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.
ACS Nano,
Год журнала:
2024,
Номер
18(5), С. 4308 - 4319
Опубликована: Янв. 23, 2024
The
intrinsic
roadblocks
for
designing
promising
Pt-based
oxygen
reduction
reaction
(ORR)
catalysts
emanate
from
the
strong
scaling
relationship
and
activity–stability–cost
trade-offs.
Here,
a
carbon-supported
Pt
nanoparticle
Mn
single
atom
(PtNP–MnSA/C)
as
in
situ
constructed
PtNP–MnSA
pairs
are
demonstrated
to
be
an
efficient
catalyst
circumvent
above
seesaws
with
only
∼4
wt
%
loadings.
Experimental
theoretical
investigations
suggest
that
MnSA
functions
not
"assist"
sites
cooperatively
facilitate
dissociation
of
O2
due
electronic
polarization,
affording
dissociative
pathway
reduced
H2O2
production,
but
also
structure
"modulator"
downshift
d-band
center
sites,
alleviating
overbinding
oxygen-containing
intermediates.
More
importantly,
serves
"stabilizer"
endow
PtNP–MnSA/C
excellent
structural
stability
low
Fenton-like
reactivity,
resisting
fast
demetalation
metal
sites.
As
result,
PtNPs–MnSA/C
shows
ORR
performance
half-wave
potential
0.93
V
vs
reversible
hydrogen
electrode
high
mass
activity
1.77
A/mgPt
at
0.9
acid
media,
which
is
19
times
higher
than
commercial
Pt/C
declines
by
5%
after
80,000
cycles.
Specifically,
reaches
power
density
1214
mW/cm2
2.87
A/cm2
H2–O2
fuel
cell.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Март 12, 2024
Abstract
The
precise
design
of
single-atom
nanozymes
(SAzymes)
and
understanding
their
biocatalytic
mechanisms
hold
great
promise
for
developing
ideal
bio-enzyme
substitutes.
While
considerable
efforts
have
been
directed
towards
mimicking
partial
bio-inspired
structures,
the
integration
heterogeneous
SAzymes
configurations
homogeneous
enzyme-like
mechanism
remains
an
enormous
challenge.
Here,
we
show
a
spatial
engineering
strategy
to
fabricate
dual-sites
with
atomic
Fe
active
center
adjacent
Cu
sites.
Compared
planar
Fe–Cu
dual-atomic
sites,
vertically
stacked
geometry
in
FePc@2D-Cu–N–C
possesses
highly
optimized
scaffolds,
favorable
substrate
affinity,
fast
electron
transfer.
These
characteristics
SAzyme
induces
biomimetic
O
2
activation
through
homogenous
enzymatic
pathway,
resembling
functional
mechanistic
similarity
natural
cytochrome
c
oxidase.
Furthermore,
it
presents
appealing
alternative
P450
3A4
drug
metabolism
drug–drug
interaction.
findings
are
expected
deepen
fundamental
atomic-level
next-generation
nanozymes.
Advanced Functional Materials,
Год журнала:
2024,
Номер
34(29)
Опубликована: Март 17, 2024
Abstract
The
oxygen
reduction
reaction
(ORR)
plays
a
fundamental
role
in
sustainable
energy
technologies.
However,
the
creation
of
non‐precious
metal
electrocatalysts
with
high
ORR
activity
and
durability
under
all
pH
conditions
is
great
significance
but
remains
challenging.
Herein,
aim
to
overcome
this
challenge
by
creating
Fe
single
atom
catalyst
on
2D
defect‐containing
nitrogen‐doped
carbon
support
(Fe
1
/DNC)
via
microenvironment
engineering
strategy.
Microkinetic
modeling
reveals
that
FeN
4
(OH)
moieties
are
real
active
sites
conditions.
Due
synergistic
promotion
effect
denser
accessible
defect‐induced
electronic
properties,
/DNC
achieves
extraordinary
alkaline,
acidic,
neutral
conditions,
half‐wave
potentials
0.95,
0.82,
0.70
V,
respectively.
Moreover,
negligible
performance
decay
observed
stability
methanol
tolerance
tests.
Zn‐air
battery
employing
delivers
remarkable
peak
power
density
long‐term
operational
durability.
Theoretical
analysis
provides
compelling
evidence
defects
adjacent
can
endow
an
inductive
reshape
properties
balance
OOH*
formation
OH*
reduction.
This
work
offers
insight
into
regulation
asymmetric
coordination
structure
for
boosting
electrocatalytic
stability.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(15)
Опубликована: Янв. 29, 2024
Abstract
Atomically
dispersed
metal‐nitrogen‐carbon
(M‐N‐C)
catalysts
have
exhibited
encouraging
oxygen
reduction
reaction
(ORR)
activity.
Nevertheless,
the
insufficient
long‐term
stability
remains
a
widespread
concern
owing
to
inevitable
2‐electron
byproducts,
H
2
O
.
Here,
we
construct
Co‐N‐Cr
cross‐interfacial
electron
bridges
(CIEBs)
via
interfacial
electronic
coupling
between
Cr
3
and
Co‐N‐C,
breaking
activity‐stability
trade‐off.
The
partially
occupied
3d‐orbitals
of
CIEBs
induce
rearrangement
CoN
4
sites,
lowering
Co‐OOH*
antibonding
orbital
occupancy
accelerating
adsorption
intermediates.
Consequently,
suppress
two‐electron
ORR
process
approach
apex
Sabatier
volcano
plot
for
four‐electron
pathway
simultaneously.
As
proof‐of‐concept,
is
synthesized
by
molten
salt
template
method,
exhibiting
dominant
4‐electron
selectively
extremely
low
yield
confirmed
Damjanovic
kinetic
analysis.
demonstrates
impressive
bifunctional
catalytic
activity
(▵E=0.70
V)
breakthrough
durability
including
100
%
current
retention
after
10
h
continuous
operation
cycling
performance
over
1500
Zn‐air
battery.
hybrid
configuration
understanding
mechanism
reported
here
could
shed
new
light
on
design
superdurable
M‐N‐C
catalysts.
Advanced Materials,
Год журнала:
2024,
Номер
36(32)
Опубликована: Май 30, 2024
Abstract
Rechargeable
Zn–air
batteries
(ZABs)
are
promising
for
energy
storage
and
conversion.
However,
the
high
charging
voltage
low
efficiency
hinder
their
commercialization.
Herein,
these
challenges
addressed
by
employing
precisely
constructed
multifunctional
Fe–Co
diatomic
site
catalysts
(FeCo‐DACs)
integrating
iodide/iodate
redox
into
ZABs
to
create
Zinc–air/iodide
hybrid
(ZAIHBs)
with
highly
efficient
catalyst.
The
strong
coupling
between
3d
orbitals
of
Fe
Co
weakens
excessively
binding
strength
active
sites
intermediates,
enhancing
catalytic
activities
oxygen
reduction/evolution
reaction
redox.
Consequently,
FeCo‐DACs
exhibit
outstanding
bifunctional
activity
a
small
potential
gap
(Δ
E
=
0.66
V)
stability.
Moreover,
an
performance
toward
is
obtained.
Therefore,
FeCo‐DAC‐based
ZAIHBs
up
75%
at
10
mA
cm
−2
excellent
cycling
stability
(72%
after
500
h).
This
research
offers
critical
insights
rational
design
DACs
paves
way
high‐energy
devices.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(20)
Опубликована: Март 13, 2024
The
main
group
metals
are
commonly
perceived
as
catalytically
inert
in
the
context
of
oxygen
reduction
reactions
(ORR)
due
to
delocalized
valence
orbitals.
Regulating
local
environment
and
structure
metal
center
coordinated
by
nitrogen
ligands
(M-N
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(28)
Опубликована: Май 9, 2024
The
single-atom
Fe-N-C
catalyst
has
shown
great
promise
for
the
oxygen
reduction
reaction
(ORR),
yet
intrinsic
activity
is
not
satisfactory.
There
a
pressing
need
to
gain
deeper
understanding
of
charge
configuration
and
develop
rational
modulation
strategies.
Herein,
we
have
prepared
Fe
with
co-coordination
N
O
(denoted
as
Fe-N/O-C)
adjacent
defect,
proposing
strategy
optimize
d-orbital
spin-electron
filling
sites
by
fine-tuning
first
coordination
shell.
Fe-N/O-C
exhibits
significantly
better
ORR
compared
its
counterpart
commercial
Pt/C,
much
more
positive
half-wave
potential
(0.927
V)
higher
kinetic
current
density.
Moreover,
using
catalyst,
Zn-air
battery
proton
exchange
membrane
fuel
cell
achieve
peak
power
densities
up
490
1179
mW
cm
