ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(9), P. 6280 - 6288
Published: April 21, 2023
Polymeric
carbon
nitride
(C3N4)
has
attracted
great
attention
in
photocatalysis
due
to
its
low-cost,
visible-light
response,
and
environment-friendly
merits.
However,
the
catalytic
efficiency
of
pristine
bulk
C3N4
is
severely
limited
by
poor
photoinduced
electron/hole
pair
separation
interlayer
charge
transport.
Herein,
single-atom
Cu
bridged
into
sheet
interlayers
through
thermal
condensation
self-assembly
supramolecules
precursors
melamine–cyanuric
acid
monomers.
Simultaneously,
N
vacancies
are
engineered
only
gradient
temperature.
The
bridges
serve
as
electron
channels
promote
experimental
results
calculations
demonstrate
that
break
symmetry
C3N4,
allowing
more
electrons
pass
delocalized
π-conjugated
network
sites,
which
facilitates
transfer
between
layers,
resulting
effective
pairs,
optimal
distribution,
lower
hydrogen
evolution
barrier.
As
a
result,
photocatalyst
at
stationary
point
with
1
wt
%
Pt
cocatalyst
presents
high
photocatalytic
production
rate
(11.23
mmol
g–1
h–1),
reaching
apparent
quantum
yield
31.60%
420
nm.
It
noted
still
exhibits
605.15
μmol
h–1
absence
cocatalyst.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(25), P. 14005 - 14012
Published: March 31, 2021
Abstract
Dual‐metal
single‐atom
catalysts
exhibit
superior
performance
for
oxygen
reduction
reaction
(ORR),
however,
the
synergistic
catalytic
mechanism
is
not
deeply
understood.
Herein,
we
report
a
dual‐metal
catalyst
consisted
of
Cu−N
4
and
Zn−N
on
N‐doped
carbon
support
(Cu/Zn−NC).
It
exhibits
high‐efficiency
ORR
activity
with
an
E
onset
0.98
V
1/2
0.83
V,
excellent
stability
(no
degradation
after
10
000
cycles),
surpassing
state‐of‐the‐art
Pt/C
great
mass
Pt‐free
single
atom
catalysts.
Operando
XANES
demonstrates
that
as
active
center
experiences
change
from
atomic
dispersion
to
cluster
cooperation
during
process,
then
turns
state
again
reaction.
DFT
calculation
further
indicates
adjustment
effect
Zn
d‐orbital
electron
distribution
Cu
could
benefit
stretch
cleavage
O‐O
center,
speeding
up
process
rate
determining
step
OOH*.
Joule,
Journal Year:
2022,
Volume and Issue:
6(1), P. 92 - 133
Published: Jan. 1, 2022
Artificial
photocatalytic
energy
conversion
represents
a
highly
intriguing
strategy
for
solving
the
crisis
and
environmental
problems
by
directly
harvesting
solar
energy.
The
development
of
efficient
photocatalysts
is
central
task
pushing
real-world
application
reactions.
Due
to
maximum
atomic
utilization
efficiency
distinct
advantages
outstanding
catalytic
activity,
single-atom
catalysts
(SACs)
have
emerged
as
promising
candidates
photocatalysts.
In
current
review,
recent
progresses
challenges
on
SACs
systems
are
presented.
Fundamental
principles
focusing
charge
separation/transfer
molecular
adsorption/activation
photocatalysis
systemically
explored.
We
outline
how
isolated
reactive
sites
facilitate
photogenerated
electron–hole
transfer
promote
construction
photoactivation
cycles.
widespread
adoption
in
diverse
reactions
also
comprehensively
introduced.
By
presenting
these
advances
addressing
some
future
with
potential
solutions
related
integral
over
SACs,
we
expect
shed
light
forthcoming
research
conversion.
Nature Communications,
Journal Year:
2022,
Volume and Issue:
13(1)
Published: March 11, 2022
Single-site
cocatalysts
engineered
on
supports
offer
a
cost-efficient
pathway
to
utilize
precious
metals,
yet
improving
the
performance
further
with
minimal
catalyst
loading
is
still
highly
desirable.
Here
we
have
conducted
photochemical
reaction
stabilize
ultralow
Pt
co-catalysts
(0.26
wt%)
onto
basal
plane
of
hexagonal
ZnIn2S4
nanosheets
(PtSS-ZIS)
form
Pt-S3
protrusion
tetrahedron
coordination
structure.
Compared
traditional
defect-trapped
single-site
counterparts,
protruding
single-sites
h-ZIS
photocatalyst
enhance
H2
evolution
yield
rate
by
factor
2.2,
which
could
reach
17.5
mmol
g-1
h-1
under
visible
light
irradiation.
Importantly,
through
simple
drop-casting,
thin
PtSS-ZIS
film
prepared,
and
large
amount
observable
bubbles
are
generated,
providing
great
potential
for
practical
solar-light-driven
production.
The
single
atoms
in
inhibit
recombination
electron-hole
pairs
cause
tip
effect
optimize
adsorption/desorption
behavior
H
effective
proton
mass
transfer,
synergistically
promote
thermodynamics
kinetics.
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
60(9), P. 4815 - 4822
Published: Nov. 3, 2020
Abstract
Actiniae‐like
carbon
nitride
(ACN)
bundles
were
synthesized
by
the
pyrolysis
of
an
asymmetric
supramolecular
precursor
prepared
from
L‐arginine
(L‐Arg)
and
melamine.
ACN
has
adjustable
band
gaps
(2.25
eV–2.75
eV)
hollow
microtubes
with
ultrathin
pore
walls,
which
enrich
reaction
sites,
improve
visible‐light
absorption
enhance
charge
separation.
In
presence
phenylcarbinol,
exhibited
excellent
water‐splitting
ability
(95.3
μmol
h
−1
)
in
meanwhile
phenylcarbinol
was
selectively
oxidized
to
benzaldehyde
(conversion
90.9
%,
selectivity
99.7
%)
under
solar
irradiation.
For
concurrent
reactions,
2
D
isotope
labeling,
separation,
detection
conducted
confirm
that
proton
source
released
hydrogen
is
water.
The
mechanism
water
splitting
oxidation
also
investigated.
ACS Catalysis,
Journal Year:
2021,
Volume and Issue:
11(21), P. 13266 - 13279
Published: Oct. 18, 2021
It
is
of
great
importance
to
explore
and
achieve
a
more
effective
approach
toward
the
controllable
synthesis
single-atom-based
photocatalysts
with
high
metal
content
long-term
durability.
Herein,
single-atom
platinum
(Pt)
loading
anchored
on
pore
walls
two-dimensional
β-ketoenamine-linked
covalent
organic
frameworks
(TpPa-1-COF)
presented.
Aided
by
advanced
characterization
techniques
aberration-corrected
high-angle
annular
dark-field
scanning
transmission
electron
microscopy
(AC
HAADF-STEM)
X-ray
absorption
fine
structure
(XAFS)
spectroscopy,
it
has
been
demonstrated
that
atomically
dispersed
Pt
formed
TpPa-1-COF
support
through
six-coordinated
C3N–Pt–Cl2
species.
The
optimized
Pt1@TpPa-1
catalyst
exhibits
photocatalytic
H2
evolution
rate
719
μmol
g–1
h–1
under
visible-light
irradiation,
actual
0.72
wt
%,
large
turnover
frequency
(TOF)
19.5
h–1,
activity
equivalent
3.9
48
times
higher
than
those
nanoparticles/TpPa-1
bare
TpPa-1,
respectively.
improved
performance
for
ascribed
photogenerated
charge
separation
migration
well-dispersed
active
sites
Pt.
Moreover,
density
functional
theory
(DFT)
calculations
further
reveal
role
single
atoms
in
enhanced
evolution.
Overall,
this
work
provides
some
inspiration
designing
outstanding
stability
efficiency
using
COFs
as
support.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(29)
Published: May 6, 2022
Abstract
Simultaneous
regulation
of
the
coordination
environment
single‐atom
catalysts
(SACs)
and
engineering
architectures
with
efficient
exposed
active
sites
are
strategies
for
boosting
peroxymonosulfate
(PMS)
activation.
We
isolated
cobalt
atoms
dual
nitrogen
oxygen
(Co−N
3
O
1
)
on
oxygen‐doped
tubular
carbon
nitride
(TCN)
by
pyrolyzing
a
hydrogen‐bonded
cyanuric
acid
melamine–cobalt
acetate
precursor.
The
theoretically
constructed
Co−N
moiety
TCN
exhibited
an
impressive
mass
activity
7.61×10
5
min
−1
mol
high
2
selectivity.
Theoretical
calculations
revealed
that
single
occupied
environment,
PMS
adsorption
was
promoted
energy
barriers
reduced
key
*O
intermediate
produced
.
were
attached
to
widely
used
poly(vinylidene
fluoride)
microfiltration
membrane
deliver
antibiotic
wastewater
treatment
system
97.5
%
ciprofloxacin
rejection
over
10
hours,
thereby
revealing
suitability
industrial
applications.
Energy & Fuels,
Journal Year:
2021,
Volume and Issue:
35(8), P. 6504 - 6526
Published: April 5, 2021
Graphitic
carbon
nitride
(g-C3N4),
a
polymeric
semiconductor,
has
become
rising
star
for
photocatalytic
energy
conversion
because
of
its
facile
accessibility,
metal-free
nature,
low
cost,
and
environmentally
benign
properties.
This
work
reviews
the
latest
progress
g-C3N4-based
materials
in
visible-light-driven
water
splitting
to
hydrogen.
It
begins
with
brief
history
g-C3N4,
followed
by
various
engineering
strategies
such
as
elemental
doping,
copolymerization,
crystalline
tailoring,
surface
engineering,
single-atom
modification,
elevated
decomposition.
In
addition,
synthesis
g-C3N4
different
dimensions
(0D,
1D,
2D,
3D)
configurations
series
heterojunctions
(type
II,
Z-scheme,
S-scheme,
g-C3N4/metal,
g-C3N4/carbon
heterojunctions)
were
also
discussed
their
improvement
hydrogen
production.
Lastly,
challenges
opportunities
nanomaterials
are
provided.
is
anticipated
that
this
review
will
promote
further
development
emerging
more
efficiency
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Nov. 6, 2023
Photocatalytic
two-electron
oxygen
reduction
to
produce
high-value
hydrogen
peroxide
(H2O2)
is
gaining
popularity
as
a
promising
avenue
of
research.
However,
structural
evolution
mechanisms
catalytically
active
sites
in
the
entire
photosynthetic
H2O2
system
remains
unclear
and
seriously
hinders
development
highly-active
stable
photocatalysts.
Herein,
we
report
high-loading
Ni
single-atom
photocatalyst
for
efficient
synthesis
pure
water,
achieving
an
apparent
quantum
yield
10.9%
at
420
nm
solar-to-chemical
conversion
efficiency
0.82%.
Importantly,
using
situ
synchrotron
X-ray
absorption
spectroscopy
Raman
directly
observe
that
initial
Ni-N3
dynamically
transform
into
high-valent
O1-Ni-N2
after
O2
adsorption
further
evolve
form
key
*OOH
intermediate
before
finally
forming
HOO-Ni-N2.
Theoretical
calculations
experiments
reveal
structure
reduces
formation
energy
barrier
suppresses
O=O
bond
dissociation,
leading
improved
production
activity
selectivity.