Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(40), P. 21751 - 21755
Published: Aug. 4, 2021
Abstract
Singlet
oxygen
(
1
O
2
)
is
an
excellent
active
species
for
the
selective
degradation
of
organic
pollutions.
However,
it
difficult
to
achieve
high
efficiency
and
selectivity
generation
.
In
this
work,
we
develop
a
graphitic
carbon
nitride
supported
Fe
single‐atoms
catalyst
(Fe
/CN)
containing
highly
uniform
Fe‐N
4
sites
with
loading
11.2
wt
%.
The
/CN
achieves
100
%
by
activating
peroxymonosulfate
(PMS),
which
shows
ultrahigh
p‐chlorophenol
efficiency.
Density
functional
theory
calculations
results
demonstrate
that
in
contrast
Co
Ni
single‐atom
sites,
adsorb
terminal
PMS,
can
facilitate
oxidization
PMS
form
SO
5
.−
,
thereafter
efficiently
generate
selectivity.
addition,
exhibits
strong
resistance
inorganic
ions,
natural
matter,
pH
value
during
pollutants
presence
PMS.
This
work
develops
novel
production
efficient
pollutants.
Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(8), P. 5281 - 5322
Published: Jan. 1, 2021
This
review
presents
the
recent
advances
in
synthetic
strategies,
characterisation,
and
computations
of
carbon-based
single-atom
catalysts,
as
well
their
innovative
applications
mechanisms
advanced
oxidation
technologies.
Environmental Science & Technology,
Journal Year:
2022,
Volume and Issue:
56(16), P. 11635 - 11645
Published: July 11, 2022
Single-atom
catalysts
(SACs)-based
peroxymonosulfate
(PMS)
systems
are
highly
selective
to
the
type
of
organic
pollutants
while
mechanisms
remain
ambiguous.
In
this
work,
we
carried
out
experimental
and
theoretical
investigations
reveal
origins
selectivity
radical
nonradical
pathways
in
a
designated
Co–N4–C/PMS
system.
Two
typical
[bisphenol
A
(BPA)
metronidazole
(MNZ)]
with
different
molecular
structures
were
employed
for
comparison.
We
found
that
oxidation
(SO4•–
HO•)
electron-transfer
pathway
(ETP)
co-existed
Pollutants
(e.g.,
MNZ)
high
redox
potential
degraded
primarily
by
free
radicals
rather
than
ETP,
oxidization
low-redox
BPA)
was
dominated
ETP
at
surface
region
Co–N4–C
which
overwhelmed
contributions
homogeneous
phase.
Intriguingly,
could
be
manipulated
PMS
loading,
simultaneously
increased
population
elevated
Co–N4–C-PMS*
complexes
ETP.
Findings
from
work
will
unravel
mysterious
behavior
SACs/PMS
micropollutants.
Proceedings of the National Academy of Sciences,
Journal Year:
2023,
Volume and Issue:
120(16)
Published: April 11, 2023
The
high-valent
cobalt-oxo
species
(Co(IV)=O)
is
being
increasingly
investigated
for
water
purification
because
of
its
high
redox
potential,
long
half-life,
and
antiinterference
properties.
However,
generation
Co(IV)=O
inefficient
unsustainable.
Here,
a
cobalt-single-atom
catalyst
with
N/O
dual
coordination
was
synthesized
by
O-doping
engineering.
O-doped
(Co-OCN)
greatly
activated
peroxymonosulfate
(PMS)
achieved
pollutant
degradation
kinetic
constant
73.12
min-1
g-2,
which
4.9
times
higher
than
that
Co-CN
(catalyst
without
O-doping)
those
most
reported
single-atom
catalytic
PMS
systems.
Co-OCN/PMS
realized
dominant
oxidation
pollutants
increasing
the
steady-state
concentration
(1.03
×
10-10
M)
5.9
compared
Co-CN/PMS.
A
competitive
kinetics
calculation
showed
contribution
to
micropollutant
97.5%
during
process.
Density
functional
theory
calculations
influenced
charge
density
(increased
Bader
transfer
from
0.68
0.85
e),
optimized
electron
distribution
Co
center
d-band
-1.14
-1.06
eV),
enhanced
adsorption
energy
-2.46
-3.03
eV,
lowered
barrier
key
reaction
intermediate
(*O*H2O)
formation
1.12
0.98
eV.
Co-OCN
fabricated
on
carbon
felt
flow-through
device,
continuous
efficient
removal
micropollutants
(degradation
efficiency
>85%
after
36
h
operation).
This
study
provides
new
protocol
activation
elimination
through
heteroatom-doping
metal-oxo
purification.
