Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(42), С. 28932 - 28940
Опубликована: Окт. 11, 2024
Single-crystalline
covalent
organic
frameworks
(COFs)
are
highly
desirable
toward
understanding
their
pore
chemistry
and
functions.
Herein,
two
50–100
μm
single-crystalline
three-dimensional
(3D)
COFs,
TAM-TFPB-COF
TAPB-TFS-COF,
were
prepared
from
the
condensation
of
4,4′,4″,4‴-methanetetrayltetraaniline
(TAM)
with
3,3′,5,5′-tetrakis(4-formylphenyl)bimesityl
(TFPB)
3,3′,5,5′-tetrakis(4-aminophenyl)bimesityl
(TAPB)
4,4′,4″,4‴-silanetetrayltetrabenzaldehyde
(TFS),
respectively,
in
1,4-dioxane
under
catalysis
acetic
acid.
Single-crystal
3D
electron
diffraction
reveals
triply
interpenetrated
dia-b
networks
atom
resolution,
while
isostructure
TAPB-TFS-COF
was
disclosed
by
synchrotron
single-crystal
X-ray
powder
Le
Bail
refinements.
The
nitrogen
sorption
measurements
at
77
K
disclose
microporosity
nature
both
activated
COFs
exceptionally
high
Brunauer–Emmett–Teller
surface
areas
3533
4107
m2
g–1,
representing
thus
far
record
specific
area
among
imine-bonded
COFs.
This
enables
to
exhibit
also
methane
uptake
capacities
up
28.9
wt
%
(570
cm3
g–1)
25
°C
200
bar
all
reported
far.
work
not
only
presents
structures
exceptional
but
provides
an
example
engineering
adjust
permanent
microporous
for
storage.
Chemical Society Reviews,
Год журнала:
2022,
Номер
51(15), С. 6307 - 6416
Опубликована: Янв. 1, 2022
This
review
highlights
the
recent
advances
of
metalated
covalent
organic
frameworks,
including
synthetic
strategies
and
applications,
discusses
current
challenges
future
directions.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(34)
Опубликована: Апрель 24, 2023
Abstract
Intensifying
energy
crises
and
severe
environmental
issues
have
led
to
the
discovery
of
renewable
sources,
sustainable
conversion,
storage
technologies.
Photocatalysis
is
a
green
technology
that
converts
eco‐friendly
solar
into
high‐energy
chemicals.
Covalent
organic
frameworks
(COFs)
are
porous
materials
constructed
by
covalent
bonds
show
promising
potential
for
converting
chemicals
owing
their
pre‐designable
structures,
high
crystallinity,
porosity.
Herein,
we
highlight
recent
progress
in
synthesis
COF‐based
photocatalysts
applications
water
splitting,
CO
2
reduction,
H
O
production.
The
challenges
future
opportunities
rational
design
COFs
advanced
discussed.
This
Review
expected
promote
further
development
toward
photocatalysis.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(5), С. 3248 - 3254
Опубликована: Янв. 31, 2023
Benefiting
from
their
unique
structural
merits,
three-dimensional
(3D)
large-pore
COF
materials
demonstrate
high
surface
areas
and
interconnected
large
channels,
which
makes
these
promising
in
practical
applications.
Unfortunately,
functionalization
strategies
application
research
are
still
absent
structures.
To
this
end,
a
series
of
functional
3D
stp-topologized
COFs
designed
based
on
porphyrin
or
metalloporphyrin
moieties,
named
JUC-640-M
(M
=
Co,
Ni,
H).
Interestingly,
JUC-640-H
exhibits
record-breaking
low
crystal
density
(0.106
cm3
g-1)
among
all
crystalline
materials,
along
with
the
largest
pore
size
(4.6
nm)
COFs,
area
(2204
m2
g-1),
abundant
exposed
moieties
(0.845
mmol
g-1).
Inspired
by
characteristics
photoelectrical
performance,
JUC-640-Co
is
utilized
for
photoreduction
CO2
to
CO
demonstrates
production
rate
(15.1
g-1
h-1),
selectivity
(94.4%),
stability.
It
should
be
noted
that
has
exceeded
those
reported
COF-based
materials.
This
work
not
only
produces
novel
channels
but
also
provides
new
guidance
applications
COFs.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(3), С. 1475 - 1496
Опубликована: Янв. 16, 2023
Multicomponent
reactions
(MCRs)
combine
at
least
three
reactants
to
afford
the
desired
product
in
a
highly
atom-economic
way
and
are
therefore
viewed
as
efficient
one-pot
combinatorial
synthesis
tools
allowing
one
significantly
boost
molecular
complexity
diversity.
Nowadays,
MCRs
no
longer
confined
organic
have
found
applications
materials
chemistry.
In
particular,
can
be
used
prepare
covalent
frameworks
(COFs),
which
crystalline
porous
assembled
from
monomers
exhibit
broad
range
of
properties
applications.
This
synthetic
approach
retains
advantages
small-molecule
MCRs,
not
only
strengthening
skeletal
robustness
COFs,
but
also
providing
additional
driving
forces
for
their
crystallization,
has
been
series
robust
COFs
with
diverse
The
present
perspective
article
provides
general
background
discusses
types
employed
COF
date,
addresses
related
critical
challenges
future
perspectives
inspire
MCR-based
design
new
promote
further
progress
this
emerging
field.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(37), С. 17209 - 17218
Опубликована: Сен. 9, 2022
Developing
conjugated
three-dimensional
(3D)
covalent
organic
frameworks
(COFs)
still
remains
an
extremely
difficult
task
due
to
the
lack
of
enough
3D
building
blocks.
Herein,
condensation
between
8-connected
pentiptycene-based
D2h
block
(DMOPTP)
and
4-connected
square-planar
linkers
affords
two
COFs
(named
3D-scu-COF-1
3D-scu-COF-2).
A
combination
homoaromatic
structure
former
with
2D
latter
linking
units
enables
π-electron
delocalization
over
whole
both
COFs,
endowing
them
excellent
conductivities
3.2-3.5
×
10-5
S
cm-1.
In
particular,
rigid
quadrangular
prism
shape
DMOPTP
guides
formation
a
twofold
interpenetrated
scu
topology
high-connected
permanent
porosity
large
Brunauer-Emmett-Teller
(BET)
surface
area
2340
1602
m2
g-1
for
3D-scu-COF-2,
respectively,
ensuring
effective
small
molecule
storage
mass
transport
characteristics.
This,
in
their
good
charge
properties,
renders
promising
sulfur
host
materials
lithium-sulfur
batteries
(LSBs)
high
capacities
(1035-1155
mA
h
at
0.2
C,
1
C
=
1675
g-1),
rate
capabilities
(713-757
5.0
C),
superior
cycling
stability
(71-83%
capacity
retention
2.0
after
500
cycles),
surpassing
most
LSB
cathodes
reported
thus
far.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(14), С. 8141 - 8149
Опубликована: Март 29, 2023
Lithium-sulfur
batteries
(LSBs)
have
been
considered
as
a
promising
candidate
for
next-generation
energy
storage
devices,
which
however
still
suffer
from
the
shuttle
effect
of
intermediate
lithium
polysulfides
(LiPSs).
Covalent-organic
frameworks
(COFs)
exhibited
great
potential
sulfur
hosts
LSBs
to
solve
such
problem.
Herein,
pentiptycene-based
D2h
symmetrical
octatopic
polyaldehyde,
6,13-dimethoxy-2,3,9,10,18,19,24,25-octa(4'-formylphenyl)pentiptycene
(DMOPTP),
was
prepared
and
utilized
building
block
toward
preparing
COFs.
Condensation
DMOPTP
with
4-connected
tetrakis(4-aminophenyl)methane
affords
an
expanded
[8
+
4]
connected
network
3D-flu-COF,
flu
topology.
The
non-interpenetrated
nature
topology
endows
3D-flu-COF
high
Brunauer-Emmett-Teller
surface
area
2860
m2
g-1,
large
octahedral
cavities,
cross-linked
tunnels
in
framework,
enabling
loading
capacity
(∼70
wt
%),
strong
LiPS
adsorption
capability,
facile
ion
diffusion.
Remarkably,
when
used
host
LSBs,
delivers
1249
mA
h
g-1
at
0.2
C
(1.0
=
1675
g-1),
outstanding
rate
capability
(764
5.0
C),
excellent
stability,
representing
one
best
results
among
thus
far
reported
COF-based
materials
being
competitive
state-of-the-art
inorganic
materials.
Chemical Reviews,
Год журнала:
2023,
Номер
123(23), С. 13489 - 13692
Опубликована: Ноя. 14, 2023
As
a
key
structural
parameter,
phase
depicts
the
arrangement
of
atoms
in
materials.
Normally,
nanomaterial
exists
its
thermodynamically
stable
crystal
phase.
With
development
nanotechnology,
nanomaterials
with
unconventional
phases,
which
rarely
exist
their
bulk
counterparts,
or
amorphous
have
been
prepared
using
carefully
controlled
reaction
conditions.
Together
these
methods
are
beginning
to
enable
engineering
(PEN),
i.e.,
synthesis
phases
and
transformation
between
different
obtain
desired
properties
functions.
This
Review
summarizes
research
progress
field
PEN.
First,
we
present
representative
strategies
for
direct
modulation
diverse
kinds
nanomaterials.
We
cover
ranging
from
metal
nanostructures
such
as
Au,
Ag,
Cu,
Pd,
Ru,
alloys;
oxides,
borides,
carbides;
transition
dichalcogenides
(TMDs)
2D
layered
review
growth
wet-chemical
reduction
seed-mediated
epitaxial
chemical
vapor
deposition
(CVD),
high
pressure
transformation,
electron
ion-beam
irradiation.
After
that,
summarize
significant
influence
on
various
unconventional-phase
also
discuss
potential
applications
developed
areas
including
catalysis,
electrochemical
energy
storage
(batteries
supercapacitors),
solar
cells,
optoelectronics,
sensing.
Finally,
existing
challenges
future
directions
