ACS Applied Materials & Interfaces,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 20, 2025
In
this
study,
an
ionic
liquid–ethanol
interface
strategy
is
proposed
to
synthesize
NH2-MIL-101(Fe)
nanocrystals
at
room
temperature.
The
as-synthesized
exhibit
small
crystal
sizes,
abundant
ligand
defects,
and
unsaturated
metal
sites.
present
superior
catalytic
activity
for
the
cycloaddition
reaction
of
CO2
mild
conditions
(room
temperature
1
bar
pressure),
much
higher
than
NH2-MIL-101
(Fe)
microcrystals
synthesized
by
conventional
solvothermal
method.
conversion
propylene
oxide
catalyzed
achieves
a
99%
yield
within
2.5
h,
accompanied
generation
rate
carbonate
production
per
gram
catalyst
(Rcarbonate)
52.8
mmol
g–1
h–1.
contrast,
system
employing
shows
lower
19.28%
10.28
were
further
used
treatment
simulated
industrial
flue
gas
with
volume
ratio
N2/CO2
=
85:15.
results
show
efficient
ambient
pressure,
even
relatively
low
concentrations.
This
work
not
only
offers
facile,
energy-consumed,
environmentally
benign
method
fabrication
MOF
nanostructures
but
also
provides
high-performance
systems
fixation
separation.
The
ligands
in
metal-organic
framework
(MOF)
play
as
light
absorption
center
and
transfer
photogenerated
electrons
to
metal
node
through
ligand-to-metal
charge
(LMCT)
during
photocatalysis,
energy
utilization
efficiency
is
strongly
restricted
by
the
inertness
of
ligands.
Herein,
a
ligand
updating
strategy
proposed
inserting
centers
MOFs
activate
inherent
ligands,
realizing
boosting
hot
electron
generation
photocatalytic
activities
via
cascaded
proceeding
transfer.
By
taking
PCN-777
(a
zeotype
mesoporous
Zr-containing
MOF)
an
example,
this
study
shows
that
embedded
1-pyrenecarboxylic
acid
(PCA)
can
triplet-triplet
transfer,
where
triplet
excitons
would
dissociate
into
photocarriers
migrating
Zr
cluster
LMCT
process.
As
expected,
PCN-777-PCA
exhibits
promising
activity
metallaphotocatalytic
C─N
cross-coupling
reactions
offering
abundant
for
involved
dual
photoredox
cycles.
This
work
provides
practical
method
improving
application
updating.
Abstract
Photocatalytic
hydrogen
production
is
currently
considered
a
clean
and
sustainable
route
to
meet
the
energy
environmental
issues.
Among,
heterojunction
photocatalysts
have
been
developed
improve
their
photocatalytic
efficiency.
Defect
engineering
of
attractive
due
it
can
perform
as
electron
trap
change
band
structure
optimize
interfacial
separation
rate
photogenerated
electron–hole
pairs.
Here,
MOF‐based
with
theoretically
high
reduction
oxidation
abilities
are
successfully
synthesized,
denoted
ZrO
2
/Pt/Zr‐MOF‐
X
,
tuned
linker
defectivity
through
an
in
situ
electrochemical
route.
The
rationally
calculated
from
TG
1
H
NMR
results.
A
positive
correlation
found
between
activity,
/Pt/Zr‐MOF‐6
optimized
ca.
35%
exhibits
highest
up
2923
µmol
g
−1
h
illustrating
importance
structural
defects
photocatalysts.
Ultrafast
transient
absorption
spectroscopy
spin
resonance
results
unveil
carrier
concentration
charge
efficiency
defected
heterostructure
direct
Z‐scheme
contact,
leading
its
efficient
photocatalysis
redox
power.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 27, 2025
Electron
donor–acceptor
complexes
are
commonly
employed
to
facilitate
photoinduced
radical-mediated
organic
reactions.
However,
achieving
these
photochemical
processes
with
catalytic
amounts
of
donors
or
acceptors
can
be
challenging,
especially
when
aiming
reduce
catalyst
loadings.
Herein,
we
have
unveiled
a
framework-based
heterogenization
approach
that
significantly
enhances
the
photoredox
activity
perylene
diimide
species
in
radical
addition
reactions
alkyl
silicates
by
promoting
faster
and
more
efficient
electron
complex
formation.
Besides
offering
broad
substrate
scope
alkene
hydroalkylation,
newly
developed
heterogeneous
photocatalysis
substantially
improves
turnover
numbers
comparison
previous
homogeneous
photocatalytic
systems
demonstrates
outstanding
recyclability.
These
research
findings
pave
way
for
advancement
various
practical
transformations
using
framework-supported
organocatalysts.
Advanced Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 9, 2025
Abstract
The
development
of
semiconducting
conjugated
polymers
for
photoredox
catalysis
holds
great
promise
sustainable
utilization
solar
energy.
Herein
a
new
family
porous
methylated
triazine‐based
linear
is
reported
that
enable
efficient
photoreduction
carbon
dioxide
(CO
2
)
with
water
(H
O)
vapor,
in
the
absence
any
additional
photosensitizer,
sacrificial
agents
or
cocatalysts.
It
demonstrated
key
lies
generation
triazine
linkages
through
facile
condensation
reaction
between
benzamidine
and
acetic
anhydride,
which
impedes
formation
conventional
frameworks.
also
shown
regulating
backbones
different
lengths
electron‐donated
benzyl
units
provides
means
to
modulate
their
optical
properties
exciton
dissociation,
thereby
affording
more
long‐lived
photogenerated
charge
carriers
boosting
separation
transfer.
A
high‐performance
monoxide
(CO)
production
rate
218.9
µmol
g
−1
h
achieved
≈
100%
CO
selectivity,
accompanied
by
exceptional
H
O
oxidation
oxygen
(O
).
anticipates
this
study
will
advance
synthetic
approaches
toward
polymeric
semiconductors
facilitate
possibilities
promising
potential
artificial
photocatalysis.
The
escalating
global
energy
demand
and
the
imperative
to
mitigate
carbon
emissions
have
intensified
pursuit
for
sustainable
solutions,
with
hydrogen
emerging
as
a
pivotal
clean
carrier.
Transition
metal‐based
metal‐organic
frameworks
(MOFs)
garnered
significant
attention
their
potential
in
efficient
production
due
high
surface
area,
tunable
porosity,
versatile
catalytic
properties.
Despite
notable
advancements
MOF
synthesis,
critical
challenges
related
stability,
electrical
conductivity,
scalability
continue
hinder
widespread
application.
This
review
provides
comprehensive
analysis
of
recent
progress
design
synthesis
transition
MOFs,
emphasizing
role
electrocatalytic
photocatalytic
production.
Key
synthetic
strategies
influence
on
performance
are
systematically
discussed,
alongside
identification
existing
limitations
knowledge
gaps.
By
highlighting
these
areas
proposing
pathways
future
research,
this
aims
accelerate
practical
integration
MOFs
into
economy.
