The Journal of Physical Chemistry Letters,
Год журнала:
2024,
Номер
unknown, С. 1 - 8
Опубликована: Дек. 17, 2024
Selectivity
is
an
essential
aspect
in
catalysis.
At
present,
the
improvement
of
selectivity
for
complex
reactions
with
multiple
pathways/products,
example
carbon
dioxide
reduction
reaction
(CO2RR),
can
usually
be
achieved
only
one
pathway/product.
It
still
a
challenge
to
reversibly
modulate
between
two
pathways
or
products
CO2RR
by
catalyst.
Here,
we
propose
reversible
modulation
via
spin
crossover.
By
employing
first-principles
calculations,
six
crossover
molecular
catalysts
are
found
among
17
kinds
transition
metal
embedded
porphyrin
derivatives
(ppy_TM),
where
changes
axial
ligand
configurations
switch
state
high
and
low
spin.
For
ppy_Os
ppy_Ru,
alteration
effectively
influence
CO2
into
either
formic
acid
monoxide
changing
relative
stability
key
intermediates
*COOH
*HCOO.
Current Opinion in Electrochemistry,
Год журнала:
2023,
Номер
41, С. 101371 - 101371
Опубликована: Авг. 10, 2023
Electrocatalytic
hydrogenation
of
π-bonds
in
unsaturated
organic
compounds
is
a
promising
strategy
for
electrifying
chemical
synthesis
using
renewable
energies.
This
approach
not
only
offers
an
alternative
to
the
use
molecular
hydrogen
but
also
has
potential
unlock
original
reaction
pathways
with
higher
efficiencies
or
featuring
distinct
selectivities
functional
group
tolerances.
In
this
emerging
field,
such
reactivity
engineering
can
be
ideally
explored
complexes
based
on
fundamental
understanding
underlying
mechanisms.
Recent
developments
via
electrocatalysis
and
related
key
mechanistic
features
are
presented
viewpoint.
Perspectives
drawn
highlight
less
areas
catalytic
space
point
way
improved
systems.
The Journal of Physical Chemistry Letters,
Год журнала:
2023,
Номер
14(23), С. 5377 - 5385
Опубликована: Июнь 6, 2023
We
show
that
the
ability
of
ligand
to
reorganize
electric
double
layer
(EDL)
often
dominates
electrocatalysis
contrary
their
inductive
effect
in
spectrochemical
series,
leading
counterintuitive
electrocatalysis.
With
water
oxidation
and
chlorine
evolution
as
probe
reactions,
same
catalytic
entity
with
carboxy
functionalized
exhibited
surprisingly
higher
electrochemical
activity
comparison
aggressively
electron-withdrawing
nitro
ligands,
which
is
actual
location
series.
Spectroscopic
analyses
suggest
enrichment
catalytically
active
species
substituted
via
proton
charge
assembly
EDL
turn
enhances
kinetics
overall
process.
This
demonstration
less
obvious
ligands
becoming
indispensable
suggests
a
blind
designing
solely
based
on
should
be
reconsidered
it
will
prevent
utilization
maximum
potential
molecule
Abstract
Catalytic
hydrogenation
is
one
of
the
most
important
transformations
in
both
academia
and
industry.
Compared
with
direct
molecular
hydrogen
or
transfer
hydrogenations
hydrides,
electrohydrogenation
provides
an
alternative
practical
pathway
using
proton
as
source.
In
this
review,
we
have
summarized
recent
advances
electrohydrogenations
polar
non‐polar
unsaturated
compounds
catalyzed
by
earth‐aubundant
metal
complexes.
addition,
also
present
a
detailed
discussion
scope
limitations,
plausible
mechanisms
opportunities
for
further
development.
The Journal of Physical Chemistry Letters,
Год журнала:
2024,
Номер
unknown, С. 1 - 8
Опубликована: Дек. 17, 2024
Selectivity
is
an
essential
aspect
in
catalysis.
At
present,
the
improvement
of
selectivity
for
complex
reactions
with
multiple
pathways/products,
example
carbon
dioxide
reduction
reaction
(CO2RR),
can
usually
be
achieved
only
one
pathway/product.
It
still
a
challenge
to
reversibly
modulate
between
two
pathways
or
products
CO2RR
by
catalyst.
Here,
we
propose
reversible
modulation
via
spin
crossover.
By
employing
first-principles
calculations,
six
crossover
molecular
catalysts
are
found
among
17
kinds
transition
metal
embedded
porphyrin
derivatives
(ppy_TM),
where
changes
axial
ligand
configurations
switch
state
high
and
low
spin.
For
ppy_Os
ppy_Ru,
alteration
effectively
influence
CO2
into
either
formic
acid
monoxide
changing
relative
stability
key
intermediates
*COOH
*HCOO.
