Angewandte Chemie,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 11, 2025
Abstract
The
arrangement
of
donor–acceptor
(D–A)
components
in
order
at
a
molecular
level
provides
means
to
achieve
efficient
electron‐hole
separation
for
promoting
the
activity
photocatalysts.
Herein,
we
report
coordination
assembly
D–A
molecules
with
desired
staggered
energy
levels
two
isostructural
metal‐organic
frameworks
(MOFs)
1
and
2
,
which
exhibit
high
photocatalytic
hydrogen
evolution
without
using
any
cocatalysts
photosensitizers.
modulation
active
metal
sites
MOFs
leads
an
increase
rates
from
1260
3218
µmol
h
−1
g
.
A
detailed
mechanism
study
revealed
that
bond
defined
by
assisted
centers
is
key
efficiently
generating
photogenerated
charge
carriers,
has
appropriate
affinity
proton
reduce
barrier
evolution.
Besides,
enhanced
transport
kinetics
based
on
arrayed
free
carboxyl
groups
hydrogen‐bonded
network
endows
higher
conductivity
than
thus
usage
rate
reaction
kinetics.
Advanced Energy Materials,
Journal Year:
2024,
Volume and Issue:
unknown
Published: June 27, 2024
Abstract
Artificial
photosynthesis
emerges
as
a
strategic
pathway
to
produce
hydrogen
peroxide
(H
2
O
),
an
environmentally
benign
oxidant
and
clean
energy
carrier.
Nonetheless,
in
many
heterojunction‐based
artificial
photosynthetic
systems,
the
H
productivity
is
significantly
hindered
by
poor
carrier
transport,
narrow
spectral
light
absorption,
lack
of
adequate
active
sites
for
two‐electron
oxygen
reduction
reaction.
Herein,
catalyst
architecture
with
iso‐elemental
heterojunction
formed
interfacing
Zn
3
In
S
6
nano‐flowers
ZnIn
4
nanosheets
proposed.
This
exhibits
production
rate
high
23.47
µmol
g
−1
min
under
UV–vis
irradiation,
which
attributed
minimized
contact
barrier
enhanced
lattice
match
at
/Zn
interface
thanks
aids
efficient
separation
transfer
photogenerated
carriers.
Theoretical
simulations
alongside
comprehensive
in‐situ
ex‐situ
characterizations
confirm
photo‐redox
generation
effective
dynamics
across
surface.
Moreover,
substituting
one
reduction‐type
other
non‐iso‐elemental
catalysts
like
CdIn
,
TiO
CdS
further
confirms
feasibility
superiority
proposed
configuration.
work
offers
new
perspective
on
designing
.
Small,
Journal Year:
2024,
Volume and Issue:
20(44)
Published: July 6, 2024
Abstract
Since
2020,
covalent
organic
frameworks
(COFs)
are
emerging
as
robust
catalysts
for
the
photosynthesis
of
hydrogen
peroxide
(H
2
O
),
benefiting
from
their
distinct
advantages.
However,
current
efficiency
H
production
and
solar‐to‐chemical
energy
conversion
(SCC)
remain
suboptimal
due
to
various
constraints
in
reaction
mechanism.
Therefore,
there
is
an
imperative
propose
improvement
strategies
accelerate
development
this
system.
This
comprehensive
review
delineates
recent
advances,
challenges,
utilizing
COFs
photocatalytic
production.
It
explores
fundamentals
challenges
(e.g.,
oxygen
(O
)
mass
transfer
rate,
adsorption
capacity,
response
sunlight,
electron‐hole
separation
efficiency,
charge
selectivity,
desorption)
associated
with
process,
well
advantages,
applications,
classification,
preparation
purpose.
Various
enhance
performance
highlighted.
The
aims
stimulate
further
advancements
discusses
potential
prospects,
application
areas
field.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: June 26, 2024
Abstract
Efficiently
converting
solar
energy
into
chemical
remains
a
formidable
challenge
in
artificial
photosynthetic
systems.
To
date,
rarely
has
an
system
operating
the
open
air
surpassed
highest
solar-to-biomass
conversion
efficiency
(1%)
observed
plants.
In
this
study,
we
present
three-dimension
polymeric
photocatalyst
achieving
solar-to-H
2
O
of
3.6%
under
ambient
conditions,
including
real
water,
air,
and
room
temperature.
The
impressive
performance
is
attributed
to
efficient
storage
electrons
inside
materials
via
expeditious
intramolecular
charge
transfer,
fast
extraction
stored
by
that
can
diffuse
internal
pores
self-supporting
three-dimensional
material.
This
construction
strategy
suppresses
interlayer
transfer
excitons,
polarizers
carriers,
effectively
increases
utilization
excitons
82%.
breakthrough
provides
perspective
substantially
enhance
photocatalytic
bear
substantial
implications
for
sustainable
generation
environmental
remediation.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(48)
Published: Aug. 13, 2024
Abstract
Covalent
organic
frameworks
(COFs)
have
been
demonstrated
as
promising
photocatalysts
for
hydrogen
peroxide
(H
2
O
)
production.
However,
the
construction
of
COFs
with
new
active
sites,
high
photoactivity,
and
wide‐range
light
absorption
efficient
H
production
remains
challenging.
Herein,
we
present
synthesis
a
novel
azobenzene‐bridged
2D
COF
(COF‐TPT‐Azo)
excellent
performance
on
photocatalytic
under
alkaline
conditions.
Notably,
although
COF‐TPT‐Azo
differs
by
only
one
atom
(−N=N−
vs.
−C=N−)
from
its
corresponding
imine‐linked
counterpart
(COF‐TPT‐TPA),
exhibits
significantly
narrower
band
gap,
enhanced
charge
transport,
prompted
photoactivity.
Remarkably,
when
employed
metal‐free
photocatalyst,
achieves
rate
up
to
1498
μmol
g
−1
h
at
pH
=
11,
which
is
7.9
times
higher
than
that
COF‐TPT‐TPA.
Further
density
functional
theory
(DFT)
calculations
reveal
−N=N−
linkages
are
sites
photocatalysis.
This
work
provides
prospects
developing
high‐performance
COF‐based
photocatalysts.
Advanced Materials,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 7, 2025
Abstract
Developing
multifunctional
photocatalysts
with
intelligent
self‐adjusting
is
of
great
significance
in
the
photocatalytic
process.
Herein,
a
smart
covalent
organic
framework
(Por‐HQ‐COF)
phenol‐quinone
conversion
structure
pH
changes
constructed
for
photooxidation,
photoreduction,
and
H
2
O
production.
As
photocatalyst,
Por‐HQ‐COF
can
convert
into
Por‐BQ‐COF
intelligently
trigger
including
solution
pH,
vice
versa.
The
reconstruction
not
only
significantly
alters
morphologies
specific
surface
areas
COF,
but
also
leads
to
an
entirely
change
band
energy
charge
distribution
influence
photoelectric
properties.
result,
under
acidic
conditions,
converts
automatically
photoreduce
high
concentration
Cr(VI)
Cr(III)
efficiently.
Under
neutral
superoxide
anions
(·O
−
)
initiate
accelerate
photooxidation
degrade
high‐concentration
TC.
alkaline
Por‐BQ‐COF,
effectively
photosynthesize
(1525
µmol
h
−1
g
at
λ
>
420
nm)
absence
any
sacrificial
reagents,
reveal
strong
alkalinity
lower
barrier
hydrogen
extraction
from
clarify
active
sites
This
work
provides
new
strategy
developing
fulfill
application
across
full
environment.
Advanced Materials,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 27, 2024
Abstract
Photocatalysis
leverages
solar
energy
to
overcome
the
thermodynamic
barrier,
enabling
efficient
chemical
reactions
under
mild
conditions.
It
can
greatly
reduce
reliance
on
traditional
sources
and
has
attracted
significant
research
interest.
Reticular
materials,
including
metal‐organic
frameworks
(MOFs)
covalent
organic
(COFs),
represent
a
class
of
crystalline
materials
constructed
from
molecular
building
blocks
linked
by
coordination
bonds,
respectively.
function
as
heterogeneous
catalysts,
combining
well‐defined
structures
high
tailorability
akin
homogeneous
catalysts.
In
this
review,
regulation
light
absorption,
charge
separation,
surface
in
photocatalytic
process
through
precise
molecular‐level
design
based
features
reticular
is
elaborated.
Notably,
for
MOFsmicroenvironment
modulation
around
catalytic
sites
affects
performance
delved,
with
emphasis
their
unique
dynamic
flexible
microenvironments.
For
COFs,
inherent
excitonic
effects
due
fully
nature
discussed
highlight
strategies
regulate
charge‐
and/or
energy‐transfer‐mediated
photocatalysis.
Finally,
current
challenges
future
directions
field,
aiming
provide
comprehensive
understanding
how
be
optimized
enhanced
photocatalysis
discussed.
