Angewandte Chemie,
Год журнала:
2024,
Номер
136(39)
Опубликована: Июль 9, 2024
Abstract
Tuning
the
selectivity
of
CO
2
electroreduction
reaction
(CO
RR)
solely
by
changing
electrolyte
is
a
very
attractive
topic.
In
this
study,
we
conducted
RR
in
different
aqueous
electrolytes
over
bulk
metal
electrodes.
It
was
discovered
that
controlled
could
be
achieved
modulating
cations
electrochemical
double
layer.
Specifically,
ionic
liquid
significantly
inhibits
hydrogen
evolution
(HER),
while
yielding
high
Faraday
efficiencies
toward
(FE
)
or
formate
depending
on
alkali
cations.
For
example,
product
switched
from
=97.3
%)
to
=93.5
0.1
M
KBr‐0.5
1‐octyl‐3‐methylimidazolium
bromide
(OmimBr)
CsBr‐0.5
OmimBr
solutions
pristine
Cu
foil
electrode.
situ
spectroscopy
and
theoretical
calculations
reveal
ordered
structure
generated
assembly
Omim
+
under
an
applied
negative
potential
alters
bonding
interfacial
water,
thereby
inhibiting
HER.
The
difference
presence
attributed
effect
caused
,
which
solvated
thus
affects
stabilization
intermediates
pathways.
Advanced Energy Materials,
Год журнала:
2024,
Номер
14(39)
Опубликована: Июль 29, 2024
Abstract
Electrocatalytic
CO
2
reduction
(ECR)
powered
by
renewable
electricity
is
a
promising
technology
to
mitigate
carbon
emissions
and
lessen
the
dependence
on
fossil
fuels
toward
carbon‐neutral
energy
cycle.
Metal–organic
frameworks
(MOFs)
their
derivatives,
due
excellent
intrinsic
activity,
have
emerged
as
materials
for
ECR
high‐demand
products.
However,
challenges
such
unsatisfactory
efficiency,
selectivity,
relatively
low
production
rates
hinder
industrial
scalability.
Here,
comprehensive
critical
review
presented
that
summarizes
state‐of‐the‐art
progress
in
MOF‐based
MOF‐derived
electroreduction
catalysts
from
design
functionality
perspectives.
The
fundamentals
of
reaction
(CO
RR)
over
heterogeneous
catalysts,
mechanisms,
key
faced
are
described
first
establish
solid
foundation
forthcoming
in‐depth
analyses.
MOF's
building
blocks,
properties,
shortcomings
pertinent
including
conductivity
stability,
systematically
discussed.
Moreover,
discussions
provided
design,
fabrication,
characterization,
RR
activity
pinpoint
intricate
structure‐property‐performance
relationship.
Finally,
recommendations
put
forward
enhancing
MOF
electrocatalysts
durability.
This
work
may
serve
guideline
developing
high‐performance
MOF‐related
RR,
benefiting
researchers
working
this
growing
potentially
game‐changing
area.
Growing
global
population,
escalating
energy
consumption,
and
climate
change
threaten
future
security.
Fossil
fuel
combustion,
primarily
coal,
oil,
natural
gas,
exacerbates
the
greenhouse
effect
driving
warming
through
CO
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 5, 2025
Multi-proton-coupled
electron
transfer,
multitudinous
intermediates,
and
unavoidable
competing
hydrogen
evolution
reaction
during
CO2
electroreduction
make
it
tricky
to
control
high
selectivity
for
specific
products.
Here,
we
present
spatial
confinement
of
Fe
single
atoms
(FeN2S2)
by
adjacent
FeS
clusters
(Fe4S4)
orientate
the
transition
adsorption
configuration
from
C,O-side
O-end,
which
triggers
a
shift
activated
first-step
protonation
C–C
coupling,
thus
switching
target
product
HCOOH
in
Faraday
efficiency
(FE:
90.6%)
on
FeN2S2
CH3COOH
82.3%)
Fe4S4/FeN2S2.
The
strength
*OCHO
upon
solitary
site
is
linearly
related
coordination
number
Fe–S,
with
predominantly
produced
over
single-atom
(ortho-substituted
S
atoms).
Fe4S4
cluster
functions
as
switch
reduction
product,
can
not
only
optimize
electronic
structure
neighboring
but
also
impel
complete
hydrocarbon
intermediate
*CH3,
followed
coupling
CO2*
*CH3
via
synergistic
catalysis
This
strategy
provides
new
avenue
modulate
reactant
model
desirable
pathways,
potential
applications
diverse
multistep
electrochemical
processes
controlled
selectivity.
Science China Materials,
Год журнала:
2024,
Номер
68(1), С. 21 - 38
Опубликована: Ноя. 8, 2024
Abstract
The
conversion
of
carbon
dioxide
(CO
2
)
to
the
reduced
chemical
compounds
offers
substantial
environmental
benefits
through
minimizing
emission
greenhouse
gas
and
fostering
sustainable
practices.
Recently,
unique
properties
metal-organic
frameworks
(MOFs)
make
them
attractive
candidates
for
electrocatalytic
CO
reduction
reaction
RR),
providing
many
opportunities
develop
efficient,
selective,
environmentally
processes
mitigating
emissions
utilizing
as
a
valuable
raw
material
synthesis
fuels
chemicals.
Here,
recent
advances
in
MOFs
efficient
catalysts
RR
are
summarized.
detailed
characteristics,
mechanisms,
practical
approaches
improving
efficiency,
selectivity,
durability
under
realistic
conditions
also
clarified.
Furthermore,
outlooks
on
prospects
MOF-based
electrocatalysts
provided.
Advanced Functional Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 2, 2025
Abstract
Atomically
dispersed
materials
have
been
a
thriving
research
field
due
to
their
maximum
atomic
utilization
and
remarkable
performance
in
energy
conversion
storage
systems.
Owing
the
large
radius,
strong
oxophilicity,
unique
electronic
properties,
rare‐earth
(RE)
elements
widely
investigated
as
oxide
carriers
promoters
atomically
manipulate
regulate
structure
of
active
species.
Single‐atom
state
with
an
adjustable
coordination
environment
on
N‐doped
carbon
endows
RE
metals
special
states
outstanding
catalytic
performances.
A
thorough
comprehension
modulation
mechanism
paves
way
for
construction
advanced
RE‐based
electrocatalysts
high
activity,
stability,
selectivity.
This
review
provides
widespread
insight
into
roles
modulating
properties
combined
structure–performance
relationship
electrocatalysis
processes.
The
characteristic
physical
chemical
are
highlighted,
synthetic
strategy
is
discussed.
Finally,
summary
perspectives
rational
design
development
highly
efficient
catalysts
proposed.
aims
provide
guideline
promoting
effective
functional
materials.
Electrochemical
CO2
reduction
(CO2RR)
in
membrane
electrode
assembly
(MEA)
represents
a
viable
strategy
for
converting
into
value-added
multi-carbon
(C2+)
compounds.
Therefore,
the
microstructure
of
catalyst
layer
(CL)
affects
local
gas
transport,
charge
conduction,
and
proton
supply
at
three-phase
interfaces,
which
is
significantly
determined
by
solvent
environment.
However,
microenvironment
CLs
mechanism
effect
on
C2+
selectivity
remains
elusive.
Herein,
tailored
interfacial
structure
designed
introducing
solvent-mediated
catalyst-ionomer-solvent
microenvironment.
The
acetone
surface
promotion
beneficial
unfolded
ionomers
to
uniformly
coat
catalysts,
contributes
enhancing
hydrophobicity
inhibiting
hydrogen
evolution.
Furthermore,
molecular
dynamics
(MD)
simulation
situ
ATR-SEIRAS
are
employed
elucidate
appropriate
network
with
balanced
distribution
H2O.
uniform
continuous
advantageous
CO2-to-C2+.
optimized
favors
production
products
Cu-based
MEA,
exhibiting
high
faradaic
efficiency
(FE)
80.27%
400
mA
cm-2.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
147(9), С. 7921 - 7931
Опубликована: Фев. 24, 2025
Hydrophobic
ionic
liquid
(HIL)
engineering
on
the
catalyst
surface
represents
a
simple
yet
potent
direction
for
optimizing
CO2
electroreduction
performance.
However,
pivotal
role
of
HIL
at
an
industrial
current
density
is
still
ambiguous
due
to
limited
and
conflicting
research
findings.
Herein,
HIL-engineered
oxide-derived
Cu
porous
nanoparticles
with
electron-delocalized
groups
specific
ultramicropore
structure
are
first
constructed
facilitate
CO2-to-C2+
ampere-level
densities.
The
uniformly
decorated
innovatively
demonstrated
by
positron
annihilation
lifetime
spectroscopy,
which
offers
unparalleled
advantages
in
characterization.
Bader
charge-dependent
performance
analyses
theoretical
calculations
disclose
that
N
atoms
lower
adsorption
energy
CO
atop
site
from
-0.38
-1.42
eV
through
electron
donation,
inverts
most
stable
favors
energy-efficient
dimerization
atop-bound
CO.
Operando
Raman
spectra
situ
attenuated
total
reflection-surface
enhanced
infrared
absorption
spectroscopy
indicate
adhered
increases
*CO
coverage
alters
configuration
state
abundant
high-frequency
band.
Furthermore,
staircase
potential
electrochemical
impedance
unravels
arrangement
enlarges
charge
about
1.5
times,
thereby
accelerating
electroreduction.
As
result,
achieve
prominent
C2+
productivity
Faradaic
efficiency
85.1%
formation
rate
up
2512
μmol
h-1
cm-2,
outperforming
reported
Cu-based
electrocatalysts.