Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(3)
Опубликована: Дек. 7, 2023
Abstract
Electrocatalytic
C−N
coupling
process
is
indeed
a
sustainable
alternative
for
direct
urea
synthesis
and
co‐upgrading
of
carbon
dioxide
nitrate
wastes.
However,
the
main
challenge
lies
in
unactivated
process.
Here,
we
proposed
strategy
intermediate
assembly
with
alkali
metal
cations
to
activate
at
electrode/electrolyte
interface.
Urea
activity
follows
trend
Li
+
<Na
<Cs
<K
.
In
presence
K
,
world‐record
performance
was
achieved
yield
rate
212.8±10.6
mmol
h
−1
g
on
single‐atom
Co
supported
TiO
2
catalyst
−0.80
V
versus
reversible
hydrogen
electrode.
Theoretical
calculations
operando
synchrotron‐radiation
Fourier
transform
infrared
measurements
revealed
that
energy
barriers
were
significantly
decreased
via
mediated
assembly.
By
applying
this
various
catalysts,
demonstrate
interface
universal
approach
boost
synthesis.
ACS Nano,
Год журнала:
2023,
Номер
17(4), С. 3209 - 3224
Опубликована: Фев. 14, 2023
The
electrochemical
coreduction
of
carbon
dioxide
(CO2)
and
nitrogenous
species
(such
as
NO3–,
NO2–,
N2,
NO)
for
urea
synthesis
under
ambient
conditions
provides
a
promising
solution
to
realize
carbon/nitrogen
neutrality
mitigate
environmental
pollution.
Although
an
increasing
number
studies
have
made
some
breakthroughs
in
synthesis,
the
unsatisfactory
Faradaic
efficiency,
low
yield
rate,
ambiguous
C–N
coupling
reaction
mechanisms
remain
major
obstacles
its
large-scale
applications.
In
this
review,
we
present
recent
progress
on
based
CO2
aqueous
solutions
conditions,
providing
useful
guidance
discussion
rational
design
metal
nanocatalyst,
understanding
mechanism,
existing
challenges
prospects
synthesis.
We
hope
that
review
can
stimulate
more
insights
inspiration
toward
development
electrocatalytic
technology.
Advanced Materials,
Год журнала:
2024,
Номер
36(30)
Опубликована: Июнь 14, 2024
Abstract
Urea
electrosynthesis
from
co–electrolysis
of
NO
3
−
and
CO
2
(UENC)
offers
a
promising
technology
for
achieving
sustainable
efficient
urea
production.
Herein,
diatomic
alloy
catalyst
(CuPd
1
Rh
–DAA),
with
mutually
isolated
Pd
atoms
alloyed
on
Cu
substrate,
is
theoretically
designed
experimentally
confirmed
to
be
highly
active
selective
UENC
catalyst.
Combining
theoretical
computations
operando
spectroscopic
characterizations
reveals
the
synergistic
effect
–Cu
sites
promote
via
tandem
catalysis
mechanism,
where
site
triggers
early
C–N
coupling
promotes
*CO
–to–*CO
NH
steps,
while
facilitates
subsequent
protonation
step
*COOHNH
toward
formation.
Impressively,
CuPd
–DAA
assembled
in
flow
cell
presents
highest
Faradaic
efficiency
72.1%
yield
rate
53.2
mmol
h
−1
g
cat
at
−0.5
V
versus
RHE,
representing
nearly
performance
among
all
reported
catalysts.
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Ноя. 1, 2023
Chemical
C-N
coupling
from
CO2
and
NO3-,
driven
by
renewable
electricity,
toward
urea
synthesis
is
an
appealing
alternative
for
Bosch-Meiser
production.
However,
the
unmatched
kinetics
in
NO3-
reduction
reactions
complexity
of
C-
N-species
involved
co-reduction
render
challenge
coupling,
leading
to
low
yield
rate
Faradaic
efficiency.
Here,
we
report
a
single-atom
copper-alloyed
Pd
catalyst
(Pd4Cu1)
that
can
achieve
highly
efficient
electrosynthesis.
The
regulated
matched
steering
Cu
doping
level
Pd4Cu1/FeNi(OH)2
interface.
Charge-polarized
Pdδ--Cuδ+
dual-sites
stabilize
key
*CO
*NH2
intermediates
promote
coupling.
synthesized
Pd4Cu1-FeNi(OH)2
composite
achieves
436.9
mmol
gcat.-1
h-1
efficiency
66.4%,
as
well
long
cycling
stability
1000
h.
In-situ
spectroscopic
results
theoretical
calculation
reveal
atomically
dispersed
lattice
promotes
deep
*NH2,
Pd-Cu
lower
energy
barrier
pivotal
between
*CO.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(10), С. 5149 - 5189
Опубликована: Янв. 1, 2024
This
review
summarizes
promising
strategies
including
the
design
of
catalysts
and
construction
coupled
electrocatalytic
reaction
systems,
aimed
at
achieving
selective
production
various
products
from
CO
2
electroreduction.
Advanced Materials,
Год журнала:
2024,
Номер
36(25)
Опубликована: Апрель 2, 2024
Abstract
Renewable
electricity‐powered
nitrate/carbon
dioxide
co‐reduction
reaction
toward
urea
production
paves
an
attractive
alternative
to
industrial
processes
and
offers
a
clean
on‐site
approach
closing
the
global
nitrogen
cycle.
However,
its
large‐scale
implantation
is
severely
impeded
by
challenging
C–N
coupling
requires
electrocatalysts
with
high
activity/selectivity.
Here,
cobalt‐nanoparticles
anchored
on
carbon
nanosheet
(Co
NPs@C)
are
proposed
as
catalyst
electrode
boost
yield
Faradaic
efficiency
(FE)
electrosynthesis
enhanced
coupling.
Such
Co
NPs@C
renders
superb
urea‐producing
activity
FE
reaching
54.3%
of
2217.5
µg
h
−1
mg
cat.
,
much
superior
NPs
C
counterparts,
meanwhile
shows
strong
stability.
The
affords
rich
catalytically
active
sites,
fast
reactant
diffusion,
sufficient
catalytic
surfaces‐electrolyte
contacts
favored
charge
ion
transfer
efficiencies.
theoretical
calculations
reveal
that
high‐rate
formation
*CO
*NH
2
intermediates
crucial
for
facilitating
synthesis.
Abstract
The
electrocatalytic
synthesis
of
C–N
coupling
compounds
from
CO
2
and
nitrogenous
species
not
only
offers
an
effective
avenue
to
achieve
carbon
neutrality
reduce
environmental
pollution,
but
also
establishes
a
route
synthesize
valuable
chemicals,
such
as
urea,
amide,
amine.
This
innovative
approach
expands
the
application
range
product
categories
beyond
simple
carbonaceous
in
reduction,
which
is
becoming
rapidly
advancing
field.
review
summarizes
research
progress
urea
synthesis,
using
N
,
NO
−
3
species,
explores
emerging
trends
electrosynthesis
amide
amine
nitrogen
species.
Additionally,
future
opportunities
this
field
are
highlighted,
including
amino
acids
other
containing
bonds,
anodic
reactions
water
oxidation,
catalytic
mechanism
corresponding
reactions.
critical
captures
insights
aimed
at
accelerating
development
electrochemical
reactions,
confirming
superiority
method
over
traditional
techniques.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Фев. 6, 2024
Abstract
Electrochemical
synthesis
is
a
promising
way
for
sustainable
urea
production,
yet
the
exact
mechanism
has
not
been
fully
revealed.
Herein,
we
explore
of
electrochemical
coupling
nitrite
and
carbon
dioxide
on
Cu
surfaces
towards
basis
constant-potential
method
combined
with
an
implicit
solvent
model.
The
working
electrode
potential,
which
normally
overlooked,
found
influential
both
reaction
activity.
further
computational
study
pathways
reveals
that
*CO-NH
*NH-CO-NH
as
key
intermediates.
In
addition,
through
analysis
turnover
frequencies
under
various
potentials,
pressures,
temperatures
within
microkinetic
model,
demonstrate
activity
increases
temperature,
Cu(100)
shows
highest
efficiency
among
all
three
surfaces.
electric
double-layer
capacitance
also
plays
role
in
synthesis.
Based
these
findings,
propose
two
essential
strategies
to
promote
electrodes:
increasing
surface
ratio
elevating
temperature.
