Inorganic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 19, 2024
Hydrogen
peroxide
(H2O2)
is
a
crucial
energy
carrier
with
growing
significance
in
sustainable
systems.
Covalent
organic
frameworks
(COFs)
have
recently
emerged
as
promising
materials
for
efficient
H2O2
photosynthesis,
while
transition-metal
complexes
are
recognized
their
efficacy
molecular
photocatalysts
production.
This
study
introduces
novel
π–π
interaction
strategy
to
immobilize
ruthenium
into
COFs,
using
DaTp
COF
model
system.
approach
significantly
enhances
the
photocatalytic
activity
production,
achieving
an
initial
rate
of
3276
μmol
g–1
h–1
without
scavengers
under
visible-light
irradiation
(λ
>
420
nm).
Notably,
incorporating
optimizes
oxygen
reduction
reaction
pathways,
shifting
from
less
four-electron
process
more
two-electron
process.
Density
functional
theory
calculations
further
reveal
that
not
only
broaden
light
absorption
spectrum
but
also
increase
water
affinity,
directly
contributing
generation.
These
findings
offer
strategic
framework
designing
and
enhancing
COFs
photosynthesis
applications.
ACS Nano,
Год журнала:
2024,
Номер
18(33), С. 21804 - 21835
Опубликована: Авг. 8, 2024
Covalent
organic
frameworks
(COFs)
are
crystalline
networks
with
extended
backbones
cross-linked
by
covalent
bonds.
Due
to
the
semiconductive
properties
and
variable
metal
coordinating
sites,
along
rapid
development
in
linkage
chemistry,
utilization
of
COFs
photocatalytic
CO2RR
has
attracted
many
scientists'
interests.
In
this
Review,
we
summarize
latest
research
progress
on
for
CO2
reduction.
first
part,
present
COF
linkages
that
have
been
used
CO2RR,
discuss
four
mechanisms
including
as
intrinsic
photocatalysts,
photosensitive
motifs
metalated
semiconductors
heterojunction
photocatalysts.
Then,
principles
structural
designs
functional
building
units
stacking
mode
exchange.
Finally,
outlook
challenges
provided.
This
Review
is
intended
give
some
guidance
design
synthesis
diverse
different
linkages,
various
structures,
divergent
modes
efficient
photoreduction
CO2.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Авг. 7, 2024
Consecutive
uranium
extraction
from
seawater
is
a
promising
approach
to
secure
the
long-term
supply
of
and
sustainability
nuclear
energy.
Here,
we
report
an
ultra-highly
efficient
strategy
via
studtite
nanodots
growth
with
impressive
uranyl
uptake
capacity
~
154.50
mg/g
natural
in
12
consecutive
days
(i.e.,
average
for
12.875
mg/g/day).
Uranyl
can
be
extracted
as
under
visible
light
reaction
between
adsorbed
photogenerated
H2O2
imine-based
Covalent-Organic
Framework
photocatalysts.
In
detail,
over
Tp-Bpy,
Tp-Bpy-2
Tp-Py
multiple
chelating
sites,
found
which
eluted
readily,
while
Tp-Bd
Tb-Bpy,
transformed
into
nanorods
that
more
inert
elution.
Abundant
sites
structural
regulation
COF
photocatalysts
are
proved
facilitate
formation
elution
nanodots.
The
continuous
desired
sustain
power
technology
development
up-recycle
approaches
remain
challenge.
Here
authors
employing
covalent-organic
frameworks
Advanced Functional Materials,
Год журнала:
2024,
Номер
34(52)
Опубликована: Авг. 27, 2024
Abstract
Herein,
a
rational
strategy
is
presented
to
reduce
the
energy
barrier
of
singlet
ground
state
excited
transitions,
whilst
simultaneously
reducing
losses
in
populating
triplet
states.
The
approach
relies
on
constructing
3D
space
connected
donor–acceptor
systems
COFs.
D–A
system
8‐connected
COFs
(denoted
as
COF‐1
and
COF‐2)
allows
efficient
transfer
electrons,
overcoming
traditional
electron
transport
limitations
2D
significantly
boosting
solar
utilization
efficiency
under
visible
light
irradiation.
COF‐2,
possessing
an
extended
π‐conjugated
structure
relative
COF‐1,
demonstrated
high
selectivity
for
photocatalytic
generation
H
2
O
(6.93
mmol
g
−1
h
)
natural
seawater
without
need
sacrificial
reagents,
exceeding
performance
most
previously
reported
COF‐based
photocatalysts.
this
work
offers
new
optimizing
photocatalysts
production
other
applications.
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.
Advanced Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 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.
Chemical Science,
Год журнала:
2024,
Номер
15(30), С. 11972 - 11980
Опубликована: Янв. 1, 2024
Leveraging
the
reversible
phenazine–dihydrophenazine
interconversion
in
microporous
polymers
enhances
photocatalytic
H
2
O
generation
by
improving
reduction
and
charge
separation,
showcasing
a
new
approach
for
solar-driven
chemical
conversion.
Abstract
Constitutional‐isomerized
covalent
organic
frameworks
(COFs),
constructed
by
swapping
monomers
around
imine
bonds,
have
attracted
attention
for
their
distinct
optoelectronic
properties,
which
significantly
impact
photocatalytic
performance.
However,
limited
research
has
delved
into
the
inherent
relationship
between
isomerization
and
enhancement
of
H
2
O
photosynthesis.
Herein,
a
pair
isomeric
COFs
linked
bonds
(PB‐PT‐COF
PT‐PB‐COF)
is
synthesized,
it
proved
that
exhibit
different
rate‐determining
steps
in
generation
process
,
resulting
twofold
increase
efficiency.
Specifically,
PT‐PB‐COF
demonstrates
effective
adsorption
activation
molecular
oxygen
(O
+
e
−
→
•O
),
leading
to
significant
improvement
In
contrast,
PB‐PT‐COF
exhibits
robust
interaction
with
O,
enabling
direct
oxidation
(H
h
).
This
study
provides
thorough
understanding
intrinsic
mechanism
underlying
constitutional‐isomerized
generation,
offering
insights
further
optimizing
building
units.
Covalent
organic
frameworks
(COFs)
constitute
a
promising
research
topic
for
photocatalytic
reactions,
but
the
rules
and
conformational
relationships
of
1D
COFs
are
poorly
defined.
Herein,
chain
edge
structure
is
designed
by
precise
modulation
at
atomic
level,
bonded
C,
O,
S
elements
directionally
prepared
oxygen-tolerant
photoinduced
electron
transfer-atom
transfer
radical
polymerization
(PET-ATRP)
reactions.
It
demonstrated
that
heteroatom-type
structures
(─O─,
─S─)
lead
to
decrease
in
intra-plane
conjugation,
which
restricts
effective
transport
photogenerated
electrons
along
direction
strip.
In
contrast,
all-carbon
type
(─C─)
with
higher
conjugation
not
only
reduces
energy
loss
photoexcited
also
enhances
carrier
density,
exhibits
optimal
photopolymerization
performance.
This
work
offers
valuable
guidance
exploitation
high
