Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Июль 19, 2023
Solar-driven
photosynthesis
is
a
sustainable
process
for
the
production
of
hydrogen
peroxide,
efficiency
which
plagued
by
side
reactions.
Metal-free
covalent
organic
frameworks
(COFs)
that
can
form
suitable
intermediates
and
inhibit
reactions
show
great
promise
to
photo-synthesize
H2O2.
However,
insufficient
formation
separation/transfer
photogenerated
charges
in
such
materials
restricts
H2O2
production.
Herein,
we
provide
strategy
design
donor-acceptor
COFs
greatly
boost
photosynthesis.
We
demonstrate
optimal
intramolecular
polarity
COFs,
achieved
using
amounts
phenyl
groups
as
electron
donors,
maximize
free
charge
generation,
leads
high
yield
rates
(605
μmol
g-1
h-1)
from
water,
oxygen
visible
light
without
sacrificial
agents.
Combining
in-situ
characterization
with
computational
calculations,
describe
how
triazine
N-sites
N
2p
states
play
crucial
role
H2O
activation
selective
oxidation
into
further
experimentally
be
efficiently
produced
tap,
river
or
sea
water
natural
sunlight
air
decontamination.
Chemical Society Reviews,
Год журнала:
2020,
Номер
49(12), С. 4135 - 4165
Опубликована: Янв. 1, 2020
In
the
light
of
increasing
energy
demand
and
environmental
pollution,
it
is
urgently
required
to
find
a
clean
renewable
source.
these
years,
photocatalysis
that
uses
solar
for
either
fuel
production,
such
as
hydrogen
evolution
hydrocarbon
or
pollutant
degradation,
has
shown
great
potential
achieve
this
goal.
Among
various
photocatalysts,
covalent
organic
frameworks
(COFs)
are
very
attractive
due
their
excellent
structural
regularity,
robust
framework,
inherent
porosity
good
activity.
Thus,
many
studies
have
been
carried
out
investigate
photocatalytic
performance
COFs
COF-based
photocatalysts.
critical
review,
recent
progress
advances
COF
photocatalysts
thoroughly
presented.
Furthermore,
diverse
linkers
between
building
blocks
boron-containing
connections
nitrogen-containing
summarised
compared.
The
morphologies
several
commonly
used
strategies
pertaining
activity
also
discussed.
Following
this,
applications
detailed
including
evolution,
CO2
conversion
degradation
contaminants.
Finally,
summary
perspective
on
opportunities
challenges
future
development
given.
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.
Nature Communications,
Год журнала:
2020,
Номер
11(1)
Опубликована: Янв. 23, 2020
Abstract
Uranium
is
a
key
element
in
the
nuclear
industry,
but
its
unintended
leakage
has
caused
health
and
environmental
concerns.
Here
we
report
sp
2
carbon-conjugated
fluorescent
covalent
organic
framework
(COF)
named
TFPT-BTAN-AO
with
excellent
chemical,
thermal
radiation
stability
synthesized
by
integrating
triazine-based
building
blocks
amidoxime-substituted
linkers.
shows
an
exceptional
UO
2+
adsorption
capacity
of
427
mg
g
−1
attributable
to
abundant
selective
uranium-binding
groups
on
highly
accessible
pore
walls
open
1D
channels.
In
addition,
it
ultra-fast
response
time
(2
s)
ultra-low
detection
limit
6.7
nM
suitable
for
on-site
real-time
monitoring
,
allowing
not
only
extraction
also
quality
extracted
water.
This
study
demonstrates
great
potential
COFs
radionuclide
extraction.
By
rational
designing
target
ligands,
this
strategy
can
be
extended
other
contaminants.
Journal of the American Chemical Society,
Год журнала:
2020,
Номер
142(39), С. 16723 - 16731
Опубликована: Сен. 7, 2020
While
catalysis
is
highly
dependent
on
the
electronic
structure
of
catalyst,
understanding
catalytic
performance
affected
by
electron
spin
regulation
remains
challenging
and
rare.
Herein,
we
have
developed
a
facile
strategy
to
manipulation
cobalt
state
over
covalent
organic
frameworks
(COFs),
COF-367-Co,
simply
changing
oxidation
Co
centered
in
porphyrin.
Density
functional
theory
(DFT)
calculations
together
with
experimental
results
confirm
that
CoII
CoIII
are
embedded
COF-367
S
=
1/2
0
ground
states,
respectively.
Remarkably,
photocatalytic
CO2
reduction
indicate
COF-367-CoIII
exhibits
favorable
activity
significantly
enhanced
selectivity
HCOOH,
accordingly
much
reduced
CO
CH4,
sharp
contrast
COF-367-CoII.
The
highlight
spin-state
transition
greatly
regulates
performance.
Theoretical
further
disclose
presence
COF-367-Co
preferable
formation
HCOOH
but
detrimental
its
conversion,
which
clearly
accounts
for
distinctly
different
photocatalysis
To
best
our
knowledge,
this
first
report
regulating
COFs.
Chemical Society Reviews,
Год журнала:
2020,
Номер
49(3), С. 839 - 864
Опубликована: Янв. 1, 2020
This
review
highlights
the
luminescent
and
unique
photophysical
properties
of
covalent
organic
frameworks.
Their
potential
use
in
applications
related
to
chemical
sensing,
photocatalysis,
optoelectronics
are
discussed.
Chemical Reviews,
Год журнала:
2021,
Номер
122(2), С. 2650 - 2694
Опубликована: Авг. 27, 2021
Geometrical
E
→
Z
alkene
isomerization
is
intimately
entwined
in
the
historical
fabric
of
organic
photochemistry
and
enjoying
a
renaissance
(Roth
et
al.
Angew.
Chem.,
Int.
Ed.
Engl.
1989
28,
1193–1207).
This
consequence
fundamental
stereochemical
importance
Z-alkenes,
juxtaposed
with
frustrations
thermal
reactivity
that
are
rooted
microscopic
reversibility.
Accessing
excited
state
paradigms
allow
this
latter
obstacle
to
be
circumnavigated
by
exploiting
subtle
differences
photophysical
behavior
substrate
product
chromophores:
provides
molecular
basis
for
directionality.
While
direct
irradiation
operationally
simple,
photosensitization
via
selective
energy
transfer
enables
augmentation
repertoire
include
substrates
not
directly
photons.
Through
sustained
innovation,
an
impressive
portfolio
tailored
small
molecule
catalysts
range
triplet
energies
now
widely
available
facilitate
contra-thermodynamic
thermo-neutral
reactions
generate
Z-alkene
fragments.
review
intended
serve
as
practical
guide
covering
geometric
alkenes
enabled
catalysis
from
2000
2020,
logical
sequel
excellent
treatment
Dugave
Demange
(Chem.
Rev.
2003
103,
2475–2532).
The
mechanistic
foundations
underpinning
selectivity
discussed
together
induction
models
rationales
explain
counterintuitive
directionality
these
processes
which
very
distinguish
product.
Implications
subsequent
stereospecific
transformations,
application
total
synthesis,
regioselective
polyene
isomerization,
spatiotemporal
control
pre-existing
configuration
broader
sense
discussed.
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.
ACS Catalysis,
Год журнала:
2020,
Номер
10(15), С. 8717 - 8726
Опубликована: Июль 10, 2020
Covalent
organic
frameworks
(COFs)
are
promising
candidates
as
heterogeneous
photocatalysts
because
of
their
porosity
and
tunable
light
absorption.
The
photostability
charge
separation
COFs
highly
important
to
improve
the
efficiency
photocatalytic
transformation.
In
this
work,
a
fully
conjugated
donor–acceptor
COF
is
constructed
with
benzothiadiazole
unit,
which
exhibits
high
stability
enhanced
separation.
prepared
can
efficaciously
produce
superoxide
radical
anions
under
air
visible
light,
mediate
oxidative
amine
coupling
cyclization
thioamide
1,2,4-thiadiazole
in
moderate
yield
recyclability
(18
examples).
This
study
demonstrates
great
capacity
D–A
structure
for
light-driven
synthesis.
