Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 14, 2024
While
being
important
candidate
for
heterogeneous
photocatalyst,
conjugated
polymer
typically
exhibits
random
charge
transfers
between
the
alternating
donor
and
acceptor
units,
which
severely
limits
its
catalytic
efficiency.
Herein,
inspired
by
natural
photosystem,
concept
of
guiding
migration
to
specific
reaction
sites
is
employed
significantly
boost
photocatalytic
performance
linear
polymers
(LCPs)
with
pendant
functional
groups
via
creating
programmed
charge-transfer
channels
from
backbone
moiety.
The
benzothiadiazole,
as
revealed
in
both
situ
X-ray
photoelectron
spectroscopy
(XPS)
density
theory
(DFT)
calculations,
can
act
electron
"reservoir"
that
aggregates
electrons
at
active
sites.
Moreover,
presence
channels,
evidenced
transient
absorption
(TAS),
accelerates
transfer,
preventing
recombination
holes.
As
a
result,
this
elaborately-designed
architecture,
photogenerated
move
smoothly
towards
reduction
sites,
facilitating
O
Small,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 5, 2025
Abstract
Achieving
synergistic
oxidation
and
reduction
represents
a
significant
challenge
in
the
field
of
photocatalysis.
In
this
study,
hydrothermal/in
situ
construction
Bi
atom
clusters
within
2
Sn
O
7
/ZnIn
S
4
(BSO/ZIS)
heterostructures
is
reported.
These
exhibit
self‐accelerating
charge‐transfer
mechanisms
facilitated
by
internal
electric
fields
bonding
bridges,
resulting
highly
efficient
light
absorption
capabilities.
X‐ray
photoelectron
spectroscopy
(XPS)
Kelvin
probe
force
microscopy
(KPFM),
as
well
theoretical
calculations,
indicate
that
canonical
induction
promotion
electrons
holes
lowers
activation
energy
CHO*
generation,
allowing
simultaneous
CO
toluene
over
catalyst,
enhances
proton‐coupling
electron‐transfer
processes,
unique
reaction
mechanism.
The
reactant,
Bi‐Bi
(B‐BSO/ZIS)
heterostructure
achieves
rate
to
726.3
µmol
g
−1
h
(99.9%
selectivity)
benzaldehyde
2362.0
(98.0%
selectivity),
which
increases
activity
14.6
5.7
times
compared
pristine
ZnIn
.
This
study
underscores
significance
modulating
photocatalytic
pathway
through
strategic
selection
metal
reactants,
contributing
rational
design
photocatalysts
for
enhanced
adsorption
stabilization
*H.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
unknown, P. 17654 - 17663
Published: Nov. 15, 2024
The
photosynthesis
of
hydrogen
peroxide
(H2O2)
from
pure
water
and
oxygen
using
metal-free
photocatalysts
offers
a
renewable
approach
to
convert
solar
energy
storable
chemical
energy.
However,
the
efficiency
H2O2
is
often
hindered
by
rapid
recombination
photogenerated
charge
carriers.
Herein,
we
present
an
elegantly
designed
covalent
triazine
framework
(CTF)
photocatalyst,
denoted
as
Ace-asy-CTF,
with
stepwise
electron
transfer
pathway
for
highly
efficient
H2O2.
Notably,
Ace-asy-CTF
possesses
localized
excited-state
distribution
that
created
weakly
conjugated
acetenyl
units
in
asymmetric
frameworks,
revealed
transient
spectroscopies
further
supported
theoretical
calculations.
Meanwhile,
introduced
also
serve
active
sites
reduction
reaction
(ORR).
simultaneously
enhanced
two-step
2e–
ORR
result
excellent
yield
2594
μmol
g–1
h–1,
directly
produced
without
requiring
any
sacrificial
reagents.
This
work
paves
way
development
next-generation
catalysts,
providing
feasible
benchmark
stable
Small,
Journal Year:
2024,
Volume and Issue:
20(45)
Published: July 27, 2024
Abstract
Modulating
the
electronic
properties
of
transition
metal
sites
in
photocatalysts
at
atomic
level
is
essential
for
achieving
high‐activity
carbon
dioxide
photoreduction
(CO
2
PR).
An
strategy
herein
proposed
to
engineer
In‐d‐band
center
InVO
4
by
incorporating
MnO
x
nanoparticles
and
oxygen
vacancies
(V
O
)
into
holey
nanobelts
(MnO
/V
‐InVO
),
which
synergistically
modulates
a
moderate
consequently
leads
high‐efficiency
CO
PR.
The
catalyst
with
optimized
property
exhibits
single
evolution
rate
up
145.3
µmol
g
−1
h
monoxide
(CO)
product
selectivity
92.6%,
coming
out
front
reported
‐based
materials.
It
discovered
that
modulated
favors
interaction
between
In
their
intermediates,
thereby
improves
thermodynamics
kinetics
PR‐to‐CO
reaction.
This
work
not
only
demonstrates
effective
engineering
d
orbital
low‐coordination
atoms
promote
PR,
but
also
paves
way
application
tuning
d‐band
develop
catalysts.
