The Journal of Chemical Physics,
Год журнала:
2024,
Номер
161(17)
Опубликована: Ноя. 1, 2024
The
CO
reduction
reaction
(CORR)
for
the
production
of
high-value-added
multi-carbon
(C2+)
products
is
currently
being
actively
investigated,
where
searching
high-efficiency
catalysts
with
moderate
intermediate
binding
strength
and
low
kinetic
barrier
C–C
coupling
poses
a
significant
challenge.
In
this
study,
we
employed
density
functional
theory
computations
to
design
four
synergistic
dual
sites
CORR
C2
products,
namely,
TM-P@melon,
by
co-doping
transition
metals
(TM
=
Mn,
Fe,
Co,
Ni)
phosphorus
(P)
into
polymeric
carbon
nitride
(i.e.,
melon-CN).
Mn–P@melon
Ni–P@melon
exhibit
higher
selectivity
toward
C2H5OH
C2H6,
respectively,
limiting
potentials
(C–C
energy
barriers)
−0.43
V
(0.52
eV)
−0.17
(0.26
eV),
respectively.
introduction
TM
P
atoms
not
only
narrows
band
gap
melon-CN
but
also
favors
*CHO,
providing
an
active
site
coupling,
thus
facilitating
catalytic
reaction.
Our
work
provides
rational
insights
stable,
low-cost,
efficient
that
facilitate
sustainable
high-value
chemicals
fuels.
The
electrochemical
CO2
reduction
reaction
(CO2RR)
to
produce
multicarbon
(C2+)
hydrocarbons
or
oxygenate
compounds
is
a
promising
route
obtain
renewable
fuel
valuable
chemicals;
however,
producing
C2+
at
high
current
densities
still
challenge.
Herein,
we
design
hierarchically
structured
tandem
catalysis
electrode
for
greatly
improved
catalytic
activity
and
selectivity
products.
constructed
of
sputtered
Ag
nanoparticle
layer
on
hydrophobic
polytetrafluoroethylene
(PTFE)
membrane
nitrogen-doped
carbon
(NC)-modified
Cu
nanowire
arrays.
arrays
are
in
situ
grown
PTFE
by
oxidation
CuAl
alloy,
which
the
chemical
etching
metal
Al
induces
formation
array
structure.
Within
hierarchical
configuration,
CO
can
be
efficiently
generated
an
active
then
spillover
transfer
NC-modified
layer,
Cu/NC
interfaces
enhance
*CO
trapping
adsorption.
During
CO2RR,
optimized
achieves
superior
Faradaic
efficiencies
53.5%
87.5%
ethylene
(C2H4)
products
density
519.0
mA
cm–2,
respectively,
with
C2+/C1
ratio
10.42
long-term
stability
up
50
h.
In
Raman
attenuated
total
reflection-surface
enhanced
infrared
absorption
spectroscopy
(ATR-SEIRAS)
confirm
that
Ag–Cu–NC
system
significantly
enhances
linear
adsorption
intermediates
dissociation
H2O,
improves
C–C
coupling
capability,
stabilizes
key
intermediate
*OCCOH
Catalysts,
Год журнала:
2025,
Номер
15(3), С. 199 - 199
Опубликована: Фев. 20, 2025
The
electroreduction
of
CO2
(CO2RR)
is
a
promising
and
environmentally
sustainable
approach
to
closing
the
carbon
cycle.
However,
achieving
high
activity
selectivity
for
multicarbon
(C2₊)
products
remains
significant
challenge
due
complexity
reaction
pathways.
In
this
study,
porous
carbon-supported
copper
catalysts
(CuHCS)
with
pore
sizes
120
nm
(CuHCS120)
500
(CuHCS500)
were
synthesized
tailor
microenvironment
at
electrode–electrolyte
interface
enhance
product
selectivity.
CuHCS120
achieved
maximum
faradaic
efficiency
(FE)
C2₊
46%,
double
that
CuHCS500
(23%).
contrast,
showed
higher
FE
CO
(36%)
compared
(14%)
same
potential.
In-depth
ex
situ
in
investigations
revealed
smaller
pores
promote
enrichment
adsorption
*CO
intermediates,
thereby
enhancing
C–C
coupling
formation
products.
These
findings
underscore
critical
role
structural
confinement
modulating
catalytic
provide
valuable
insights
rational
design
advanced
CO2RR.
Advanced Functional Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 1, 2025
Abstract
The
synergistic
effects
in
electrocatalysis
can
significantly
enhance
catalyst
performance
by
improving
catalytic
activity,
selectivity,
and
stability,
optimizing
reaction
mechanisms
electron
transfer
processes.
This
review
summarizes
recent
advancements
the
of
electrochemical
reduction
CO
2
(eCO
RR)
to
multi‐carbon
(C
2+
)
products.
Starting
with
fundamental
principles
eCO
RR
for
C
product
formation,
paper
outlines
producing
,
3
4
5
A
comprehensive
discussion
is
provided
on
critical
impact
structure–performance
relationship
production
Subsequently,
observed
are
classified
various
electrocatalysts
different
properties,
including
single/dual‐atom
catalysts,
multi‐centric
single‐atom
alloys,
metal‐organic
frameworks,
heterojunction
catalysts.
Finally,
challenges
achieving
selective
formation
through
discussed,
along
corresponding
strategies
overcome
obstacles.
Abstract
Electroreduction
of
carbon
dioxide
(CO
2
)
is
a
key
strategy
for
achieving
net‐zero
emissions.
Copper
(Cu)‐based
electrocatalysts
have
shown
promise
CO
conversion
into
valuable
chemicals
but
are
hindered
by
limited
C
2+
product
selectivity
due
to
competing
hydrogen
evolution
and
ineffective
dimerization
adsorbed
intermediate
(
*
CO).
Here,
functional‐group‐directed
reported
enhance
using
single‐walled
nanotubes
(SWCNTs)
as
supports.
The
catalytic
performance
Cu
nanoparticles
strongly
influenced
the
type
density
functional
groups
on
SWCNTs.
Optimized
Cu/amine‐functionalized
SWCNTs
achieved
Faradaic
efficiency
66.2%
partial
current
−270
mA
cm
−2
products
within
flow
cell,
outperforming
Cu/SWCNTs
Cu/cyano‐functionalized
Density
theory
calculations
revealed
that
electron‐donating
amine
can
facilitate
electron
transfer
from
graphite
sheet
atoms,
thereby
shifting
d‐band
center
upward.
This
shift
enhances
its
hydrogenation
derivative
adsorption
promotes
water
splitting,
leading
an
increased
tendency
generation
products.
In
situ
infrared
Raman
spectroscopy
confirm
enhancement
CHO
coverage,
facilitating
C─C
coupling.
work
provides
molecular
framework
exploring
interactions
between
active
metals
in
electrolysis,
offering
insights
designing
catalysts
broad
range
electrocatalytic
processes.
Chemical Communications,
Год журнала:
2024,
Номер
60(77), С. 10618 - 10628
Опубликована: Янв. 1, 2024
Explores
C–C
coupling
in
CO
2
reduction,
focusing
on
atomic/electronic
structure
modulation,
electron
transfer,
adsorption,
and
carbon
chain
growth.
Optimizing
catalysts
enhances
for
multi-carbon
products.
