Macromolecular Rapid Communications,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 12, 2025
Abstract
Photocatalytic
production
of
hydrogen
peroxide
(H
2
O
)
represents
a
significant
approach
to
achieving
sustainable
energy
generation
through
solar
energy,
addressing
both
shortages
and
environmental
pollution.
Among
various
photocatalytic
materials,
covalent
organic
frameworks
(COFs)
have
gained
widespread
attention
in‐depth
research
due
their
unique
advantages,
including
high
porosity,
predesignability,
atomic‐level
tunability.
In
recent
years,
progress
has
been
made
in
the
development,
performance
enhancement,
mechanistic
understanding
COF‐based
photocatalysts.
This
review
focuses
on
latest
advancements
H
using
COFs,
particularly
emphasizing
rational
design
COF
structures
regulate
catalytic
exploring
fundamental
processes
involved
photocatalysis.
Based
current
achievements
this
field,
paper
also
discusses
existing
challenges
future
opportunities,
aiming
provide
reference
for
application
COFs
production.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(49)
Published: Aug. 14, 2023
Abstract
Benefiting
from
the
excellent
structural
tunability,
robust
framework,
ultrahigh
porosity,
and
rich
active
sites,
covalent
organic
frameworks
(COFs)
are
widely
recognized
as
promising
photocatalysts
in
chemical
conversions,
emerged
hydrogen
peroxide
(H
2
O
)
photosynthesis
2020.
H
,
serving
an
environmental‐friendly
oxidant
a
liquid
fuel,
has
attracted
increasing
researchers
to
explore
its
potential.
Over
past
few
years,
numerous
COFs‐based
developed
with
encouraging
achievements
production,
whereas
no
comprehensive
review
articles
exist
summarize
this
specific
significant
area.
Herein
we
provide
systematic
overview
of
advances
challenges
COFs
photocatalytic
production.
We
first
introduce
priorities
photosynthesis.
Then,
various
strategies
improve
efficiency
discussed.
The
perspective
outlook
for
future
emerging
field
finally
offered.
This
timely
will
pave
way
development
highly
efficient
practical
production
value‐added
chemicals
not
limited
.
Advanced Materials,
Journal Year:
2022,
Volume and Issue:
35(24)
Published: Dec. 23, 2022
Abstract
Organic
photochemistry
is
intensely
developed
in
the
1980s,
which
nature
of
excited
electronic
states
and
energy
electron
transfer
processes
are
thoroughly
studied
finally
well‐understood.
This
knowledge
from
molecular
organic
can
be
transferred
to
design
covalent
frameworks
(COFs)
as
active
visible‐light
photocatalysts.
COFs
constitute
a
new
class
crystalline
porous
materials
with
substantial
application
potentials.
Featured
outstanding
structural
tunability,
large
porosity,
high
surface
area,
excellent
stability,
unique
photoelectronic
properties,
potential
candidates
various
research
areas
(e.g.,
photocatalysis).
review
aims
provide
state‐of‐the‐art
insights
into
COF
photocatalysts
(pristine,
functionalized,
hybrid
COFs)
for
transformations.
The
catalytic
reaction
mechanism
COF‐based
influence
dimensionality
crystallinity
on
heterogenous
photocatalysis
performance
also
discussed,
followed
by
perspectives
prospects
main
challenges
opportunities
future
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(43)
Published: Sept. 5, 2023
Singlet
oxygen
(1
O2
)
is
an
excellent
reactive
species
(ROSs)
for
the
selective
conversion
of
organic
matter,
especially
in
advanced
oxidation
processes
(AOPs).
However,
due
to
huge
dilemma
synthesizing
single-site
type
catalysts,
control
and
regulation
1
generation
AOPs
still
challenging
underlying
mechanism
remains
largely
obscure.
Here,
taking
advantage
well-defined
flexibly
tunable
sites
covalent
frameworks
(COFs),
we
report
first
achievement
precisely
regulating
ROSs
peroxymonosulfate
(PMS)-based
by
site
engineering
COFs.
Remarkably,
COFs
with
bipyridine
units
(BPY-COFs)
facilitate
PMS
activation
via
a
nonradical
pathway
100
%
,
whereas
biphenyl-based
(BPD-COFs)
almost
identical
structures
activate
produce
radicals
(⋅OH
SO4.-
).
The
BPY-COFs/PMS
system
delivers
boosted
performance
degradation
target
pollutants
from
water,
which
ca.
9.4
times
that
its
BPD-COFs
counterpart,
surpassing
most
reported
PMS-based
systems.
Mechanism
analysis
indicated
highly
electronegative
pyridine-N
atoms
on
BPY-COFs
provide
extra
adsorb
terminal
H
PMS,
resulting
simultaneous
adsorption
O
one
pyridine
ring,
facilitates
cleavage
S-O
bond
generate
.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(31)
Published: June 7, 2023
In
this
work,
we
innovatively
assembled
two
types
of
traditional
photosensitizers,
that
is
pyridine
ruthenium/ferrum
(Ru(bpy)32+
/Fe(bpy)32+
)
and
porphyrin/metalloporphyrin
complex
(2HPor/ZnPor)
by
covalent
linkage
to
get
a
series
dual
photosensitizer-based
three-dimensional
metal-covalent
organic
frameworks
(3D
MCOFs),
which
behaved
strong
visible
light-absorbing
ability,
efficient
electron
transfer
suitable
band
gap
for
highly
photocatalytic
hydrogen
(H2
evolution.
Rubpy-ZnPor
COF
achieved
the
highest
H2
yield
(30
338
μmol
g-1
h-1
with
apparent
quantum
efficiency
(AQE)
9.68
%@420
nm,
showed
one
best
performances
among
all
reported
based
photocatalysts.
Furthermore,
in
situ
produced
was
successfully
tandem
used
alkyne
hydrogenation
≈99.9
%
conversion
efficiency.
Theoretical
calculations
reveal
both
photosensitizer
units
MCOFs
can
be
photoexcited
thus
contribute
optimal
activity.
This
work
develops
general
strategy
shows
great
potential
using
multiple
photosensitive
materials
field
photocatalysis.
Advanced Functional Materials,
Journal Year:
2024,
Volume and Issue:
unknown
Published: March 10, 2024
Abstract
Covalent
organic
frameworks
(COFs)
attract
significant
attention
due
to
their
ordered,
crystalline,
porous,
metal‐free,
and
predictable
structures.
These
unique
characteristics
offer
great
opportunities
for
the
diffusion
transmission
of
photogenerated
charges
during
photocatalysis.
Currently,
a
considerable
number
COFs
are
used
as
metal‐free
semiconductor
photocatalysts.
This
review
aims
understand
relationships
between
structure
photocatalysis
performance
provides
in‐depth
insight
into
synthetic
strategy
improve
performance.
Subsequently,
focuses
on
structural
motif
in
sustainable
photocatalytic
hydrogen
evolution,
carbon
dioxide
reduction,
peroxide
generation,
compound
transformations.
Last,
conjunction
with
progress
achieved
challenges
yet
be
overcome,
candid
discussion
is
undertaken
regarding
field
COF
photocatalysis,
accompanied
by
presentation
potential
research
avenues
future
directions.
seeks
provide
readers
comprehensive
understanding
pivotal
role
robust
guidance
innovative
utilization
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(20), P. 13167 - 13180
Published: Sept. 28, 2023
Covalent–organic
frameworks
(COFs),
as
promising
metal-free
porous
catalysts,
have
become
a
hot
research
topic
in
the
field
of
(photo)catalysis.
Herein,
series
β-ketoenamine
COFs
are
synthesized
using
different
amino
and
aldehyde
monomers,
these
exhibit
diverse
characteristics
terms
crystallinity,
chemical
structure,
microscopic
morphology,
optoelectronic
properties.
TpBD-(CH3)2
from
2,4,6-triformylphloroglucinol
o-tolidine
exhibits
an
extended
π-conjugated
structure
higher
crystallinity
well
more
suitable
redox
potential,
which
greatly
enhances
photocatalytic
activity
benzylamine
oxidation.
Besides,
increased
number
hydroxyl
groups
on
trialdehyde-based
monomer
contributes
to
ketoamines
TpTAB
skeleton,
is
favorable
for
photocatalysis.
Meanwhile,
can
rapidly
increase
their
own
temperature
through
internal
structural
evolution
under
light
irradiation,
thus
boosting
oxidative
coupling
amines
with
high
efficiency.
This
work
could
provide
some
guidance
rational
design
functional
advanced
organic
transformations.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(18), P. 9378 - 9418
Published: Jan. 1, 2024
Organic
transformation
by
light-driven
catalysis,
especially,
photocatalysis
and
photothermal
denoted
as
photo(thermal)
is
an
efficient,
green,
economical
route
to
produce
value-added
compounds.
In
recent
years,
owing
their
diverse
structure
types,
tunable
pore
sizes,
abundant
active
sites,
metal-organic
framework
(MOF)-based
catalysis
has
attracted
broad
interest
in
organic
transformations.
this
review,
we
provide
a
comprehensive
systematic
overview
of
MOF-based
for
First,
the
general
mechanisms,
unique
advantages,
strategies
improve
performance
MOFs
are
discussed.
Then,
outstanding
examples
transformations
over
introduced
according
reaction
type.
addition,
several
representative
advanced
characterization
techniques
used
revealing
charge
kinetics
intermediates
presented.
Finally,
prospects
challenges
field
proposed.
This
review
aims
inspire
rational
design
development
materials
with
improved
catalysis.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(11)
Published: Jan. 18, 2023
Covalent
organic
frameworks
(COFs)
have
received
broad
interest
owing
to
their
permanent
porosity,
high
stability,
and
tunable
functionalities.
COFs
with
long-range
π-conjugation
photosensitizing
building
blocks
been
explored
for
sustainable
photocatalysis.
Herein,
we
report
the
first
example
of
COF-based
energy
transfer
Ni
catalysis.
A
pyrene-based
COF
sp2
carbon-conjugation
was
synthesized
used
coordinate
NiII
centers
through
bipyridine
moieties.
Under
light
irradiation,
enhanced
in
facilitated
excitation
catalyze
borylation
trifluoromethylation
reactions
aryl
halides.
The
showed
two
orders
magnitude
higher
efficiency
these
than
its
homogeneous
control
could
be
recovered
reused
without
significant
loss
catalytic
activity.