePc/Eu
)
to
enhance
spin
state
performance
Fe
center
through
precisely
designed,
synthetic
approach.
The
Eu─O
bond
promotes
electron
delocalization
shifts
from
low‐spin
intermediate‐spin,
increasing
e
g
occupancy.
This
modification
optimizes
adsorption
oxygen‐containing
intermediates
lowers
barrier.
Notably,
increased
accelerates
charge
transfer
releasing
more
unpaired
electrons,
improving
kinetics.
Furthermore,
f‐band
serves
buffer
layer
compensation
during
ORR,
further
stabilizing
covalency
electronic
atomic
boosting
durability.
one‐batch
synthesis
produces
exceeding
300
g
FePc/Eu
,
achieving
half‐wave
potential
0.931
V
(vs
RHE)
at
cost
less
than
1/15
commercial
Pt/C.
It
demonstrates
exceptional
aluminum–air
batteries,
highlighting
its
significant
application
potential.
