Abstract
The
high‐performance
and
sustainable
electrocatalysts
toward
oxygen
reduction
reaction
(ORR)
evolution
(OER)
are
essential
for
rechargeable
Zn‐air
batteries
(ZABs).
In
this
paper,
a
natural
all‐components
bamboo
is
provided
as
the
carbon
source,
melamine
cobalt
chloride
nitrogen
sources,
respectively.
As
result,
unique
helical
nanotubes
(HCNTs)
encapsulated
nanoparticles
prepared,
which
acted
ORR/OER
to
improve
ZABs
performance.
resultant
HCNTs
contribute
high
activities
via
exposing
more
Co─N
sites,
providing
excellent
electron
conductivity,
facilitating
mass
transfer
of
reactant.
assembled
liquid
showed
maximum
output
power
density
226
mW
cm
−2
low
voltage
gap
0.85
V
330
h
cycles.
flexible
all‐solid‐state
achieved
with
59.4
charge–discharge
cycles
over
25
h.
functional
theory
(DFT)
calculations
reveal
that
increase
at
effectively
regulates
electronic
structure
Co,
optimizing
binding
affinity
intermediates
resulting
in
overpotentials.
This
work
paves
way
transforming
renewable
biomass
into
versatile
electrocatalysts,
boosts
development
next‐generation
energy
storage
conversion
devices.
ACS Catalysis,
Год журнала:
2023,
Номер
13(14), С. 9427 - 9441
Опубликована: Июль 3, 2023
Iron-
and
nitrogen-doped
carbon
(Fe–N–C)
materials
have
been
suggested
as
the
most
promising
replacement
for
Pt-based
catalysts
in
oxygen
reduction
reaction
(ORR)
owing
to
FeN4
active
moiety.
Based
on
relationship
between
binding
energy
catalytic
activity,
Fe–N–C
has
a
very
strong
energy;
hence,
hard
desorb
final
intermediate
of
*OH.
Herein,
we
provide
an
effective
method
tuning
moiety
using
phosphine-gas
treatment
Fe–N–C.
Combined
analyses
experimental
computational
results
reveal
that
conventional
is
transformed
into
FeN3PO
through
P-doping
post-treatment.
Furthermore,
propose
ORR
mechanism
unique
based
microkinetic
model,
which
*OH
intermediates
are
considered.
Compared
moiety,
facilitates
desorption,
thereby
enhancing
activity
both
alkaline
acidic
electrolytes.
The
effects
performance
also
validated
anion
exchange
membrane
fuel
cells
(AEMFCs)
proton
(PEMFCs).
Advanced Materials,
Год журнала:
2024,
Номер
36(32)
Опубликована: Май 29, 2024
Demetalation
caused
by
the
electrochemical
dissolution
of
metallic
Fe
atoms
is
a
major
challenge
for
practical
application
Fe─N─C
catalysts.
Herein,
an
efficient
single
Mn
active
site
constructed
to
improve
strength
Fe─N
bond,
inhibiting
demetalation
effect
Fe─N─C.
acts
as
electron
donor
inducing
more
delocalized
electrons
reduce
oxidation
state
increasing
density,
thereby
enhancing
bond
and
Fe.
The
oxygen
reduction
reaction
pathway
dissociation
Fe─Mn
dual
sites
can
overcome
high
energy
barriers
direct
O─O
modulate
electronic
states
Proceedings of the National Academy of Sciences,
Год журнала:
2024,
Номер
121(4)
Опубликована: Янв. 17, 2024
Nonradicals
are
effective
in
selectively
degrading
electron-rich
organic
contaminants,
which
unfortunately
suffer
from
unsatisfactory
yield
and
uncontrollable
composition
due
to
the
competitive
generation
of
radicals.
Herein,
we
precisely
construct
a
local
microenvironment
carbon
nitride–supported
high-loading
(~9
wt.%)
Fe
single-atom
catalyst
(Fe
SAC)
with
sulfur
via
facile
supermolecular
self-assembly
strategy.
Short-distance
S
coordination
boosts
peroxymonosulfate
(PMS)
activation
generates
high-valent
iron–oxo
species
IV
=O)
along
singlet
oxygen
(
1
O
2
),
significantly
increasing
yield,
PMS
utilization,
p
-chlorophenol
reactivity
by
6.0,
3.0,
8.4
times,
respectively.
The
nonradicals
is
controllable
simply
changing
content.
In
contrast,
long-distance
both
radicals
nonradicals,
could
not
promote
reactivity.
Experimental
theoretical
analyses
suggest
that
short-distance
upshifts
d
-band
center
atom,
i.e.,
being
close
Fermi
level,
changes
binding
mode
between
atom
site
generate
=O
high
yield.
S-coordinated
SAC
exhibits
excellent
application
potential
various
water
matrices.
These
findings
can
guide
rational
design
robust
SACs
toward
selective
utilization.
ACS Catalysis,
Год журнала:
2024,
Номер
14(9), С. 6952 - 6964
Опубликована: Апрель 18, 2024
The
coordination
engineering
of
Fe–N–C
single-atom
catalysts
(SACs)
through
introducing
heteroatom
dopants
has
attracted
widespread
attention
in
the
oxygen
reduction
reaction
(ORR).
However,
common
regularity
for
tuning
ORR
activity
by
coordinated
and
environmental
heteroatoms
not
been
sufficiently
studied.
Herein,
we
study
on
100
SACs
with
S,
P,
B
diverse
shells
density
functional
theory
calculations.
Based
energy
level
distribution
frontier
orbits
molecular
orbital
theory,
it
is
found
that
origin
hybridization
orbitals
Fe
3dz2,
3dyz
(3dxz),
O2*/OH*
intermediates,
where
hybrid
are
adjusted
heteroatoms,
then
protonation
process
O2*
or
OH*
intermediate
determined.
Moreover,
Fe–O
bond
length,
d-orbital
gap
spin
states,
center,
valence
state
site
can
be
used
as
structural
descriptors
to
predict
governed
potential-determining
steps.
Our
rationalize
superior
performance
S
atoms
doped
second
shell
those
first
shell,
well
fact
P
more
suitable
a
atom
than
enhance
Fe–N–C,
available
experimental
references.
Thanks
descriptors,
codoping
synergistic
effect
between
predicted
confirmed
greatly
activity.
This
provides
unified
mechanistic
understanding
trend
among
regulated
heteroatoms.
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.
Abstract
Developing
efficient
metal‐nitrogen‐carbon
(M‐N‐C)
single‐atom
catalysts
for
oxygen
reduction
reaction
(ORR)
is
significant
the
widespread
implementation
of
Zn‐air
batteries,
while
synergic
design
matrix
microstructure
and
coordination
environment
metal
centers
remains
challenges.
Herein,
a
novel
salt
effect‐induced
strategy
proposed
to
engineer
N
P
coordinated
atomically
dispersed
Fe
atoms
with
extra‐axial
Cl
on
interlinked
porous
carbon
nanosheets,
achieving
superior
catalyst
(denoted
as
Fe‐NP‐Cl‐C)
ORR
batteries.
The
hierarchical
nanosheet
architecture
can
provide
rapid
mass/electron
transfer
channels
facilitate
exposure
active
sites.
Experiments
density
functional
theory
(DFT)
calculations
reveal
distinctive
Fe‐N
2
‐Cl
sites
afford
significantly
reduced
energy
barriers
promoted
kinetics
ORR.
Consequently,
Fe‐NP‐Cl‐C
exhibits
distinguished
performance
half‐wave
potential
(E
1/2
)
0.92
V
excellent
stability.
Remarkably,
assembled
battery
based
delivers
an
extremely
high
peak
power
260
mW
cm
−2
large
specific
capacity
812
mA
h
g
−1
,
outperforming
commercial
Pt/C
most
reported
congeneric
catalysts.
This
study
offers
new
perspective
structural
optimization
engineering
electrocatalysis
conversion
devices.
Energy & Environmental Science,
Год журнала:
2024,
Номер
17(14), С. 4847 - 4870
Опубликована: Янв. 1, 2024
Based
on
the
advancements
in
atomically
dispersed
multi-site
catalysts
for
FZABs,
this
review
discusses
design
methodologies
to
regulate
performance
of
bifunctional
oxygen
electrocatalysts
from
electronic
and
geometric
structures.
ACS Applied Materials & Interfaces,
Год журнала:
2024,
Номер
16(10), С. 12398 - 12406
Опубликована: Фев. 27, 2024
The
metal-nitrogen-carbon
(M-N-C)-based
catalysts
are
promising
to
replace
PGM
(platinum
group
metal)
accelerate
oxygen
reduction
reaction
due
their
excellent
electrocatalytic
performance.
However,
the
inferior
intrinsic
activity
and
poor
active
site
density
confining
further
improvement
in
Modulating
electronic
structure
reasonably
designing
pore
widely
acknowledged
effective
strategies
boost
of
M-N-C
catalysts.
it
is
a
great
challenge
form
abundant
pores
regulate
via
facile
method.
Herein,
hierarchical,
porous
dual-atom
catalyst
FeNi-NPC-1000
has
been
architectured
by
Na
