Environmental Science & Technology,
Год журнала:
2023,
Номер
57(34), С. 12922 - 12930
Опубликована: Авг. 15, 2023
FeOCl
is
a
highly
effective
candidate
material
for
advanced
oxidation
process
(AOP)
catalysts,
but
there
remain
enormous
uncertainties
about
the
essence
of
its
outstanding
activity.
Herein,
we
clearly
elucidate
mechanism
involved
in
FeOCl-catalyzed
perdisulfate
(PDS)
activation,
and
role
surface
hydroxyls
bridging
electron
transfer
between
Fe
sites
PDS
onto
FeOCl/H2O
interface
highlighted.
ATR-FTIR
Raman
analyses
reveal
that
phosphate
could
suppress
activity
via
substituting
hydroxyls,
demonstrating
essential
hydroxyl
activation.
By
use
X-ray
absorption
fine
structure
density
functional
theory
calculations,
found
polar
experienced
prominent
hydrolyzation,
which
enriched
abundant
electrons
within
microarea
around
site,
leading
to
stronger
attraction
PDS.
As
result,
adsorption
was
obviously
enhanced,
bond
length
O–O
adsorbed
lengthened,
from
atoms
also
promoted.
This
work
proposed
new
strategy
PDS-based
AOP
development
hint
building
efficient
heterogeneous
catalysts
regulating
hydroxylation
active
sites.
Environmental Science & Technology,
Год журнала:
2024,
Номер
58(12), С. 5616 - 5626
Опубликована: Март 12, 2024
Advanced
oxidation
processes
(AOPs),
such
as
hydroxyl
radical
(HO•)-
and
sulfate
(SO4•–)-mediated
oxidation,
are
attractive
technologies
used
in
water
wastewater
treatments.
To
evaluate
the
treatment
efficiencies
of
AOPs,
monitoring
primary
radicals
(HO•
SO4•–)
well
secondary
generated
from
reaction
HO•/SO4•–
with
matrices
is
necessary.
Therefore,
we
developed
a
novel
chemical
probe
method
to
examine
five
key
simultaneously,
including
HO•,
SO4•–,
Cl•,
Cl2•–,
CO3•–.
Five
probes,
nitrobenzene,
para-chlorobenzoic
acid,
benzoic
2,4,6-trimethylbenzoic
2,4,6-trimethylphenol,
were
selected
this
study.
Their
bimolecular
rate
constants
diverse
first
calibrated
under
same
conditions
minimize
systematic
errors.
Three
typical
AOPs
(UV/H2O2,
UV/S2O82–,
UV/HSO5–)
tested
obtain
steady-state
concentrations.
The
effects
dissolved
organic
matter,
Br–,
concentration
inspected.
Our
results
suggest
that
five-probe
can
accurately
measure
HO•-
SO4•–-mediated
when
Br–
DOM
less
than
4.0
μM
15
mgC
L–1,
respectively.
Overall,
practical
easily
accessible
determine
multiple
simultaneously.
Environmental Science & Technology,
Год журнала:
2024,
Номер
58(13), С. 6030 - 6038
Опубликована: Март 22, 2024
Increasing
radical
yields
to
reduce
UV
fluence
requirement
for
achieving
targeted
removal
of
micropollutants
in
water
would
make
UV-based
advanced
oxidation
processes
(AOPs)
less
energy
demanding
the
context
United
Nations'
Sustainable
Development
Goals
and
carbon
neutrality.
We
herein
demonstrate
that,
by
switching
radiation
source
from
conventional
low-pressure
at
254
nm
(UV254)
emerging
Far-UVC
222
(UV222),
fluence-based
concentration
HO•
UV/peroxydisulfate
(UV/PDS)
AOP
increases
6.40,
2.89,
6.00
times
deionized
water,
tap
surface
respectively,
with
SO4•–
also
5.06,
5.81,
55.47
times,
respectively.
The
enhancement
generation
is
confirmed
using
a
kinetic
model.
pseudo-first-order
degradation
rate
constants
16
UV222/PDS
are
predicted
be
1.94–13.71
higher
than
those
UV254/PDS
AOP.
Among
tested
matrix
components,
chloride
nitrate
decrease
but
increase
Compared
AOP,
decreases
formation
potentials
carbonaceous
disinfection
byproducts
(DBPs)
nitrogenous
DBPs.
Abstract
With
maximum
utilization
of
active
metal
sites,
more
and
researchers
have
reported
using
single
atom
catalysts
(SACs)
to
activate
persulfate
(PS)
for
organic
pollutants
removal.
In
SACs,
atoms
(Fe,
Co,
Cu,
Mn,
etc.)
different
substrates
(porous
carbon,
biochar,
graphene
oxide,
carbon
nitride,
MOF,
MoS
2
,
others)
are
the
basic
structural.
Metal
atoms,
substances,
connected
chemical
bonds
all
a
great
influence
on
electronic
structures
that
directly
affect
activation
process
PS
degradation
efficiency
pollutants.
However,
there
few
relevant
reviews
about
interaction
between
substances
during
process.
this
review,
SACs
with
species
summarized
investigate
metal−support
evaluate
their
effects
oxidation
reaction
Furthermore,
how
reactive
pathways
also
discussed.
Finally,
challenges
prospects
in
PS‐AOPs
proposed.
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.
