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.
Advanced Materials,
Год журнала:
2023,
Номер
36(11)
Опубликована: Дек. 2, 2023
Photocatalytic
hydrogen
evolution
(PHE)
via
water
splitting
using
semiconductor
photocatalysts
is
an
effective
path
to
solve
the
current
energy
crisis
and
environmental
pollution.
Heterojunction
photocatalysts,
containing
two
or
more
semiconductors,
exhibit
better
PHE
rates
than
those
with
only
one
owing
altered
band
alignment
at
interface
stronger
driving
force
for
charge
separation.
Traditional
binary
metal
sulfide
(BMS)-based
heterojunction
such
as
CdS,
MoS
ACS Catalysis,
Год журнала:
2024,
Номер
14(5), С. 3298 - 3307
Опубликована: Фев. 15, 2024
The
discovery
of
acid-stable
and
highly
active
electrocatalysts
for
the
oxygen
evolution
reaction
(OER)
is
crucial
in
quest
high-performance
water-splitting
technologies.
Herein,
a
heterostructured
RuO2–CeO2
electrocatalyst
was
constructed
by
using
lattice-matching
strategy.
interfacial
Ru–O–Ce
bridge
structure
provided
channel
electron
transfer
between
Ru
Ce,
creating
lattice
stress
that
distorts
local
RuO2.
resulting
catalyst
exhibited
attractive
stability
with
negligible
decay
after
1000
h
OER
0.5
M
H2SO4,
along
high
activity
an
overpotential
only
180
mV
at
10
mA
cm–2.
In
situ
attenuated
total
reflectance
surface-enhanced
infrared
absorption
spectroscopy
(ATR-SEIRAS),
differential
electrochemical
mass
spectrometry
(DEMS),
density
functional
theory
(DFT)
calculations
were
used
to
reveal
interface
noninterface
RuO2
sites
enabled
oxide
path
mechanism
(OPM)
enhanced
adsorbate
(AEM-plus),
respectively,
during
OER.
simultaneous
independent
pathways
accessible
matching
guides
improved
design
acidic
media.
ACS Catalysis,
Год журнала:
2024,
Номер
14(8), С. 5936 - 5948
Опубликована: Апрель 3, 2024
The
asymmetric
oxygen
vacancies
on
the
surface
of
doped
oxides
and
at
interface
between
metal
oxide
are
commonly
regarded
as
real
active
sites
for
molecular
activation
reaction,
owing
to
their
unique
electronic
perturbation
properties.
However,
essential
rules
modulating
local
structure
promote
capacity
still
ambiguous.
In
this
work,
a
series
interfacial
vacancy
sites,
Pt/Ce–Ov–M
(Ov,
vacancy,
M
=
Y,
La,
Pr,
Nd),
with
different
coordination
environments
were
constructed
based
Pt/Ce0.95M0.05O2−δ
materials.
experimental
data
theoretical
calculation
results
prove
that
site
can
capture
electrons
from
Pt
d-bands
d-
f-bands,
acting
an
electron
enrichment
center.
elevated
d-band
center
upward
Fermi
level
significantly
boost
transfer
unoccupied
π2p*
orbital
O2,
achieving
O2
through
π-electron
feedback
mechanism.
Remarkably,
Pt/Ce–Ov–Y
in
Pt/Ce0.95Y0.05O2−δ
highest
delocalized
density
exhibited
best
behaviors
catalytic
activity
aerobic
oxidation
5-hydroxymethylfurfural.
This
work
reveals
over
metal-oxide
catalysts
is
highly
dependent
d/f-orbital
valence-electron
modulation,
providing
more
insights
into
effect
vacancy-localized
performance.
Advanced Energy Materials,
Год журнала:
2023,
Номер
14(7)
Опубликована: Дек. 22, 2023
Abstract
The
electrochemical
nitrate
reduction
reaction
(NO
3
RR)
is
an
environment‐friendly
and
promising
alternative
to
the
conventional
Haber–Bosch
ammonia
synthesis
process,
which
a
complex
process
of
proton‐coupled
electron
transfer.
Hereon,
amorphous
CeO
x
support
introduced
construct
Cu/a‐CeO
heterostructure
prepared
provide
sufficient
*H
synergistically
catalyze
NO
RR.
achieves
maximum
yield
1.52
mmol
h
−1
mg
cat
.
In
flow
cell,
NH
reaches
17.93
at
1
A
cm
−2
,
exceeds
most
state‐of‐the‐art
catalysts.
situ
X‐ray
diffraction
(XRD)
in
Raman
observe
that
catalyst
undergoes
structural
reconfiguration
under
operating
conditions,
thus
confirming
Cu
2
O
not
true
active
center
catalytic
process.
Furthermore,
characterizations
density
functional
theory
(DFT)
calculations
demonstrate
modulates
electronic
structure
overcomes
higher
potential
barrier
required
for
decomposition
water
on
Cu,
greatly
facilitates
hydrolysis
provides
H‐coverage
rate
hydrogenation
−
realizing
dynamic
equilibrium
between
production
consumption
hydrogen.
This
component
design
strategy
centered
opens
up
new
pathway
Advanced Functional Materials,
Год журнала:
2024,
Номер
34(37)
Опубликована: Апрель 21, 2024
Abstract
Electrocatalytic
hydrogen
evolution
reaction
(HER)
via
alkaline
water
splitting
holds
great
promise
for
industrial
clean
production
but
is
frustrated
by
limited
catalytic
activity
and
inferior
stability
under
high
current
density.
Elaborate
manipulating
of
heterostructure
on
robust
electrodes
essential
challenging
accelerating
HER
kinetics
with
durability.
Herein,
a
nickel
mesh
electrode,
offering
mechanical
stability,
directly
engineered
layers
multiple
heterostructures
(r‐Mn–Ni/CoP)
facile
one‐pot
electrodeposition
followed
surface
reconstruction
strategy.
The
abundant
composed
crystalline
CoP,
NiP,
amorphous
region,
additional
Mn
doping
considerably
manipulate
the
electronic
structure
optimized
charge
transfer;
while
in
situ
surface‐reconstructed
hydrophilic
nanoflakes
enable
rapid
wetting
active
sites
to
electrolyte.
Consequently,
r‐Mn–Ni/CoP
requires
only
134
mV
overpotential
at
density
100
mA
cm
−2
,
superior
monophasic
undoped
samples,
majority
reported
catalysts.
Remarkably,
an
electrolyzer
cathode
demonstrates
extraordinary
voltage
1.734
V
300
stable
operation
800
h.
finding
provides
feasible
strategy
fabrication
nonprecious‐metal‐based
electrocatalysts
toward
electrolysis.
Advanced Energy Materials,
Год журнала:
2024,
Номер
14(23)
Опубликована: Март 26, 2024
Abstract
Transition‐metal‐based
compounds
have
been
intensively
explored
as
efficient
electrocatalysts
for
hydrogen
evolution
reaction
(HER).
Feasible
reconstruction
to
the
real
active
sites,
which
is
yet
be
identified,
endows
promotion
of
HER
activity.
Here,
it
reported
that
incoming
S
coordinates
and
anion
vacancies
prompt
structural
S‐doped
Co
3
O
4
on
carbon
cloth
(S‐Co
/CC)
during
HER.
A
list
in
situ
studies
reveals
sites
are
“metallic
surface‐adparticles”
system
embracing
metallic
scaffold
dilute
coverage
coordinated
δ+
.
Reaction
mechanism
exploration
illustrates
interfacial
perimeters
between
moieties
considerably
facilitate
adsorption
H*,
improve
kinetics
water
dissociation,
consequently
promote
The
exemplified
sulfide‐mediated
topotactic
transformation
strategy
extended
preparation
S,
Fe
codoped
Ni(OH)
2
(S‐NiFe/CC)
a
bifunctional
electrocatalyst.
assembled
exchange
membrane
electrolyzer
achieves
current
density
1.0
cm
−2
at
1.72
V,
showing
excellent
capability
catalyzing
overall
splitting
ampere
level.
This
study,
feasible
enables
facile
identify
would
inspire
development
other
electrochemical
hydrogenation
reaction.
Abstract
Modifying
the
coordination
or
local
environments
of
single‐,
di‐,
tri‐,
and
multi‐metal
atom
(SMA/DMA/TMA/MMA)‐based
materials
is
one
best
strategies
for
increasing
catalytic
activities,
selectivity,
long‐term
durability
these
materials.
Advanced
sheet
supported
by
metal
atom‐based
have
become
a
critical
topic
in
fields
renewable
energy
conversion
systems,
storage
devices,
sensors,
biomedicine
owing
to
maximum
utilization
efficiency,
precisely
located
centers,
specific
electron
configurations,
unique
reactivity,
precise
chemical
tunability.
Several
offer
excellent
support
are
attractive
applications
energy,
medical
research,
such
as
oxygen
reduction,
production,
hydrogen
generation,
fuel
selective
detection,
enzymatic
reactions.
The
strong
metal–metal
metal–carbon
with
metal–heteroatom
(i.e.,
N,
S,
P,
B,
O)
bonds
stabilize
optimize
electronic
structures
atoms
due
interfacial
interactions,
yielding
activities.
These
provide
models
understanding
fundamental
problems
multistep
This
review
summarizes
substrate
structure‐activity
relationship
different
active
sites
based
on
experimental
theoretical
data.
Additionally,
new
synthesis
procedures,
physicochemical
characterizations,
biomedical
discussed.
Finally,
remaining
challenges
developing
efficient
SMA/DMA/TMA/MMA‐based
presented.