Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 31, 2024
Abstract
Porous
organic
polymers
have
shown
great
potential
in
photocatalytic
CO
2
reduction
due
to
their
unique
tunable
structure
favoring
gas
adsorption
and
metal
sites
integration.
However,
efficient
photocatalysis
porous
is
greatly
limited
by
the
low
surface
reactivity
electron
mobility
of
bulk
structure.
Herein,
we
incorporate
TiO
nanoparticles
Ni(II)
into
a
layered
cationic
imidazolium
polymer
(IP),
which
moieties
free
anions
can
stabilize
key
intermediates
enhance
reaction
kinetics
reduction.
During
reaction,
/NiIP
situ
exfoliated
nanosheets
(NSs)
with
more
accessible
active
shorten
transport
pathways.
The
formed
/NiIP‐NSs
exhibit
an
impressively
high
production
rate
as
54.9
mmol
⋅
g
−1
h
selectivity
99.9
%.
embedding
could
improve
efficiency
so
facilitate
photochemical
stripping
process
polymer.
Moreover,
assistance
possess
excellent
stability
during
recycling
experiments
comparison
rapidly
declined
activity
NiIP‐NSs.
This
work
presents
new
strategy
construct
highly
photocatalysts
for
Accounts of Chemical Research,
Год журнала:
2024,
Номер
57(16), С. 2437 - 2447
Опубликована: Авг. 8, 2024
ConspectusTo
tackle
the
energy
and
environmental
concerns
world
faces,
much
attention
is
given
to
catalytic
reactions
converting
methane
(CH4)
carbon
dioxide
(CO2)
as
abundant
C1
resources
into
value-added
chemicals
with
high
efficiency
selectivity.
In
oxidative
conversion
of
CH4
methanol,
it
necessary
solve
requirement
strong
oxidants
due
large
bond-dissociation
(BDE)
C–H
bonds
in
achieve
suppression
overoxidation
smaller
BDE
bond
methanol
product.
On
other
hand,
efficiently
perform
CO2
reduction,
proton-coupled
electron
transfer
(PCET)
processes
are
required
since
reduction
potential
becomes
positive
by
using
processes;
however,
under
acidic
conditions
for
PCET,
hydrogen
evolution
protons
competitive
reduction.
Thus,
indispensable
develop
efficient
catalysts
selective
Recently,
we
have
developed
toward
alleviation
mentioned
above.
Concerning
oxidation,
inspired
metalloenzymes
that
oxidize
hydrophobic
organic
substrates,
a
second
coordination
sphere
(SCS)
was
introduced
an
FeII
complex
bearing
pentadentate
N-heterocyclic
carbene
ligand,
used
catalyst
oxidation
aqueous
media.
Consequently,
selectively
oxidized
83%
selectivity
turnover
number
500.
contrast,
when
substrate
complex,
products
were
obtained
negligible
yield,
which
comparable
control
experiment
without
catalyst.
Therefore,
SCS
can
capture
only
substrates
such
release
hydrophilic
medium
suppressing
("catch-and-release"
mechanism).
photocatalytic
NiII
complexes
N2S2-chelating
ligands
catalysts,
been
monoxide
dehydrogenase,
also
binding
site
Lewis-acidic
metal
ions
Ni
complex.
When
Mg2+
applied
moderate
Lewis
acid,
Mg2+-bound
allowed
us
remarkable
enhancement
afford
CO
product
over
99%
quantum
yield
11.4%.
Divalent
besides
showed
similar
impacts
on
whereas
monovalent
exhibited
almost
no
effects
trivalent
exclusively
promoted
evolution.
this
Account,
highlight
our
recent
progress
manipulations
resources.
Applied Organometallic Chemistry,
Год журнала:
2025,
Номер
39(2)
Опубликована: Янв. 12, 2025
ABSTRACT
The
catalytic
conversion
of
carbon
dioxide
(CO
2
)
into
valuable
energy
under
light
sources
is
one
the
effective
ways
to
achieve
cycle.
reported
nonprecious
metal
complex
catalysts
still
show
shortcomings
low
activity
and
selectivity
in
visible‐light–driven
CO
reduction,
especially
aqueous
systems.
Herein,
we
report
three
dinuclear
mixed‐valence
Co
(II)/Co
(III)
complexes
1
–
3
bearing
macrocyclic
ligands
that
exhibit
high
for
photocatalytic
reduction
an
system.
Moreover,
TON
reach
as
4100
96%,
respectively,
which
about
4.9
times
higher
than
mononuclear
(II)
4
.
Through
electrochemical
DFT
calculations,
found
increase
due
synergistic
effect
between
two
centers,
site
stabilizes
*COOH
intermediate
reduces
barrier
rate‐determining
step,
thereby
increasing
activity.
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 25, 2025
The
iron(III)
chloride
compound
6,6'-di(3,5-ditert-butyl-2-hydroxybenzene)-2,2'-bipyridine
(Fe(tbudhbpy)Cl)
can
effectively
catalyze
the
electrochemical
CO2
reduction
in
N,N-dimethylformamide.
Density
functional
calculations
were
conducted
to
investigate
mechanism
and
unravel
governing
factors
of
product
selectivity.
results
suggest
that
initial
catalyst,
Fe(tbudhbpy)Cl
(formally
FeIII-Cl),
undergoes
two
steps,
accompanied
by
dissociation
Cl-,
leading
formation
active
ferrous
radical
intermediate
2
FeI).
Without
phenol,
attacks
generate
FeIII-carboxylate
FeIII-CO2,
followed
a
one-electron
FeII-CO2,
which
reacts
with
another
produce
CO.
This
aligns
experimental
result
CO
is
main
when
phenol
absent.
In
contrast,
presented,
triple
reduced
species
3
protonated
at
its
ligand
N
site
yield
3pt(N)
Fe0-NH),
subsequently
performs
nucleophilic
attack
on
afford
formate.
process
occurs
via
an
orthogonal
electron/proton
transfer
mechanism,
where
electrons
one
proton
are
transferred
from
moiety.
redox
noninnocent
nature
thus
crucial
for
formate
formation,
as
it
facilitates
electron
shuttling,
enabling
through
this
unusual
effectively.
