Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 27, 2025
The
electrooxidation
of
5-hydroxymethylfurfural
(HMF)
to
2,5-furandicarboxylic
acid
(FDCA),
a
monomer
for
degradable
bioplastic,
is
promising
strategy
biomass
upgrade
and
yet
requires
well-designed
catalysts
with
high
efficiency
selectivity.
Taking
advantage
the
open
metal
sites
metal–organic
frameworks
(MOFs),
quasi-MOFs
represent
viable
catalysts,
but
poor
designability
unpredictable
structures
hinder
their
development.
In
this
work,
Ni-based
quasi-MOF
was
rationally
designed
synthesized
by
controlled
ligand
engineering.
Compared
fully
occupied
clusters
in
pristine
MOFs,
accessible
Ni
can
efficiently
convert
HMF
FDCA
remarkable
Faradaic
(99.2%)
selectivity
(98.3%).
situ
characterizations
mechanistic
analysis
revealed
that
created
partial
disconnection
are
critical
formation
high-valent
active
species
oxidation.
Moreover,
serving
as
anode
an
integrated
electrolysis
system,
such
not
only
reduce
cell
voltage
hydrogen
generation
also
produce
high-purity
good
yield,
offering
new
opportunity
simultaneous
production
value-added
chemicals
sustainable
hydrogen.
Advanced Functional Materials,
Год журнала:
2024,
Номер
34(24)
Опубликована: Фев. 5, 2024
Abstract
Photoelectrochemical
(PEC)
technology
offers
new
opportunities
for
pushing
the
renewable
energy‐driven
ammonia
synthesis
toward
a
practical
level,
while
still
facing
unsatisfactory
efficiency
due
to
obstacle
of
dissociating
inert
nitrogen
triple‐bonds.
Herein,
novel
donor‐site‐acceptor
system
is
constructed
in
covalent
organic
frameworks
tackle
this
challenge
highly
efficient
PEC
synthesis.
Highly
active
boron
site
elaborately
embedded
between
donor
and
acceptor
units,
which
can
be
effectively
activated
with
continuous
electron
flow
upon
photoexcitation.
With
assistance
solar
irradiation,
stubborn
dissociation
successfully
changed
from
passive
endothermic
reaction
spontaneous
exothermic
process,
completely
eliminating
energy
barrier
rate‐determining
step
facilitating
overall
kinetics.
The
proof‐of‐concept
achieved
an
excellent
NRR
performance
remarkable
Faradaic
91.6%,
reaching
target
set
by
U.S.
Department
Energy
(90%).
Nanoscale,
Год журнала:
2024,
Номер
16(11), С. 5487 - 5503
Опубликована: Янв. 1, 2024
A
timely
review
on
the
recent
advances
of
metal–organic
framework-based
step-scheme
heterojunctions
with
respect
to
their
synthesis,
structures
and
applications
is
provided.
Advanced Energy Materials,
Год журнала:
2024,
Номер
14(39)
Опубликована: Июль 29, 2024
Abstract
Electrocatalytic
CO
2
reduction
(ECR)
powered
by
renewable
electricity
is
a
promising
technology
to
mitigate
carbon
emissions
and
lessen
the
dependence
on
fossil
fuels
toward
carbon‐neutral
energy
cycle.
Metal–organic
frameworks
(MOFs)
their
derivatives,
due
excellent
intrinsic
activity,
have
emerged
as
materials
for
ECR
high‐demand
products.
However,
challenges
such
unsatisfactory
efficiency,
selectivity,
relatively
low
production
rates
hinder
industrial
scalability.
Here,
comprehensive
critical
review
presented
that
summarizes
state‐of‐the‐art
progress
in
MOF‐based
MOF‐derived
electroreduction
catalysts
from
design
functionality
perspectives.
The
fundamentals
of
reaction
(CO
RR)
over
heterogeneous
catalysts,
mechanisms,
key
faced
are
described
first
establish
solid
foundation
forthcoming
in‐depth
analyses.
MOF's
building
blocks,
properties,
shortcomings
pertinent
including
conductivity
stability,
systematically
discussed.
Moreover,
discussions
provided
design,
fabrication,
characterization,
RR
activity
pinpoint
intricate
structure‐property‐performance
relationship.
Finally,
recommendations
put
forward
enhancing
MOF
electrocatalysts
durability.
This
work
may
serve
guideline
developing
high‐performance
MOF‐related
RR,
benefiting
researchers
working
this
growing
potentially
game‐changing
area.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(42), С. 28932 - 28940
Опубликована: Окт. 11, 2024
Single-crystalline
covalent
organic
frameworks
(COFs)
are
highly
desirable
toward
understanding
their
pore
chemistry
and
functions.
Herein,
two
50–100
μm
single-crystalline
three-dimensional
(3D)
COFs,
TAM-TFPB-COF
TAPB-TFS-COF,
were
prepared
from
the
condensation
of
4,4′,4″,4‴-methanetetrayltetraaniline
(TAM)
with
3,3′,5,5′-tetrakis(4-formylphenyl)bimesityl
(TFPB)
3,3′,5,5′-tetrakis(4-aminophenyl)bimesityl
(TAPB)
4,4′,4″,4‴-silanetetrayltetrabenzaldehyde
(TFS),
respectively,
in
1,4-dioxane
under
catalysis
acetic
acid.
Single-crystal
3D
electron
diffraction
reveals
triply
interpenetrated
dia-b
networks
atom
resolution,
while
isostructure
TAPB-TFS-COF
was
disclosed
by
synchrotron
single-crystal
X-ray
powder
Le
Bail
refinements.
The
nitrogen
sorption
measurements
at
77
K
disclose
microporosity
nature
both
activated
COFs
exceptionally
high
Brunauer–Emmett–Teller
surface
areas
3533
4107
m2
g–1,
representing
thus
far
record
specific
area
among
imine-bonded
COFs.
This
enables
to
exhibit
also
methane
uptake
capacities
up
28.9
wt
%
(570
cm3
g–1)
25
°C
200
bar
all
reported
far.
work
not
only
presents
structures
exceptional
but
provides
an
example
engineering
adjust
permanent
microporous
for
storage.
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 7, 2025
Designing
and
developing
novel
photochromic
materials
with
additional
functions
such
as
photothermal
conversion
photocatalysis
are
challenging
but
meaningful
objectives.
Crystalline
naphthalenediimide
(NDI)-based
hybrids
an
attractive
class
of
multifunctional
fast-response
photoinduced
electron
transfer
charge
separation
properties.
They
promising
photocatalysts.
Herein,
a
hybrid
material,
EuPMo11O39(L)1.5(H2O)2]·DMA
(EuMo-NDI)
(L
=
N,N'-di(1-oxido-4-pyridyl)-1,4,5,8-naphthalenediimide),
was
prepared
solvothermal
method,
integrating
photoactive
NDI
derivative
Eu-substituted
polyoxometalate.
EuMo-NDI
exhibits
0D
structure
sensitive
behavior
under
UV-vis
light
irradiation
due
to
between
its
components.
The
colored
sample
demonstrated
efficient
near-infrared
the
strong
absorption
photogenerated
radical
anion
NDI•-
mixed
valence
heteropoly
blue
in
region.
Meanwhile,
is
easily
excited
presence
donors
form
species,
which
can
activate
inert
O2
superoxide
O2•-.
exhibited
high
photocatalytic
activity
for
C-3
thiocyanation
indoles
mild
conditions
using
white
driving
force.
This
work
provides
effective
avenue
design
photocatalysts
platforms.
Journal of Materials Chemistry A,
Год журнала:
2024,
Номер
12(12), С. 7036 - 7046
Опубликована: Янв. 1, 2024
An
imine-linked
covalent
organic
framework
based
on
benzotrithiophene
generates
superoxide
and
singlet
oxygen
to
carry
out
blue-light-driven
selective
aerobic
sulfoxidation.
