ACS Applied Polymer Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 5, 2024
Metal-free
polymeric
photocatalysts
with
tunable
building
blocks,
ample
redox-active
centers,
and
exceptional
light-harvesting
capability
have
emerged
as
promising
candidates
for
generating
hydrogen
peroxide
(H2O2)
through
the
oxygen
reduction
reaction
(ORR)
water
oxidation
(WOR).
The
slow
kinetics
of
WOR
process
coupled
rapid
charge
recombination
nevertheless
impedes
efficient
generation
H2O2.
Herein,
a
thiophene
functionalized
linear
conjugated
polymer
(DEB-Tp-S2)
was
fabricated
effective
overall
H2O2
photoproduction.
DEB-Tp-S2
exhibits
high
initial
photocatalytic
yield
rate
2762
μmol
g–1
h–1
in
absence
sacrificial
additives
possesses
outstanding
cycling
stability.
Experimental
density
functional
theory
(DFT)
results
exhibit
that
moieties
can
reduce
strength
O–H
bond
H2O,
which
promotes
4e–
process,
thereby
suppressing
improving
proton
supply.
This
work
reveals
indispensable
role
chemical
structure
engineering
optimizing
their
offers
fresh
insights
into
design
achieving
production.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Март 11, 2025
Photocatalysis
provides
a
sustainable
and
environment-friendly
strategy
to
produce
H2O2,
yet
the
catalytic
efficiency
of
H2O2
overall
photosynthesis
(O2
+
2H2O
→
2H2O2)
needs
be
further
improved,
especially
in
absence
additional
cocatalysts,
photosensitizers
sacrificial
agents.
Here
we
find
that
hydrogen-bonded
organic
frameworks
can
serve
as
photocatalysts
for
under
above-mentioned
conditions.
Specifically,
constructed
donor–acceptor
framework
exhibits
high
photocatalytic
activity
photosynthesis,
with
production
rate
681.2
μmol
g-1
h-1.
The
control
experiments
theoretical
calculation
revealed
structures
not
only
accelerate
charge
separation
transfer
but
also
optimize
reaction
pathways,
which
significantly
boosts
photosynthesis.
This
work
insights
into
design
development
efficient
A
series
were
developed
production.
These
materials
are
shown
facilitate
pathway
toward
H2O2.
Advanced Functional Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 4, 2025
Abstract
Covalent
organic
frameworks
(COFs)
are
promising
for
photocatalytic
H₂O₂
generation.
However,
imine‐linked
COFs
often
suffer
from
poor
charge
separation
and
low
performance.
Therefore,
constructing
sp
2
carbon‐linked
with
extended
π‐conjugation
is
very
significant
in
boosting
the
properties,
but
their
synthesis
challenging
due
to
reversibility
of
C═C
bond.
Here,
two
vinylene‐linked
COFs:
BBT‐ACN
COF‐1
COF‐2
designed.
To
investigate
effects
different
structures
on
exciton
binding
energy
(
E
b
),
designed
possesses
a
Donor–Acceptor
(D–A)
structure
electron‐deficient
benzobisthiazole
(BBT)
as
acceptor
benzotrithiophene
donor,
while
latter
holds
π‐A
pyrene
π‐unit
BBT
acceptor.
Both
show
production
activity
two‐step
2e
−
oxygen
reduction
reaction
(ORR).
As
anticipated,
D–A
structured
exhibits
lower
value,
its
H
O
rate
pure
water
air
reaches
up
2.50
mmol
g⁻¹
h⁻¹,
≈3
times
higher
than
that
(0.91
h⁻¹).
This
study
reveals
fully
‐carbon‐linked
beneficial
production,
which
provides
an
effective
approach
designing
high‐performance
photocatalysts.
Angewandte Chemie,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 11, 2025
Abstract
Traditional
H
2
O
photocatalysis
primarily
depends
on
photoexcited
electrons
and
holes
to
drive
oxygen
reduction
water
oxidation,
respectively.
However,
singlet
(
1
),
often
underappreciated,
plays
a
pivotal
role
in
production.
Meanwhile,
photocatalytic
biomass
conversion
has
attracted
attention,
yet
studies
combining
synthesis
with
valorization
remain
rare
typically
yield
low‐value
products.
Herein,
strategy
of
furfuryl
alcohol
(FFA)
coupled
the
efficient
co‐production
is
reported,
enabled
by
covalent
organic
frameworks
(COFs)
induced,
‐participated
Achmatowicz
rearrangement.
This
study
introduces
polyimide‐based
COF‐N
0‐3
tailored
nitrogen
content,
representing
an
unprecedently
platform
for
Remarkably,
reducing
content
COF
enhances
production,
significantly
boosting
generation
rate.
In
FFA,
primary
pathway
production
rearrangement,
achieving
rate
ten
times
higher
than
that
reliant
reaction
pure
water,
reaching
4549
µmol
g⁻¹
h⁻¹.
Mechanism
revealed
selectively
engaged
bypassing
hole
oxidation
trigger
producing
valuable
6‐hydroxy‐(2H)‐pyranone
99%
92%
selectivity.
work
establishes
coupling
simultaneous
biochemicals,
offering
transformative
approach
sustainable
photocatalysis.
Advanced Functional Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 17, 2025
Abstract
The
5–10
nm
exciton
diffusion
distance
for
most
organic
semiconductors
is
much
less
than
the
particle
size
of
2D
covalent
frameworks
(COFs).
As
a
result,
local
structure
change
in
small
domain
COFs,
rather
whole
particles,
could
effectively
promote
charge
transfer
photocatalysis.
Herein,
three‐component
condensation
used
to
preparing
four
mixed
imine‐
and
thiazole‐linked
donor‐acceptor
(D–A)
COFs.
In
contrast
100%
imine
ca.
90%
10%
materials
have
77–95%
higher
photocatalytic
hydrogen
peroxide
(H
2
O
)
production
rate
pure
water
due
more
prolonged
lifetime
excitation
state.
particular,
USTB‐10‐S
exhibits
H
generation
5041
µmol
g
−1
h
.
Coupling
with
benzyl
alcohol
as
sacrificial
reagent,
its
further
increased
16152
,
superior
COF‐based
photocatalysts.
This
work
illustrates
proof‐of‐concept
that
COFs
tiny
amount
able
significantly
enhance
separation
thus
performance,
inspiring
development
defect
engineering
field
ACS Catalysis,
Год журнала:
2024,
Номер
unknown, С. 18669 - 18678
Опубликована: Дек. 6, 2024
The
electronic
configuration
mismatch
between
the
TiO2
support
and
MoSx
cocatalyst
induces
spontaneous
free-electron
transfer
in
an
unfavorable
direction,
resulting
stronger
O2
adsorption
on
Mo
active
sites
causing
limited
H2O2
production.
Herein,
we
propose
a
strategy
for
directional
to
produce
electron-enriched
Mo(4
–
δ)+
via
introducing
Ag
mediator
into
TiO2/MoSx
photocatalyst,
which
aims
weaken
improving
production
activity.
To
achieve
this,
core–shell
Ag@MoSx
was
ingeniously
constructed
surface
synthesize
TiO2/Ag@MoSx
photocatalyst.
resultant
achieves
significantly
enhanced
rate
of
16.13
mmol
g–1
h–1
with
AQY
value
8.79%,
surpassing
TiO2/Ag
by
10.0
237.2
times,
respectively.
Theoretical
calculations
experimental
results
reveal
that
incorporation
system
can
facilitate
cocatalyst.
This
causes
creation
increase
antibonding-orbital
occupancy
Mo–Oads,
ultimately
weakening
Mo–Oads
bond
enabling
high
activity
study
provides
valuable
insights
optimizing
reactant
efficient
artificial
photosynthesis.
Advanced Functional Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 30, 2024
Abstract
Heterojunction
engineering
has
been
deemed
one
of
the
most
promising
strategies
for
promoting
charge
separation
and
improving
solar‐to‐chemicals
efficiency.
Howbeit,
constructing
well‐defined
nanoheterojunction
with
superior
photocatalytic
activity
H
2
O
generation
a
clear
reaction
mechanism
remains
formidable
challenge.
Herein,
an
in
situ
vulcanization
way
to
synthesize
intriguing
2D/1D
Bi
3
TiNbO
9
/Bi
S
heterojunction
by
growing
nanorods
on
microsheet
is
used
first
time,
where
S‐scheme
transfer
formed
that
facilitates
spatial
carriers.
Moreover,
grown
can
optimize
interfacial
electronic
structure
energy
barriers.
As
result,
yield
rate
reach
810(2)
µmol
g
−1
h
without
any
sacrificial
agents
cocatalysts,
≈6.18
≈18.0
times
pristine
,
respectively.
Importantly,
unveiled
unprecedented
stability,
remaining
≈95.46(2)%
initial
after
13
continuous
cycles.
This
work
highlights
innovative
strategy
engineer
oxide
perovskite/metal
sulfide
nanocomposite
catalysts
artificial
photosynthesis
opening
new
opportunities
achieving
highly
efficient
photocatalyst
systems.
