Accounts of Chemical Research,
Год журнала:
2022,
Номер
55(14), С. 1912 - 1927
Опубликована: Июнь 27, 2022
ConspectusAs
one
of
the
most
attractive
members
in
porous
materials
family,
covalent
organic
frameworks
(COFs)
have
been
reported
thousands
times
since
their
first
discovery
2005,
covering
design,
synthesis,
and
applications.
However,
an
overwhelming
majority
these
COFs
are
based
on
two-dimensional
(2D)
topologies
while
three-dimensional
(3D)
numbered
fewer
than
100
up
to
date.
In
fact,
baring
enhanced
specific
surface
area,
interconnected
channels,
well-exposed
functional
moieties,
highly
adjustable
structures,
3D
often
more
competitive
various
application
fields
like
adsorption,
separation,
chemical
sensing,
heterogeneous
catalysis
compared
with
2D
counterparts.
significant
crystallization
problems
poor
stabilities,
which
might
be
attributed
void
absence
π-π
stacking,
raised
severe
limitations
over
research
COFs.
To
solve
problems,
elaborate
synthesis
regulations
or
moderate
functionalization
conditions
required.
More
importantly,
strategies
for
enhancing
stabilities
vital
importance
further
development
practical
applications.In
this
Account,
we
review
design
principles,
approaches,
stability
regulation
methods
toward
We
begin
discussion
some
essential
elements
construction
COF
including
topologies,
interpenetrations,
linkages,
synthetic
methods.
After
that,
focus
several
COFs,
situ
approaches
(utilizing
generated
linkages
as
active
sites),
bottom-up
(embedding
moieties
from
predesigned
building
blocks),
postsynthesis
modification
(covalent
metalation
pristine
frameworks).
At
last,
highlight
durable
amplification
is
important
framework
application.
This
target
could
achieved
through
not
only
introduction
extra
strengthening
force,
such
hydrophobic
effects,
coulomb
repulsion,
steric
hindrance
but
also
utilization
robust
enhance
material
nature.Due
high
interpenetrated
multifarious
functionalities,
promising
demonstrated
excellent
performance
great
potential
a
wide
range
adsorption
catalysis,
energy
storage,
so
on.
Although
has
limited
by
serious
restriction,
efforts
devoted
researchers
past
decade,
mass
developed
control,
regulation,
enhancement
expect
practically
utilized
future
advances
preparation,
materials.
Chemical Reviews,
Год журнала:
2020,
Номер
120(16), С. 8814 - 8933
Опубликована: Янв. 22, 2020
Covalent
organic
frameworks
(COFs)
are
a
class
of
crystalline
porous
polymers
with
permanent
porosity
and
highly
ordered
structures.
Unlike
other
polymers,
significant
feature
COFs
is
that
they
structurally
predesignable,
synthetically
controllable,
functionally
manageable.
In
principle,
the
topological
design
diagram
offers
geometric
guidance
for
structural
tiling
extended
polygons,
polycondensation
reactions
provide
synthetic
ways
to
construct
predesigned
primary
high-order
Progress
over
past
decade
in
chemistry
these
two
aspects
undoubtedly
established
base
COF
field.
By
virtue
availability
units
diversity
topologies
linkages,
have
emerged
as
new
field
materials
offer
powerful
molecular
platform
complex
tailor-made
functional
development.
Here
we
target
comprehensive
review
field,
historic
overview
survey
advances
topology
reactions,
illustrate
features
diversities,
scrutinize
development
potential
various
functions
through
elucidating
structure–function
correlations
based
on
interactions
photons,
electrons,
holes,
spins,
ions,
molecules,
discuss
key
fundamental
challenging
issues
need
be
addressed,
predict
future
directions
from
chemistry,
physics,
perspectives.
Chemical Society Reviews,
Год журнала:
2020,
Номер
50(1), С. 120 - 242
Опубликована: Дек. 7, 2020
Covalent
organic
frameworks
offer
a
molecular
platform
for
integrating
units
into
periodically
ordered
yet
extended
2D
and
3D
polymers
to
create
topologically
well-defined
polygonal
lattices
built-in
discrete
micropores
and/or
mesopores.
The Innovation,
Год журнала:
2021,
Номер
2(1), С. 100076 - 100076
Опубликована: Янв. 10, 2021
Covalent
organic
frameworks
(COFs)
are
a
new
type
of
crystalline
porous
polymers
known
for
chemical
stability,
excellent
structural
regularity,
robust
framework,
and
inherent
porosity,
making
them
promising
materials
capturing
various
types
pollutants
from
aqueous
solutions.
This
review
thoroughly
presents
the
recent
progress
advances
COFs
COF-based
as
superior
adsorbents
efficient
removal
toxic
heavy
metal
ions,
radionuclides,
pollutants.
Information
about
interaction
mechanisms
between
summarized
macroscopic
microscopic
standpoints,
including
batch
experiments,
theoretical
calculations,
advanced
spectroscopy
analysis.
The
adsorption
properties
assessed
compared
with
other
widely
used
adsorbents.
Several
commonly
strategies
to
enhance
materials'
performance
relationship
property
sorption
ability
also
discussed.
Finally,
summary
perspective
on
opportunities
challenges
proposed
provide
some
inspiring
information
designing
fabricating
environmental
pollution
management.
Abstract
Covalent
organic
frameworks
(COFs)
are
an
emerging
class
of
functional
nanostructures
with
intriguing
properties,
due
to
their
unprecedented
combination
high
crystallinity,
tunable
pore
size,
large
surface
area,
and
unique
molecular
architecture.
The
range
properties
characterized
in
COFs
has
rapidly
expanded
include
those
interest
for
numerous
applications
ranging
from
energy
environment.
Here,
a
background
overview
is
provided,
consisting
brief
introduction
porous
materials
the
design
feature
COFs.
Then,
recent
advancements
as
designer
platform
plethora
emphasized
together
discussions
about
strategies
principles
involved.
Finally,
challenges
remaining
this
type
material
real
outlined.
Angewandte Chemie International Edition,
Год журнала:
2019,
Номер
59(13), С. 5050 - 5091
Опубликована: Май 30, 2019
Abstract
A
new
approach
has
been
developed
to
design
organic
polymers
using
topology
diagrams.
This
strategy
enables
covalent
integration
of
units
into
ordered
topologies
and
creates
a
polymer
form,
that
is,
frameworks.
is
breakthrough
in
chemistry
because
it
sets
molecular
platform
for
synthesizing
with
predesignable
primary
high‐order
structures,
which
central
aim
over
century
but
unattainable
traditional
principles.
field
its
own
features
are
distinct
from
conventional
polymers.
Review
summarizes
the
fundamentals
as
well
major
progress
by
focusing
on
used
including
principles,
synthetic
strategies,
control
methods.
We
scrutinize
built‐in
functions
specific
structures
revealing
various
interplays
mechanisms
involved
expression
function.
propose
fundamental
issues
be
addressed
future
directions
physics,
materials,
application
perspectives.
Chemical Society Reviews,
Год журнала:
2020,
Номер
50(3), С. 1813 - 1845
Опубликована: Дек. 17, 2020
Covalent
organic
frameworks
(COFs)
are
crystalline
porous
materials
constructed
from
molecular
building
blocks
using
diverse
linkage
chemistries.
Their
modular
construction
system
allows
not
only
for
tailor-made
design
but
also
an
immense
variety
of
blocks,
opening
the
door
to
numerous
different
functionalities
and
potential
applications.
As
a
consequence,
large
number
that
can
act
as
light-harvesters,
semiconductors,
ligands,
binding
sites
or
redox
centers
have
recently
been
integrated
into
scaffolds
COFs.
This
unique
combination
reticular
chemistry
with
control
intrinsic
properties
paves
way
towards
new
semiconducting
(opto-)electronic
applications
such
sensors,
photocatalysts
-electrodes,
supercapacitor
battery
materials,
solar-harvesting
devices
light
emitting
diodes.
With
developments
regarding
motif,
highly
stable
still
tunable
COFs
developed
even
under
harsh
conditions.
Further,
stacking
modes
distances
in
investigated
powerful
means
optical
electrical
characteristics
these
self-assembled
frameworks.
Advanced
understanding
optoelectronic
processes
has
enabled
their
implementation
promising
real-world
review
highlights
key
concepts
synthesis
electro-
photoactive
well
our
frameworks,
hence
establishing
paradigm
rational
well-defined
novel
devices.
Abstract
Covalent
organic
frameworks
(COFs),
connecting
different
units
into
one
system
through
covalent
bonds,
are
crystalline
porous
materials
with
2D
or
3D
networks.
Compared
conventional
such
as
inorganic
zeolite,
active
carbon,
and
metal‐organic
frameworks,
COFs
a
new
type
of
well‐designed
pore
structure,
high
surface
area,
outstanding
stability,
easy
functionalization
at
the
molecular
level,
which
have
attracted
extensive
attention
in
various
fields,
energy
storage,
gas
separation,
sensing,
photoluminescence,
proton
conduction,
magnetic
properties,
drug
delivery,
heterogeneous
catalysis.
Herein,
recent
advances
metal‐free
versatile
platform
for
catalysis
wide
range
chemical
reactions
presented
synthetic
strategy
promising
catalytic
applications
COF‐based
catalysts
(including
photocatalysis)
summarized.
According
to
types
reactions,
this
review
is
divided
following
five
parts
discussion:
achiral
catalysis,
chiral
conversion,
photocatalytic
conversion
water
splitting
reduction
carbon
dioxide),
pollutant
degradation.
Furthermore,
remaining
challenges
prospects
also
presented.
Angewandte Chemie International Edition,
Год журнала:
2019,
Номер
59(9), С. 3624 - 3629
Опубликована: Ноя. 27, 2019
Abstract
The
construction
of
2D
and
3D
covalent
organic
frameworks
(COFs)
from
functional
moieties
for
desired
properties
has
gained
much
attention.
However,
the
influence
COFs
dimensionality
on
their
functionalities,
which
can
further
assist
in
COF
design,
never
been
explored.
Now,
by
selecting
designed
precursors
topology
diagrams,
porphyrinic
(2D‐PdPor‐COF
3D‐PdPor‐COF)
are
synthesized.
By
model
building
Rietveld
refinement
powder
X‐ray
diffraction,
2D‐PdPor‐COF
crystallizes
as
sheets
while
3D‐PdPor‐COF
adopts
a
five‐fold
interpenetrated
pts
topology.
Interestingly,
compared
with
2D‐PdPor‐COF,
showed
interesting
properties,
including
1)
higher
CO
2
adsorption
capacity;
2)
better
photocatalytic
performance;
3)
size‐selective
photocatalysis.
Based
this
study,
we
believe
that
incorporation
moieties,
definitely
functionalities.
Journal of the American Chemical Society,
Год журнала:
2019,
Номер
141(42), С. 16810 - 16816
Опубликована: Сен. 26, 2019
π-Conjugated
two-dimensional
covalent
organic
frameworks
(2D
COFs)
are
emerging
as
a
novel
class
of
electroactive
materials
for
(opto)electronic
and
chemiresistive
sensing
applications.
However,
understanding
the
intricate
interplay
between
chemistry,
structure,
conductivity
in
π-conjugated
2D
COFs
remains
elusive.
Here,
we
report
detailed
characterization
electronic
properties
two
samples
consisting
Zn-
Cu-phthalocyanine-based
pyrazine-linked
COFs.
These
synthesized
by
condensation
metal-phthalocyanine
(M
=
Zn
Cu)
pyrene
derivatives.
The
obtained
polycrystalline-layered
p-type
semiconductors
both
with
band
gap
∼1.2
eV.
A
record
device-relevant
mobility
up
to
∼5
cm2/(V
s)
is
resolved
dc
limit,
which
represents
lower
threshold
induced
charge
carrier
localization
at
crystalline
grain
boundaries.
Hall
effect
measurements
(dc
limit)
terahertz
(THz)
spectroscopy
(ac
combination
density
functional
theory
(DFT)
calculations
demonstrate
that
varying
metal
center
from
Cu
phthalocyanine
moiety
has
negligible
(∼5
×
10-7
S/cm),
(∼1012
cm-3),
scattering
rate
(∼3
1013
s-1),
effective
mass
(∼2.3m0)
majority
carriers
(holes).
Notably,
transport
found
be
anisotropic,
hole
mobilities
being
practically
null
in-plane
finite
out-of-plane
these
