Advanced Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 28, 2024
Abstract
Membrane‐based
reverse
electrodialysis
is
globally
recognized
as
a
promising
technology
for
harnessing
osmotic
energy.
However,
its
practical
application
greatly
restricted
by
the
poor
anti‐fouling
ability
of
existing
membrane
materials.
Inspired
structural
and
functional
models
natural
cytochrome
c
oxidases
(C
O),
first
use
atomically
precise
homonuclear
diatomic
iron
composites
high‐performance
energy
conversion
membranes
with
excellent
demonstrated.
Through
rational
tuning
atomic
configuration
sites,
oxidase‐like
activity
can
be
precisely
tailored,
leading
to
augmentation
ion
throughput
capacity.
Composite
featuring
direct
Fe‐Fe
motif
configurations
embedded
within
cellulose
nanofibers
(CNF/Fe‐DACs‐P)
surpass
state‐of‐the‐art
CNF‐based
power
densities
ca.
6.7
W
m
−2
44.5‐fold
enhancement
in
antimicrobial
performance.
Combined,
experimental
characterization
density
theory
simulations
reveal
that
sites
metal‐metal
interactions
achieve
ideally
balanced
adsorption
desorption
intermediates,
thus
realizing
superior
activity,
enhanced
ionic
flux,
antibacterial
activity.
Abstract
Crystalline
γ‐FeO(OH)
dominantly
possessing
─
OH
terminals
(𝛾‐FeO(OH)
c
),
polycrystalline
containing
multiple
O,
OH,
and
Fe
pc
α‐Fe
2
O
3
majorly
surface
are
used
as
electrocatalysts
to
study
the
effect
of
on
electrocatalytic
nitrate
reduction
reaction
(eNO
RR)
selectivity
stabilization
intermediates.
Brunauer‐Emmett‐Teller
analysis
electrochemically
determined
area
suggest
a
high
active
117.79
m
g
−1
(ECSA:
0.211
cm
)
for
𝛾‐FeO(OH)
maximizing
accessibility
adsorption
exhibiting
selective
eNO
RR
NH
at
pH
7
with
yield
rate
18.326
mg
h
−2
,
>85%
Faradaic
efficiency
(FE),
least
nine‐times
catalyst‐recyclability.
15
N‐
D‐labeling
combined
in
situ
IR
Raman
studies
validate
ions
generation
nitrite
hydroxyl
amine
A
kinetic
isotope
(KIE)
value
2.1
indicates
H
proton
source
proton‐coupled
electron
transfer
rate‐limiting
step.
The
rotating‐ring
disk
electrochemical
(RRDE)
subsequent
Koutecký‐Levich
reveal
electron‐transfer
constant
(k)
2e‐
is
5.7
×
10
−6
s
.
This
provides
direct
evidence
formation
dominant
pathway
γ‐FeO(OH).
ACS Sustainable Chemistry & Engineering,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 22, 2025
Nitrogen
reduction
reaction
(NRR)
offers
a
sustainable
alternative
to
the
energy-intensive
Haber–Bosch
process
for
ammonia
synthesis
under
ambient
conditions
while
also
mitigating
serious
global
warming
impact
of
fossil
fuels.
However,
competing
hydrogen
evolution
remains
significant
challenge
in
NRR
systems.
In
this
work,
we
propose
Bi-doped
CuFe
nanoclusters
loaded
on
3D
copper
foams
(CFs)
as
an
enhanced
N2
electrocatalyst
NRR.
The
catalyst
exhibited
superior
activity
compared
undoped
counterpart,
achieving
high
yield
216.1
μg
h–1
cm–2
with
Faradaic
efficiency
46.8%
at
−0.4
V
vs
reversible
electrode.
Importantly,
showed
good
selectivity
minimal
N2H4
byproduct
generation
and
excellent
stability.
Bismuth
incorporation
induced
lattice
expansion
electronic
defects,
which
turn
created
structural
defects
oxygen
vacancies.
These
changes
effectively
promoted
adsorption
activation
molecules.
Comprehensive
characterization
revealed
that
Bi
doping
decreased
vacancy
density
bulk
phase
but
increased
surface.
This
phenomenon
expanded
spacing,
inhibiting
H*
combination
produce
H2,
surface
vacancies
regulated
strength
NxHy
intermediates
during
electrocatalytic
process.
Density
functional
theory
calculations
further
confirmed
active
sites,
well
subsequent
hydrogenation
steps,
leading
lower
energy
barrier
distal
pathway
NH3
formation.
Moreover,
Zn–N2
battery
assembled
Bi–CuFe/CF
shows
power
14.01
mW
cm–2,
enables
simultaneous
production
supply,
gives
it
potential
field
energy.
work
demonstrates
promising
approach
developing
efficient
electrocatalysts
by
structure
modulation,
contributing
transition
toward
low-carbon
economy.
Advanced Materials,
Год журнала:
2024,
Номер
36(41)
Опубликована: Сен. 2, 2024
Abstract
Electrocatalytic
C‐N
coupling
between
NO
3
‐
and
CO
2
has
emerged
as
a
sustainable
route
for
urea
production.
However,
identifying
catalytic
active
sites
designing
efficient
electrocatalysts
remain
significant
challenges.
Herein,
the
synthesis
of
Cu‐doped
MnO
nanotube
(denoted
Cu‐MnO
)
with
stable
Cu
δ+
‐oxygen
vacancies
(O
vs
)‐Mn
3+
dual
is
reported.
Compared
pure
,
doping
can
effectively
enhance
production
performance
in
co‐reduction
.
Thus,
catalyst
exhibits
maximum
Faradaic
efficiency
(FE)
54.7%
highest
yield
rate
116.7
mmol
h
−1
g
cat.
flow
cell.
Remarkably,
remains
over
78
across
wide
potential
range.
Further
experimental
theoretical
results
elucidate
unique
role
solid‐solution
stabilizing
‐O
‐Mn
endowing
superior
structural
electrochemical
stabilities.
This
thermodynamically
promotes
formation
kinetically
lowers
energy
barrier
coupling.
