Advanced Science,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 24, 2024
Abstract
Semiconductor‐based
photoelectrochemical
(PEC)
organic
transformations
usually
show
radical
characteristics,
in
which
the
reaction
selectivity
is
often
difficult
to
precisely
control
due
nonselectivity
of
radicals.
Accordingly,
several
simple
reactions
(e.g.,
oxidations
alcohols,
aldehydes,
and
other
small
molecules)
have
been
widely
studied,
while
more
complicated
processes
like
C─C
coupling
remain
challenging.
Herein,
a
synergistic
heterogeneous/homogeneous
PEC
strategy
developed
achieve
controllable
radical‐induced
mediated
by
copper‐coordination
effect
at
semiconductor/electrolyte
interfaces,
additionally
exerts
significant
impact
on
product
regioselectivity.
Through
experimental
studies
theoretical
simulations,
this
study
reveals
that
copper‐chloride
complex
effectively
regulates
formation
chloride
radicals,
typical
hydrogen
atom
transfer
agent,
semiconductor
surfaces
stabilizes
heterogeneous
interfaces
suppressing
surface
passivation.
Taking
Minisci
(the
between
2‐phenylquinoline
cyclohexane)
as
model,
yield
target
reaches
up
90%
TiO
2
photoanodes
with
95%
long‐term
stability
over
100
h.
Moreover,
such
exhibits
broad
scope
can
be
used
for
functionalization
various
heteroaromatic
hydrocarbons.
Advanced Functional Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 30, 2024
Abstract
Photoelectrochemical
solar
to
hydrogen
production
is
a
promising
way
achieve
carbon
neutrality,
but
severe
charge
recombination
in
photoanodes
limits
the
conversion
efficiency.
Herein,
Au
nanoparticles
and
Co(OH)
x
co‐sensitized
bismuth
vanadate
(BiVO
4
)
construct
AuCo(OH)
/BiVO
photoanode
for
significantly
enhancing
performance
of
photoelectrochemical
water
splitting.
This
process
improves
bulk
carrier
separation
efficiency,
surface
kinetics
oxidation,
electron
density
BiVO
through
plasmon
resonance
(SPR)
oxygen
evolution
catalysts
effect.
Additionally,
enhancement
*O
*OOH
generation
accelerate
reaction
kinetics.
Consequently,
constructed
demonstrates
an
excellent
photocurrent
6.2
mA
cm
−2
at
1.23
V
versus
reversible
electrode
stable
continuous
output
within
42
h.
work
contributes
developing
high‐efficiency
high‐stability
H
2
SPR
effect
catalysts.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(38)
Опубликована: Июль 3, 2024
Abstract
Proton
supply
is
as
critical
O
2
activation
for
artificial
photosynthesis
of
hydrogen
peroxide
(H
)
via
two‐electron
oxygen
reduction
reaction
(2e
−
ORR).
However,
proton
release
water
dissociation
frequently
hindered
because
the
sluggish
oxidation
(WOR),
extremely
limiting
efficiency
photocatalytic
H
production.
To
tackle
this
challenge,
carboxyl‐enriched
supramolecular
polymer
(perylene
tetracarboxylic
acid—PTCA)
elaborately
prepared
by
molecular
self‐assembly
overall
.
Interestingly,
interconversion
between
carboxyl
Brønsted
acid
and
its
conjugated
base
realizes
rapid
circulation.
Through
efficient
tandem
transfer
process,
spatial
effect
greatly
enhanced
with
reduced
barrier.
This
significantly
facilitates
2e
ORR
to
synthesize
in
meanwhile
promotes
4e
WOR
evolve
Consequently,
as‐developed
PTCA
exhibits
a
remarkable
yield
185.6
μM
h
−1
pure
air
atmosphere
under
visible
light
illumination.
More
impressively,
an
appreciable
78.6
can
be
well
maintained
anaerobic
system
owing
situ
generation
WOR.
Our
study
presents
novel
concept
constructing
pathway
enable
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 23, 2025
The
sluggish
water
oxidation
reaction
(WOR)
is
considered
the
kinetic
bottleneck
of
artificial
photosynthesis
due
to
complicated
four-electron
and
four-proton
transfer
process.
Herein,
we
find
that
WOR
can
be
kinetically
nearly
barrierless
on
four
representative
photoanodes
(i.e.,
α-Fe2O3,
TiO2,
WO3,
BiVO4)
under
concentrated
light
irradiation,
wherein
rate-limiting
O-O
bond
formation
step
driven
by
accumulated
surface
photogenerated
holes
exhibit
a
superior
fourth-order
kinetics.
activation
energy
about
0.03
eV
for
pathway,
which
quantitatively
estimated
combining
Population
model
Butler-Volmer
with
Eyring-like
equation
further
confirmed
density
functional
theory
calculations.
rate
this
condition
shows
more
than
1
order
magnitude
enhancement
compared
first-,
second-,
or
third-order
Focusing
high-density
form
adjacent
FeV═O
intermediates
effectively
activate
surface-adsorbed
H2O
molecules
via
hydrogen-bonding
effect,
as
revealed
operando
Raman
measurements
ab
initio
molecular
dynamics
simulations.
This
work
discloses
systematic
understanding
internal
relations
between
orders
future
study.
