Environmental Science & Technology,
Год журнала:
2023,
Номер
57(47), С. 19012 - 19022
Опубликована: Авг. 21, 2023
A
carbon-based
advanced
oxidation
process
is
featured
for
the
nonradical
electron-transfer
pathway
(ETP)
from
electron-donating
organic
compounds
to
activated
persulfate
complexes,
enabling
it
as
a
green
technology
selective
of
pollutants
in
complex
water
environments.
However,
thermodynamic
and
kinetic
behaviors
regime
had
been
ambiguous
due
neglect
influence
pH
on
mechanisms.
In
this
study,
three
kinds
were
divided
ETP
regime:
(i)
physio-adsorption,
(ii)
adsorption-dominated
(oxidation
rate
slightly
surpasses
adsorption
rate),
(iii)
oxidation-dominated
outpaces
rate).
The
differential
attributed
physicochemical
properties
pollutants.
For
example,
hydrophobicity,
molecular
radius,
positive
electrostatic
potential
controlled
mass-transfer
stage
reactants
(peroxydisulfate
(PDS)
organics).
Meanwhile,
other
descriptors,
including
Fukui
index,
potential,
electron
cloud
density
regulated
processes
thus
kinetics
oxidation.
Most
importantly,
pathways
these
could
be
altered
by
adjusting
chemistry.
This
study
reveals
principles
developing
efficient
systems
selectively
remove
recycle
wastewater.
Environmental Science & Technology,
Год журнала:
2022,
Номер
56(9), С. 5611 - 5619
Опубликована: Апрель 20, 2022
Rapid
generation
of
high-valent
cobalt-oxo
species
(Co(IV)═O)
for
the
removal
organic
contaminants
has
been
challenging
because
low
conversion
efficiency
Co(III)/Co(II)
and
high
activation
energy
barrier
Co(II)-oxidant
complex.
Herein,
we
introduced
nitrogen
(N)
vacancies
into
graphite
carbon
nitride
imbedded
with
cobalt
carbonate
(CCH/CN–Vn)
in
a
peroxymonosulfate
(PMS)/visible
light
system
to
break
limitations
conventional
two-electron
transfer
path.
These
N
enhanced
electron
distribution
Co
3d
orbital
lowered
cleave
O–O
bond
PMS
Co(II)-PMS
complex,
achieving
modulation
major
active
from
1O2
Co(IV)═O.
The
developed
synergistic
that
exhibited
adsorption
oxidation
showed
remarkable
selectivity
contaminant
performance
inorganic
(Cl–,
NO3–,
HCO3–,
HPO4–)
(HA)
even
practical
aqueous
matrices
(tap
water
secondary
effluent).
This
study
provides
novel
mechanistic
perspective
modulate
nonradical
path
refractory
treatment
via
defect
engineering.
Environmental Science & Technology,
Год журнала:
2021,
Номер
55(22), С. 15390 - 15399
Опубликована: Ноя. 3, 2021
The
iron(II)-activated
peroxymonosulfate
[Fe(II)/PMS]
process
is
effective
in
degrading
organic
contaminants
with
a
rapid
oxidation
stage
followed
by
slow
one.
Nevertheless,
prior
studies
have
greatly
underestimated
the
degradation
rates
of
and
ignored
differences
kinetics
mechanism
these
two
stages.
In
this
work,
we
investigated
mechanisms
under
acidic
conditions
combining
stopped-flow
spectrophotometric
method
batch
experiments.
were
rapidly
oxidized
rate
constants
0.18–2.9
s–1
stage.
Meanwhile,
both
Fe(IV)
SO4•–
active
oxidants
contributed
differently
to
different
Additionally,
presence
Cl–
promoted
phenol
estradiol
but
effects
Br–
humic
acid
on
differed
from
those
contrast,
was
amounts
generated
small
This
work
updates
fundamental
understanding
process.
Environmental Science & Technology,
Год журнала:
2022,
Номер
56(12), С. 8765 - 8775
Опубликована: Май 12, 2022
As
an
efficient
active
oxidant
for
the
selective
degradation
of
pollutants
in
wastewater,
high-valent
copper
species
Cu(III)
with
persulfate
activation
has
attracted
substantial
attention
some
Cu-based
catalysts.
However,
systematic
study
a
catalyst
structure
and
mechanism
about
peroxydisulfate
(PDS)
is
challenging
owing
to
coexistence
multiple
Cu
structural
symmetry
PDS.
Herein,
we
anchored
atom
two
pyridinic
N
atoms
synthesize
single-atom
(CuSA-NC).
Experimental
characterizations
theoretical
calculations
complemented
each
other
well
because
uniform
atomic
sites.
The
was
identified
as
site,
unsaturated
Cu-N2
configuration
more
conductive
PDS
than
saturated
Cu-N4
configuration.
Benefiting
from
generation
Cu(III),
CuSA-NC
exhibited
obvious
anti-interference
performance
pollutant
complex
matrix.
superior
catalytic
activity
compared
that
reported
catalysts
good
durability
continuous-flow
experiment
further
revealed
potential
practical
applications.
This
work
strongly
deepens
understanding
sites
under
develops
approach
actual
water
purification.