Direct
formic
acid
fuel
cell
(DFAFC)
is
an
efficient
power
generation
device,
due
to
its
high
energy
density,
low
crossover
and
emission.
However,
the
anodic
reaction
of
DFAFC,
oxidation
(FAOR),
inevitably
proceeds
through
indirect
pathway,
adsorbing
carbon
monoxide
intermediate
(CO
Angewandte Chemie International Edition,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 8, 2025
Electrocatalytic
glycerol
oxidation
reaction
(GOR)
to
produce
high-value
formic
acid
(FA)
is
hindered
by
high
formation
potential
of
active
species
and
sluggish
C-C
bond
cleavage
kinetics.
Herein,
Ni
single-atom
(NiSA)
Co
(CoSA)
dual
sites
anchored
on
nitrogen-doped
carbon
nanotubes
embedded
with
Ni0.1Co0.9
alloy
(Ni0.1Co0.9@NiSACoSA-NCNTs)
are
constructed
for
electrochemical
GOR.
Remarkably,
it
can
reach
10
mA
cm-2
at
a
low
1.15
V
versus
the
reversible
hydrogen
electrode
(vs.
RHE)
realize
formate
selectivity
93.27
%
even
conversion
98.81
1.45
vs.
RHE.
The
GOR
mechanism
pathway
systematically
elucidated
via
experimental
analyses
theoretical
calculations.
It
revealed
that
hydroxyl
(*OH)
be
produced
during
NiSA,
CoSA,
synergistically
optimizes
electronic
structure
CoSA
sites,
reducing
energy
barriers
*OH-mediated
bonds
dehydrogenation
C1
intermediates.
This
decreases
number
intermediates
steps
GOR-to-FA,
thus
increasing
production
efficiency.
After
coupling
evolution
in
membrane
assembly
cell,
14.26
g
23.10
L
H2
100
108
h.
Advanced Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 8, 2024
Abstract
Constructing
built‐in
electric
field
(BIEF)
in
heterojunction
catalyst
is
an
effective
way
to
optimize
adsorption/desorption
of
reaction
intermediates,
while
its
precise
tailor
achieve
efficient
bifunctional
electrocatalysis
remains
great
challenge.
Herein,
the
hollow
Mo/MoS
Vn
nanoreactors
with
tunable
BIEFs
are
elaborately
prepared
simultaneously
promote
hydrogen
evolution
(HER)
and
urea
oxidation
(UOR)
for
sustainable
production.
The
BIEF
induced
by
sulfur
vacancies
can
be
modulated
from
0.79
0.57
0.42
mV
nm
−1
,
exhibits
a
parabola‐shaped
relationship
HER
UOR
activities,
V1
nanoreactor
moderate
presents
best
activity.
Theoretical
calculations
reveal
that
evidently
facilitate
breakage
N─H
bond
UOR.
electrolyzer
assembled
delivers
cell
voltage
1.49
V
at
100
mA
cm
−2
which
437
lower
than
traditional
water
electrolysis,
also
excellent
durability
200
h.
Life
cycle
assessment
indicates
HER||UOR
system
possesses
notable
superiority
across
various
environment
impact
energy
consumption.
This
work
provide
theoretical
experimental
direction
on
rational
design
advanced
materials
energy‐saving
eco‐friendly
Inorganic Chemistry,
Год журнала:
2024,
Номер
63(38), С. 17662 - 17671
Опубликована: Сен. 6, 2024
Electrolysis
of
infinite
seawater
is
a
promising
and
sustainable
approach
for
clean
hydrogen
production.
However,
it
remains
big
challenge
to
accomplish
corrosion-resistant
chlorine-free
electrolysis
at
low
power
input.
Herein,
the
bimetallic
nickel-iron
sulfide-based
electrocatalytic
nanoarrays
are
constructed
by
facile
hydrothermal
sulfidation
redox-etched
iron
foam
(IF),
which
manifests
an
effective
reliable
strategy
sulfion
oxidation
reaction
(SOR)
assist
alkaline
achievement
energy-saving
production
value-added
upcycling.
The
resulting
NiFeS
Advanced Functional Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 13, 2024
Abstract
Electrocatalytic
valorization
of
glycerol
to
formate
is
considered
be
a
promising
sustainable
approach;
however,
it
holds
great
challenges
increase
catalyst
activity
and
deliver
market‐demanded
chemicals
with
high
Faradaic
efficiency
(FE)
selectivity
under
industrial‐level
current
density.
Herein,
hierarchically
structured
phosphorus
vacancy‐enriched
nickel
phosphide
porous
nanoarrays
by
copper
doping,
denoted
as
CuNiP/CuO
x
‐V
P
,
are
constructed
via
facile
glycol‐mediated
solvothermal
approach.
The
yields
an
industry‐level
1
A
cm
−2
at
the
ultralow
potential
1.75
V,
while
showing
notable
FE
(96.94%)
(96.76%)
over
wide
range
potentials.
Impressively,
two‐electrode
electrolyzer
linked
H
2
evolution
possesses
exceptional
that
merely
requires
cell
voltage
1.45
V
40
mA
exhibiting
(97.53%)
for
production
surpassing
vast
majority
previously
reported
precious
metal
electrocatalysts.
Microscopic
electrochemical
characterizations
manifest
composed
NiP
nanosheets
attached
aggregated
CuO
particles
featuring
superaerophobic‐hydrophilic
morphology
enables
increased
active
sites,
favorable
electronic
redistribution,
thus
boosted
electrocatalytic
performance.
This
study
demonstrates
effective
electrode
discovery,
going
from
synthesis
structure‐activity
relationship
subsequently
developing
more
highly
electrocatalysts
energy‐saving
coproduction
valuable
chemicals.
Angewandte Chemie,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 8, 2025
Abstract
Electrocatalytic
glycerol
oxidation
reaction
(GOR)
to
produce
high‐value
formic
acid
(FA)
is
hindered
by
high
formation
potential
of
active
species
and
sluggish
C−C
bond
cleavage
kinetics.
Herein,
Ni
single‐atom
(Ni
SA
)
Co
(Co
dual
sites
anchored
on
nitrogen‐doped
carbon
nanotubes
embedded
with
0.1
0.9
alloy
@Ni
‐NCNTs)
are
constructed
for
electrochemical
GOR.
Remarkably,
it
can
reach
10
mA
cm
−2
at
a
low
1.15
V
versus
the
reversible
hydrogen
electrode
(vs.
RHE)
realize
formate
selectivity
93.27
%
even
conversion
98.81
1.45
vs.
RHE.
The
GOR
mechanism
pathway
systematically
elucidated
via
experimental
analyses
theoretical
calculations.
It
revealed
that
hydroxyl
(*OH)
be
produced
during
,
synergistically
optimizes
electronic
structure
sites,
reducing
energy
barriers
*OH‐mediated
bonds
dehydrogenation
C
1
intermediates.
This
decreases
number
intermediates
steps
GOR‐to‐FA,
thus
increasing
production
efficiency.
After
coupling
evolution
in
membrane
assembly
cell,
14.26
g
23.10
L
H
2
100
108
h.