Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(26)
Published: April 18, 2024
Abstract
Electrocatalytic
carbon
dioxide
reduction
reaction
(CO
2
RR)
to
produce
ethylene
(C
H
4
)
is
conducive
sustainable
development
of
energy
and
environment.
At
present,
most
electrocatalysts
for
C
production
are
limited
the
heavy
metal
copper,
meanwhile,
achieving
metal‐free
catalysis
remains
a
challenge.
Noted
piperazine
with
sp
3
N
hybridization
beneficial
CO
capture,
but
RR
performance
mechanism
have
been
lacking.
Herein,
based
on
linkage
engineering,
we
construct
novel
high‐density
catalytic
array
via
introducing
into
crystalline
microporous
aminal‐linked
covalent
organic
frameworks
(COFs).
Thanks
its
high
density,
strong
capture
capacity
great
hydrophilicity,
COF
successfully
achieves
conversion
Faraday
efficiency
up
19.1
%,
which
stand
out
in
all
reported
electrocatalysts.
In
addition,
series
imine‐linked
COFs
synthesized
combined
DFT
calculations
demonstrate
critical
role
enhancing
kinetics
RR.
Therefore,
this
work
reveals
extraordinary
potential
engineering
break
through
some
bottlenecks.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(21), P. 7870 - 7907
Published: Jan. 1, 2024
This
review
highlights
the
structure–activity
relationship
of
ECO
2
RR,
provides
a
detailed
summary
advanced
materials
by
analyzing
electrocatalytic
applications
and
reaction
mechanisms,
discusses
challenges
in
both
devices.
ACS Nano,
Journal Year:
2024,
Volume and Issue:
18(21), P. 13745 - 13754
Published: May 13, 2024
The
quest
for
sustainable
urea
production
has
directed
attention
toward
electrocatalytic
methods
that
bypass
the
energy-intensive
traditional
Haber–Bosch
process.
This
study
introduces
an
approach
to
synthesis
through
coreduction
of
CO2
and
NO3–
using
copper-doped
molybdenum
diselenide
(Cu–MoSe2)
with
Cu–Mo
dual
sites
as
electrocatalysts.
activity
Cu–MoSe2
electrode
is
characterized
by
a
yield
rate
1235
μg
h–1
mgcat.–1
at
−0.7
V
versus
reversible
hydrogen
maximum
Faradaic
efficiency
23.43%
−0.6
RHE.
Besides,
continuous
enhanced
average
9145
can
be
achieved
in
flow
cell.
These
figures
represent
substantial
advancement
over
baseline
MoSe2
electrode.
Density
functional
theory
(DFT)
calculations
elucidate
Cu
doping
accelerates
*NO2
deoxygenation
significantly
decreases
energy
barriers
C–N
bond
formation.
Consequently,
demonstrates
more
favorable
pathway
production,
enhancing
both
feasibility
offers
valuable
insights
into
design
understanding
facilitated
electrochemical
pathways.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(10), P. 7707 - 7716
Published: May 2, 2024
Nonthermal
plasma
(NTP)
offers
the
potential
for
converting
CH4
with
CO2
into
liquid
products
under
mild
conditions,
but
controlling
selectivity
and
manipulating
intermediate
species
remain
significant
challenges.
Here,
we
demonstrate
effectiveness
of
Cu/UiO-66-NH2
catalyst
in
promising
conversion
oxygenates
within
a
dielectric
barrier
discharge
NTP
reactor
ambient
conditions.
The
10%
achieved
an
impressive
53.4%
overall
selectivity,
C2+
accounting
∼60.8%
total
products.
In
situ
plasma-coupled
Fourier-transform
infrared
spectroscopy
(FTIR)
suggests
that
Cu
facilitates
cleavage
surface
adsorbed
COOH
(*COOH),
generating
*CO
enabling
its
migration
to
particles.
This
surface-bound
then
undergoes
C–C
coupling
hydrogenation,
leading
ethanol
production.
Further
analysis
using
CO
diffuse
reflection
FTIR
1H
nuclear
magnetic
resonance
indicates
generated
is
more
effective
than
gas-phase
(g)
promoting
formation.
work
provides
valuable
mechanistic
insights
production
during
plasma-catalytic
oxidation
These
findings
hold
broader
implications
rational
design
efficient
catalysts
this
reaction,
paving
way
advancements
sustainable
fuel
chemical
Advanced Functional Materials,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 8, 2024
Abstract
Electrocatalytic
nitrate
reduction
to
ammonia
(NO
3
RR)
in
a
neutral
medium
is
green
and
effective
strategy
for
treating
pollution
meanwhile
producing
ammonia.
However,
the
insufficient
active
hydrogen
(H
*
)
on
catalyst
surface
resulting
from
sluggish
Volmer
step
2
O
→
H
+
OH
−
),
competitive
evolution
reaction
(HER)
caused
by
coupling
severely
restrict
enhancement
of
NO
RR
activity.
Herein,
hydration‐effect
boosted
‐rich
facilitating
electrosynthesis
proposed.
The
introduction
hydration‐effect‐promoting
element
aluminum
into
copper‐based
forming
CuAlO
,
which
adjusts
electron
density
distribution
system,
significantly
promotes
generation
medium.
Moreover,
rapid
charge
transfer
at
CuO/CuAlO
interface
facilitates
kinetics
diffusion.
More
importantly,
Al
weakens
overly
strong
adsorption
intermediates
CuO,
thereby
accelerating
hydrogenation
process
suppressing
HER.
Thus,
under
conditions,
reached
Faradaic
efficiency
an
yield
as
high
97.81
±
1.94%
10.21
0.64
mg
h
−1
cm
−2
−1.0
V
versus
RHE
toward
RR.
Advanced Functional Materials,
Journal Year:
2023,
Volume and Issue:
34(12)
Published: Dec. 15, 2023
Abstract
Precisely
regulating
surface
reconstruction
of
copper
(Cu)
chalcogenides‐based
catalysts
to
promote
the
multicarbon
(C
2+
)selectivity
electrochemical
CO
2
reduction
reaction
(CO
RR)
is
hampered
by
challenging
control
intractable
anions
and
optimal
Cu
δ+
(0
<
δ
1).
Herein,
a
porous
carbon‐supported
selenides
electrocatalyst
that
can
remarkably
improve
C
‐product
yield
especially
unveil
time‐revolved
RR
process
enable
high
‐selectivity,
most
notably
for
ethanol
constructed.
The
Faradic
efficiency
(FE)
‐products
achieved
as
≈85.2%
with
partial
current
density
229.5
mA
cm
−2
.
Operando
infrared
spectroscopy
functional
theory
(DFT)
calculations
unravel
Se
vacancies
(
V
)
formation
brings
closer
neighboring
+
atoms
activates
sites,
thereby
rendering
efficient
generation
key
intermediates
*
CHO)
lowering
C–C
coupling
barrier
production.
appearance
metallic
shorten
next‐nearest
0
–Cu
distance
O
atom
bridge
in,
leading
preferential
OC
H
4
towards
instead
C–O
bond
cleavage
form
ethylene.
This
work
opens
avenue
designing
suitable
local
atomic
structures
engage
targeted
products.
