Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 13, 2024
Abstract
Achieving
a
balance
between
high
selectivity
and
uptake
is
formidable
challenge
for
the
purification
of
acetylene
from
mixtures
with
carbon
dioxide,
particularly
when
seeking
to
maximize
both
C
2
H
adsorption
capacity
/CO
separation
in
crystalline
porous
materials.
In
this
study,
leveraging
principles
reticular
chemistry,
we
selected
two
tetracarboxylate‐based
linkers
combined
them
Cu
2+
ions
synthesize
isoreticular
dicopper
paddle‐wheel‐based
metal‐organic
frameworks
(MOFs):
Cu‐TPTC
(terphenyl‐3,3’,5,5’‐tetracarboxylic
acid,
4
TPTC)
Cu‐ABTC
(3,3,5,5‐azobenzenetetracarboxylic
ABTC).
The
structural
sorption
analyses
revealed
that
Cu‐ABTC,
despite
having
slightly
smaller
pores
due
strategic
replacement
phenyl
ring
an
azo
group
tetratopic
ligands,
maintains
porosity
compared
Cu‐TPTC.
Furthermore,
outperforms
terms
(196
cm
3
g
−1
at
298
K
1
bar)
(16.5~5.6).
These
findings
were
corroborated
by
dynamic
breakthrough
experiments
computational
modeling.
This
research
highlights
potential
contraction
strategy
enhancing
MOFs
sophisticated
gas
processes.
One-step
adsorptive
separation
of
high-purity
ethylene
(C2H4)
from
the
mixtures
with
ethane
(C2H6)
or
propylene
(C3H6)
is
crucial
importance
in
petrochemical
industry.
Nevertheless,
development
porous
materials
that
possess
both
high
adsorption
capacities
and
selectivities
C2H6
C3H6
over
C2H4
still
a
formidable
challenge.
Herein,
we
present
microporous
pillar-layered
metal-organic
framework
(MOF)
exhibits
excellent
uptake
(4.73
mmol
g-1)
(8.05
at
298
K
1
bar,
leading
to
for
equimolar
C2H6/C2H4
(1.6)
C3H6/C2H4
(16.4),
respectively.
Breakthrough
column
experiments
demonstrate
MOF
could
achieve
one-step
acquisition
polymer-grade
(>
99.9%)
during
separations.
Noteworthily,
mixture
(2/5,
v/v),
99.5%)
can
be
directly
harvested
recovered,
productivities
86.23
31.05
L
kg-1
respectively,
surpassing
many
well-developed
adsorbents
separation.
Theoretical
calculations
reveal
nonpolar
pore
surface
bearing
accessible
N
O
atoms
affords
more
hydrogen
bonding
interactions
than
C2H4,
accounting
affinity
order
>
C2H4.
This
work
may
offer
valuable
insights
into
design
construction
high-performance
MOFs
purification.
Advanced Functional Materials,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 29, 2025
Abstract
One‐step
purification
of
C
2
H
4
from
a
four‐component
CO
/C
6
mixture
with
single
adsorbent
is
great
significance
but
very
challenging.
Herein
feasible
and
general
strategy
reported
for
constructing
chemical
traps
in
MOF
featuring
an
electronegative
microenvironment
the
pore
wall
one‐step
mixture.
The
enzyme‐mimicking
Zn‐OH
sites
CFA‐Zn‐OH,
acting
as
trap,
can
efficiently
fix
while
ensures
preferential
adsorption
impurities,
thus
leading
to
Mechanism
studies
reveal
that
CFA‐Zn‐OH
chemically
impurity
reversible
manner
form
bicarbonate
Zn‐HCO
3
,
mimicking
carbonic
anhydrase.
In
addition,
negative
electrostatic
potential
allows
preferentially
capture
ensuring
Column
breakthrough
experiments
validated
its
ability
on
purity
99.9%
be
directly
harvested.
Inorganic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 22, 2025
The
exploration
of
the
solvent
effect
on
metal–organic
framework
(MOF)
structure
is
crucial
for
promoting
their
structural
chemistry
and
expanding
potential
applications.
Metal-triazolate-dicarboxylate
pillared-layer
frameworks,
featuring
adjustable
pore
structures,
exhibit
considerable
promise
gas
adsorption
Under
identical
conditions,
two
distinct
topological
structures
were
successfully
synthesized
using
different
solvents:
Zn-mfa-atz-rob
(rob-type)
Zn-mfa-atz-pcu
(pcu-type).
In
synthetic
process,
serves
as
a
template
agent,
resulting
in
substantially
structures.
utilization
H2O/EtOH
yielded
rob-type
framework,
whereas
DMF/H2O/MeOH
produced
pcu-type
framework.
Additionally,
breakthrough
experiments
revealed
that
efficiently
generated
high-purity
C2H4
(>99.9%)
single
step
at
ambient
temperature
from
equimolar
quaternary
CO2/C2H2/C2H6/C2H4
mixtures.
Advanced Functional Materials,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 28, 2025
Abstract
Constructing
a
metal‐free
adsorbent
for
one‐step
separation
of
C
2
H
4
from
mixture
gas
C2,
is
great
significance
and
challenging.
Here,
porous
aromatic
cage
(
PAC‐1
)
based
on
aldehyde‐amine
condensation
reported
with
diamond‐like
interconnected
cavity‐channel
pores
purification
ethylene.
exhibits
superior
(52.6
cm
3
g
−1
6
(46.7
uptakes
as
well
impressive
/C
selectivity
(1.5)
(1.4),
remaining
at
the
forefront
advanced
‐selective
adsorbents
non‐metallic
materials.
The
adsorption
enthalpy
(Q
st
23.6
kJ
mol
,
which
requires
less
energy
to
regenerate
than
conventional
MOF
Breakthrough
experiments
demonstrate
that
can
reduce
penetration
rate
or
through
adsorbent,
present
quite
valuable
gas.
Molecular
simulations
DFT
studies
have
shown
oxygen
sites
C─H
in
channels
are
more
favorable
anchor
interaction
over
by
1.48
kcal
C─H…π
point
cavity
preferred
1.16
turn
results
.
