ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(17), P. 12991 - 13014
Published: Aug. 15, 2024
Single-atom
catalysts
(SACs)
exhibit
remarkable
100%
atomic
economy,
making
them
highly
efficient
in
various
fields,
including
production
processes,
energy
systems,
and
environmental
remediation.
However,
the
migration
agglomeration
of
single
atoms
significantly
diminish
reactivity
increase
operating
cost
catalyst.
Due
to
size
effect,
space
confinement
electron
are
stabilized,
overall
catalytic
performance
is
also
improved.
The
effect
can
be
enhanced
by
modifying
supporting
materials
with
ordered
regular
pore
structures
improving
binding
mode
between
support
atom.
In
this
Review,
confined
functional
structure
will
explained
for
synthesis
SACs.
It
elucidates
mechanisms
formation
elaborates
how
improves
performance.
This
Review
helpful
better
understanding,
controlling,
utilizing
design
SACs
impressive
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(43)
Published: Sept. 5, 2023
Singlet
oxygen
(1
O2
)
is
an
excellent
reactive
species
(ROSs)
for
the
selective
conversion
of
organic
matter,
especially
in
advanced
oxidation
processes
(AOPs).
However,
due
to
huge
dilemma
synthesizing
single-site
type
catalysts,
control
and
regulation
1
generation
AOPs
still
challenging
underlying
mechanism
remains
largely
obscure.
Here,
taking
advantage
well-defined
flexibly
tunable
sites
covalent
frameworks
(COFs),
we
report
first
achievement
precisely
regulating
ROSs
peroxymonosulfate
(PMS)-based
by
site
engineering
COFs.
Remarkably,
COFs
with
bipyridine
units
(BPY-COFs)
facilitate
PMS
activation
via
a
nonradical
pathway
100
%
,
whereas
biphenyl-based
(BPD-COFs)
almost
identical
structures
activate
produce
radicals
(⋅OH
SO4.-
).
The
BPY-COFs/PMS
system
delivers
boosted
performance
degradation
target
pollutants
from
water,
which
ca.
9.4
times
that
its
BPD-COFs
counterpart,
surpassing
most
reported
PMS-based
systems.
Mechanism
analysis
indicated
highly
electronegative
pyridine-N
atoms
on
BPY-COFs
provide
extra
adsorb
terminal
H
PMS,
resulting
simultaneous
adsorption
O
one
pyridine
ring,
facilitates
cleavage
S-O
bond
generate
.
Environmental Science & Technology,
Journal Year:
2024,
Volume and Issue:
58(24), P. 10415 - 10444
Published: June 7, 2024
Persulfate
(PS)-based
advanced
oxidation
processes
(AOPs)
for
pollutant
removal
have
attracted
extensive
interest,
but
some
controversies
about
the
identification
of
reactive
species
were
usually
observed.
This
critical
review
aims
to
comprehensively
introduce
basic
concepts
and
rectify
cognitive
biases
appeals
pay
more
attention
experimental
details
in
PS-AOPs,
so
as
accurately
explore
reaction
mechanisms.
The
scientifically
summarizes
character,
generation,
different
species.
It
then
highlights
complexities
analysis
electron
paramagnetic
resonance,
uncertainties
use
probes
scavengers,
necessities
determination
scavenger
concentration.
importance
choice
buffer
solution,
operating
mode,
terminator,
filter
membrane
is
also
emphasized.
Finally,
we
discuss
current
challenges
future
perspectives
alleviate
misinterpretations
toward
mechanisms
PS-AOPs.
Environmental Science & Technology,
Journal Year:
2023,
Volume and Issue:
57(42), P. 16141 - 16151
Published: Sept. 11, 2023
This
study
constructed
hollow
multishelled
microreactors
with
a
nanoconfined
microenvironment
for
degrading
ofloxacin
(OFX)
through
peroxymonosulfate
(PMS)
activation
in
Fenton-like
advanced
oxidation
processes
(AOPs),
resulting
adequate
contaminant
mineralization.
Among
the
microreactors,
triple-shelled
Co-based
microsphere
(TS-Co/HM)
exhibited
optimal
performance;
its
OFX
degradation
rate
was
0.598
min-1,
which
higher
than
that
of
Co3O4
nanoparticles
by
8.97-fold.
The
structural
tuning
Co/HM
promoted
formation
oxygen
vacancies
(VO),
then
facilitated
evolution
high-valence
cobalt-oxo
(Co(IV)═O)
and
shifted
entire
t2g
orbital
Co
atom
upward,
promoting
catalytic
reactions.
Co(IV)═O
identified
using
phenylmethyl
sulfoxide
(PMSO)
probe
situ
Raman
spectroscopy,
theoretical
calculations
were
conducted
to
identify
lower
energy
barrier
on
defect-rich
catalyst.
Furthermore,
TS-Co/HM
catalyst
remarkable
stability
inorganic
(Cl-,
H2PO4-,
NO3-),
organic
(humic
acid),
real
water
samples
(tap
water,
river
hospital
water),
continuous
flow
system
microreactor.
could
enrich
reactants
cavities,
prolong
residence
time
molecules,
increase
utilization
efficiency
Co(IV)═O.
work
describes
an
process
involving
contaminants
elimination.
Our
results
may
encourage
use
structures
inform
design
catalysts
AOPs.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Nov. 20, 2023
Carbon-defect
engineering
in
metal
single-atom
catalysts
by
simple
and
robust
strategy,
boosting
their
catalytic
activity,
revealing
the
carbon
defect-catalytic
activity
relationship
are
meaningful
but
challenging.
Herein,
we
report
a
facile
self-carbon-thermal-reduction
strategy
for
carbon-defect
of
single
Fe-N4
sites
ZnO-Carbon
nano-reactor,
as
efficient
catalyst
Fenton-like
reaction
degradation
phenol.
The
vacancies
easily
constructed
adjacent
to
during
synthesis,
facilitating
formation
C-O
bonding
lowering
energy
barrier
rate-determining-step
Consequently,
Fe-NCv-900
with
exhibits
much
improved
than
Fe-NC-900
without
abundant
vacancies,
13.5
times
improvement
first-order
rate
constant
phenol
degradation.
shows
high
(97%
removal
ratio
only
5
min),
good
recyclability
wide-ranging
pH
universality
(pH
range
3-9).
This
work
not
provides
rational
improving
catalysts,
also
deepens
fundamental
understanding
on
how
periphery
environment
affects
property
performance
metal-N4
sites.
Advanced Materials,
Journal Year:
2024,
Volume and Issue:
36(28)
Published: April 24, 2024
Abstract
State‐of‐the‐art
Fenton‐like
reactions
are
crucial
in
advanced
oxidation
processes
(AOPs)
for
water
purification.
This
review
explores
the
latest
advancements
heterogeneous
metal‐based
catalysts
within
AOPs,
covering
nanoparticles
(NPs),
single‐atom
(SACs),
and
ultra‐small
atom
clusters.
A
distinct
connection
between
physical
properties
of
these
catalysts,
such
as
size,
degree
unsaturation,
electronic
structure,
state,
their
impacts
on
catalytic
behavior
efficacy
reactions.
In‐depth
comparative
analysis
metal
NPs
SACs
is
conducted
focusing
how
particle
size
variations
metal‐support
interactions
affect
species
pathways.
The
highlights
cutting‐edge
characterization
techniques
theoretical
calculations,
indispensable
deciphering
complex
structural
characteristics
active
sites
downsized
particles.
Additionally,
underscores
innovative
strategies
immobilizing
onto
membrane
surfaces,
offering
a
solution
to
inherent
challenges
powdered
catalysts.
Recent
advances
pilot‐scale
or
engineering
applications
Fenton‐like‐based
devices
also
summarized
first
time.
paper
concludes
by
charting
new
research
directions,
emphasizing
catalyst
design,
precise
identification
reactive
oxygen
species,
in‐depth
mechanistic
studies.
These
efforts
aim
enhance
application
potential
nanotechnology‐based
AOPs
real‐world
wastewater
treatment.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: July 9, 2024
Abstract
Developing
eco-friendly
catalysts
for
effective
water
purification
with
minimal
oxidant
use
is
imperative.
Herein,
we
present
a
metal-free
and
nitrogen/fluorine
dual-site
catalyst,
enhancing
the
selectivity
utilization
of
singlet
oxygen
(
1
O
2
)
decontamination.
Advanced
theoretical
simulations
reveal
that
synergistic
fluorine-nitrogen
interactions
modulate
electron
distribution
polarization,
creating
asymmetric
surface
configurations
electron-deficient
nitrogen
vacancies.
These
properties
trigger
selective
generation
from
peroxymonosulfate
(PMS)
improve
neighboring
reactive
species,
facilitated
by
contaminant
enrichment
at
fluorine-carbon
Lewis-acid
adsorption
sites.
Utilizing
these
insights,
synthesize
catalyst
through
montmorillonite
(MMT)-assisted
pyrolysis
(NFC/M).
This
method
leverages
role
MMT
as
an
in-situ
layer-stacked
template,
enabling
controlled
decomposition
carbon,
nitrogen,
fluorine
precursors
resulting
in
enhanced
structural
adaptability,
site
accessibility,
mass-transfer
capacity.
The
NFC/M
demonstrates
impressive
290.5-fold
increase
phenol
degradation
efficiency
than
single-site
analogs,
outperforming
most
metal-based
catalysts.
work
not
only
underscores
potential
precise
electronic
manipulations
design
but
also
advances
development
efficient
sustainable
solutions
purification.
Proceedings of the National Academy of Sciences,
Journal Year:
2024,
Volume and Issue:
121(4)
Published: Jan. 17, 2024
Nonradicals
are
effective
in
selectively
degrading
electron-rich
organic
contaminants,
which
unfortunately
suffer
from
unsatisfactory
yield
and
uncontrollable
composition
due
to
the
competitive
generation
of
radicals.
Herein,
we
precisely
construct
a
local
microenvironment
carbon
nitride–supported
high-loading
(~9
wt.%)
Fe
single-atom
catalyst
(Fe
SAC)
with
sulfur
via
facile
supermolecular
self-assembly
strategy.
Short-distance
S
coordination
boosts
peroxymonosulfate
(PMS)
activation
generates
high-valent
iron–oxo
species
IV
=O)
along
singlet
oxygen
(
1
O
2
),
significantly
increasing
yield,
PMS
utilization,
p
-chlorophenol
reactivity
by
6.0,
3.0,
8.4
times,
respectively.
The
nonradicals
is
controllable
simply
changing
content.
In
contrast,
long-distance
both
radicals
nonradicals,
could
not
promote
reactivity.
Experimental
theoretical
analyses
suggest
that
short-distance
upshifts
d
-band
center
atom,
i.e.,
being
close
Fermi
level,
changes
binding
mode
between
atom
site
generate
=O
high
yield.
S-coordinated
SAC
exhibits
excellent
application
potential
various
water
matrices.
These
findings
can
guide
rational
design
robust
SACs
toward
selective
utilization.
