ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(10), P. 7308 - 7320
Published: April 25, 2024
The
rational
design
and
modification
of
heterojunction
photocatalysts
aimed
at
achieving
fast
charge
transport
efficient
photocatalytic
performance
is
a
central
goal
solar-light-driven
water
splitting
hydrogen
evolution,
yet
this
remains
challenge.
Herein,
we
prepare
hierarchical
photocatalyst
composed
few-layer
violet
phosphorene
(VP),
cadmium
sulfide
(CdS)
nanoparticles
(NPs),
Pd
single
atoms
(SAs)
by
facile
one-step
ball-milling
strategy.
underlying
VP/CdS
p–n
heterojunctions
are
verified
to
adopt
S-scheme
directional
transfer
combining
in
situ
irradiated
X-ray
photoelectron
spectroscopy
electron
paramagnetic
resonance.
atomically
dispersed
sites
the
low-valence
state
coupled
with
synergistically
achieve
ultrafast
(2.2
ps),
which
interfacial
Pd–S
Pd–P
bonds
serve
as
channels.
In
addition,
density-functional
theory
calculations
reveal
key
role
enhancement
light-harvesting
capacity
optimization
proton
adsorption
thermodynamics.
A
visible-light
production
rate
82.5
mmol
h–1
g–1
attained
an
optimal
1
wt
%
Pd–5
photocatalyst,
manifests
54-fold
increase
respect
that
CdS
NPs,
addition
apparent
quantum
efficiency
(AQE)
25.7%
420
nm.
This
work
showcases
valid
combination
SAs
for
separation
promoting
others.
Advanced Functional Materials,
Journal Year:
2024,
Volume and Issue:
34(38)
Published: May 11, 2024
Abstract
Emerging
step‐scheme
(S‐scheme)
heterostructures
hold
unique
superiority
in
steering
directional
charge
transport
and
reinforcing
redox
capacity,
yet
rational
modification
of
S‐scheme
by
single
atoms
(SAs)
for
efficient
photocatalytic
H
2
evolution
is
rarely
reported.
In
this
work,
Pd
SAs‐modulated
organic–inorganic
g‐C
3
N
4
/CdS
are
designed
prepared
a
one‐pot
mechanochemical
approach
allowing
nanosheets/CdS
nanoparticles
to
confine
atomically
dispersed
co‐catalysts.
The
charge‐transfer
pathway
corroborated
combination
situ
irradiated
X‐ray
photoelectron
spectroscopy,
electron
paramagnetic
resonance,
Kelvin
probe
force
microscopy.
Density
functional
theory
(DFT)
calculations,
high‐angle
annular
dark‐field
scanning
transmission
microscopy,
absorption
fine
structure
identify
Pd‐S
Pd‐N
atomic
moieties
underpinned
the
electronic
interaction
between
SAs
heterostructures,
which
d
‐band
center
optimized
proton
adsorption
thermodynamically.
Further,
alongside
concert
boost
rapid
migration
photogenerated
electrons
(1.05
ps)
via
Pd─S
Pd─N
bond‐derived
channels.
A
maximal
rate
85.66
mmol
h
−1
g
achieved
1
wt%
Pd‐20
hierarchical
composites.
This
work
may
guide
design
high‐efficiency
S‐scheme‐based
photocatalysts
solar‐to‐H
conversion
beyond.
Small,
Journal Year:
2023,
Volume and Issue:
20(21)
Published: Dec. 10, 2023
Abstract
To
address
charge
recombination
in
photocatalysis,
the
prevalent
approach
involves
use
of
noble
metal
cocatalysts.
However,
precise
factors
influencing
this
performance
variability
based
on
cocatalyst
selection
have
remained
elusive.
In
study,
CdS
hollow
spheres
loaded
with
distinct
nanoparticles
(Pt,
Au,
and
Ru)
are
investigated
by
femtosecond
transient
absorption
(fs‐TA)
spectroscopy.
A
more
pronounced
internal
electric
field
leads
to
creation
a
larger
Schottky
barrier,
order
Pt‐CdS
>
Au‐CdS
Ru‐CdS.
Owing
these
varying
barrier
heights,
interface
electron
transfer
rate
(
K
e
)
efficiency
η
metal‐CdS
acetonitrile
(ACN)
exhibit
following
trend:
Ru‐CdS
Pt‐CdS.
trends
for
water
different
(Ru‐CdS
Au‐CdS)
due
influence
water,
leading
consumption
photogenerated
electrons
affecting
metal/CdS
state.
Although
displays
highest
,
its
overall
photocatalytic
performance,
particularly
H
2
production,
lags
behind
that
backflow
from
Ru
CdS.
This
work
offers
fresh
perspective
origin
differences
provides
valuable
insights
design
construction.
