Electrochemically Driven Selective Olefin Epoxidation by Cobalt–TAML Catalyst
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 29, 2025
Epoxides
are
versatile
chemical
intermediates
that
used
in
the
manufacture
of
diversified
industrial
products.
For
decades,
thermochemical
conversion
has
long
been
employed
as
primary
synthetic
route.
However,
it
several
drawbacks,
such
harsh
and
explosive
operating
conditions,
well
a
significant
greenhouse
gas
emissions
problem.
In
this
study,
we
propose
an
alternative
electrocatalytic
epoxidation
reaction,
using
[CoIII(TAML)]-
(TAML
=
tetraamido
macrocyclic
ligand)
molecular
catalyst.
Under
ambient
catalyst
selectively
epoxidized
olefin
substrates
water
oxygen
atom
source,
affording
efficient
catalytic
olefins
with
broad
substrate
scope.
Notably,
achieved
>60%
Faradaic
efficiency
(FE)
>90%
selectivity
for
cyclohexene
epoxidation,
which
other
heterogeneous
electrocatalysts
have
never
attained.
Electrokinetic
studies
shed
further
light
on
detailed
mechanism
involved
rate-limiting
proton-coupled
electron
transfer
process,
forming
reactive
cobalt
active
species
embedded
2e-oxidized
TAML.
Operando
voltammetry-electrospray
ionization
mass
spectrometry
(VESI-MS)
paramagnetic
resonance
(EPR)
analyses
were
utilized
to
identify
intermediate
during
by
[CoIII(TAML)]-.
Our
findings
offer
new
possibility
sustainable
feedstock
production
electrochemical
methods.
Язык: Английский
Enhanced electrocatalytic H2O2 production using Ar jet plasma-polymerized trimethoxyphenylsilane forming Lewis acid sites
Applied Surface Science,
Год журнала:
2025,
Номер
unknown, С. 162676 - 162676
Опубликована: Фев. 1, 2025
Язык: Английский
In situ uncovering the catalytic cycle of electrochemical and chemical oxygen reduction mediated by iron porphyrin
Chemical Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
As
one
of
the
critical
reactions
in
biotransformation
and
energy
conversion
processes,
oxygen
reduction
reaction
(ORR)
catalyzed
by
iron
porphyrins
has
been
widely
explored
electrochemical,
spectroscopic,
theoretical
methods.
However,
experimental
identification
all
proposed
intermediates
catalytic
cycle
is
rather
challenging
mechanistic
studies
ORR
driven
electrochemical
or
chemical
Herein,
we
report
application
mass
spectrometry
(EC-MS)
(CR-MS)
to
situ
uncover
ORRs
mediated
an
porphyrin
molecular
catalyst.
Five
crucial
iron-oxygen
detected
both
EC-MS
CR-MS
help
build
whole
indicate
details
4e-/4H+
pathway
produce
H2O
ORRs.
By
combining
MS
methods
with
spectroscopic
characterize
study
selectivities,
this
work
provides
a
comparison
model
porphyrin.
Язык: Английский
Ligand‐Insertion Strategy for Constructing 2D Conjugated Metal‐Organic Framework with Large Pore Size for Electrochemical Analytics
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
64(1)
Опубликована: Сен. 25, 2024
Two-dimensional
conjugated
metal-organic
frameworks
(2D
c-MOFs)
have
shown
great
promise
in
various
electrochemical
applications
due
to
their
intrinsic
electrical
conductivity.
A
large
pore
aperture
is
a
favorable
feature
of
this
type
material
because
it
facilitates
the
mass
transport
chemical
species
and
electrolytes.
In
work,
we
propose
ligand
insertion
strategy
which
linear
inserted
into
linkage
between
multitopic
ligands,
extending
metal
ion
unit
-M-ligand-M-,
for
construction
2D
c-MOFs
with
apertures,
utilizing
only
small
ligands.
As
proof-of-concept
trial
strategy,
c-MOF
mesopores
3.2
nm
was
synthesized
using
commercially
available
ligands
hexahydrotriphenylene
2,5-dihydroxybenzoquinone.
The
facilitation
diffusion
redox
by
size
MOF
demonstrated
through
series
probes.
With
feature,
showed
superior
performance
analysis
variety
biological
species.
Язык: Английский
Ligand‐Insertion Strategy for Constructing 2D Conjugated Metal‐Organic Framework with Large Pore Size for Electrochemical Analytics
Angewandte Chemie,
Год журнала:
2024,
Номер
137(1)
Опубликована: Сен. 25, 2024
Abstract
Two‐dimensional
conjugated
metal–organic
frameworks
(2D
c
‐MOFs)
have
shown
great
promise
in
various
electrochemical
applications
due
to
their
intrinsic
electrical
conductivity.
A
large
pore
aperture
is
a
favorable
feature
of
this
type
material
because
it
facilitates
the
mass
transport
chemical
species
and
electrolytes.
In
work,
we
propose
ligand
insertion
strategy
which
linear
inserted
into
linkage
between
multitopic
ligands,
extending
metal
ion
unit
‐M‐ligand‐M‐,
for
construction
2D
‐MOFs
with
apertures,
utilizing
only
small
ligands.
As
proof‐of‐concept
trial
strategy,
‐MOF
mesopores
3.2
nm
was
synthesized
using
commercially
available
ligands
hexahydrotriphenylene
2,5‐dihydroxybenzoquinone.
The
facilitation
diffusion
redox
by
size
MOF
demonstrated
through
series
probes.
With
feature,
showed
superior
performance
analysis
variety
biological
species.
Язык: Английский
Mapping Reaction Pathways by In Situ Step Sweep Voltammetry Flow Electrochemical Mass Spectrometry
Xi Cui,
Jianxiong Chen,
Hong Yi
и другие.
Analytical Chemistry,
Год журнала:
2024,
Номер
96(44), С. 17765 - 17772
Опубликована: Окт. 22, 2024
A
step
sweep
voltammetry
(SSV)
flow
electrochemical
(EC)
mass
spectrometry
(MS)
platform
was
developed
for
real-time
and
Язык: Английский
Iron Porphyrin-Based Composites for Electrocatalytic Oxygen Reduction Reactions
Molecules,
Год журнала:
2024,
Номер
29(23), С. 5655 - 5655
Опубликована: Ноя. 29, 2024
The
oxygen
reduction
reaction
(ORR)
is
one
of
the
most
critical
reactions
in
energy
conversion
systems,
and
it
facilitates
efficient
chemical
into
electrical
energy,
which
necessary
for
modern
technology.
Developing
cost-effective
catalysts
ORRs
crucial
advancing
effectively
applying
renewable
technologies
such
as
fuel
cells,
metal–air
batteries,
electrochemical
sensors.
In
recent
years,
iron
porphyrin-based
composites
have
emerged
ideal
facilitating
effective
due
to
their
unique
structural
characteristics,
abundance,
advances
synthesis,
excellent
catalytic
properties,
mimic
natural
enzymatic
systems.
However,
many
articles
focused
on
reviewing
frameworks
or
metalloporphyrins
general,
necessitating
research
specifically
addressing
porphyrin.
This
review
discusses
porphyrin
an
catalyst
ORRs.
It
provides
a
comprehensive
knowledge
application
electrocatalytic
ORRs,
focusing
integration
with
conductive
supports,
mechanism,
efficacy.
also
challenges
recommendations
address
these
challenges.
Язык: Английский