Donor-acceptor
(D-A)-type
conjugated
microporous
polymers
(CMPs)
are
considered
promising
photocatalytic
materials
due
to
their
easily
tunable
structures
and
optical
properties.
However,
the
rational
combination
of
D
A
units
design
D-A-type
CMPs
with
efficient
electron-hole
separation
transfer
dynamics
remains
an
ongoing
challenge.
Herein,
we
employed
Density
Functional
Theory
(DFT)
calculations
evaluate
16
potential
D-A
pair
combinations
respective
dynamics.
These
consisted
M-salens
(M
=
Zn,
Cu,
Co,
Ni)
as
bromine-containing
monomers
four
alkyne-based
monomers:
2,4,6-tris(4-ethynylphenyl)-1,3,5-triazine
(TEPT),
4,4″-diethyl-5'-(4-ethynylphenyl)-1,
1':3',1″-terphenyl
(TEPB),
tris(4-ethynylphenyl)
amine
(TEPA),
3,7-diethyl-10-(4-ethynylphenyl)-10H-phenothiazine
(TEPP).
Eight
were
obtained
via
DFT
calculation,
ranking
follows:
Zn-salen-TEPA
>
Zn-salen-TEPP
Zn-salen-TEPT
Cu-salen-TEPP
Cu-salen-TEPA
Cu-salen-TEPT
Ni-salen-TEPT
Co-salen-TEPT.
Based
on
these
results,
three
pairs
exhibiting
highest
selected
for
synthesis
corresponding
subsequent
photoelectric
characterization.
Experimental
enhancements
aligned
closely
predictions.
Notably,
aerobic
oxidative
amidation
diverse
aldehydes
amines
catalyzed
by
under
blue
LED
irradiation
achieved
a
yield
up
97%,
which
surpassed
performance
most
reported
works.
This
work
offers
novel
perspectives
endowed
highly
activity.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(48)
Published: Sept. 3, 2024
Abstract
Intramolecular
charge
separation
driving
force
and
linkage
chemistry
between
building
blocks
are
critical
factors
for
enhancing
the
photocatalytic
performance
of
metal‐covalent
organic
framework
(MCOF)
based
photocatalyst.
However,
robust
achieving
both
simultaneously
has
yet
to
be
challenging
despite
ongoing
efforts.
Here
we
develop
a
fully
π‐conjugated
vinylene‐linked
multivariate
donor‐π‐acceptor
MCOF
(D‐π‐A,
termed
UJN‐1)
by
integrating
benzyl
cyanides
linker
with
multiple
functional
electron‐rich
triphenylamine
electron‐deficient
copper‐cyclic
trinuclear
units
(Cu‐CTUs)
moieties,
featuring
strong
intramolecular
force,
extended
conjugation
degree
skeleton,
abundant
active
sites.
The
incorporation
Cu‐CTUs
acceptor
electron‐withdrawing
ability
concomitantly
giant
can
efficiently
accelerate
photogenerated
electrons
transfer
from
Cu‐CTUs,
revealing
experiments
theoretical
calculations.
Benefiting
synergistically
effect
D‐π‐A
configuration
vinylene
linkage,
highly‐efficient
spatial
is
achieved.
Consequently,
UJN‐1
exhibits
an
excellent
CO
formation
rate
114.8
μmol
g
−1
in
4
h
without
any
co‐catalysts
or
sacrificial
reagents
under
visible
light,
outperforming
those
analogous
MCOFs
imine‐linked
(UJN‐2,
28.9
)
COF
Cu‐CTU
sites
(UJN‐3,
50.0
),
emphasizing
role
designing
novel
COFs‐based
Advanced Functional Materials,
Journal Year:
2024,
Volume and Issue:
34(33)
Published: May 9, 2024
Abstract
Modulating
of
electronic
structure
photocatalyst
and
integration
dual
channel
pathway
are
promising
strategy
for
efficient
photosynthesis
hydrogen
peroxide
(H
2
O
)
from
pure
water
without
sacrificial
agent
oxygen
exposure.
In
this
work,
nontoxic
aromatic
dialdehyde
is
used
to
replace
the
commonly
toxic
formaldehyde
form
resorcinol‐phthalaldehyde
resins
through
a
hydrothermal
method.
The
introducing
ring
as
π
spacer
increases
separation
distance
electrons
holes
avoid
their
recombination.
H
can
be
produced
via
integrated
reduction
reaction
(ORR)
oxidation
(WOR)
due
suitable
energy
band
positions
spatially
separated
sites.
Resorcinol‐p‐phthalaldehyde
(RP)
resin
exhibits
yield
3351
µmol
g
−1
h
with
high
apparent
quantum
(AQY)
14.9%
at
420
nm
solar‐to‐chemical
conversion
(SCC)
efficiency
1.54%.
This
work
provides
simple
modulate
charge
redox
on
molecular
level
design.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(30), P. 11972 - 11980
Published: Jan. 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.
ChemSusChem,
Journal Year:
2024,
Volume and Issue:
unknown
Published: May 4, 2024
Abstract
The
design
of
photocatalytic
supramolecular
systems
composing
semiconductors
and
molecular
metal
complexes
for
CO
2
reduction
has
attracted
increasing
attention.
system
combines
the
structural
merits
complexes,
where
semiconductor
harvests
light
undertakes
oxidative
site,
while
complex
provides
activity
reduction.
intermolecular
charge
transfer
plays
crucial
role
in
ensuring
performance.
Here,
we
review
progress
highlight
interfacial
pathways,
as
well
their
state‐of‐the‐art
characterization
methods.
remaining
challenges
prospects
further
photocatalysts
are
also
presented.
