Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(46)
Опубликована: Авг. 12, 2024
Abstract
Electrooxidation
of
biomass‐derived
glycerol
which
is
regarded
as
a
main
byproduct
industrial
biodiesel
production,
an
innovative
strategy
to
produce
value‐added
chemicals,
but
currently
showcases
slow
kinetics,
limited
Faraday
efficiency,
and
unclear
catalytic
mechanism.
Herein,
we
report
high‐efficiency
electrooxidation
into
formate
via
Cu
doped
NiCo
alloy
catalyst
supported
on
nickel
foam
(Cu−NiCo/NF)
in
coupled
system
paired
with
nitrate
reduction.
The
designed
Cu−NiCo/NF
delivers
only
1.23
V
vs
.
RHE
at
10
mA
cm
−2
,
record
efficiency
93.8
%.
superior
performance
ascribed
the
rapid
generation
Ni
III
−OOH
Co
species
favorable
coupling
surface
*O
reactive
intermediates.
Using
bifunctional
catalyst,
synchronously
produces
NH
3
formate,
showing
290
mV
lower
than
hydrogen
evolution
reaction,
together
excellent
long‐term
stability
for
up
144
h.
This
work
lays
out
new
guidelines
reliable
strategies
from
design
electrochemical
refinery.
Advanced Functional Materials,
Год журнала:
2024,
Номер
34(33)
Опубликована: Март 30, 2024
Abstract
Integration
of
more
thermodynamically
favorable
valorization
biomass
(e.g.,
glycerol),
compared
to
sluggish
oxygen
evolution,
with
H
2
production
is
great
significance
for
energy‐saving
electrosynthesis
value‐added
chemicals.
However,
its
widespread
deployment
has
been
challenged
by
costly
electrocatalysts
and
large
overpotential
reaching
an
industrial‐relevant
current
density
(≥400
mA
cm
−2
).
Herein,
carbon
shell‐encapsulated
manganese‐doped
cobalt
nitride
nanoarrays
immobilizing
on
nickel
foam,
denoted
Mn‐CoN@C/NF,
are
crafted
via
hydrothermal
method
ammoniation.
As
a
bifunctional
electrocatalyst,
the
Mn‐CoN@C/NF
manifests
extraordinary
activity
glycerol
oxidation
reaction
(GOR)
ultralow
potential
1.37
V
(versus
RHE)
at
400
,
in
conjunction
evolution
(HER)
low
31
mV
10
.
A
record
high
Faradaic
efficiency
(97.7%)
formate
GOR
delivered
1.35
(vs
RHE).
Impressively,
two‐electrode
electrolyzer
capitalizing
as
catalysts
reaches
800
1.83
V,
delivering
electricity‐saving
15.0%
pure
water
splitting.
DFT
calculations
substantiate
that
Mn
species
within
Mn‐CoN
not
only
optimize
hydrogen
adsorption
kinetics
HER,
but
also
elevate
Co
3+
active
sites’
GOR.
This
work
offers
efficient
avenue
coproduction
valuable
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(14)
Опубликована: Фев. 15, 2024
As
a
sustainable
valorization
route,
electrochemical
glycerol
oxidation
reaction
(GOR)
involves
in
formation
of
key
OH*
and
selective
adsorption/cleavage
C-C(O)
intermediates
with
multi-step
electron
transfer,
thus
suffering
from
high
potential
poor
formate
selectivity
for
most
non-noble-metal-based
electrocatalysts.
So,
it
remains
challenging
to
understand
the
structure-property
relationship
as
well
construct
synergistic
sites
realize
high-activity
high-selectivity
GOR.
Herein,
we
successfully
achieve
dual-high
performance
low
potentials
superior
GOR
by
forming
Lewis
Brønsted
acid
Ni-alloyed
Co-based
spinel.
The
optimized
NiCo
oxide
solid-acid
electrocatalyst
exhibits
(1.219
V@10
mA/cm
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 8, 2024
The
local
acidity
at
the
anode
surface
during
electrolysis
is
apparently
stronger
than
that
in
bulk
electrolyte
due
to
deprotonation
from
reactant,
which
leads
deteriorated
electrocatalytic
performances
and
product
distributions.
Here,
an
anode-electrolyte
interfacial
regulation
strategy
has
been
proposed
inhibit
acidification
of
enhance
activity
selectivity
anodic
reactions.
As
a
proof
concept,
CeO
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(46)
Опубликована: Авг. 12, 2024
Abstract
Electrooxidation
of
biomass‐derived
glycerol
which
is
regarded
as
a
main
byproduct
industrial
biodiesel
production,
an
innovative
strategy
to
produce
value‐added
chemicals,
but
currently
showcases
slow
kinetics,
limited
Faraday
efficiency,
and
unclear
catalytic
mechanism.
Herein,
we
report
high‐efficiency
electrooxidation
into
formate
via
Cu
doped
NiCo
alloy
catalyst
supported
on
nickel
foam
(Cu−NiCo/NF)
in
coupled
system
paired
with
nitrate
reduction.
The
designed
Cu−NiCo/NF
delivers
only
1.23
V
vs
.
RHE
at
10
mA
cm
−2
,
record
efficiency
93.8
%.
superior
performance
ascribed
the
rapid
generation
Ni
III
−OOH
Co
species
favorable
coupling
surface
*O
reactive
intermediates.
Using
bifunctional
catalyst,
synchronously
produces
NH
3
formate,
showing
290
mV
lower
than
hydrogen
evolution
reaction,
together
excellent
long‐term
stability
for
up
144
h.
This
work
lays
out
new
guidelines
reliable
strategies
from
design
electrochemical
refinery.
