ACS Applied Nano Materials,
Год журнала:
2024,
Номер
7(21), С. 24986 - 24995
Опубликована: Окт. 23, 2024
The
photocatalytic
bromination
of
arene
C–H
bonds
is
a
crucial
and
sustainable
transformation
in
organic
synthesis
chemistry.
However,
traditional
methods
suffer
from
low
efficiency,
poor
selectivity,
environmental
concerns
bromine
sources.
Herein,
we
report
decavanadate-modified
graphite
nitride
carbon
catalyst
(V10-g-C3N4)
that
exhibits
remarkable
performance
the
arene,
utilizing
nontoxic
KBr
as
source
under
visible-light
irradiation.
"electron
sponge"
property
decavanadate
catalysts
not
only
enhances
catalytic
activity
by
suppressing
recombination
photogenerated
carriers
(electrons
holes)
but
also
improves
activation
molecular
oxygen
via
single-electron
transfer
(SET),
further
enhancing
efficiency.
In
addition,
electrostatic
interaction
between
exhibited
high
stability
after
five
cycles,
without
significant
decrease.
g-C3N4
primarily
absorbs
substrates
through
π–π
interactions,
while
offers
Lewis-acid-type
anchoring
sites
for
O2,
enabling
both
O2
SET
process.
Fluorescence
quenching,
radical
trapping,
electron
paramagnetic
resonance
(EPR)
experiments
highlight
pivotal
importance
holes
substrate
activation,
underscoring
role
electrons
activating
to
•O2–.
This
work
provides
insights
into
semiconductor,
light-induced
green
Abstract
Utilizing
polymeric
catalysts
to
generate
hydrogen
peroxide
(H
2
O
)
via
photocatalysis
for
various
industrial
applications
is
a
promising
avenue,
but
the
application
potential
constrained
by
their
low
charge
separation
efficiency
and
capacity
oxygen
adsorption
activation.
Herein,
catalyst
(NiRF)
modified
with
Ni
metal
sites
on
resorcinol‐formaldehyde
(RF)
resin
presented,
which
can
efficiently
produce
H
through
in
pure
water.
The
optimal
NiRF‐5
exhibits
an
impressive
generation
rate
of
up
31.75
m
g
−1
h
under
visible
light
irradiation,
significantly
outperforming
most
reported
date.
Experimental
results
coupled
theoretical
calculations
simulation,
indicate
that
incorporation
nickel
ions
modulates
band
structure
NiRF
provides
active
conducive
transformation
oxygen.
regulate
ensure
suitable
configuration
energy.
This
work
novel
design
concept
RF‐based
photocatalysts
offers
approach
development
methods
efficient
photocatalytic
production
.
Chemocatalytic
synthesis
of
lactic
acid
(LA)
from
biomass
sugars
involves
heat-absorbing
multistep
cascade
reactions
mediated
by
different
active
sites,
often
encountering
unsatisfactory
selectivity.
Here,
a
hole-localized
carbon
nitride-based
photocatalyst
(C-CNN)
is
constructed
covalent
binding
heptazine
and
triazole
skeleton
via
C─N
bonds
further
conjugated
interaction
with
activated
carbon,
achieving
the
complete
conversion
various
to
LA
(up
98.6%
selectivity)
at
room
temperature
for
2
h.
The
introduced
electron
donor
in
C-CNN
can
not
only
enhance
adsorption
sugar
enhanced
aldose-to-ketose
isomerization
over
localized
hole
(Lewis
acid)
on
skeleton,
but
also
modulate
valence
band
oxidation
circumvent
formation
•OH
•O2
‒
selective
C3‒C4
cleavage
ketose,
thus
realizing
exclusive
LA.
Moreover,
near-infrared
light
absorption
endowed
supply
sufficient
interface
photothermal
effect
ambient
production.
Life
cycle
assessment
shows
that
photocatalytic
system
has
good
prospects
industrialization
terms
both
energy
environment.
This
work
offers
novel
insights
into
multidirectional
utilization
solar
value-added
through
rational
modulation
sites.
