Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Окт. 11, 2024
Rational
design
of
robust
photocatalytic
systems
to
direct
capture
and
in-situ
convert
diluted
CO2
from
flue
gas
is
a
promising
but
challenging
way
achieve
carbon
neutrality.
Here,
we
report
new
type
host-guest
photocatalysts
by
integrating
CO2-enriching
ionic
liquids
photoactive
metal-organic
frameworks
PCN-250-Fe2M
(M
=
Fe,
Co,
Ni,
Zn,
Mn)
for
artificial
photosynthetic
reduction
in
gas-solid
phase.
As
result,
[Emim]BF4(39.3
wt%)@PCN-250-Fe2Co
exhibits
record
high
CO2-to-CO
rate
313.34
μmol
g−1
h−1
under
pure
atmosphere
153.42
(15%)
with
about
100%
selectivity.
In
scaled-up
experiments
1.0
g
catalyst
natural
sunlight
irradiation,
the
concentration
could
be
significantly
decreased
below
85%
10%,
respectively,
indicating
its
industrial
application
potential.
Further
theoretical
calculations
reveal
that
not
only
benefit
enrichment,
also
form
synergistic
effect
Co2+
sites
PCN-250-Fe2Co,
resulting
significant
Gibbs
energy
barrier
during
rate-determining
step
conversion.
Artificial
fuel
authors
system
frameworks,
greatly
enhancing
conversion
efficiency.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(43), С. 23802 - 23813
Опубликована: Окт. 23, 2023
The
conversion
of
CO2
to
a
sole
carbonaceous
product
using
photocatalysis
is
sustainable
solution
for
alleviating
the
increasing
levels
emissions
and
reducing
our
dependence
on
nonrenewable
resources
such
as
fossil
fuels.
However,
developing
photoactive,
metal-free
catalyst
that
highly
selective
efficient
in
reduction
reaction
(CO2RR)
without
need
sacrificial
agents,
cocatalysts,
photosensitizers
challenging.
Furthermore,
due
poor
solubility
water
kinetically
thermodynamically
favored
hydrogen
evolution
(HER),
designing
photocatalyst
Here,
we
propose
molecular
engineering
approach
design
photoactive
polymer
with
high
permeability
low
diffusivity,
promoting
mass
transfer
while
suppressing
HER.
We
have
incorporated
contorted
triptycene
scaffold
"internal
free
volume
(IMFV)"
enhance
gas
active
site
by
creating
channels
through
inefficient
packing
chains.
Additionally,
introduced
pyrene
moiety
promote
visible-light
harvesting
capability
charge
separation.
By
leveraging
these
qualities,
exhibited
CO
generation
rate
77.8
μmol
g-1
h-1,
selectivity
∼98%
good
recyclability.
importance
IMFV
was
highlighted
replacing
unit
planar
scaffold,
which
led
reversal
favoring
HER
over
CO2RR
water.
In
situ
electron
paramagnetic
resonance
(EPR),
time-resolved
photoluminescence
spectroscopy
(TRPL),
diffuse
reflectance
infrared
Fourier
transform
(DRIFTS)
techniques,
further
supported
theoretical
calculations,
were
employed
enlighten
mechanistic
insight
exclusively
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
146(1), С. 487 - 499
Опубликована: Дек. 29, 2023
Improving
the
electronic
conductivity
and
structural
robustness
of
covalent
organic
frameworks
(COFs)
is
paramount.
Here,
we
covalently
cross-link
a
2D
COF
with
polypyrrole
(Ppy)
chains
to
form
quasi-3D
COF.
The
3D
shows
well-defined
reflections
in
SAED
patterns
distinctly
indexed
its
modeled
crystal
structure.
This
knitting
layers
conjugated
units
improves
from
10–9
10–2
S
m–1.
boost
affirmed
by
presence
density
states
near
Fermi
level
COF,
this
elevates
COF's
valence
band
maximum
0.52
eV
respect
parent
pyrrole-functionalized
which
agrees
well
opto–electro
gaps.
extent
HOMO
elevation
suggests
predominant
existence
polaron
state
(radical
cation),
giving
rise
strong
EPR
signal,
most
likely
sourced
cross-linking
chains.
A
supercapacitor
devised
COF20-Ppy
records
high
areal
capacitance
377.6
mF
cm–2,
higher
than
that
loaded
noncovalently
linked
Thus,
acts
as
"conjugation
bridge"
across
layers,
lowering
gap
providing
polarons
additional
conduction
pathways.
marks
far-reaching
approach
converting
many
COFs
into
highly
ordered
conducting
ones.
Advanced Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 9, 2024
Abstract
The
global
energy
crisis
and
environmental
concerns
are
driving
research
into
renewable
sustainable
conversion
storage
technologies.
Solar
energy,
as
an
ideal
resource,
has
significant
potential
to
contribute
the
goal
of
net‐zero
carbon
emissions
if
effectively
harnessed
converted
a
reliable
storable
form
energy.
Photocatalysts
have
convert
sunlight
chemical
carriers.
In
this
respect,
covalent
organic
frameworks
(COFs)
shown
great
promise
due
their
tunable
structure
on
different
length
scales,
high
surface
areas,
beneficial
optical
properties
such
broad
visible
light
absorption.
This
review
offers
comprehensive
overview
key
developments
in
COF‐based
photocatalysts
for
various
applications,
including
water
splitting,
hydrogen
peroxide
generation,
transformations,
dioxide
nitrogen
reduction.
underlying
mechanisms,
essential
principles
material
design,
structure‐function
relationships
COFs
photocatalytic
applications
discussed.
challenges
faced
by
also
summarized
strategies
enhance
performance
explained,
improving
crystallinity,
regulating
molecular
structures,
tailoring
linkages,
incorporating
cocatalysts.
Finally,
critical
proposed
utilization
photocatalytically
generated
chemicals
value‐added
products.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Окт. 11, 2024
Rational
design
of
robust
photocatalytic
systems
to
direct
capture
and
in-situ
convert
diluted
CO2
from
flue
gas
is
a
promising
but
challenging
way
achieve
carbon
neutrality.
Here,
we
report
new
type
host-guest
photocatalysts
by
integrating
CO2-enriching
ionic
liquids
photoactive
metal-organic
frameworks
PCN-250-Fe2M
(M
=
Fe,
Co,
Ni,
Zn,
Mn)
for
artificial
photosynthetic
reduction
in
gas-solid
phase.
As
result,
[Emim]BF4(39.3
wt%)@PCN-250-Fe2Co
exhibits
record
high
CO2-to-CO
rate
313.34
μmol
g−1
h−1
under
pure
atmosphere
153.42
(15%)
with
about
100%
selectivity.
In
scaled-up
experiments
1.0
g
catalyst
natural
sunlight
irradiation,
the
concentration
could
be
significantly
decreased
below
85%
10%,
respectively,
indicating
its
industrial
application
potential.
Further
theoretical
calculations
reveal
that
not
only
benefit
enrichment,
also
form
synergistic
effect
Co2+
sites
PCN-250-Fe2Co,
resulting
significant
Gibbs
energy
barrier
during
rate-determining
step
conversion.
Artificial
fuel
authors
system
frameworks,
greatly
enhancing
conversion
efficiency.
