Abstract
Hierarchical
porous
materials
have
attracted
the
attention
of
researchers
due
to
their
enormous
specific
surface
area,
maximized
active
site
utilization
efficiency,
and
unique
structure
properties.
In
this
context,
metal–organic
frameworks
(MOFs)
offer
a
mix
properties
that
make
them
particularly
appealing
as
tunable
substrates
containing
highly
sites.
This
review
focuses
on
recent
advances
in
types
synthetic
strategies
hierarchical
MOFs
derived
materials.
Furthermore,
it
highlights
relationship
between
mass
diffusion
transport
structures
pore
size
with
examples
simulations,
while
identifying
potential
limitations.
On
basis,
how
synthesis
conditions
affect
electrochemical
based
different
is
discussed,
highlighting
prospects
challenges
for
synthetization,
well
further
scientific
research
practical
applications.
Finally,
some
insights
into
current
future
design
ideas
advanced
are
presented.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(16), С. 9254 - 9263
Опубликована: Апрель 13, 2023
Developing
adsorbents
with
multiple
merits
in
capacity,
selectivity,
mass
transfer,
and
stability
toward
C2H2/CO2
separation
is
crucial
challenging
for
producing
high-purity
C2H2
advanced
polymers
the
electronic
industry.
Here,
we
demonstrate
a
vertex
strategy
to
create
combining
these
through
rationally
designing
groups
of
wavy-shaped
framework
layered
2D
metal-organic
frameworks
(MOFs)
finely
regulate
local
conformation
stacking
interactions,
which
creates
optimal
inter-
intralayer
space
realize
simultaneous
improvement
adsorption
thermodynamics
kinetics.
Two
new
hydrolytically
stable
MOFs,
ZUL-330
ZUL-430,
were
prepared,
diverse
experiments
modeling
on
both
equilibrium
diffusion
performed.
Record
selectivities
coupled
extraordinary
dynamic
capacities
achieved
mixtures
different
proportions
(50/50
or
10/5,
v/v),
along
small
barrier
fast
transfer.
Consequently,
polymer-grade
(99.9%)
electronic-grade
(99.99%)
obtained
excellent
productivities
up
∼6
mmol
cm-3.
Chemical Reviews,
Год журнала:
2023,
Номер
123(10), С. 6545 - 6611
Опубликована: Май 15, 2023
The
modularity
and
synthetic
flexibility
of
metal-organic
frameworks
(MOFs)
have
provoked
analogies
with
enzymes,
even
the
term
MOFzymes
has
been
coined.
In
this
review,
we
focus
on
molecular
catalysis
energy
relevance
in
MOFs,
more
specifically
water
oxidation,
oxygen
carbon
dioxide
reduction,
as
well
hydrogen
evolution
context
MOF-enzyme
analogy.
Similar
to
catalyst
encapsulation
MOFs
leads
structural
stabilization
under
turnover
conditions,
while
motifs
that
are
synthetically
out
reach
a
homogeneous
solution
phase
may
be
attainable
secondary
building
units
MOFs.
Exploring
unique
possibilities
specific
groups
second
third
coordination
sphere
around
catalytic
active
site
incorporated
facilitate
catalysis.
A
key
difference
between
enzymes
is
fact
concentrations
latter
often
considerably
higher,
leading
charge
mass
transport
limitations
severe
than
those
enzymes.
High
also
put
limit
distance
catalysts,
thus
available
space
for
higher
engineering.
As
important
MOF-borne
catalysis,
system
perspective
chosen
highlight
concepts
address
issue.
detailed
section
light-driven
reactivity
sets
stage
concise
review
currently
literature
utilizing
principles
from
Nature
design
preparation
MOF-based
materials.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(26)
Опубликована: Апрель 28, 2023
Pore
size
plays
a
critical
role
in
determining
the
performance
of
metal-organic
frameworks
(MOFs)
catalysis,
sensing,
and
gas
storage
or
separation.
However,
revealing
pore-size/property
relationship
remains
extremely
challenging
because
ideal
structure
models
possessing
different
pore
sizes
but
having
same
components
are
lacking.
In
this
work,
solvent-coordination
directed
swelling
method
was
developed
for
modulating
ratio
between
large
narrow
phases
flexible
MOF,
MIL-88B.
Pore-size-dependent
sensitivity
selectivity
were
studied
first
time
MIL-88B
samples.
The
optimized
MIL-88B-20
%
sample
showed
one
best
sensing
performances
among
all
reported
MOF-based
H2
S-sensing
materials.
This
work
not
only
provides
to
synthesize
pore-size
properties,
also
may
inspire
development
high-performance
ACS Nano,
Год журнала:
2023,
Номер
17(13), С. 12629 - 12640
Опубликована: Июнь 23, 2023
Dehydration
is
a
basic
phenomenon
in
ion
transport
through
confined
nanochannels,
but
how
it
affects
trans-membrane
selectivity
has
not
been
understood
due
to
lack
of
characterization
techniques
and
suitable
pore
structures.
Herein,
hydration
number
distributions
typical
alkali
metal
ions
were
characterized
by
combining
uniform
subnanochannels
ZIF-8-based
membranes
with
the
situ
liquid
time-of-flight
secondary
mass
spectrometry
(ToF-SIMS)
technique,
revealing
that
steric
hindrance
induced
dehydration
neutral
ZIF-8
windows.
The
reduction
size
partial
increased
intrapore
velocity
for
monovalent
cations.
highest
entropy
value
maximum
changes
resulting
from
drove
fast
efficient
selective
Li+
over
other
alkaline
ions,
leading
Li+/Rb+
5.2.
at
entrance
membrane
pores
was
shown
account
majority
overall
barriers,
being
dominant
element
transport.
High
energy
(>1500
kJ/mol)
hindered
earth
achieving
ultrahigh
monovalent/bivalent
cation
(∼104).
These
findings
uncover
crucial
role
barriers
size-based
trans-subnanochannel
transport,
providing
guidelines
designing
specific
sizes
promote
desired
solutes.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Апрель 23, 2024
Abstract
The
size
and
defects
in
crystalline
inorganic
materials
are
of
importance
many
applications,
particularly
catalysis,
as
it
often
results
enhanced/emerging
properties.
So
far,
applying
the
strategy
modulation
chemistry
has
been
unable
to
afford
high-quality
functional
Metal–Organic
Frameworks
(MOFs)
nanocrystals
with
minimized
while
exhibiting
maximized
defects.
We
report
here
a
general
sustainable
for
design
highly
defective
ultra-small
tetravalent
MOFs
(Zr,
Hf)
crystals
(ca.
35%
missing
linker,
4–6
nm).
Advanced
characterizations
have
performed
shed
light
on
main
factors
governing
crystallization
mechanism
identify
nature
nanoMOFs
showed
exceptional
performance
peptide
hydrolysis
reaction,
including
high
reactivity,
selectivity,
diffusion,
stability,
show
emerging
tailorable
reactivity
selectivity
towards
bond
formation
simply
by
changing
reaction
solvent.
Therefore,
these
M(IV)-MOFs
particles
open
new
perspectives
development
heterogeneous
MOF
catalysts
dual
functions.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Фев. 3, 2025
Abstract
In
the
realm
of
heterogeneous
catalysis,
diffusion
reactants
into
catalytically
active
sites
stands
as
a
pivotal
determinant
influencing
both
turnover
frequency
and
geometric
selectivity
in
product
formation.
While
accelerated
can
elevate
reaction
rates,
it
often
entails
compromise
selectivity.
Porous
catalysts,
including
metal-organic
covalent
organic
frameworks,
confront
formidable
obstacles
regulating
reactant
rates.
Consequently,
chemical
functionality
catalysts
typically
governs
This
study
presents
an
approach
harnessing
length
to
achieve
improved
manipulation
reactant-active
site
residence
time
at
augment
kinetics.
Through
deployment
thin
film
composed
porous
framework
catalyst,
we
illustrate
how
programming
within
cross-flow
microfluidic
catalytic
reactor
concurrently
amplify
(exceeding
1000-fold)
enhance
(
~
2-fold)
relative
conventional
nano/microcrystals
catalyst
one-pot
reactor.
diffusion-programed
strategy
represents
robust
solution
surmount
constraints
imposed
by
bulk
marking
advancement
design
catalyst-driven
reactions.
Frontiers in Chemistry,
Год журнала:
2022,
Номер
10
Опубликована: Июнь 29, 2022
Due
to
the
intensification
of
greenhouse
effect
and
emphasis
on
utilization
CO2
resources,
enrichment
separation
have
become
a
current
research
focus
in
environment
energy.
Compared
with
other
technologies,
pressure
swing
adsorption
has
advantages
low
cost
high
efficiency
been
widely
used.
The
design
preparation
high-efficiency
adsorbents
is
core
technology.
Therefore,
high-performance
porous
materials
attracted
increasing
attention.
Porous
specific
surface
area,
capacity,
regeneration
energy,
good
cycle
performance,
moisture
resistance
focused
on.
This
article
summarizes
optimization
by
then
applies
them
field
adsorption.
internal
laws
between
pore
structure,
chemistry,
performance
adsorbent
are
discussed.
Further
development
requirements
for
treatment
industrial
waste
gas
prospected.
structural
carbon
still
focus.
With
applications
environmental
conditions,
integrity,
mechanical
strength
water
need
be
met.
Green Chemical Engineering,
Год журнала:
2022,
Номер
3(3), С. 210 - 227
Опубликована: Фев. 5, 2022
The
cycloaddition
of
CO2
to
epoxides
afford
cyclic
organic
carbonates
is
an
increasingly
relevant
non-reductive
strategy
convert
useful
products
able
serve
as
high-boiling
solvents,
chemical
intermediates,
and
monomers
for
the
preparation
more
sustainable
polymers.
development
efficient
robust
heterogeneous
catalysts
such
transformation
is,
therefore,
crucial
can
be
carried
out
by
several
strategies
that
often
require
sophisticated
and/or
expensive
networks,
linkers,
or
compounds.
A
different
approach
CO2-epoxide
coupling
applying
surface
science
methodologies
graft
molecular
fragments
single
atoms
on
various
supports
leading
well-defined
active
sites.
In
this
context,
organometallic
chemistry
(SOMC),
along
with
comparable
methodologies,
a
valuable
efficient,
single-site
Lewis
acids
target
reaction
metal
oxides,
whereas,
other
grafting
applied
prepare
analogous
kinds
surfaces.
Finally,
we
discuss
very
recent
advances
in
application
atom
towards
highly
epoxides.
Overall,
show
prepared
facile
hold
significant
potential
future
synthesis
from
CO2.