ACS Catalysis,
Год журнала:
2022,
Номер
12(24), С. 15157 - 15167
Опубликована: Ноя. 28, 2022
In
the
design
of
photocatalysts
for
C(sp3)–H
selective
oxidation,
photogenerated
holes
have
been
regarded
as
critical
dissociation.
However,
poor
charge-transfer
efficiency
restricts
localization
on
surface
catalyst.
Herein,
a
Z-scheme
structure
modulated
by
interfacial
chemical
bonding
is
constructed
via
in
situ
growth
Cs3Bi2Br9
nanodots
(CBB)
defective
BiOBr
nanosheets
(d-BiOBr)
photocatalytic
toluene
oxidation.
Benefited
from
internal
electric
field,
Bi–Br
bond
becomes
direct
channel
to
accelerate
electron
transfer
conduction
band
d-BiOBr
valence
CBB,
resulting
higher
charges
CBB/d-BiOBr.
By
diffuse
reflectance
infrared
Fourier
transform
spectroscopy,
paramagnetic
resonance,
and
density
functional
theory
calculations,
proved
be
essential
adsorption
dissociation
bond.
The
optimized
CBB/d-BiOBr
performs
well
oxidation
benzaldehyde
benzyl
alcohol,
giving
conversion
rate
up
72.3
μmol
h–1
selectivity
nearly
100%.
activity
26.6-fold
6.8-fold
that
pristine
respectively.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(17), С. 7720 - 7730
Опубликована: Март 30, 2022
Photoelectrocatalytic
(PEC)
glycerol
oxidation
offers
a
sustainable
approach
to
produce
dihydroxyacetone
(DHA)
as
valuable
chemical,
which
can
find
use
in
cosmetic,
pharmaceutical
industries,
etc.
However,
it
still
suffers
from
the
low
selectivity
(≤60%)
that
substantially
limits
application.
Here,
we
report
PEC
of
DHA
with
75.4%
over
heterogeneous
photoanode
Bi2O3
nanoparticles
on
TiO2
nanorod
arrays
(Bi2O3/TiO2).
The
be
maintained
at
∼65%
under
relatively
high
conversion
(∼50%).
existing
p-n
junction
between
and
promotes
charge
transfer
thus
guarantees
photocurrent
density.
Experimental
combined
theoretical
studies
reveal
prefers
interact
middle
hydroxyl
facilitates
selective
DHA.
Comprehensive
reaction
mechanism
suggest
follows
two
parallel
pathways,
including
electrophilic
OH*
(major)
lattice
oxygen
(minor)
oxidations.
Finally,
designed
self-powered
system,
achieving
productivity
1.04
mg
cm-2
h-1
>70%
H2
0.32
mL
h-1.
This
work
may
shed
light
potential
strategy
for
biomass
valorization
toward
value-added
products
via
anode
surface
engineering.
Advanced Materials,
Год журнала:
2022,
Номер
34(29)
Опубликована: Март 19, 2022
Abstract
Whilst
the
photocatalytic
technique
is
considered
to
be
one
of
most
significant
routes
address
energy
crisis
and
global
environmental
challenges,
solar‐to‐chemical
conversion
efficiency
still
far
from
satisfying
practical
industrial
requirements,
which
can
traced
suboptimal
bandgap
electronic
structure
photocatalysts.
Strain
engineering
a
universal
scheme
that
finely
tailor
materials,
hence
supplying
novel
avenue
boost
their
performance.
Accordingly,
explore
promising
directions
for
certain
breakthroughs
in
strained
photocatalysts,
an
overview
on
recent
advances
strain
basics
effect,
creations
as
well
characterizations
simulations
level
provided.
Besides,
potential
applications
photocatalysis
are
summarized,
vision
future
controllable‐electronic‐structure
photocatalysts
by
also
given.
Finally,
perspectives
challenges
strain‐promoted
discussed,
placing
emphasis
creation
decoupling
modification
theoretical
frameworks.
Energy & Environmental Science,
Год журнала:
2023,
Номер
17(2), С. 518 - 530
Опубликована: Дек. 7, 2023
A
new
all-in-one
design
concept
of
constructing
photochromic
single
atom
photocatalysts
is
proposed
to
achieve
both
high
activity
and
selectivity
photocatalytic
CO
2
-to-CH
4
conversion.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(7)
Опубликована: Дек. 29, 2023
Abstract
Photocatalytic
conversion
of
CO
2
and
H
O
into
fuels
oxygen
is
a
highly
promising
solution
for
carbon‐neutral
recycling.
Traditionally,
researchers
have
studied
reduction
oxidation
separately,
overlooking
potential
synergistic
interplay
between
these
processes.
This
study
introduces
an
innovative
approach,
spatial
synergy,
which
encourages
progress
by
bringing
the
two
half‐reactions
atomic
proximity.
To
facilitate
this,
we
developed
defective
ZnIn
S
4
‐supported
single‐atom
Cu
catalyst
(Cu−SA/D−ZIS),
demonstrates
remarkable
catalytic
performance
with
rates
112.5
μmol
g
−1
h
water
52.3
,
exhibiting
six‐fold
enhancement
over
D−ZIS.
The
structural
characterization
results
indicated
that
trapping
effect
vacancy
associates
on
copper
led
to
formation
unsaturated
coordination
structure,
Cu‐S
3
consequently
giving
rise
Zn
′
V
⋅⋅
“
defect
complexes.
FT‐IR
studies
coupled
theoretical
calculations
reveal
spatially
”,
where
breakage
O−H
in
synchronized
*COOH,
significantly
lowering
energy
barrier.
Notably,
this
and,
first
time,
substantiates
synergy
through
combination
experimental
analyses,
providing
fresh
insight
optimizing
photocatalytic
system.
ACS Catalysis,
Год журнала:
2024,
Номер
14(7), С. 4791 - 4798
Опубликована: Март 14, 2024
Solar
photocatalytic
technology
has
exhibited
significant
potential
for
upgrading
the
value-added
chemicals
industry
through
efficient
C–H
bond
activation,
such
as
selective
toluene
oxidation.
However,
improvement
in
activation
of
is
still
a
challenge.
Herein,
(110)
facet-exposed
BiOBr
(EC-BiOBr)
synthesized
via
facile
crystal
facet
control
strategy
an
increasing
exposure
Lewis
acid
sites,
confirmed
by
situ
Fourier-transform
infrared
spectroscopy
(FT-IR)
using
ammonia
probe
molecule.
In
FT-IR
results
substantiated
improved
absorption
capacity
EC-BiOBr
toluene.
Density
functional
theory
(DFT)
calculations
indicated
that
acid–base
pairs
formed
Bi
sites
and
O
can
adsorb
directionally,
precisely
matching
orbit
spaces
conduction
band
(Bi
6p
state)
valence
(O
2p
Br
4p
states).
Benefiting
from
oriented
adsorption
toluene,
electron
could
transfer
to
photogenerated
hole
precisely,
thus
achieving
activation.
Compared
(001)
(H–BiOBr),
11-fold
conversion
rate
(from
233
2460
μmol
g–1
h–1)
was
observed
group,
benzaldehyde
formation
increased
1623
h–1.
Active
species
identification
DFT
revealed
superoxide
radicals
were
involved
primary
reactive
subsequent
oxidation
benzyl
generated
This
work
highlights
importance
surface
regulated
strategy,
which
conducive
rational
design
photocatalysts
with
high
performance
