ACS Applied Materials & Interfaces,
Journal Year:
2024,
Volume and Issue:
16(29), P. 37896 - 37905
Published: July 16, 2024
The
selective
oxidation
of
alcohols
into
aldehydes
is
a
basic
and
significant
procedure,
with
great
potential
for
scientific
research
industrial
applications.
However,
as
an
important
factor
in
the
C(sp3)–H
activation
process,
high
selectivity
generally
difficult
to
achieve
due
fact
that
more
easily
activated
properties
are
compared
alcohols.
Herein,
by
ingenious
decoration
eosin
Y
Zr-based
metal–organic
framework
(MOF–808),
EY@MOF–808
was
prepared
regulator
aerobic
benzyl
corresponding
aldehydes,
possessing
applicability
benzylic
various
substituents.
By
anchoring
on
Zr6O4(OH)4
clusters
MOF–808
maintaining
open
metal
nodes
binding
effects,
alcohol
substrates
were
selectively
coordinated
unsaturated
adjacent
Y,
which
ensured
excited
rapidly
generate
carbon
radicals
hydrogen
atom
transfer
(HAT)
process.
rapid
electron
(ET)
simultaneously
produced
reactive
oxygen
species
(O2•–)
then
combination
both
further
promote
generation
benzaldehydes.
weak
interaction
benzaldehydes
skeleton
allowed
it
dissociate
rapidly,
thus
preventing
overoxidation.
Under
catalysis
EY@MOF–808,
than
99%.
In
contrast,
gave
only
benzoic
acid
products
under
same
conditions,
demonstrated
superiority
regulatory
EY@MOF–808.
Taking
advantage
heterogeneity
MOF,
recycled
four
times
without
decrease
its
avoided
quenching
effect
Y.
organic
functional
units
postdecorated
MOF-based
photocatalyst
strategy
exhibits
promising
new
perspective
approach
sustainably
regulating
inert
oxidation.
Advanced Functional Materials,
Journal Year:
2024,
Volume and Issue:
34(49)
Published: Aug. 17, 2024
Abstract
Covalent
organic
frameworks
(COFs)
are
a
promising
class
of
polymers
with
the
merits
robust
framework,
ultrahigh
porosity,
and
molecularly
precise
backbones,
which
reveals
great
potential
for
solar‐to‐chemical
energy
conversion
in
context
mitigating
environmental
crises.
However,
photochemical
activities
individual
COFs
not
as
desired,
primarily
due
to
their
limited
light
absorption,
insufficient
dissociation
photogenerated
excitons
readily
recombined
carriers.
Recently,
COFs‐based
metal‐free
heterojunctions
synergistic
effects
provide
feasible
route
boost
photocatalytic
activity
more
environmentally
friendly
cost‐competitive
manners.
Herein,
it
is
first
systematically
overview
advances
from
heterojunction
types,
heterointerfaces
interactions,
primary
design
mechanisms.
Then,
typical
photocatalysts
(e.g.,
g‐C
3
N
4
‐COFs,
carbon
materials‐COFs,
polymer
semiconductor‐COFs,
COFs‐COFs
heterojunction)
summarized.
Finally,
challenges
long‐term
outlooks
future
offered
terms
efficiency,
yield,
stability,
cost
reaction
mechanisms,
well
standardized
evaluation
method
activities.
It
anticipated
that
this
review
can
deliver
new
insights
into
fundamental
engineering
conversion,
further
accelerate
development
area.
Advanced Energy Materials,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 19, 2025
Abstract
Photocatalytic
H
2
O
synthesis
from
and
is
considered
to
be
one
of
the
most
promising
alternative
approaches
for
manufacturing
.
Developing
highly
active
selective
photocatalysts
significant
in
achieving
efficient
photosynthesis.
Herein,
an
ethynyl‐linked
donor–acceptor
covalent
organic
framework
(COF),
named
EBBT‐COF,
prepared
condensation
reaction
between
electron‐deficient
unit
4,4′,4″‐(1,3,5‐benzenetriyltri‐2,1‐ethynediyl)tris‐benzenamine
electron‐rich
benzo[1,2‐b:3,4‐b′:5,6‐b″]trithiophene‐2,5,8‐tricarboxaldehyde.
Powder
X‐ray
diffraction
N
adsorption
isotherm
unveil
crystalline
porous
hcb
network
EBBT‐COF
with
pores
size
centered
at
ca
2.3
nm.
Spectroscopic
characterizations
demonstrate
excellent
visible‐light
absorption
capacity
enhanced
photo‐induced
charge
separation
transport
efficiency
owing
its
architecture.
Density
functional
theory
calculations
electrochemical
tests
indicate
high
activity
selectivity
toward
2e
−
reduction
water
oxidation
triethynylbenzene
trithiophene
moieties
accelerate
‐to‐H
O‐to‐H
conversion,
respectively.
These
merits
enable
a
photocatalyst
generation
yield
rate
5
686
µmol
g
−1
h
,
optimal
apparent
quantum
15.14%,
solar‐to‐chemical
conversion
1.17%
(λ
>
400
nm),
representing
best
performance
among
COF‐based
reported
thus
far.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 5, 2024
Lithium
(Li)
metal
batteries
with
remarkable
energy
densities
are
restrained
by
short
lifetime
and
low
Coulombic
efficiency
(CE),
resulting
from
the
accumulative
Li
dendrites
dead
during
cycling.
Here,
we
prepared
a
new
three-dimensional
(3D)
covalent
organic
framework
(COF)
dense
lithiophilic
sites
(heteoatom
weight
contents
of
32.32
wt
%)
as
an
anodic
protective
layer
batteries.
The
3D
COF
was
synthesized
using
[6+4]
synthesis
strategy
inducing
flexible
6-connected
cyclotriphosphazene
derivative
aldehyde
4-connected
porphyrin-based
tetraphenylamines.
Both
phosphazene
porphyrin
rings
in
served
electron-rich
sites,
enhancing
homogeneous
Small,
Journal Year:
2024,
Volume and Issue:
20(44)
Published: July 7, 2024
Photocatalytic
hydrogen
peroxide
production
from
water
and
oxygen
offers
a
clean
sustainable
alternative
to
the
conventional
energy-intensive
anthraquinone
oxidation
method.
Compared
powdered
covalent
triazine
frameworks
(CTFs),
film
morphology
of
CTFs
provides
better
connectivity
in
2D,
yielding
several
advantages:
more
efficient
connections
between
active
sites,
reduced
electron-hole
pair
recombination,
increased
resistance
superoxide
radical
induced
corrosion,
decreased
light
scattering.
Leveraging
these
benefits,
it
has
incorporated
dual
sites
for
both
reduction
reaction
(ORR)
(WOR)
into
CTF
system.
This
dual-active
demonstrated
an
exceptional
rate
19
460
µmol
h⁻¹
m⁻
