Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(40)
Опубликована: Авг. 15, 2023
Abstract
Heteroatom
doping
has
emerged
as
a
highly
effective
strategy
to
enhance
the
activity
of
metal‐based
electrocatalysts
toward
oxygen
evolution
reaction
(OER).
It
is
widely
accepted
that
does
not
switch
OER
mechanism
from
adsorbate
(AEM)
lattice‐oxygen‐mediated
(LOM),
and
enhanced
attributed
optimized
binding
energies
intermediates.
However,
this
seems
inconsistent
with
fact
overpotential
doped
(<300
mV)
considerably
smaller
than
limit
AEM
(>370
mV).
To
determine
origin
inconsistency,
we
select
phosphorus
(P)‐doped
nickel‐iron
mixed
oxides
model
observe
enhances
covalency
metal‐oxygen
bonds
drive
pathway
transition
LOM,
thereby
breaking
adsorption
linear
relation
between
*OH
*OOH
in
AEM.
Consequently,
obtained
P‐doped
display
small
237
mV
at
10
mA
cm
−2
.
Beyond
P,
similar
also
observed
on
sulfur
doping.
These
findings
offer
new
insights
into
substantially
originating
heteroatom
Valence
tuning
of
transition
metal
oxides
is
an
effective
approach
to
design
high-performance
catalysts,
particularly
for
the
oxygen
evolution
reaction
(OER)
that
underpins
solar/electric
water
splitting
and
metal-air
batteries.
Recently,
high-valence
(HVOs)
are
reported
show
superior
OER
performance,
in
association
with
fundamental
dynamics
charge
transfer
intermediates.
Particularly
considered
adsorbate
mechanism
(AEM)
lattice
oxygen-mediated
(LOM).
High-valence
states
enhance
performance
mainly
by
optimizing
e
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(40)
Опубликована: Авг. 15, 2023
Abstract
Heteroatom
doping
has
emerged
as
a
highly
effective
strategy
to
enhance
the
activity
of
metal‐based
electrocatalysts
toward
oxygen
evolution
reaction
(OER).
It
is
widely
accepted
that
does
not
switch
OER
mechanism
from
adsorbate
(AEM)
lattice‐oxygen‐mediated
(LOM),
and
enhanced
attributed
optimized
binding
energies
intermediates.
However,
this
seems
inconsistent
with
fact
overpotential
doped
(<300
mV)
considerably
smaller
than
limit
AEM
(>370
mV).
To
determine
origin
inconsistency,
we
select
phosphorus
(P)‐doped
nickel‐iron
mixed
oxides
model
observe
enhances
covalency
metal‐oxygen
bonds
drive
pathway
transition
LOM,
thereby
breaking
adsorption
linear
relation
between
*OH
*OOH
in
AEM.
Consequently,
obtained
P‐doped
display
small
237
mV
at
10
mA
cm
−2
.
Beyond
P,
similar
also
observed
on
sulfur
doping.
These
findings
offer
new
insights
into
substantially
originating
heteroatom
