Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(36)
Published: June 28, 2023
Constructing
a
powerful
photocatalytic
system
that
can
achieve
the
carbon
dioxide
(CO2
)
reduction
half-reaction
and
water
(H2
O)
oxidation
simultaneously
is
very
challenging
but
meaningful
task.
Herein,
porous
material
with
crystalline
topological
network,
named
viCOF-bpy-Re,
was
rationally
synthesized
by
incorporating
rhenium
complexes
as
reductive
sites
triazine
ring
structures
oxidative
via
robust
-C=C-
bond
linkages.
The
charge-separation
ability
of
viCOF-bpy-Re
promoted
low
polarized
π-bridges
between
units,
efficient
enables
photogenerated
electron-hole
pairs,
followed
an
intramolecular
charge-transfer
process,
to
form
electrons
involved
in
CO2
holes
participate
H2
O
simultaneously.
shows
highest
catalytic
monoxide
(CO)
production
rate
(190.6
μmol
g-1
h-1
about
100
%
selectivity)
oxygen
(O2
evolution
(90.2
among
all
catalysts
sacrificial
agents.
Therefore,
successfully
achieved,
this
exhibited
excellent
stability
catalysis
process
for
50
hours.
structure-function
relationship
confirmed
femtosecond
transient
absorption
spectroscopy
density
functional
theory
calculations.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(15)
Published: Jan. 21, 2022
As
hot
topics
in
the
chemical
conversion
of
CO2
,
photo-/electrocatalytic
reduction
and
use
as
a
supporter
for
energy
storage
have
shown
great
potential
utilization
.
However,
many
obstacles
still
exist
on
road
to
realizing
highly
efficient
conversion,
such
inefficient
uptake/activation
mass
transport
catalysts.
Covalent
organic
frameworks
(COFs),
kind
porous
material,
been
widely
explored
catalysts
owing
their
unique
features.
In
particular,
COF-based
functional
materials
containing
diverse
active
sites
(such
single
metal
sites,
nanoparticles,
oxides)
offer
storage.
This
Minireview
discusses
recent
breakthroughs
basic
knowledge,
mechanisms,
pathways
strategies
that
addition,
challenges
prospects
are
also
introduced.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(38), P. 20837 - 20848
Published: Aug. 25, 2023
Coupled
photocatalysis
without
cocatalysts
can
maximize
the
utilization
of
photons
and
atoms,
which
puts
forward
higher
demands
on
photocatalysts.
Polymeric
carbon
nitride
(CN)
has
become
most
promising
photocatalyst,
but
still
suffers
from
major
drawbacks
insufficient
catalytic
sites
low
quantum
efficiency.
Herein,
we
report
a
fluid
shear
stress-assisted
molecular
assembly
to
prepare
ultrathin-nanosheet-assembled
acanthosphere-like
CN
(ASCN)
with
nitrogen
vacancy
(Nv)
carbonyl
modification.
Shear
stress
breaks
stacking
interactions
between
layers
cuts
stacked
structure
into
ultrathin
layers,
are
further
reassembled
acanthosphere
bundles
driven
by
"centrifugal
force".
Benefitted
greatly
nature
that
provides
more
exposed
active
improves
charge
carrier
separation,
ASCN-3
exhibits
20-fold
activity
than
bulk
counterpart
toward
oxygen
reduction
H2O2
coupled
4-methoxybenzyl
alcohol
(4-MBA)
oxidation
anisaldehyde
(AA),
significantly
increased
turnover
frequency
(TOF)
values
(TOF:
1.69
h–1
for
1.02
AA).
Significantly,
95.8%
conversion
4-MBA
nearly
100%
selectivity.
High
apparent
yields
11.7%
9.3%
at
420
nm
achieved
photosynthesis
oxidation.
Mechanism
studies
suggest
induces
holes
concentrated
neighboring
melem
unit
directly
oxidize
Cα–H
bond
produce
radicals,
Nv
as
adsorption
site
traps
electrons
form
superoxide
radical
combines
shed
protons
H2O2.
This
work
presents
simple
physical
method
break
layered
stack
creating
hierarchical
photocatalysis.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(34)
Published: April 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,
Journal Year:
2023,
Volume and Issue:
145(5), P. 3248 - 3254
Published: Jan. 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,
Journal Year:
2022,
Volume and Issue:
144(27), P. 12390 - 12399
Published: June 29, 2022
The
reaction
of
5,5′-([2,2′-bipyridine]-5,5′-diyl)diisophthalaldehyde
(BPDDP)
with
cyclohexanediamine
and
[benzidine
(BZ)/[2,2′-bipyridine]-5,5′-diamine
(BPDA)],
respectively,
affords
a
nitrogen-rich
porous
organic
cage
BPPOC
two
two-dimensional
(2D)
covalent
frameworks
(COFs),
USTB-1
USTB-2
(USTB
=
University
Science
Technology
Beijing),
under
suitable
conditions.
Interestingly,
single-crystal
X-ray
diffraction
structure
is
able
to
successfully
transform
into
(newly
converted
COFs
denoted
as
USTB-1c
USTB-2c,
respectively)
upon
exchange
the
imine
unit
in
by
BZ
BPDA.
Such
transformation
also
enables
isolation
analogous
(USTB-3c
USTB-4c)
on
basis
an
isostructural
cage,
BTPOC,
which
derived
from
5,5′-([2,2′-bithiophene]-4,4′-diyl)diisophthalaldehyde
(BTDDP)
cyclohexanediamine.
However,
conventional
solvothermal
between
BTDDP
BPDA
leads
impure
phase
USTB-4
containing
incompletely
aldehyde
groups
due
limited
solubility
building
block.
newly
prepared
have
been
characterized
nuclear
magnetic
resonance
spectroscopy,
Fourier
infrared
scanning
electron
microscopy,
transmission
microscopy.
In
particular,
absorb
iodine
vapor
uptake
5.64
g
g–1,
breaking
cage's
(POC's)
record
value
3.78
g–1.
Nevertheless,
cage-derived
exhibit
improved
adsorption
capability
comparison
directly
synthesized
counterparts,
highest
5.80
g–1
for
USTB-1c.
mechanism
investigation
unveils
superiority
nitrogen
atoms
sulfur
POCs
capture
assistance
definite
crystal
structures.
This,
combination
porosity,
synergistically
influences
capacity
COFs.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(17), P. 9520 - 9529
Published: April 19, 2023
Covalent
organic
frameworks
(COFs)
hold
the
potential
in
converting
CO2
with
water
into
value-added
fuels
and
O2
to
save
deteriorating
ecological
environment.
However,
reaching
high
yield
selectivity
is
a
grand
challenge
under
metal-,
photosensitizer-,
or
sacrificial
reagent-free
conditions.
Here,
inspired
by
microstructures
of
natural
leaves,
we
designed
triazine-based
COF
membranes
integration
steady
light-harvesting
sites,
efficient
catalytic
center,
fast
charge/mass
transfer
configuration
fabricate
novel
artificial
leaf
for
first
time.
Significantly,
record
CO
1240
μmol
g–1
4
h
reaction,
approximately
100%
selectivity,
long
lifespan
(at
least
16
cycles)
were
achieved
gas–solid
conditions
without
using
any
metal,
photosensitizer,
reagent.
Unlike
existing
knowledge,
chemical
structural
unit
triazine-imide-triazine
unique
physical
form
membrane
are
predominant
such
remarkable
photocatalysis.
This
work
opens
new
pathway
simulating
photosynthesis
leaves
may
motivate
relevant
research
future.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: April 29, 2023
The
precise
construction
of
photocatalysts
with
diatomic
sites
that
simultaneously
foster
light
absorption
and
catalytic
activity
is
a
formidable
challenge,
as
both
processes
follow
distinct
pathways.
Herein,
an
electrostatically
driven
self-assembly
approach
used,
where
phenanthroline
used
to
synthesize
bifunctional
LaNi
within
covalent
organic
framework.
La
Ni
site
acts
optically
catalytically
active
center
for
photocarriers
generation
highly
selective
CO2-to-CO
reduction,
respectively.
Theory
calculations
in-situ
characterization
reveal
the
directional
charge
transfer
between
La-Ni
double-atomic
sites,
leading
decreased
reaction
energy
barriers
*COOH
intermediate
enhanced
conversion.
As
result,
without
any
additional
photosensitizers,
15.2
times
enhancement
CO2
reduction
rate
(605.8
μmol·g-1·h-1)
over
benchmark
framework
colloid
(39.9
improved
CO
selectivity
(98.2%)
are
achieved.
This
work
presents
potential
strategy
integrating
centers
enhance
photocatalytic
reduction.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(7), P. 4316 - 4329
Published: March 15, 2023
Photocatalytic
CO2
reduction
holds
great
promise
for
synchronously
addressing
carbon
neutrality
and
producing
fuels,
although
enhancing
the
photocatalyst
activity
tuning
product
selectivity
remain
enormous
challenges.
Herein,
we
synthesized
four
crystalline
porous
benzothiadiazole-based
covalent
organic
frameworks
(COFs)
with
different
carbonyl
groups
reported
a
dual
metalation
strategy
to
fabricate
Co
Ni
dual-metal
sites
anchored
on
COFs
by
interaction
between
metal
thiadiazole
high-performance
photoreduction.
Among
as-synthesized
metalated
Co/Ni
sites,
CoNi–COF-3
achieved
an
impressive
CO
generation
rate
of
2567
μmol
g–1
h–1
92.2%,
which
were
significantly
higher
than
those
single
sites.
Experimental
theoretical
results
revealed
that
superior
photocatalytic
performance
was
attributed
synergic
effect
fully
β-ketoenamine-tautomerized
COF-3
configuration
not
only
facilitated
photogenerated
charge
carrier
dynamics
but
also
reduced
energy
barriers
*COOH
formation
promoted
adsorption
desorption.
This
work
provides
valuable
insights
into
future
design
improved
COF
photocatalysts
conversion.