Metalloporphyrin-based
porous
organic
polymers
that
behave
as
advanced
biomimetic
nanoreactors
have
drawn
continuous
attention
for
heterogeneous
CO2
cycloaddition
conversion
in
the
past
decades.
However,
use
of
homogeneous
onium
salts,
usually
acting
nucleophilic
cocatalysts,
may
increase
cost
product
purification
and
cause
additional
environmental
problems.
In
this
contribution,
a
new
aluminum
porphyrin-based
hyper-cross-linked
polymer
modified
by
imidazolium
salts
(denoted
Im@Al-HCP)
has
been
successfully
constructed
first
time.
The
two-step
process
hyper-cross-linking
reaction
combined
with
postsynthetic
modification
endows
catalyst
large
surface
area
(about
213
m2·g–1),
good
adsorption
capacity
(up
to
1.45
mmol·g–1),
highly
dispersed
cooperative
active
sites.
Accordingly,
bifunctional
Im@Al-HCP
exhibits
an
outstanding
catalytic
activity,
recyclability,
broad
substrate
generality
without
cocatalysts
solvents
under
mild
conditions.
particular,
high
turnover
frequency
(TOF)
value
up
5000
h–1
can
be
acquired,
which
far
exceeds
most
reported
catalysts
identical
addition,
as-made
recycled
at
least
six
times
obvious
loss
activity.
This
work
not
only
bring
some
inspirations
construction
multifunctional
but
also
provides
great
potential
industrial
applications
cycloadditions.
Journal of CO2 Utilization,
Journal Year:
2024,
Volume and Issue:
84, P. 102854 - 102854
Published: June 1, 2024
The
greenhouse
gas
(GHG)
emissions
from
fossil
fuel
combustion
and
carbon
dioxide
(CO2)
cause
global
warming
climate
change.
In
this
study,
we
synthesized
three
porphyrin-based
azo-porous
organic
polymers
(PBPOP1,
PBPOP2,
PBPOP3)
that
enable
the
capture
one-step
conversion
of
CO2.
These
catalysts
effectively
CO2
molecules
over
N2
in
a
post-combustion
environment.
PBPOP3
exhibited
an
enhanced
CO2/N2
selectivity
at
313
K,
with
value
534.
We
characterized
azo-POPs
using
FT-IR,
13C
solid-state
NMR,
XRD,
TGA,
HR-FESEM.
evaluated
adsorption
properties
Brunauer–Emmett–Teller
analysis,
which
included
adsorption–desorption
isotherms,
NLDFT
pore-size
distribution,
298,
313,
353
K.
fixation
styrene
oxide
phenyl
glycidyl
ether
was
performed
for
to
carbonate
(tetra-n-butylammonium
bromide
used
as
co-catalyst).
Thus,
our
findings
can
be
reducing
amount
atmosphere
by
synthesizing
azo-POP
catalysts.
Chemical Communications,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 25, 2024
Recent
works
on
practical
and
recyclable
catalysts
for
the
cycloaddition
of
CO
2
to
epoxides
are
reviewed
with
an
eye
use
inexpensive,
readily-available,
non-toxic
materials
future
emerging
designs.
Poly(ionic
liquid)s
(PILs)
are
considered
efficient
and
attractive
heterogeneous
catalysts
for
CO2
cycloaddition
with
epoxides
because
of
the
reactions
that
proceed
without
cocatalysts
solvents.
Nowadays,
it
is
widely
believed
preparation
PILs
can
be
simply
realized
via
common
monomers
by
Menshutkin
reaction,
but
most
exhibit
low
surface
areas
due
to
intermolecular
packing.
It
a
challenge
obtain
porous
diverse
functional
groups
activate
substrates.
In
this
contribution,
we
utilized
Menshutkin-type
reaction
three-dimensional
contorted
manufacture
new
kind
porphyrin-functionalized
microporous
PIL
first
time.
worth
noting
metal-free
containing
porphyrin,
imidazole,
imidazolium
active
promote
activation
achieve
cycloadditions
under
relatively
mild
conditions.
After
metalation,
their
catalytic
activities
have
been
enhanced
significantly
more
moderate
Moreover,
both
metal-based
recycled
at
least
six
times
any
obvious
decrease
in
activity.
Finally,
apparent
activated
energies
calculated
from
kinetic
study
demonstrate
possible
mechanism.
This
work
not
only
provides
an
strategy
constructing
designing
also
highlights
promising
method
activating
converting
into
fine
chemicals
Chemical Communications,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
Hyper-cross-linked
polymers
functionalized
with
different
metal
complexes
showed
excellent
catalytic
properties
for
two
kinds
of
CO
2
cyclization
reactions
under
ambient
conditions.
Multifunctionalization
of
porous
organic
polymers
(POPs)
toward
cooperative
CO2
catalysis
has
attracted
so
much
attention
in
recent
years,
but
it
still
remains
a
huge
challenge
to
scientists.
In
this
contribution,
concise
and
efficient
method
construct
aluminum
porphyrin-based
hyper-cross-linked
ionic
been
demonstrated
for
the
first
time,
which
are
featured
with
high
surface
areas
hierarchical
structures.
Obviously,
preparation
metalloporphyrin-based
tetraphenylmethane-derived
three-dimensional
structures
is
beneficial
introduction
abundant
active
sites
formation
By
regulating
locations
amounts
make
them
highly
dispersed
easily
accessible,
catalytic
activity
as-maded
catalyst
can
be
greatly
improved
cycloaddition
conversion
cyclic
carbonates
without
cocatalysts
solvents,
providing
highest
initial
turnover
frequency
up
8400
h-1
heterogeneous
catalysts
reported
date.
addition,
recovered
by
filtration
reused
at
least
ten
times
significant
decrease
activity.
This
work
not
only
presents
promising
strategy
improve
controlling
site
proximity
via
different
synthetic
methods
also
offers
an
attractive
perspective
field
conversion.
