ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
15(3), P. 1477 - 1486
Published: Jan. 9, 2025
Electronic
perturbation
induced
by
the
microenvironment
regulation
adjacent
to
FeN4
sites
anchored
on
metal–N–C
materials
will
accelerate
its
oxygen
reduction
reaction
(ORR)
kinetics.
Herein,
we
report
a
fine-tuning
in
charge
configuration
of
through
defect-rich
N/S-doped
carbon
nest
derived
from
chemically
cross-linked
pyrrole/thiophene
copolymer
(CCPPT)
with
sp3-hybridized
cross-linker.
Compared
(PPT)
without
cross-linker,
CCPPT
knitted
three-dimensional
(3D)
network
delivers
higher
defect
density
and
∼2-fold
sulfur
retention
after
pyrolysis.
The
structural
characterizations
combined
theoretical
calculations
suggest
that
vacancy
defects
(Cvd)
FeN4/S2
moiety
together
induce
redistribution
resultant
CC-Fe1/NSC
CCPPT,
reducing
adsorption
strength
oxygen-containing
intermediates
energy
barrier
ORR.
As
expected,
shows
an
impressive
half-wave
potential
∼0.91
V
vs
reversible
hydrogen
electrode
(RHE),
surpassing
both
PPT-derived
Fe1/NSC
(0.88
V)
commercial
Pt/C
(0.86
V).
This
work
provides
distinctive
path
manipulate
single-atom
catalysts
toward
ORR
or
even
beyond.
Advanced Materials,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 18, 2024
Abstract
For
traditional
metal
complexes,
intricate
chemistry
is
required
to
acquire
appropriate
ligands
for
controlling
the
electron
and
steric
hindrance
of
active
centers.
Comparatively,
preparation
single‐atom
catalysts
much
easier
with
more
straightforward
effective
accesses
arrangement
control
The
presence
coordination
atoms
or
neighboring
functional
on
supports'
surface
ensures
stability
single‐atoms
their
interactions
individual
substantially
regulate
performance
Therefore,
collaborative
interaction
between
surrounding
environment
enhances
initiation
reaction
substrates
formation
transformation
crucial
intermediate
compounds,
which
imparts
significant
catalytic
efficacy,
rendering
them
a
valuable
framework
investigating
correlation
structure
activity,
as
well
mechanism
in
organic
reactions.
Herein,
comprehensive
overviews
both
homogeneous
complexes
reactions
are
provided.
Additionally,
reflective
conjectures
about
advancement
synthesis
also
proposed
present
reference
later
development.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 13, 2024
Nanographenes
are
among
the
fastest-growing
materials
used
for
oxygen
reduction
reaction
(ORR)
thanks
to
their
low
cost,
environmental
friendliness,
excellent
electrical
conductivity,
and
scalable
synthesis.
The
perspective
of
replacing
precious
metal-based
electrocatalysts
with
functionalized
graphene
is
highly
desirable
reducing
costs
in
energy
conversion
storage
systems.
Generally,
enhanced
ORR
activity
nanographenes
typically
deemed
originate
from
heteroatom
doping
effect,
size
defects
and/or
synergistic
effect.
All
these
factors
can
efficiently
modify
charge
distribution
on
sp
ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
15(3), P. 1477 - 1486
Published: Jan. 9, 2025
Electronic
perturbation
induced
by
the
microenvironment
regulation
adjacent
to
FeN4
sites
anchored
on
metal–N–C
materials
will
accelerate
its
oxygen
reduction
reaction
(ORR)
kinetics.
Herein,
we
report
a
fine-tuning
in
charge
configuration
of
through
defect-rich
N/S-doped
carbon
nest
derived
from
chemically
cross-linked
pyrrole/thiophene
copolymer
(CCPPT)
with
sp3-hybridized
cross-linker.
Compared
(PPT)
without
cross-linker,
CCPPT
knitted
three-dimensional
(3D)
network
delivers
higher
defect
density
and
∼2-fold
sulfur
retention
after
pyrolysis.
The
structural
characterizations
combined
theoretical
calculations
suggest
that
vacancy
defects
(Cvd)
FeN4/S2
moiety
together
induce
redistribution
resultant
CC-Fe1/NSC
CCPPT,
reducing
adsorption
strength
oxygen-containing
intermediates
energy
barrier
ORR.
As
expected,
shows
an
impressive
half-wave
potential
∼0.91
V
vs
reversible
hydrogen
electrode
(RHE),
surpassing
both
PPT-derived
Fe1/NSC
(0.88
V)
commercial
Pt/C
(0.86
V).
This
work
provides
distinctive
path
manipulate
single-atom
catalysts
toward
ORR
or
even
beyond.
