Analytical Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 25, 2025
Accurately
sensing
the
spatial
distribution
of
temperature,
one
most
fundamental
parameters,
is
crucial
for
understanding
mechanism
physicochemical
process
in
confined
space.
However,
traditional
methods
temperature
measurement
often
show
a
very
limited
resolution
and
sensitivity.
Herein,
we
develop
surface-enhanced
Raman
spectroscopy
(SERS)
nanosensor
to
measure
within
hollow
carbon
nanospheres
(HCNSs)
study
light-promoted
Fenton-like
catalyzed
by
Fe
single-atom
anchored
on
HCNSs.
Based
temperature-dependent
SERS
spectra
phenyl
isocyanide
adsorbed
Au
nanoparticles,
gradient
nanocavity
surface
HCNSs,
induced
light-irradiation,
sensed
with
sensitivity
0.8
°C.
Furthermore,
combining
local
reaction
kinetics-temperature
relationship,
clarify
that
oxidation
phenol
peroxymonosulfate
occurs
at
thus
providing
sound
evidence
homogeneous
mechanism.
Besides
new
strategy
submicrometer
resolution,
this
work
also
shows
feasibility
through
locating
reactive
site.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Янв. 18, 2025
In
this
study,
we
introduce
a
highly
effective
non-metallic
iodine
single-atom
catalyst
(SAC),
referred
to
as
I-NC,
which
is
strategically
confined
within
nitrogen-doped
carbon
(NC)
scaffold.
This
configuration
features
distinctive
C-I
coordination
that
optimizes
the
electronic
structure
of
nitrogen-adjacent
sites.
As
result,
arrangement
enhances
electron
transfer
from
peroxymonosulfate
(PMS)
active
sites,
particularly
electron-deficient
carbon.
followed
by
deprotonation
process
generates
radical
(SO5•-).
Subsequently,
SO5•-
undergoes
disproportionation
reaction,
leading
production
singlet
oxygen
(1O2).
Furthermore,
energy
barrier
for
rate-limiting
step
generation
in
I-NC
significantly
lower
at
1.45
eV,
compared
1.65
eV
NC
reduction
effectively
overcomes
kinetic
obstacles,
thereby
facilitating
an
enhanced
1O2.
Consequently,
exhibits
remarkable
catalytic
efficiency
and
unmatched
reactivity
PMS
activation.
leads
accelerated
degradation
pollutants,
evidenced
relatively
high
observed
rate
constant
(kobs
~
0.436
min-1)
other
metallic
SACs.
study
offers
valuable
insights
into
rational
design
SACs,
showcasing
their
promising
potential
Fenton-like
reactions
water
treatment
applications.
Advanced Functional Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 28, 2025
Abstract
Precise
manipulation
of
coordination
structure
single‐atom
sites
and
establishment
schematic
microenvironment‐oxidation
pathway
relations
remain
significant
challenges
in
Fenton‐like
chemistry.
Herein,
incorporating
sulfur
heteroatoms
into
the
higher
shell
FeN
4
(Fe‐NSC)
exhibited
a
volcano
trend
p
‐hydroxybenzoic
acid
oxidation,
aligning
with
number
positions
dopant.
Specifically,
S
moderate
electronegativity
larger
atomic
radii
triggers
long‐range
electronic
interactions,
which
provoke
Fe
3d
orbital
splitting
spin
electron
rearrangement,
resulting
crossover
states
d
xy
2
yz
1
xz
z
21
.
As
result,
partial
filling
e
g
t
orbitals
σ/π
antibonding
between
2p
optimized
adsorption–desorption
behaviors
key
oxygenated
intermediates
from
peroxymonosulfate
activation.
Thus,
optimal
binding
configuration
weakens
Fe─O
bonding
accelerates
PMS
dissociation
to
yield
C‐S‐N
Fe‐O*,
subsequently
couples
form
O
nearly
100%
selectivity.
The
Fe‐NSC‐functionalized
membrane
outstanding
long‐term
reusability
continuous
flow
reactor
further
validated
practical
application
perspective.
This
study
provides
insight
at
both
levels
for
rational
design
spin‐polarized
catalysts
its
functions
fine‐tuning
oxidation
pathways
environmental
catalysis.
