Abstract
Fixing
the
greenhouse
gas
CO
2
through
epoxide
helps
to
mitigate
worldwide
ecological
troubles.
The
applications
of
metal‐free
and
solvent‐free
catalysts
remain
a
challenge
for
catalytic
conversion.
In
this
work,
an
array
quaternary
ammonium
salts
derived
from
polyethyleneimine
with
hydroxyl
groups
([PEI‐GDMAB‐C
n
]Br)
were
constructed
by
reaction
branched
PEI
molecular
weight
10000
glycidyl
alkyl
dimethylammonium
bromide.
A
range
experiments
designed
demonstrate
that
[PEI‐GDMAB‐C
]Br
can
be
considered
as
valid
homogeneous
catalyst
‐epoxide
cycloaddition
reaction.
Among
]Br,
18
catalyzed
model
epichlorohydrin
under
optimized
conditions
(T=80
°C,
1.0
atm
,
1
mol%,
ECH
15
mmol,
16
h)
conversion
achieved
at
97.5
%.
Moreover,
exhibited
stable
reusability
broad
substrate
applicability,
which
was
used
in
following
cycle
succinctly,
because
self‐separated
properties
temperature
control.
process
detected
pseudo‐first‐order
after
kinetic
studies
E
calculated
50.65
kJ/mol.
combinatorial
mechanism
hydrogen
bonding
bromide
ions
is
suggested
explain
remarkable
performance
bifunctional
catalyst.
Abstract
The
catalytic
cycloaddition
of
CO
2
to
epoxides
produce
valuable
cyclic
carbonates
represents
a
simple
and
promising
strategy
for
utilization,
circumventing
the
ineffective
reduction
process.
Despite
current
progresses,
there
remains
an
impending
demand
highly‐active,
cost‐effective
stable
catalysts
especially
ideal
heterogeneous
systems.
Herein,
we
report
preparation
heteroatom‐containing
zeolites
through
two‐step
process
comprising
framework
dealumination
subsequent
heteroatom
incorporation,
their
applications
in
epoxides.
Characterization
results
reveal
successful
incorporation
heteroatoms
into
derive
Lewis
acidic
M‐Beta
(M
=
Ti,
Zr
or
Hf).
as‐prepared
acids
show
remarkable
performance
model
reaction
propylene
oxide
with
assistance
potassium
iodide
under
solvent‐free
conditions.
parameters
have
been
optimized
employing
Ti‐Beta
catalyst
substrate
scope
has
investigated.
Finally,
impact
acidity
on
is
discussed
actual
bifunctional
Ti‐Beta/KI
system
proposed,
which
important
significance
understanding
Abstract
Carbon
dioxide
based
degradable
polycarbonate
can
be
obtained
through
the
copolymerization
reaction
of
carbon
with
epoxide
in
presence
a
catalyst.
This
polymer
has
attracted
much
attention
recent
years
owing
to
its
environmentally
friendly
and
sustainable
characteristics,
excellent
material
properties.
Due
unique
properties,
CO2-based
wide
range
applications
many
fields
such
as
electronic
electrical
parts,
automotive
medical
devices,
aerospace
equipment,
power
radiation
protection
products.
Therefore,
numerous
catalytic
systems
have
been
explored
for
CO2/epoxide
process,
which
zinc
catalyst
longest
history
greatest
variety.
In
this
short
review,
significant
advances
catalysts
transformation
CO2
are
demonstrated,
covering
both
heterogeneous
homogeneous
catalysts.
Moreover,
benefits
drawbacks
system
described,
outlook
large-scale
industrial
applicati
ons
future
is
also
represented.
1
Introduction
2
Heterogeneous
Zinc
Catalysts
3
Homogeneous
4
Overview
5
Conclusion
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 26, 2025
Sustainable
conversion
of
epoxides
and
propargylic
amines
using
CO2
could
produce
valuable
chemical
products.
Efficient
generally
requires
harsh
conditions
such
as
noble-metal
catalysts,
cocatalysts,
toxic
solvents,
thereby
underscoring
the
crucial
need
for
environmentally
friendly
non-noble-metal
metal–organic
framework
(MOF)
catalysts.
In
this
study,
we
designed
a
novel
zinc-based
with
5-fold
interpenetrating
diamond
framework,
specifically
{[Zn(DMTDC)(bpy)]·H2O}n
(Zn-MOF-2),
where
H2DMTDC
represents
3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic
acid
bpy
denotes
4,4′-bipyridine.
Zn-MOF-2
serves
bifunctional
heterogeneous
catalyst
to
promote
cyclization
reaction
propargylamine
under
mild
conditions.
The
isolated
yields
resulting
cyclic
carbonates
oxazolidinones
were
92%
93%,
respectively.
Notably,
maintained
good
catalytic
activity
after
five
cycles
in
both
types
conversion.
Control
experiments
confirmed
effective
Zn2+
Lewis
sites
Zn-MOF-2.
isostructural
CPO-5
assembled
from
4,4′-biphenyldicarboxylic
has
also
been
demonstrated
catalyze
cycloaddition
but
an
inferior
performance
catalyzing
carboxyl
amines.
This
result
shows
that
thiophene
ring
ligand
plays
pronounced
role
performance.
research
will
enhance
development
MOF
catalysts
CO2.
Molecules,
Год журнала:
2025,
Номер
30(7), С. 1599 - 1599
Опубликована: Апрель 3, 2025
CO2
is
a
greenhouse
gas
and
nontoxic,
easily
available
renewable
C1
feedstock.
H2
clean
cheap
reductant
that
can
be
obtained
from
energy.
Olefins
are
platform
chemicals
produced
variety
of
raw
materials
such
as
petroleum,
coal
biomass.
The
production
carboxylic
acids
by
combining
olefins,
sustainable
very
promising
protocol.
However,
only
few
advances
in
this
topic
have
been
achieved
because
novel
catalysts
need
to
developed.
In
work,
we
demonstrate
simple
iridium-based
catalyst
could
efficiently
promote
the
synthesis
C2+
via
reaction
olefins
with
H2.
was
effectively
accelerated
catalytic
system
at
170
°C,
which
may
applied
various
olefin
substrates.
mechanism
studied
through
series
control
experiments.
findings
contribute
advancing
valuable
products
green
chemicals.
Advanced Sustainable Systems,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 21, 2025
Abstract
For
green
chemical
synthesis,
designing
a
metal‐free
heterogeneous
organocatalyst
is
very
challenging
as
it
offers
an
environment‐friendly
route
over
conventional
metal‐based
catalysts.
Covalent
organic
frameworks
(COFs)
have
huge
potential
to
be
explored
organocatalysts
because
they
contain
several
important
features
in
one
system,
viz.
high
specific
surface
area,
metal‐free,
desired
functionalization,
and
outstanding
stability.
Herein,
─SO
3
H
group
anchored
COF
synthesized,
TFR‐PDS‐COF
by
employing
Schiff
base
extended
condensation
reaction.
The
material
highly
crystalline
nature,
exhibiting
moderate
BET
area
(115
m
2
g
−1
)
NH
uptake
capacity
(1045
µmol
).
chemisorption
property
toward
suggests
the
acidic
nature
of
material,
which
motivate
explore
acid‐catalyzed
Initially,
amination
epoxide,
classic
example
epoxide
activation
reaction
chosen.
exhibit
good
catalytic
activity
epoxides
β‐amino
alcohol
synthesis
for
both
simple
complex
systems
at
room
temperature
under
solvent‐free
conditions.
catalyst
exhibits
recyclability
cycles
with
retention
its
framework.
has
been
employed
other
acid
reactions
such
cycloaddition
acetalization
reactions,
displays
excellent
conversion
selectivity.
All
these
results
suggest
that
candidate
large‐scale
sustainable
acid‐catalytic
reactions.
ACS Applied Materials & Interfaces,
Год журнала:
2023,
Номер
15(48), С. 56305 - 56313
Опубликована: Ноя. 27, 2023
Herein,
we
present
a
membrane-based
system
designed
to
capture
CO2
from
dilute
mixtures
and
convert
the
captured
into
value-added
products
in
single
integrated
process
operated
continuously
under
mild
conditions.
Specifically,
demonstrate
that
quaternized
poly(4-vinylpyridine)
(P4VP)
membranes
are
selective
separation
also
catalytically
active
for
cyclic
carbonate
synthesis
cycloaddition
of
epichlorohydrin.
We
further
P4VP
can
integrate
capture,
including
down
0.1
kPa
CO2,
with
conversion
carbonates
at
57
°C
atmospheric
pressure.
The
catalytic
membrane
acts
as
both
medium,
providing
an
energy-efficient
alternative
sorbent-based
compression,
transport,
storage.
is
potentially
tunable
variety
products,
chemicals
fuels
not
limited
carbonates,
which
would
be
transformative
shift
carbon
utilization
technology.
