ACS Applied Nano Materials,
Год журнала:
2024,
Номер
7(4), С. 4220 - 4227
Опубликована: Фев. 14, 2024
Creating
high-performance
single-atom
catalysts
for
the
electrochemical
nitrogen
reduction
reaction
(NRR)
is
a
crucial
approach.
Two-dimensional
metal–organic
frameworks
(MOFs)
have
captured
significant
attention
as
NRR
due
to
their
lightweight
and
large
pores.
Using
density
functional
theory
(DFT)
calculations,
we
explored
series
of
TM3C18N6X12
(X
=
S
or
NH,
TM
Mo,
Cr,
W,
Fe,
Mn,
Os,
Ni,
Ir,
Pd,
Pt,
Rh)
two-dimensional
potential
through
three-step
screening
strategy.
The
influence
coordinating
atoms
around
transition
metal
also
examined,
specifically,
TMS4
TMS2(NH)2.
Our
findings
indicate
that
Os3C18S12N6
MOF
exhibits
best
activity
selectivity,
with
an
overpotential
only
0.28
V
along
distal
pathway,
which
lower
than
most
reported
materials.
adsorption
activation
N2
are
influenced
by
σ-acceptance-π*
donation
mechanism.
Additionally,
established
descriptors
related
valence
electron
(ΔQTMXTM)
magnetic
moment
(μTM–μX)
explore
relationship
between
catalytic
descriptors.
This
work
can
offer
valuable
insights
designing
promising
electrocatalysts
based
on
MOFs.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(13)
Опубликована: Фев. 3, 2023
We
demonstrate
the
great
feasibility
of
MBenes
as
a
new
class
tandem
catalysts
for
electrocatalytic
nitrate
reduction
to
ammonia
(NO3
RR).
As
proof
concept,
FeB2
is
first
employed
model
MBene
catalyst
NO3
RR,
showing
maximum
NH3
-Faradaic
efficiency
96.8
%
with
corresponding
yield
25.5
mg
h-1
cm-2
at
-0.6
V
vs.
RHE.
Mechanistic
studies
reveal
that
exceptional
RR
activity
arises
from
catalysis
mechanism,
is,
B
sites
activate
NO3-
form
intermediates,
while
Fe
dissociate
H2
O
and
increase
*H
supply
on
promote
intermediate
hydrogenation
enhance
-to-NH3
conversion.
ACS Energy Letters,
Год журнала:
2023,
Номер
8(3), С. 1281 - 1288
Опубликована: Фев. 3, 2023
Electrocatalytic
NO
reduction
to
NH3
(NORR)
offers
a
prospective
approach
attain
both
harmful
removal
and
efficient
electrosynthesis.
Main-group
p-block
metals
are
promising
NORR
candidates
but
still
lack
adequate
exploration.
Herein,
Sb
single
atoms
confined
in
amorphous
MoO3
(Sb1/a-MoO3)
designed
as
an
catalyst,
exhibiting
the
highest
yield
rate
of
273.5
μmol
h–1
cm–2
NO-to-NH3
Faradaic
efficiency
91.7%
at
−0.6
V
vs
RHE.
In
situ
spectroscopic
characterizations
theoretical
computations
reason
that
outstanding
performance
Sb1/a-MoO3
arises
from
isolated
Sb1
sites,
which
can
optimize
adsorption
*NO/*NHO
lower
reaction
energy
barriers
simultaneously
exhibit
higher
affinity
than
H2O/H
species.
Moreover,
our
strategy
be
extended
prepare
Bi1/a-MoO3,
showing
high
property,
demonstrating
immense
potential
metal
single-atom
catalysts
toward
high-performing
electrocatalysis.
Nano Letters,
Год журнала:
2023,
Номер
23(5), С. 1735 - 1742
Опубликована: Фев. 14, 2023
We
design
single-atom
W
confined
in
MoO3-x
amorphous
nanosheets
(W1/MoO3-x)
comprising
W1-O5
motifs
as
a
highly
active
and
durable
NORR
catalyst.
Theoretical
operando
spectroscopic
investigations
reveal
the
dual
functions
of
to
(1)
facilitate
activation
protonation
NO
molecules
(2)
promote
H2O
dissociation
while
suppressing
*H
dimerization
increase
proton
supply,
eventually
resulting
self-tandem
mechanism
W1/MoO3-x
greatly
accelerate
energetics
NO-to-NH3
pathway.
As
result,
exhibits
highest
NH3-Faradaic
efficiency
91.2%
NH3
yield
rate
308.6
μmol
h-1
cm-2,
surpassing
that
most
previously
reported
catalysts.
Angewandte Chemie,
Год журнала:
2023,
Номер
135(13)
Опубликована: Фев. 3, 2023
Abstract
We
demonstrate
the
great
feasibility
of
MBenes
as
a
new
class
tandem
catalysts
for
electrocatalytic
nitrate
reduction
to
ammonia
(NO
3
RR).
As
proof
concept,
FeB
2
is
first
employed
model
MBene
catalyst
NO
RR,
showing
maximum
NH
‐Faradaic
efficiency
96.8
%
with
corresponding
yield
25.5
mg
h
−1
cm
−2
at
−0.6
V
vs.
RHE.
Mechanistic
studies
reveal
that
exceptional
RR
activity
arises
from
catalysis
mechanism,
is,
B
sites
activate
−
form
intermediates,
while
Fe
dissociate
H
O
and
increase
*H
supply
on
promote
intermediate
hydrogenation
enhance
‐to‐NH
conversion.
Journal of Materials Chemistry A,
Год журнала:
2023,
Номер
11(13), С. 6814 - 6819
Опубликована: Янв. 1, 2023
In
single
atoms
confined
in
amorphous
MoO
3
(In
1
/a-MoO
)
are
reported
to
be
an
efficient
catalyst
for
NO
electroreduction
NH
,
attributed
the
ability
of
single-site
inhibit
hydrogen
evolution
and
optimize
NO-to-NH
hydrogenation
energetics.
Nanoscale,
Год журнала:
2023,
Номер
15(39), С. 16056 - 16067
Опубликована: Янв. 1, 2023
Tailoring
the
coordination
environment
is
an
effective
strategy
to
modulate
electronic
structure
and
catalytic
activity
of
atomically
dispersed
transition-metal
(TM)
catalysts,
which
has
been
widely
investigated
for
single-atom
catalysts
but
received
less
attention
emerging
double-atom
(DACs).
Herein,
based
on
first-principles
calculations,
taking
commonly
studied
N-coordinated
graphene-based
DACs
as
references,
we
explored
effect
engineering
behaviors
towards
electrocatalytic
nitrogen
reduction
reaction
(NRR),
realized
through
replacing
one
N
atom
by
B
or
O
form
B,
O,
co-coordinated
DACs.
We
found
that
co-coordination
could
significantly
strengthen
N2
adsorption
alter
pattern
TM
dimer
active
center,
greatly
facilitates
activation.
Moreover,
DACs,
linear
scaling
relationship
between
binding
strengths
key
intermediates
can
be
attenuated.
Consequently,
Mn2
exhibiting
ultralow
limiting
potential
-0.27
V,
climb
peak
volcano.
In
addition,
experimental
feasibility
this
DAC
system
was
also
identified.
Overall,
benefiting
from
effect,
chemical
performance
NRR
boosted.
This
phenomena
understood
adjusted
center
due
changes
its
microenvironment,
affects
strength
(pattern)
pathways,
leading
enhanced
selectivity.
work
highlights
importance
in
developing
other
important
reactions.
ACS Sustainable Chemistry & Engineering,
Год журнала:
2024,
Номер
12(7), С. 2783 - 2789
Опубликована: Фев. 2, 2024
Electrochemical
nitrite-to-ammonia
reduction
(NO2RR)
holds
great
promise
for
converting
harmful
NO2–
into
valuable
NH3.
Herein,
we
develop
Co
single
atoms
dispersed
on
a
C3N4
substrate
(Co1/C3N4)
as
an
efficient
catalyst
toward
the
NO2RR.
Experimental
and
theoretical
investigations
reveal
that
single-atom
sites
can
effectively
active
optimize
formation
energy
of
key
*NOH
intermediate
to
promote
→
NH3
energetics.
Remarkably,
Co1/C3N4
equipped
in
flow
cell
delivers
exceptional
NH3–Faradaic
efficiency
97.9%
yield
rate
1080.3
μmol
h–1cm–2
at
industrial-level
current
density
355
mA
cm–2,
along
with
long-term
durability
100
h
electrolysis,
showing
considerable
potential
practical
electrosynthesis.
Abstract
The
efficiency
of
photocatalytic
hydrogen
evolution
is
currently
limited
by
poor
light
adsorption,
rapid
recombination
photogenerated
carriers,
and
ineffective
surface
reaction
rate.
Although
heterojunctions
with
innovative
morphologies
structures
can
strengthen
built‐in
electric
fields
maximize
the
separation
charges.
However,
how
to
rational
design
novel
multidimensional
simultaneously
improve
above
three
bottleneck
problems
still
a
research
imperative.
Herein,
unique
Cu
2
O─S@graphene
oxide
(GO)@Zn
0.67
Cd
0.33
S
Three
dimensional
(3D)
hollow
heterostructure
designed
synthesized,
which
greatly
extends
carrier
lifetime
effectively
promotes
H
production
rate
reached
48.5
mmol
g
−1
h
under
visible
after
loading
Ni
2+
on
heterojunction
surface,
97
times
higher
than
that
pure
Zn
nanospheres.
Furthermore,
reach
77.3
without
cooling,
verifying
effectiveness
photothermal
effect.
Meanwhile,
in
situ
characterization
density
flooding
theory
calculations
reveal
efficient
charge
transfer
at
p‐n
3D
interface.
This
study
not
only
reveals
detailed
mechanism
depth
but
also
rationalizes
construction
superior
heterojunctions,
thus
providing
universal
strategy
for
materials‐by‐design
high‐performance
heterojunctions.