Scientia Sinica Chimica,
Год журнала:
2024,
Номер
54(3), С. 353 - 369
Опубликована: Фев. 4, 2024
Methane,
which
is
abundant
and
affordable,
not
only
a
high-quality
fossil
fuel,
but
also
new
material
for
synthesizing
high-value
chemicals.
Due
to
its
inertness,
the
direct
conversion
of
methane
requires
high
activation
energy
usually
harsh
reaction
conditions
or
strong
oxidizing
agents.
Directly
converting
into
valuable
under
mild
promising
technique,
can
reduce
thermodynamic
barrier
in
methane,
avoid
common
problems
peroxides
catalyst
deactivation,
it
still
huge
challenge.
In
this
review,
research
progress
anaerobic
systems
aerobic
catalyzed
C2
value-added
chemicals
reviewed.
The
construction
catalysts
elaborated
discussed
detail
from
aspects
active
centers
mechanism.
Finally,
we
take
look
at
challenges
facing
area
propose
potential
solutions.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 6, 2025
The
integration
of
ligand-to-metal
charge
transfer
(LMCT)
catalytic
paradigms
with
radical
intermediates
has
transformed
the
selective
functionalization
inert
C-H
bonds,
facilitating
use
nonprecious
metal
catalysts
in
demanding
transformations.
Notably,
aerobic
carbonylation
methane
to
acetic
acid
remains
formidable
due
rapid
oxidation
methyl
radicals,
producing
undesired
C1
oxygenates.
We
present
an
iron
terpyridine
catalyst
utilizing
LMCT
achieve
exceptional
C2/C1
selectivity
through
synergistic
photoexcitation,
generation,
and
carbonylation.
Mechanistic
studies
highlight
critical
roles
Fe(II)
Fe-carbonyl
complexes
bypassing
via
a
rebound-like
pathway,
unlocking
unprecedented
efficiency
Chemical Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
A
porous
aluminium
metal–organic
framework
confined
mono-copper(
ii
)
hydroxyl
species
serves
as
an
efficient
catalyst
for
the
direct
conversion
of
methane
into
acetic
acid
using
O
2
oxidant
in
water
with
excellent
productivity
and
selectivity.
Photothermal
catalysis
effectively
increases
catalytic
activity
by
using
the
photothermal
effect
of
metal
nanomaterials;
however,
combination
strong
light
absorption
and
high
performance
remains
a
challenge.
Here,
we
demonstrate
hexagonal
~5-nanometer-thick
palladium
antimony
(chemical
formula
as
Pd
8
Sb
3
)
nanosheets
(NSs)
that
exhibit
within
full
spectral
localized
surface
plasmon
resonance
(LSPR)
effects
in
visible
region.
Such
LSPR
features
lead
to
effects,
NSs
aqueous
dispersion
enables
enhanced
methane
(CH
4
conversion
formaldehyde
(HCHO)
under
full-spectrum
irradiation
at
1.7
watts
per
square
centimeter,
leading
selectivity
~98.7%,
productivity
~665
millimoles
gram
catalyst,
~700
times
higher
than
NSs.
Mechanism
investigations
suggest
different
radicals
were
generated
on
(·OH)
(·O
2
−
),
where
displays
stronger
adsorption
strength
CH
facilitates
oxidation
HCHO.
Besides,
ability
therapy
for
breast
cancer.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(43), С. 29364 - 29372
Опубликована: Окт. 19, 2024
Bimetallic
alloys
exhibit
remarkable
properties
in
catalysis
and
energy
storage,
while
their
precise
synthesis
at
the
subnanoscale
remains
a
formidable
challenge
due
to
immiscible
nature
thermodynamics.
In
this
study,
we
engineer
an
atomically
dispersed
CuPd
alloy
with
average
size
of
1.5
nm
loaded
on
CuO
phosphomolybdic
acid
(PMA)
coassembly
subnanosheets
(CuO-PMA
SNSs).
Driven
by
high
vibrational
entropy,
Cu
atoms
could
escape
from
supports
bond
adjacent
Pd
single
atoms,
leading
situ
formation
alloys.
Furthermore,
strategy
can
also
be
utilized
for
synthesizing
ZnPt
1
nm,
thereby
providing
general
pathway
design
subnanoalloys.
The
fully
exposed
Cu–Pd
pairs
subnanoalloys
significantly
enhance
adsorption
coverage
surface
*CO
during
electrochemical
reduction
CO2,
enhanced
stability
ethenone
intermediates
facilitating
production
C2
compounds.
resulting
subnanoalloy
exhibits
Faradaic
efficiency
46.5
±
2.1%
CO2-to-acetate
electroreduction
achieves
acetate
productivity
99
2.8
μmol
cm–2
−0.7
V
versus
RHE.
Abstract
A
crystalline
porous
bipyridine‐based
Bpy‐COF
with
a
high
BET
surface
area
(1864
m
2
g
−1
)
and
uniform
mesopore
(4.0
nm)
is
successfully
synthesized
from
1,3,5‐tris‐(4’‐formyl‐biphenyl‐4‐yl)triazine
5,5'‐diamino‐2,2'‐bipyridine
via
solvothermal
method.
After
Cu(I)‐loading,
the
resultant
Cu(I)‐Bpy‐COF
remained
ordered
structure
evenly
distributed
Cu(I)
ions
at
single‐atom
level.
Using
as
heterogeneous
catalyst,
conversions
for
cycloaddition
reactions
are
achieved
within
short
time
(40
min)
25
°C
in
water
medium.
Moreover,
proves
to
be
applicable
aromatic
aliphatic
azides
alkynes
bearing
various
substituents
such
ester,
hydroxyl,
amido,
pyridyl,
thienyl,
bulky
triphenylamine,
fluorine,
trifluoromethyl
groups.
The
remain
almost
constant
after
five
cycles.
Additionally,
antiepileptic
drug
(rufinamide)
prepared
by
simple
one‐step
reaction
using
Cu(I)‐Bpy‐COF,
proving
its
practical
feasibility
pharmaceutical
synthesis.
