Abstract
Single‐atom
catalysts
(SACs)
anchored
on
defective
supports
offer
exceptional
catalytic
efficiency
but
face
challenges
in
stabilizing
isolated
metal
atoms
and
optimizing
metal‐support
interactions.
Here,
a
defect‐driven
strategy
is
reported
to
construct
3D
dendritic
SAC
comprising
interwoven
ultrathin
TiO
2
nanowires
(NWs)
with
abundant
oxygen
vacancies
(OVs)
that
stabilize
atomically
dispersed
cobalt
(Co)
sites.
Using
hydrothermal
synthesis
followed
by
acid
etching
calcination,
Ti─Co─Ti
motifs
are
engineered
at
OVs
site.
The
architecture
provides
multiscale
porosity
charge
transport,
achieving
syngas
production
rates
of
28.4
mmol
g
−1
·h
(CO)
13.9
(H
)
high
turnover
frequency
(TOF)
10.6
min
,
surpassing
many
other
state‐of‐the‐art
Co‐based
SACs.
In
situ
Raman
electron
paramagnetic
resonance
(EPR)
analysis
reveal
consumption
during
Co
anchoring,
while
density
functional
theory
(DFT)
validates
redistribution
from
Ti
Co,
enabling
efficient
transfer
inducing
strong
electronic
interactions
enhance
CO
adsorption
activation.
results
highlight
the
interplay
between
atomic‐scale
coordination
environments
macroscale
architectural
order
harnessing
potential
SACs
1D
NWs.
Chemical Society Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
This
review
examines
the
strategies
of
symmetry
breaking
(charge/coordination/geometric)
in
single-atom
catalysts
to
regulate
active
site
electronic
structures,
greatly
enhancing
catalytic
performance.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 3, 2025
The
catalytic
oxidation
of
benzene
faces
challenges
in
achieving
high
activity
and
selectivity.
While
single-atom
catalysts
present
intriguing
potential
for
this
transformation,
their
practical
implementation
is
hindered
by
intrinsic
limitations
the
mass-specific
activity.
In
context,
few-atom
cluster
have
emerged
as
an
alternative,
leveraging
well-defined
metal
ensemble
effects
that
enable
precisely
tailored
active
sites
enhanced
interatomic
synergies.
Herein,
we
introduce
atomic
supported
on
a
graphitic
carbonitride
(CN)
catalyst
(Cu3/CN),
exhibiting
excellent
performance
selective
to
phenol,
with
superior
turnover
frequency
(TOF)
Cu1/CN
(719
h-1
vs
280
h-1)
suppressing
phenol
selectivity
nanoparticle
CuNP/CN
(95.3%
77.2%).
Multimodal
mechanistic
investigations
unambiguously
identify
critical
role
adsorbed
O*
Cu
site
(Cu═O*)
C-H-oxidation,
verified
both
situ
spectroscopic
monitoring
ex
surface
analysis.
Complementary
density
functional
theory
calculations
validate
(Cu3)
features
higher
d-band
center
larger
charge
transfer
H2O2
molecule
than
isolated
Cu1
site.
sufficient
stretches
O-O
bond
facilitate
formation
Cu═O*
species.
Furthermore,
resulting
Cu3
demonstrates
significant
hybridization
O
2p
orbitals
3d
at
Fermi
level,
which
endows
it
activation.
appropriate
effect
unique
architecture
key
its
performances.
This
work
establishes
structure-performance
correlation
highlights
optimizing
functionality.
Advanced Functional Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 14, 2025
Abstract
Carbon‐supported
single‐atom
catalysts
(CS‐SACs)
have
attracted
tremendous
attention
in
environmental
remediation
fields,
however,
the
role
of
ubiquitously
existing
carbon
defects
on
support
regulating
electronic
structure
active
metal
sites
has
long
been
overlooked.
Herein,
a
selective
pyridinic
N
etching
strategy
is
proposed
to
controllably
fabricate
specific
pentagon
supports
anchored
with
Co‐N
4
sites.
Theoretical
and
experimental
results
reveal
that
can
induce
upward
shifting
Co
d‐band
center
increase
electron
density
dxz
dz
2
orbitals,
indicating
its
indispensable
center.
As
result,
efficient
transfer
realized
between
atom
peroxymonsulfate
(PMS).
Moreover,
energy
barriers
for
crucial
oxygen
intermediate
are
reduced,
which
facilitates
generation
singlet
(
1
O
).
Consequently,
catalyst
(C5‐Co‐N
)
achieved
remarkable
TOF
value
(9.37
min
−1
Fenton‐like
reaction,
surpassing
state‐of‐the‐art
reported
so
far.
This
work
not
only
provides
CS‐SACs
but
also
deepens
fundamental
understanding
how
regulate
catalytic
performance
metal‐N
