iScience,
Год журнала:
2023,
Номер
26(7), С. 107100 - 107100
Опубликована: Июнь 16, 2023
Electrochemical
reduction
of
nitrite
(NO2-)
can
satisfy
the
necessity
for
NO2-
contaminant
removal
and
deliver
a
sustainable
pathway
ammonia
(NH3)
generation.
Its
practical
application
yet
requires
highly
efficient
electrocatalysts
to
boost
NH3
yield
Faradaic
efficiency
(FE).
In
this
study,
CoP
nanoparticle-decorated
TiO2
nanoribbon
array
on
Ti
plate
(CoP@TiO2/TP)
is
verified
as
high-efficiency
electrocatalyst
selective
NH3.
When
measured
in
0.1
M
NaOH
with
NO2-,
freestanding
CoP@TiO2/TP
electrode
delivers
large
849.57
μmol
h-1
cm-2
high
FE
97.01%
good
stability.
Remarkably,
subsequently
fabricated
Zn-NO2-
battery
achieves
power
density
1.24
mW
while
delivering
714.40
μg
cm-2.
ACS Catalysis,
Год журнала:
2022,
Номер
12(4), С. 2505 - 2512
Опубликована: Фев. 3, 2022
Electrochemical
N2
reduction
(NRR)
to
ammonia
is
seriously
limited
by
the
competing
hydrogen
evolution
reaction
(HER),
but
atomic-scale
factors
controlling
HER/NRR
competition
are
unknown.
Herein
we
unveil
mechanism,
thermodynamics,
and
kinetics
determining
efficiency
on
state-of-the-art
NRR
electrocatalyst,
Ru-N4,
using
grand
canonical
ensemble
density
functional
theory
(GCE-DFT).
We
show
that
NRR/HER
intermediates
coadsorb
catalyst
where
suppress
HER
selectivity
determined
initial
step
forming
*NNH
or
*H.
Our
results
provide
crucial
insight
into
complex
competition,
necessity
of
GCE-DFT
calculations,
suggest
ways
improve
selectivity.
Advanced Materials,
Год журнала:
2023,
Номер
36(1)
Опубликована: Апрель 20, 2023
This
topical
review
focuses
on
the
distinct
role
of
carbon
support
coordination
environment
single-atom
catalysts
(SACs)
for
electrocatalysis.
The
article
begins
with
an
overview
atomic
configurations
in
SACs,
including
a
discussion
advanced
characterization
techniques
and
simulation
used
understanding
active
sites.
A
summary
key
electrocatalysis
applications
is
then
provided.
These
processes
are
oxygen
reduction
reaction
(ORR),
evolution
(OER),
hydrogen
(HER),
nitrogen
(NRR),
dioxide
(CO
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(23), С. 10193 - 10200
Опубликована: Май 19, 2022
Integrated/cascade
plasma-enabled
N2
oxidation
and
electrocatalytic
NOx–
(where
x
=
2,
3)
reduction
reaction
(pNOR-eNOx–RR)
holds
great
promise
for
the
renewable
synthesis
of
ammonia
(NH3).
However,
corresponding
activated
effects
process
plasma
toward
O2
molecules
mechanism
eNOx–RR
to
NH3
are
unclear
need
be
further
uncovered,
which
largely
limits
large-scale
deployment
this
integration
technology.
Herein,
we
systematically
investigate
activation
recombination
processes
molecules,
more
meaningfully,
at
a
microscopic
level
is
also
decoupled
using
copper
(Cu)
nanoparticles
as
representative
electrocatalyst.
The
concentration
produced
NOx
in
pNOR
system
confirmed
function
length
spark
discharge
well
volumetric
ratio
feeding
gas.
successive
protonation
key
N-containing
intermediates
(e.g.,
−NH2)
detected
with
situ
infrared
spectroscopy.
Besides,
Raman
spectroscopy
reveals
dynamic
reconstruction
Cu
during
process.
nanoparticle-driven
pNOR-eNOx–RR
can
finally
achieve
high
yield
rate
∼40
nmol
s–1
cm–2
Faradaic
efficiency
nearly
90%,
overperforming
benchmarks
reported
literature.
It
anticipated
that
work
will
stimulate
practical
development
green
electrosynthesis
directly
from
air
water
under
ambient
conditions.
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Июль 28, 2023
Electrocatalytic
reduction
of
waste
nitrates
(NO3-)
enables
the
synthesis
ammonia
(NH3)
in
a
carbon
neutral
and
decentralized
manner.
Atomically
dispersed
metal-nitrogen-carbon
(M-N-C)
catalysts
demonstrate
high
catalytic
activity
uniquely
favor
mono-nitrogen
products.
However,
reaction
fundamentals
remain
largely
underexplored.
Herein,
we
report
set
14;
3d-,
4d-,
5d-
f-block
M-N-C
catalysts.
The
selectivity
NO3-
to
NH3
media,
with
specific
focus
on
deciphering
role
NO2-
intermediate
cascade,
reveals
strong
correlations
(R=0.9)
between
for
NH3.
Moreover,
theoretical
computations
reveal
associative/dissociative
adsorption
pathways
evolution,
over
normal
M-N4
sites
their
oxo-form
(O-M-N4)
oxyphilic
metals.
This
work
provides
platform
designing
multi-element
NO3RR
cascades
single-atom
or
hybridization
extended
surfaces.
Journal of Materials Chemistry A,
Год журнала:
2021,
Номер
10(4), С. 1742 - 1749
Опубликована: Дек. 24, 2021
Amorphous
VSe
2−
x
nanosheets
with
abundant
Se-vacancies
(V
Se
)
showed
dramatically
enhanced
NRR
activity
and
selectivity,
attributed
to
the
amorphization-triggered
that
promote
impeding
H
2
evolution.
ACS Catalysis,
Год журнала:
2022,
Номер
12(11), С. 6651 - 6662
Опубликована: Май 20, 2022
Aimed
toward
the
pursuit
of
manufacturing
ammonia
in
a
carbon-neutral
and
decentralized
manner,
electrocatalytic
nitrate
reduction
reaction
(NO3RR)
not
only
promises
an
effective
route
for
synthesis
but
also
offers
potential
advantages
to
wastewater
remediation.
Here,
we
describe
efficacy
bioinspired,
atomically
dispersed
catalysts
NO3RR
aqueous
media
via
catalytic
cascade.
Compared
nanoparticles
with
extended
surfaces,
are
largely
underexplored
this
field,
despite
their
intrinsic
selectivity
mono-nitrogen
species
over
dinitrogen
counterparts.
Herein,
specifically
report
on
series
nitrogen-coordinated
mono-
bimetallic,
dispersed,
iron-
molybdenum-based
electrocatalysts
NO3RR.
The
key
role
*NO2/NO2–
intermediates
was
identified
both
computationally
experimentally,
wherein
Fe–N4
sites
Mo–N4/*O–Mo–N4
carried
distinct
associative
dissociative
adsorption
NO3–
molecules,
respectively.
By
integrating
individual
Fe
Mo
single
bimetallic
catalyst,
unique
pathways
were
synergized,
achieving
Faradaic
efficiency
94%
ammonia.
Furthermore,
robustness
FeMo–N–C
catalyst
highlighted
by
five
consecutive
12
h
electrolysis
cycles
being
maintained
above
90%
entire
60
h.
utilization
cascades,
synergizing
heterogeneous
single-atom
sites,
is
unconstrained
linear
scaling
relations
sheds
light
designing
highly
selective,
efficient,
durable
synthesis.