Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 2, 2024
Abstract
Metal–organic
frameworks
(MOFs)
have
been
widely
studied
due
to
their
versatile
applications
and
easily
tunable
structures.
However,
heteroatom‐metal
coordination
dominates
the
MOFs
community,
rational
synthesis
of
carbon–metal
coordination‐based
remains
a
significant
challenge.
Herein,
two‐dimensional
(2D)
based
on
silver–carbon
linkages
are
synthesized
through
between
silver(I)
salt
isocyanide‐based
monomers
at
ambient
condition.
The
as‐synthesized
2D
possess
well‐defined
crystalline
structures
staggered
AB
stacking
mode.
Most
interestingly,
these
MOFs,
without
π–π
layers,
exhibit
narrow
band
gaps
down
1.42
eV.
As
electrochemical
catalysts
for
converting
CO
2
CO,
such
demonstrate
Faradaic
efficiency
over
92
%.
Surprisingly,
reduction
catalyzed
by
indicates
favorable
adsorption
*COOH
active
carbon
sites
isocyanide
groups
rather
than
silver
sites.
This
is
attributed
critical
σ
donor
role
isocyanides
corresponding
ligand‐to‐metal
charge–transfer
effect.
work
not
only
paves
way
toward
new
family
metal–isocyanide
but
also
offers
rare
platform
understanding
electrocatalysis
processes
strongly
polarized
species.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Окт. 11, 2024
Rational
design
of
robust
photocatalytic
systems
to
direct
capture
and
in-situ
convert
diluted
CO2
from
flue
gas
is
a
promising
but
challenging
way
achieve
carbon
neutrality.
Here,
we
report
new
type
host-guest
photocatalysts
by
integrating
CO2-enriching
ionic
liquids
photoactive
metal-organic
frameworks
PCN-250-Fe2M
(M
=
Fe,
Co,
Ni,
Zn,
Mn)
for
artificial
photosynthetic
reduction
in
gas-solid
phase.
As
result,
[Emim]BF4(39.3
wt%)@PCN-250-Fe2Co
exhibits
record
high
CO2-to-CO
rate
313.34
μmol
g−1
h−1
under
pure
atmosphere
153.42
(15%)
with
about
100%
selectivity.
In
scaled-up
experiments
1.0
g
catalyst
natural
sunlight
irradiation,
the
concentration
could
be
significantly
decreased
below
85%
10%,
respectively,
indicating
its
industrial
application
potential.
Further
theoretical
calculations
reveal
that
not
only
benefit
enrichment,
also
form
synergistic
effect
Co2+
sites
PCN-250-Fe2Co,
resulting
significant
Gibbs
energy
barrier
during
rate-determining
step
conversion.
Artificial
fuel
authors
system
frameworks,
greatly
enhancing
conversion
efficiency.
Advanced Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 6, 2024
Abstract
Electrochemical
reduction
of
CO
2
(CO
RR)
to
value‐added
liquid
fuels
is
a
highly
attractive
solution
for
carbon‐neutral
recycling,
especially
C
2+
products.
However,
the
selectivity
control
preferable
products
great
challenge
due
complex
multi‐electron
proton
transfer
process.
In
this
work,
series
Cu
atomic
dispersed
catalysts
are
synthesized
by
regulating
coordination
structures
optimize
RR
selectivity.
‐SNC
catalyst
with
uniquely
asymmetrical
coordinated
CuN
‐CuNS
site
shows
high
ethanol
selective
FE
62.6%
at
−0.8
V
versus
RHE
and
60.2%
0.9
in
H‐Cell
Flow‐Cell
test,
respectively.
Besides,
nest‐like
structure
beneficial
mass
process
selection
catalytic
situ
experiments
theory
calculations
reveal
reaction
mechanisms
such
ethanol.
The
S
atoms
weaken
bonding
ability
adjacent
carbon
atom,
which
accelerates
from
*CHCOH
generate
*CHCHOH,
resulting
This
work
indicates
promising
strategy
rational
design
asymmetrically
single,
dual,
or
tri‐atom
provides
candidate
material
produce
ACS Catalysis,
Год журнала:
2024,
Номер
15(1), С. 529 - 542
Опубликована: Дек. 20, 2024
The
electrochemical
oxidation
of
ethylene
glycol
(EG)
derived
from
polyethylene
terephthalate
(PET)
plastic
into
value-added
chemicals,
coupled
with
hydrogen
evolution,
offers
a
promising
approach
to
addressing
pollution.
However,
the
mechanisms
by
which
adsorption
key
reaction
intermediates
affects
EG
(EGOR)
are
not
well
understood.
To
investigate
this,
we
synthesized
two
model
catalysts:
amorphous-phase
CoNiOOH/NF
and
CoNiOOH–Ni3S2/NF
an
amorphous/crystalline
interface.
Detailed
characterizations
theoretical
calculations
demonstrate
that
interface
in
shifts
d-band
center
upward,
enhancing
*OH
compared
amorphous
CoNiOOH/NF.
Enhanced
is
crucial
for
promoting
C–C
bond
cleavage
subsequent
dehydrogenation.
In
situ
infrared
absorption
spectroscopy
(IRAS)
reveal
formate
(FA)
primarily
formed
through
glycolic
acid,
followed
oxidation.
Notably,
achieves
industrial-level
current
densities
500
mA
cm–2
at
ultralow
potential
1.45
V
vs
RHE,
Faradaic
efficiency
(FE)
96.6%
FA
productivity
3.14
mmol
h–1
1.70
RHE.
This
study
valuable
insights
designing
efficient
heterojunction
catalysts
upcycling
PET
plastics.
Abstract
Metal‐organic
cages
(MOCs)
are
a
class
of
compounds
formed
through
the
coordination
metal
ions
with
organic
ligands
to
create
well‐defined
and
cage‐like
structure.
These
unique
structures
offer
versatile
environments
for
catalyzing
wide
range
chemical
reactions.
The
catalytic
capabilities
MOCs
significantly
influenced
by
nature
ions,
functional
ligands,
cage
Notably,
confined
spaces
within
can
lead
enhanced
reaction
efficiencies,
particularly
in
processes
such
as
light‐induced
hydrogen
generation
photocatalytic
reduction
CO₂.
Furthermore,
show
great
potential
photo‐organic
synthesis
due
structure,
which
provides
environment
allows
encapsulating
molecules,
making
them
useful
improving
selectivity
efficiency
process.
This
review
reports
development
photocatalysis,
focusing
on
structural
design
regulation
strategy
build
production,
CO
2
reduction,
transformation.
Insights
into
photocatalysis
discussed
including
challenges
further
research
direction
MOC‐based
photocatalysis.
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 24, 2025
Electrochemical
conversion
of
CO2
into
methanol
has
received
extensive
attention
in
recent
years
since
is
an
efficient
energy
carrier
and
industrial
feedstock.
However,
the
selectivity
to
remains
unsatisfied.
In
this
work,
Sb-doped
Cs3Cu2I5
first
rationally
developed
for
electrochemical
reduction,
achieving
remarkable
high
methanol.
UV–vis
absorption,
X-ray
photoelectron
spectroscopy
(XPS),
density
functional
theory
(DFT)
calculations
show
that
Sb
dopants
narrow
band
gap
enhance
metal–ligand
hybridization
due
introduction
5p
orbitals,
which
accordingly
charge
transfer.
addition,
Cu–Sb
pair
Sb@Cs3Cu2I5
perovskite
synergistically
catalyzes
conversion.
The
Cu
sites
serve
absorption
activation,
while
stabilize
intermediate
*OCH2
through
Sb–O
bond
superior
oxygen
affinity.
plasma-treated
sample
with
electron-deficient
exhibits
best
as
88.38%.
This
work
provides
new
insight
highly
metal
halide
perovskite-based
catalysts
Energy & Fuels,
Год журнала:
2025,
Номер
39(6), С. 3169 - 3175
Опубликована: Янв. 31, 2025
The
electrochemical
reduction
of
carbon
dioxide
to
value-added
chemicals
using
renewable
energy
sources
represents
a
promising
approach
for
implementing
an
artificial
cycle.
However,
with
the
advancement
high-performance
catalysts,
reaction
microenvironment
gas
diffusion
electrodes
(GDEs)
has
become
critical
factor
affecting
performance
CO2
CO.
It
is
essential
understand
and
control
surrounding
catalytic
sites
as
it
can
mediate
transport
reactants
influence
pathways.
This
paper
describes
design
realization
controllable
interfacial
GDEs
by
spraying
Ag
nanoparticles
hydrophobic
polytetrafluoroethylene
(PTFE)
nanoparticle
mixture
onto
paper.
Experimental
characterization
results
reveal
that
mass
H2O
related
wettability,
which
be
regulated
PTFE.
Through
modulating
property
interface,
hydrogen
evolution
was
effectively
inhibited,
Faradaic
efficiencies
(FEs)
partial
current
densities
CO
were
significantly
improved.
A
FE
98%
achieved
high
density
450
mA/cm2,
shows
potential
industrial
application.
ACS Applied Materials & Interfaces,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 6, 2025
Targeted
construction
of
Lewis
acidic-basic
sites
in
the
skeleton
coordination
polymers
(CPs)
can
greatly
enhance
their
catalytic
efficiency
due
to
synergistic
effect
acidic
and
basic
sites.
However,
research
on
validating
coexistence
for
boosting
activity
CPs
toward
Knoevenagel
condensation
(KC)
reaction,
widely
applied
synthesis
high-added-value
intermediates
products
under
mild
conditions,
is
missing
so
far.
Based
above
consideration,
we
have
artificially
constructed
introduced
vacancy
framework
a
new
flexible
cerium
CP
{Ce-CP:
[Ce3+Ce4+(obb2-)3(OH)(H2O)(DMF)]∞}
(DMF:
N,N-dimethylformamide)
via
applying
functional
ligand
4,4'-oxidibenzoate
(obb2-)
with
bridging
O
atom
as
site
removing
coordinating
solvent
molecules
counterions
form
unsaturated
(Ce-CUSs)
Interestingly,
Ce-CP
exhibits
reversible
structural
transformation
associated
desolvation
resolvation
process.
The
resulting
(LAB-Ce-CP)
been
confirmed
by
CO2
temperature-programmed
desorption
(TPD)
NH3
combined
pyrrole-TPD
(NH3-Py-TPD)
first
time.
Benefiting
from
well
flexibility
framework,
LAB-Ce-CP
shows
high
excellent
recyclability
KC
reactions.
Moreover,
found
that
(1)
activation
temperature
plays
critical
role
its
porosity,
exposure
sites,
thus
reactivity;
(2)
stronger
electron-withdrawing
ability
substituent
groups
benzaldehyde
derivatives
smaller
size
reactants
lead
higher
yield
product
turnover
number
(TON)
value
when
disparity
electron-donating
abilities
between
not
significant.
Hence,
this
work
has
exploited
strategy
designing
heterogeneous
catalysts
active
catalysis
capability
