Angewandte Chemie,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 2, 2025
Abstract
The
catalytic
potential
of
flexible
metal–organic
frameworks
(MOFs)
remains
underexplored,
particularly
in
liquid‐phase
reactions.
This
study
employs
MIL‐53(Cr),
a
prototypical
“breathing”
MOF
capable
structural
adaptation
via
pore
size
modulation,
as
photocatalyst
for
the
dehalogenation
aryl
halides.
Powder
X‐ray
diffraction
and
Pair
Distribution
Function
analyses
reveal
that
organic
solvents
influence
opening,
while
substrates
products
dynamically
adjust
framework
configuration
during
catalysis.
flexibility
enables
precise
tuning
photocatalytic
efficiency
solvent‐mediated
control
aperture.
results
demonstrate
dynamic
behavior
MIL‐53(Cr)
facilitates
enhanced
activity
selectivity,
advancing
application
MOFs
tunable,
enzyme‐mimicking
catalysts.
These
findings
pave
way
rational
design
next‐generation
photocatalysts.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(6), С. 3002 - 3035
Опубликована: Янв. 1, 2024
The
present
review
summarizes
the
current
state-of-the-art
in
MOF-based
heterojunctions
three
important
photocatalytic
processes:
hydrogen
evolution
reaction,
CO
2
photoreduction
and
photodegradation
of
dyes.
Chemical Society Reviews,
Год журнала:
2023,
Номер
52(22), С. 7949 - 8004
Опубликована: Янв. 1, 2023
Photocatalytic
organic
reactions,
harvesting
solar
energy
to
produce
high
value-added
chemicals,
have
attracted
increasing
attention
as
a
sustainable
approach
address
the
global
crisis
and
environmental
issues.
Reticular
framework
materials,
including
metal-organic
frameworks
(MOFs)
covalent
(COFs),
are
widely
considered
promising
candidates
for
photocatalysis
owing
their
crystallinity,
tailorable
pore
environment
extensive
structural
diversity.
Although
design
synthesis
of
MOFs
COFs
been
intensively
developed
in
last
20
years,
applications
photocatalytic
transformations
still
preliminary
stage,
making
systematic
summary
necessary.
Thus,
this
review
aims
provide
comprehensive
understanding
useful
guidelines
exploration
suitable
MOF
COF
photocatalysts
towards
appropriate
reactions.
The
commonly
used
reactions
categorized
facilitate
identification
reaction
types.
From
practical
viewpoint,
fundamentals
experimental
design,
active
species,
performance
evaluation
external
conditions,
discussed
detail
easy
experimentation.
Furthermore,
latest
advances
COFs,
composites,
comprehensively
summarized
according
actual
sites,
together
with
discussion
structure-property
relationship.
We
believe
that
study
will
be
helpful
researchers
novel
reticular
various
synthetic
applications.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(23), С. 16229 - 16236
Опубликована: Май 30, 2024
Employing
covalent
organic
frameworks
(COFs)
for
the
photocatalytic
CO2
reduction
reaction
(CDRR)
to
generate
high-value
chemical
fuels
and
mitigate
greenhouse
gas
emissions
represents
a
sustainable
catalytic
conversion
approach.
However,
achieving
superior
CDRR
performance
is
hindered
by
challenges
of
low
charge
separation
efficiency,
poor
stability,
high
preparation
costs
associated
with
COFs.
Herein,
in
this
work,
we
utilized
perfluorinated
metallophthalocyanine
(MPcF16)
biomolecule
compound
ellagic
acid
(EA)
as
building
blocks
actualize
functional
named
EPM-COF
(M
=
Co,
Ni,
Cu).
The
designed
EPCo-COF,
featuring
cobalt
metal
active
sites,
demonstrated
an
impressive
CO
production
rate
selectivity
(CDRR).
Moreover,
following
alkaline
treatment
(EPCo-COF-AT),
COF
exposed
carboxylic
anion
(COO–)
hydroxyl
group
(OH),
thereby
enhancing
electron-donating
capability
EA.
This
modification
achieved
heightened
17.7
mmol
g–1
h–1
outstanding
97.8%
efficient
CDRR.
Theoretical
calculations
further
illustrated
that
EPCo-COF-AT
functionalized
COO–
OH
can
effectively
alleviate
energy
barriers
involved
process,
which
facilitates
proton-coupled
electron
transfer
processes
enhances
on
sites
within
EPCo-COF-AT.
ACS Catalysis,
Год журнала:
2024,
Номер
14(3), С. 1951 - 1961
Опубликована: Янв. 22, 2024
Photocatalytic
conversion
of
CO2
into
valuable
hydrocarbon
fuels
holds
great
promise
in
addressing
emerging
energy
shortages
and
environmental
crises
while
fulfilling
pressing
societal
national
development
demands.
Nonetheless,
its
efficiency
is
hindered
by
restricted
chemisorption,
rapid
electron–hole
recombination,
weak
redox
capability.
Drawing
inspiration
from
the
distinctive
characteristics
Schiff-based
covalent
organic
frameworks
(COFs),
including
substantial
specific
surface
area,
unique
pore
structure,
an
abundance
weakly
alkaline
nitrogen
elements,
we
employ
TPA-COF
to
enhance
chemisorption
activation
acidic
molecules,
as
validated
CO2-temperature-programmed
desorption
analysis.
Furthermore,
anchoring
CsPbBr3
quantum
dots
(QDs)
onto
COF
facilitates
effective
spatial
separation
photoinduced
charge
carriers
with
strong
capability,
resulting
formation
S-scheme
heterojunctions
between
QDs
substantiated
situ
irradiation
X-ray
photoelectron
spectroscopy,
femtosecond
transient
absorption
density
functional
theory
simulations.
As
anticipated,
optimized
COF/QDs
heterostructures
exhibit
remarkable
enhancements
photoreduction
performance
absence
any
molecule
cocatalyst
or
scavenger,
yielding
CO
CH4
at
rates
41.2
13.7
μmol
g–1,
respectively.
This
work
provides
insights
novel
organic/inorganic
heterojunction
photocatalysts
separation,
offering
potential
for
sustainable
artificial
photosynthesis.
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.
