Advanced Materials,
Год журнала:
2024,
Номер
36(19)
Опубликована: Фев. 12, 2024
Abstract
Dual‐metal
center
catalysts
(DMCs)
have
shown
the
ability
to
enhance
oxygen
reduction
reaction
(ORR)
owing
their
distinctive
structural
configurations.
However,
precise
modulation
of
electronic
structure
and
in‐depth
understanding
synergistic
mechanisms
between
dual
metal
sites
DMCs
at
atomic
level
remain
challenging.
Herein,
mimicking
ferredoxin,
Fe‐based
(Fe
2
N
6
‐S)
are
strategically
designed
fabricated,
in
which
additional
Fe
S
synchronously
installed
near
serve
as
“dual
modulators”
for
coarse‐
fine‐tuning
modulation,
respectively.
The
as‐prepared
‐S
catalyst
exhibits
enhanced
ORR
activity
outstanding
Zinc‐air
(Zn–air)
battery
performance
compared
conventional
single
site
catalysts.
theoretical
experimental
results
reveal
that
introducing
second
creates
a
adsorption
alters
O
configuration
effectively
activates
O─O
bond,
while
effect
downward
shift
d‐band
center,
facilitating
release
OH*.
Additionally,
local
engineering
heteroatom
further
facilitates
formation
rate‐determining
step
OOH*,
thus
accelerating
kinetics.
Advanced Functional Materials,
Год журнала:
2023,
Номер
33(20)
Опубликована: Фев. 22, 2023
Abstract
Developing
low‐cost
single‐atom
catalysts
(SACs)
with
high‐density
active
sites
for
oxygen
reduction/evolution
reactions
(ORR/OER)
are
desirable
to
promote
the
performance
and
application
of
metal–air
batteries.
Herein,
Fe
nanoparticles
precisely
regulated
single
atoms
supported
on
waste
biomass
corn
silk
(CS)
based
porous
carbon
ORR
OER.
The
distinct
hierarchical
structure
hollow
tube
morphology
critical
boosting
ORR/OER
through
exposing
more
accessible
sites,
providing
facile
electron
conductivity,
facilitating
mass
transfer
reactant.
Moreover,
enhanced
intrinsic
activity
is
mainly
ascribed
high
(4.3
wt.%)
loading
content
in
as‐synthesized
catalyst.Moreover,
ultra‐high
N
doping
(10
can
compensate
insufficient
OER
conventional
FeNC
catalysts.
When
as‐prepared
assembled
as
air‐electrodes
flexible
Zn–air
batteries,
they
perform
a
peak
power
density
101
mW
cm
−2
,
stable
discharge–charge
voltage
gap
0.73
V
>44
h,
which
shows
great
potential
Zinc–air
battery.
This
work
provides
an
avenue
transform
renewable
materials
into
bifunctional
electrocatalysts
structure.
Advanced Energy Materials,
Год журнала:
2022,
Номер
13(5)
Опубликована: Дек. 16, 2022
Abstract
Single
atom
catalysts
(SACs)
comprised
of
nitrogen‐coordinated
transition
metal
(TM–N–C)
moieties
show
encouraging
performance
towards
the
oxygen
reduction
reaction
(ORR).
Nevertheless,
for
reactions
involving
multiple
intermediates,
single‐atom
sites
fail
to
satisfactorily
optimize
adsorption
all
intermediates.
Here,
a
facile
strategy
is
reported
construct
Fe,
P
dual‐atom
in
multimodal
porous
carbon
(Fe,P‐DAS@MPC),
and
its
superiority
synergistically
boosting
ORR
demonstrated.
Fe,P‐DAS@MPC
exhibits
excellent
with
substantially
positive
onset
potential
(
E
=
1.02
V)
half‐wave
1/2
0.92
V).
Theoretical
analysis
unveils
cooperative
effect
composed
adjacent
Fe
atoms,
aiding
hydrogen
bonding
interaction
can
promote
adsorption/desorption
Additionally,
Zn–air
battery
based
on
shows
high
peak
power
density
exceptional
cycling
stability.
These
findings
provide
novel
avenue
design
electrocatalysts
practical
energy
conversion
applications.
Advanced Materials,
Год журнала:
2023,
Номер
36(11)
Опубликована: Дек. 16, 2023
Abstract
The
development
of
facile,
efficient
synthesis
method
to
construct
low‐cost
and
high‐performance
single‐atom
catalysts
(SACs)
for
oxygen
reduction
reaction
(ORR)
is
extremely
important,
yet
still
challenging.
Herein,
an
atomically
dispersed
N,
S
co‐doped
carbon
with
abundant
vacancy
defects
(NSC‐vd)
anchored
Fe
single
atoms
(SAs)
reported
a
inductive
effect
proposed
promoting
electrocatalytic
ORR.
optimized
catalyst
featured
stable
Fe─N
3
1
active
sites
exhibits
excellent
ORR
activity
high
turnover
frequency
mass
activity.
In
situ
Raman,
attenuated
total
reflectance
surface
enhanced
infrared
absorption
spectroscopy
reveal
the
exhibit
different
kinetic
mechanisms
in
acidic
alkaline
solutions.
Operando
X‐ray
spectra
SAs/NSC‐vd
electrolyte
closely
related
coordination
structure.
Theoretical
calculation
reveals
upshifted
d
band
center
facilitates
adsorption
O
2
accelerates
kinetics
process
*OH
reduction.
around
balance
OOH*
formation
reduction,
thus
synergetically
process.
Advanced Materials,
Год журнала:
2023,
Номер
36(17)
Опубликована: Июль 27, 2023
Abstract
Manipulating
the
coordination
environment
and
electron
distribution
for
heterogeneous
catalysts
at
atomic
level
is
an
effective
strategy
to
improve
electrocatalytic
performance
but
remains
challenging.
Herein,
atomically
dispersed
Fe
Co
anchored
on
nitrogen,
phosphorus
co‐doped
carbon
hollow
nanorod
structures
(FeCo‐NPC)
are
rationally
designed
synthesized.
The
as‐prepared
FeCo‐NPC
catalyst
exhibits
significantly
boosted
kinetics
greatly
upshifts
half‐wave
potential
oxygen
reduction
reaction.
Furthermore,
when
utilized
as
cathode,
also
displays
excellent
zinc‐air
battery
performance.
Experimental
theoretical
results
demonstrate
that
introduction
of
single
atoms
with
Co‐N/P
around
isolated
induces
asymmetric
distribution,
resulting
in
suitable
adsorption/desorption
ability
intermediates
optimized
reaction
barrier,
thereby
improving
activity.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(36)
Опубликована: Июль 15, 2023
Electrocatalysts
for
highly
efficient
oxygen
reduction
reaction
(ORR)
are
crucial
energy
conversion
and
storage
devices.
Single-atom
catalysts
with
maximized
metal
utilization
altered
electronic
structure
the
most
promising
alternatives
to
replace
current
benchmark
precious
metals.
However,
atomic
level
understanding
of
functional
role
each
species
at
anchoring
sites
is
still
unclear
poorly
elucidated.
Herein,
we
report
Fe
single
atom
sulfur
groups
near
atomically
dispersed
centers
(Fe1/NSOC)
ORR.
The
Fe1/NSOC
delivers
a
half-wave
potential
0.92
V
vs.
RHE,
which
much
better
than
those
commercial
Pt/C
(0.88
V),
atoms
on
N-doped
carbon
(Fe1/NC,
0.89
V)
reported
nonprecious
catalysts.
spectroscopic
measurements
reveal
that
presence
group
induces
formation
epoxy
FeN4S2
centers,
not
only
modulate
but
also
participate
catalytic
process
improve
kinetics.
density
theory
calculations
demonstrate
existence
engineer
charges
reactive
center
facilitate
reductive
release
OH*
(rate-limiting
step),
thus
boosting
overall
efficiency.
Nano-Micro Letters,
Год журнала:
2023,
Номер
15(1)
Опубликована: Окт. 13, 2023
Abstract
Single-atom
catalysts
(SACs)
have
garnered
increasingly
growing
attention
in
renewable
energy
scenarios,
especially
electrocatalysis
due
to
their
unique
high
efficiency
of
atom
utilization
and
flexible
electronic
structure
adjustability.
The
intensive
efforts
towards
the
rational
design
synthesis
SACs
with
versatile
local
configurations
significantly
accelerated
development
efficient
sustainable
electrocatalysts
for
a
wide
range
electrochemical
applications.
As
an
emergent
coordination
avenue,
intentionally
breaking
planar
symmetry
by
adding
ligands
axial
direction
metal
single
atoms
offers
novel
approach
tuning
both
geometric
structures,
thereby
enhancing
electrocatalytic
performance
at
active
sites.
In
this
review,
we
briefly
outline
burgeoning
research
topic
axially
coordinated
provide
comprehensive
summary
recent
advances
synthetic
strategies
Besides,
challenges
outlooks
field
also
been
emphasized.
present
review
provides
in-depth
understanding
SACs,
which
could
bring
new
perspectives
solutions
fine
regulation
structures
catering
high-performing
electrocatalysis.
Advanced Energy Materials,
Год журнала:
2023,
Номер
13(13)
Опубликована: Фев. 2, 2023
Abstract
Single‐atom
Fe‐N‐C
(denoted
as
Fe
1
‐N‐C)
catalysts
exhibit
inadequate
bifunctional
activities
to
conquer
the
sluggish
oxygen
reduction
and
evolution
reaction
(ORR/OER),
hindering
their
practical
applications
in
rechargeable
Zn‐air
batteries
(ZABs).
Here,
by
employing
‐N‐C
hollow
nanorods
ORR‐active
support,
OER‐active
NiFe‐layered
double
hydroxide
(NiFe‐LDH)
nanodots
are
evenly
decorated
through
a
spatially
confined
process
form
NiFe‐LDH/Fe
heterostructure
with
abundant
accessible
catalytic
sites.
The
not
only
enhances
ORR
activity
of
pristine
but
also
realizes
efficient
ORR/OER
one
monolithic
catalyst.
Theoretical
calculations
reveal
that
introducing
NiFe‐LDH
results
donation
electrons
matrix
thus
lowers
Fe‐
d
band
center
Fe‐N
4
sites,
dramatically
narrowing
energy
barriers
rate‐limiting
steps.
As
result,
deliver
remarkable
half‐wave
potential
0.90
V
versus
reversible
hydrogen
electrode,
surpassing
bare
commercial
Pt/C.
Impressively,
integrated
show
outstanding
performance
small
overpotential
gap
0.65
V.
liquid‐state
ZABs
an
air‐cathode
catalyst
peak
power
density
205
mW
cm
−2
long‐term
cycling
stability
up
400
h.