Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 17, 2024
Abstract
Während
Molybdän‐Distickstoffkomplexe
eine
wichtige
Rolle
als
katalytische
Modellsysteme
der
Nitrogenase
gespielt
haben,
erwiesen
sich
die
entsprechenden
Wolframkomplexe
in
den
meisten
Fällen
katalytisch
inaktiv.
Hier
stellen
wir
einen
modifizierten
pentadentaten
tetrapodalen
(pentaPod)
Phosphinliganden
vor,
bei
dem
zwei
Dimethylphosphinogruppen
des
pentaPod
Me
(P5
)‐Liganden
durch
Phospholan
(Pln)
ersetzt
wurden.
daraus
abgeleitete
Molybdänkomplex
[Mo(N
2
)P5
Pln
]
22
Äquivalente
NH
3
erzeugt,
generiert
analoge
[W(N
7
aus
N
Gegenwart
von
180
Äquivalenten
SmI
(THF)
/H
O.
Letzterer
ist
damit
erste
Wolframkomplex,
chemokatalytisch
umwandelt.
Im
Gegensatz
dazu
erzeugt
Wolframkomplex
geringfügig
überstöchiometrisch
Ammoniak
.
Die
Gründe
für
diese
Reaktivitätsunterschiede
werden
mit
Hilfe
spektroskopischen
und
elektrochemischen
Methoden
untersucht.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(18), С. 12750 - 12757
Опубликована: Апрель 26, 2024
Interest
in
applying
proton-coupled
electron
transfer
(PCET)
reagents
reductive
electro-
and
photocatalysis
requires
strategies
that
mitigate
the
competing
hydrogen
evolution
reaction.
Photoexcitation
of
a
PCET
donor
to
charge-separated
state
(CSS)
can
produce
powerful
H-atom
capable
being
electrochemically
recycled
at
comparatively
anodic
potential
corresponding
its
ground
state.
However,
challenge
is
designing
mediator
with
sufficiently
long-lived
excited
for
bimolecular
reactivity.
Here,
we
describe
ferrocene-derived
photoelectrochemical
exhibiting
an
unusually
CSS
(τ
∼
0.9
μs).
In
addition
detailed
photophysical
studies,
proof-of-concept
stoichiometric
catalytic
transformations
are
presented,
which
illustrate
promise
this
approach.
Journal of Physics Conference Series,
Год журнала:
2025,
Номер
2964(1), С. 012095 - 012095
Опубликована: Фев. 1, 2025
Abstract
Improving
the
activation
and
adsorption
of
N
2
by
catalysts
is
crucial
for
developing
efficient
nitrogen
reduction
catalysts.
Doping
defect
engineering
are
important
methods
addressing
these
issues.
a
certain
amount
Mo
in
CoS
beneficial
increasing
active
positions,
which
heightens
attachment
.
Due
to
unique
structure
sulfur
vacancy,
it
advantageous
weaken
N≡N
bond,
thus
enhancing
efficiency
electrocatalysis
from
NH
3
Therefore,
this
work
focuses
on
designing
Mo-doped
electrocatalyst
with
an
abundance
vacancies
enhance
its
electrocatalytic
performance
reduction.
The
Vs-Mo/CoS-8%
achieves
impressive
yield
38.19
μg
h
−1
mg
cat
Faraday
23.99%
at
electrical
potential
−0.45
V
(
vs
RHE).
Furthermore,
demonstrates
long-term
stability
up
24
hours.
This
study
not
only
broadens
diversity
available
electrocatalysts
but
also
provides
new
ideas
stable
ones.
Physical Chemistry Chemical Physics,
Год журнала:
2024,
Номер
26(30), С. 20684 - 20689
Опубликована: Янв. 1, 2024
A
series
of
binuclear
iron
phthalocyanine-based
molecules
were
designed
to
regulate
the
Fe
electronic
structure
for
electrocatalytic
nitrogen
reduction
theoretically.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(33)
Опубликована: Май 23, 2024
Abstract
Ammonia
(NH
3
)
is
industrially
produced
from
dinitrogen
(N
2
and
dihydrogen
(H
by
the
Haber–Bosch
process,
although
H
prepared
fossil
fuels,
reaction
requires
harsh
conditions.
On
other
hand,
microorganisms
have
fixed
nitrogen
under
ambient
Recently,
well‐defined
molecular
transition
metal
complexes
been
found
to
work
as
catalyst
convert
N
into
NH
reactions
with
chemical
reductants
proton
sources
Among
them,
involvement
of
both
‐splitting
pathway
proton‐coupled
electron
transfer
be
very
effective
for
high
catalytic
activity.
Furthermore,
direct
electrocatalytic
photocatalytic
conversions
recently
achieved.
In
addition
formation
,
selective
conversion
hydrazine
silylation
silylamines
reported.
Catalytic
C−N
bond
has
more
established
afford
cyanate
anion
(NCO
−
Further
development
nitrogen‐containing
compounds
well
green
ammonia
synthesis
leading
use
an
energy
carrier
expected.
Abstract
The
invention
of
technologies
that
can
activate,
transform,
and
upgrade
small
molecules
is
a
significant
challenge.
starting
point
for
many
such
molecular
catalysts.
Their
well‐defined
active
sites,
multitude
tools
to
characterize
their
reactions,
synthetic
flexibility
makes
logical
points.
However,
it
increasingly
clear
challenges
exist
in
the
applications
catalysts
at
scales
needed
address
modern
chemical
energy
demands.
In
this
review,
we
discuss
selected
classes
electrocatalysts
highlight
development
key
features.
Of
special
interest
are
proton‐coupled
transformations
H
2
,
O
N
CO
related
molecules.
We
also
frame
important
thermodynamic
features
different
using
new
approaches
ask
forward
looking
questions
about
practical
systems.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(44), С. 30204 - 30211
Опубликована: Окт. 28, 2024
Reagents
capable
of
concerted
proton-electron
transfer
(CPET)
reactions
can
access
reaction
pathways
with
lower
barriers
compared
to
stepwise
involving
electron
(ET)
and
proton
(PT).
To
realize
reductive
multielectron/proton
transformations
CPET,
one
approach
that
has
shown
recent
promise
involves
coupling
a
cobaltocene
ET
site
protonated
arylamine
Brønsted
acid
PT
site.
This
strategy
colocalizes
the
electron/proton
in
matter
compatible
CPET
step
net
electrocatalysis.
probe
generality
such
an
class
C,C'-diaryl-
