Nickel-based
metal-organic
frameworks
(MOFs)
with
flexible
structure
units
provide
a
broad
platform
for
designing
highly
efficient
electrocatalysts,
especially
alkaline
oxygen
evolution
reaction
(OER).
However,
the
stability
of
MOFs
under
harsh
and
dynamic
conditions
poses
significant
challenges,
resulting
in
ambiguous
structure-activity
relationships
MOFs-based
OER
research.
Herein,
Ni-benzenedicarboxylic
acid-based
MOF
(NiBDC)
is
selected
as
prototypical
catalyst
to
elucidate
its
real
active
sites
pathway
different
states.
Electrochemical
measurements
combined
X-ray
absorption
spectroscopy
(XAS)
Raman
reveal
that
complete
reconstruction
NiBDC
β-NiOOH
chronoamperometry
activation
process
responsible
significantly
increased
performance.
In
situ
XAS
results
further
demonstrate
electro-oxidation
into
γ-NiOOH
at
high-potential
state
(above
1.6
V
vs
RHE).
Furthermore,
collective
evidences
from
key
intermediates
isotope-labeled
products
definitely
unravel
potential
dependence
mechanism:
low-potential
proceeds
mainly
through
lattice
oxygen-mediated
mechanism,
while
adsorbate
mechanism
emerges
predominant
state.
Interestingly,
dynamically
changing
can
not
only
reduce
required
overpotential
but
also
improve
electrochemical
catalysts
Advanced Materials,
Год журнала:
2024,
Номер
36(31)
Опубликована: Май 23, 2024
Rationally
designed
defects
in
a
crystal
can
confer
unique
properties.
This
study
showcases
novel
dual-defects
engineering
strategy
to
tailor
the
electrochemical
response
of
metal-organic
framework
(MOF)
materials
used
for
energy
storage.
Salicylic
acid
(SA)
is
identified
as
an
effective
modulator
control
MOF-74
growth
and
induce
structural
defects,
cobalt
cation
doping
adopted
introducing
second
type
defect.
The
resulting
engineered
bimetallic
MOF
exhibits
discharging
capacity
218.6
mAh
g
Chemical Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 18, 2025
The
electrocatalytic
technique,
as
an
efficient
energy
storage
and
conversion
technology,
has
attracted
significant
attention
to
address
exhaustion
environmental
pollution.
Usually,
the
activity
selectivity
of
reactions
are
largely
dominated
by
dynamic
process
occurring
on
electrocatalysts.
Therefore,
high-performance
electrocatalysts,
which
can
dominate
pathway
barrier
reactions,
great
significance
for
advancement
technique.
Metal-organic
frameworks
(MOFs),
emerging
crystalline
porous
materials,
present
structural
component
advantages
including
well-defined
structure,
high
surface
area,
large
porosity,
diverse
components,
easy
tailorability,
demonstrating
fantastic
potential
precise
fabrication
In
this
Review,
strategies
in
electrocatalysts
based
MOF-related
materials
specifically
introduced
from
aspects
catalytic
site
design
microenvironment
modulation
around
sites.
Furthermore,
representative
progress
achieved
various
applications
employing
MOF-based
is
systematically
summarized,
with
special
emphasis
MOFs
performance
optimization.
Finally,
remaining
challenges
future
perspectives
further
highlighted.
Advanced Functional Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Июнь 26, 2024
Abstract
Electrocatalysis
represents
an
efficient
and
eco‐friendly
approach
to
energy
conversion,
enabling
the
sustainable
synthesis
of
valuable
chemicals
fuels.
The
deliberate
engineering
electrocatalysts
is
crucial
improving
efficacy
scalability
electrocatalysis.
Notably,
occurrence
in
situ
amorphization
within
has
been
observed
during
various
electrochemical
processes,
influencing
conversion
efficiency
catalytic
mechanism
understanding.
Of
note,
dynamic
transformation
catalysts
into
amorphous
structures
complex,
often
leading
configurations.
Therefore,
revealing
this
process
understanding
function
species
are
pivotal
for
elucidating
structure‐activity
relationship
electrocatalysts,
which
will
direct
creation
highly
catalysts.
This
review
examines
mechanisms
behind
structure
formation,
summarizes
characterization
methods
detecting
species,
discusses
strategies
controlling
(pre)catalyst
properties
conditions
that
influence
amorphization.
It
also
emphasizes
importance
spontaneously
formed
oxidation
reduction
reactions.
Finally,
it
addresses
challenges
electrocatalysts.
aiming
guide
efficient,
selective,
stable
reactions,
inspire
future
advancements
field.
It
remains
a
grand
challenge
to
develop
electrocatalysts
with
simultaneously
high
activity,
long
durability,
and
low
cost
for
the
oxygen
evolution
reaction
(OER),
originating
from
two
competing
pathways
often
trade-off
performances.
The
adsorbed
mechanism
(AEM)
suffers
sluggish
kinetics
due
linear
scaling
relationship,
while
lattice
(LOM)
causes
unstable
structures
escape.
We
propose
MoZnFeCoNi
high-entropy
alloy
(HEA)
incorporating
AEM-promoter
Mo
LOM-active
Zn
achieve
dual
activation
stabilization
efficient
durable
OER.
Density
functional
theory
chemical
probe
experiments
confirmed
dual-mechanism
activation,
representative
Co-Co
†
-Mo
sites
facilitating
AEM
Zn-O
-Ni
enhancing
LOM,
resulting
in
an
ultralow
OER
overpotential
(η
10
=
221
mV).
multielement
interaction,
structure,
carbon
network
notably
enhance
structural
stability
catalysis
(>1500
hours
at
100
mA
cm
−2
).
Our
work
offers
viable
approach
concurrently
activity
by
designing
HEA
catalysts
enable
synergy.
