Proceedings of the National Academy of Sciences,
Год журнала:
2024,
Номер
121(37)
Опубликована: Сен. 5, 2024
Peroxymonosulfate-based
electrochemical
advanced
oxidation
processes
(PMS-EAOPs)
have
great
potential
for
sustainable
water
purification,
so
an
in-depth
understanding
of
its
catalytic
mechanism
is
imperative
to
facilitate
practical
application.
Herein,
the
performance
enhancement
and
electroenhanced
PMS
activation
by
single-atom
Fe
catalyst
modified
carbon
felt
was
investigated.
Compared
with
anode,
cathode
exhibited
faster
bisphenol
A
degradation
(
k
=
0.073
vs.
anode
0.015
min
−1
),
increased
consumption
(98.8
10.3%),
order
magnitude
reduction
dissolution
(0.068
0.787
mg
L
).
Mass
transfer
a
key
factor
limiting
activation,
while
electrostriction
in
hydrophobic
region
caused
electric
field
(CEF)
significantly
mass
coefficient
m,
1.49
×
10
−4
2.68
−5
m
s
The
enhanced
synergistic
result
between
electroactivation
catalyst-activation,
which
controlled
applied
current
density.
1
O
2
direct
electron
are
main
active
species
pathway,
achieve
high
efficiency
over
pH
3
10.
Density
functional
theory
calculations
prove
CEF
increases
adsorption
energy,
lengthens
O–O
bond
PMS,
promotes
charge
transfer.
flow-through
convection
unit
achieves
operation
removal
(99.5%
97.5%),
low
electrical
energy
(0.15
kWh
log
–1
–3
leaching
(0.81%
total
single
atom
Fe).
This
work
reveals
critical
role
fields
modulating
Fenton-like
activity,
may
advance
development
other
electrocatalytic
applications.
Proceedings of the National Academy of Sciences,
Год журнала:
2024,
Номер
121(3)
Опубликована: Янв. 8, 2024
The
studies
on
the
origin
of
versatile
oxidation
pathways
toward
targeted
pollutants
in
single-atom
catalysts
(SACs)/peroxymonosulfate
(PMS)
systems
were
always
associated
with
coordination
structures
rather
than
perspective
pollutant
characteristics,
and
analysis
mechanism
commonality
is
lacking.
In
this
work,
a
variety
(M-SACs,
M:
Fe,
Co,
Cu)
fabricated
via
pyrolysis
process
using
lignin
as
complexation
agent
substrate
precursor.
Sixteen
kinds
commonly
detected
various
references
selected,
their
ln
k
obs
values
M-SACs/PMS
correlated
well
(
R
2
=
0.832
to
0.883)
electrophilic
indexes
(reflecting
electron
accepting/donating
ability
pollutants)
energy
gap
0.801
0.840)
between
complexes.
Both
transfer
(ETP)
radical
can
be
significantly
enhanced
systems,
while
was
overwhelmed
by
ETP
lower
indexes.
contrast,
higher
represented
weaker
electron-donating
capacity
complexes,
which
resulted
accompanied
noticeable
oxidation.
addition,
different
regulated
gaps
complexes
pollutants.
As
result,
Fenton-like
activities
could
modulated
reaction
pathways,
determined
both
sites.
This
work
provided
strategy
establish
PMS-based
AOP
tunable
capacities
for
high-efficiency
organic
decontamination.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(8)
Опубликована: Янв. 8, 2024
Achieving
the
complete
mineralization
of
persistent
pollutants
in
wastewater
is
still
a
big
challenge.
Here,
we
propose
an
efficient
photo-self-Fenton
reaction
for
degradation
different
using
high-density
(Ag:
22
wt
%)
atomically
dispersed
AgCo
dual
sites
embedded
graphic
carbon
nitride
(AgCo-CN).
Comprehensive
experimental
measurements
and
density
functional
theory
(DFT)
calculations
demonstrate
that
Ag
Co
AgCo-CN
play
critical
role
accelerating
photoinduced
charge
separation
forming
self-Fenton
redox
centers,
respectively.
The
bimetallic
exhibited
excellent
photocatalytic
performance
toward
phenol
even
under
extreme
conditions
due
to
pathway
situ
generation
hydrogen
peroxide
producing
main
active
oxygen
species
(⋅OH
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Авг. 22, 2024
Catalytic
peroxymonosulfate
(PMS)
activation
processes
don't
solely
rely
on
electron
transfer
from
dominant
metal
centers
due
to
the
complicated
composition
and
interface
environment
of
catalysts.
Herein
synthesis
a
cobalt
based
metal-organic
framework
containing
polyvanadate
[V4O12]4−
cluster,
Co2(V4O12)(bpy)2
(bpy
=
4,4'-bipyridine),
is
presented.
The
catalyst
demonstrates
superior
degradation
activity
toward
various
micropollutants,
with
higher
highest
occupied
molecular
orbital
(HOMO),
via
nonradical
attack.
X-ray
absorption
spectroscopy
density
functional
theory
(DFT)
calculations
demonstrate
that
Co
sites
act
as
both
PMS
trapper
donor.
In
situ
spectral
characterizations
DFT
reveal
terminal
oxygen
atoms
in
sponge
could
interact
hydrogen
form
bonds,
promoting
generation
SO5*
intermediate
dynamic
pull
direct
process.
Further,
exhibits
long-term
water
purification
ability,
up
40
h,
towards
actual
wastewater
discharged
an
ofloxacin
production
factory.
This
work
not
only
presents
efficient
for
environmental
remediation
pathway,
but
also
provides
fundamental
insights
into
Fenton-like
reaction
mechanism.
Peroxymonosulfate
might
centers.
Here,
authors
found
formation
bond
between
[V4O12]
4−
provided
extra
channel
achieving
activation.
Proceedings of the National Academy of Sciences,
Год журнала:
2024,
Номер
121(9)
Опубликована: Фев. 20, 2024
Effectively
managing
sewage
sludge
from
Fenton
reactions
in
an
eco-friendly
way
is
vital
for
technology’s
viability
pollution
treatment.
This
study
focuses
on
across
various
treatment
stages,
including
generation,
concentration,
dehydration,
and
landfill,
employs
chemical
composite
MoS
2
to
facilitate
green
resource
utilization
of
all
types
sludge.
,
with
exposed
Mo
4+
low-coordination
sulfur,
enhances
iron
cycling
creates
acidic
microenvironment
the
surface.
The
-modified
exhibits
outstanding
(>95%)
phenol
pollutant
degradation
hydrogen
peroxide
peroxymonosulfate-based
systems,
unlike
unmodified
modified
maintains
excellent
activity
water
conditions
multiple
anions,
allowing
extended
over
14
d.
Notably,
generated
oxygen
demand
(COD)
modification
process
can
be
efficiently
eliminated
through
reaction,
ensuring
effluent
COD
compliance
enabling
utilization.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Март 12, 2024
Abstract
Electronic
structure
modulation
of
active
sites
is
critical
important
in
Fenton
catalysis
as
it
offers
a
promising
strategy
for
boosting
H
2
O
activation.
However,
efficient
generation
hydroxyl
radicals
(•OH)
often
limited
to
the
unoptimized
coordination
environment
sites.
Herein,
we
report
rational
design
and
synthesis
iron
oxyfluoride
(FeOF),
whose
strongly
coordinate
with
most
electronegative
fluorine
atoms
characteristic
moiety
F-(Fe(III)O
3
)-F,
effective
activation
potent
•OH
generation.
Results
demonstrate
that
plays
pivotal
role
lowering
local
electron
density
optimizing
electronic
structures
sites,
thus
facilitating
rate-limiting
adsorption
subsequent
peroxyl
bond
cleavage
reactions.
Consequently,
FeOF
exhibits
significant
pH-adaptive
yield
(~450
µM)
high
selectivity,
which
1
~
orders
magnitude
higher
than
state-of-the-art
iron-based
catalysts,
leading
excellent
degradation
activities
against
various
organic
pollutants
at
neutral
condition.
This
work
provides
fundamental
insights
into
function
atomic
level,
may
inspire
sustainable
environmental
remediation.
Advanced Materials,
Год журнала:
2024,
Номер
36(32)
Опубликована: Апрель 30, 2024
Abstract
Single
atom
catalysts
(SACs)
are
atomic‐level‐engineered
materials
with
high
intrinsic
activity.
Catalytic
centers
of
SACs
typically
the
transition
metal
(TM)–nonmetal
coordination
sites,
while
functions
coexisting
non‐TM‐bonded
functionalities
usually
overlooked
in
catalysis.
Herein,
scalable
preparation
carbon‐supported
cobalt‐anchored
(CoCN)
controlled
Co─N
sites
and
free
functional
N
species
is
reported.
The
role
metal‐
nonmetal‐bonded
for
peroxymonosulfate
(PMS)‐driven
Fenton‐like
reactions
first
systematically
studied,
revealing
their
contribution
to
performance
improvement
pathway
steering.
Experiments
computations
demonstrate
that
3
C
plays
a
vital
formation
surface‐confined
PMS*
complex
trigger
electron
transfer
promote
kinetics
because
optimized
electronic
state
Co
centers,
nonmetal‐coordinated
graphitic
act
as
preferable
pollutant
adsorption
additional
PMS
activation
accelerate
transfer.
Synergistically,
CoCN
exhibits
ultrahigh
activity
p
‐hydroxybenzoic
acid
oxidation,
achieving
complete
degradation
within
10
min
an
turnover
frequency
0.38
−1
,
surpassing
most
reported
materials.
These
findings
offer
new
insights
into
versatile
inspire
rational
design
high‐performance
complicated
heterogeneous
systems.
