Angewandte Chemie,
Год журнала:
2024,
Номер
136(32)
Опубликована: Июнь 3, 2024
Abstract
Directly
coupling
N
2
and
CO
to
synthesize
urea
by
photocatalysis
paves
a
sustainable
route
for
synthesis,
but
its
performance
is
limited
the
competition
of
photogenerated
electrons
between
,
as
well
underutilized
holes.
Herein,
we
report
an
efficient
synthesis
process
involving
holes
in
respectively
converting
over
redox
heterojunction
consisting
WO
3
Ni
single‐atom‐decorated
CdS
(Ni
1
‐CdS/WO
).
For
photocatalytic
from
pure
water,
attained
yield
rate
78
μM
h
−1
apparent
quantum
0.15
%
at
385
nm,
which
ranked
among
best
reported.
Mechanistic
studies
reveal
that
was
converted
into
NO
species
⋅OH
radicals
generated
component,
meanwhile,
transformed
*CO
site
electrons.
The
were
further
coupled
form
*OCNO
intermediate,
then
gradually
urea.
This
work
emphasizes
importance
reasonably
utilizing
reduction
reactions.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(32)
Опубликована: Июнь 3, 2024
Abstract
Directly
coupling
N
2
and
CO
to
synthesize
urea
by
photocatalysis
paves
a
sustainable
route
for
synthesis,
but
its
performance
is
limited
the
competition
of
photogenerated
electrons
between
,
as
well
underutilized
holes.
Herein,
we
report
an
efficient
synthesis
process
involving
holes
in
respectively
converting
over
redox
heterojunction
consisting
WO
3
Ni
single‐atom‐decorated
CdS
(Ni
1
‐CdS/WO
).
For
photocatalytic
from
pure
water,
attained
yield
rate
78
μM
h
−1
apparent
quantum
0.15
%
at
385
nm,
which
ranked
among
best
reported.
Mechanistic
studies
reveal
that
was
converted
into
NO
species
⋅OH
radicals
generated
component,
meanwhile,
transformed
*CO
site
electrons.
The
were
further
coupled
form
*OCNO
intermediate,
then
gradually
urea.
This
work
emphasizes
importance
reasonably
utilizing
reduction
reactions.
Advanced Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 23, 2025
Abstract
The
co‐electrolysis
of
CO
2
and
NO
3
−
to
synthesize
urea
has
become
an
effective
pathway
alternate
the
conventional
Bosch‐Meiser
process,
while
complexity
C‐/N‐containing
intermediates
for
C−N
coupling
results
in
electrosynthesis
unsatisfactory
efficiency.
In
this
work,
electronic
spin
state
modulation
maneuver
with
oxygen
vacancies
(Ov)
is
unveiled
effectively
meliorate
oriented
generation
key
*
NH
coupling,
furnishing
ultrahigh
yield
2175.47
µg
mg
−1
h
Faraday
efficiency
70.1%.
Mechanistic
studies
expound
that
Ov
can
induce
conversion
high‐spin
Ni
2+
(t
2g
6
e
g
)
Ni@CeO
2−x
low‐spin
3+
1
),
which
markedly
enhances
hybridization
degree
3d
N
2p
orbitals
NO,
facilitating
selective
formation
.
Notably,
situ
generated
serve
as
a
localized
proton
donor
promote
electroreduction
on
adjacent
site
Ce
−O
exclusively
afford
CO,
followed
by
each
other
efficiently
urea.
strategy
tailored
switching
active
provides
reliable
reference
rectify
structure
electrocatalysts
directional
valorization.
ACS Energy Letters,
Год журнала:
2024,
Номер
9(9), С. 4624 - 4632
Опубликована: Авг. 30, 2024
Urea
electrosynthesis
by
coelectrolysis
of
NO3–
and
CO2
(UENC)
represents
a
promising
method
to
enable
efficient
sustainable
urea
production.
In
this
work,
isolated
Cu
alloyed
Ru
(Cu1Ru)
is
developed
as
highly
active
selective
UENC
catalyst.
Combined
theoretical
computations
in
situ
spectroscopic
measurements
reveal
the
synergistic
effect
Cu1–Ru
site
Ru–Ru
on
Cu1Ru
promote
via
tandem
catalysis
pathway,
which
drives
*NO2/CO2
coupling
followed
*CO2NO2-to-*CO2NH
step.
The
formed
*CO2NH
then
migrates
from
adjacent
promotes
*CO2NH⃗*CO2NH2
→
*COOHNH2
steps
toward
generation.
Impressively,
achieves
high
performance
flow
cell,
exhibiting
yield
rate
21.04
mmol
h–1
gcat–1
Faradaic
efficiency
51.27%
at
−0.6
V,
outperforming
most
reported
catalysts.
Advanced Materials,
Год журнала:
2024,
Номер
36(52)
Опубликована: Ноя. 26, 2024
Abstract
Electrocatalytic
carbon
dioxide
(CO
2
)
conversion
into
valuable
chemicals
paves
the
way
for
realization
of
recycling.
Downsizing
catalysts
to
single‐atom
(SACs),
dual‐atom
(DACs),
and
sub‐nanocluster
(SNCCs)
has
generated
highly
active
selective
CO
transformation
reduced
products.
This
is
due
introduction
numerous
sites,
unsaturated
coordination
environments,
efficient
atom
utilization,
confinement
effect
compared
their
nanoparticle
counterparts.
Herein,
recent
Cu‐based
SACs
are
first
reviewed
newly
emerged
DACs
SNCCs
expanding
catalysis
electrocatalytic
reduction
RR)
high‐value
products
discussed.
Tandem
SAC–nanocatalysts
(NCs)
(SAC–NCs)
also
discussed
RR
Then,
non‐Cu‐based
SACs,
DACs,
SAC–NCs,
theoretical
calculations
various
transition‐metal
summarized.
Compared
previous
achievements
less‐reduced
products,
this
review
focuses
on
double
objective
achieving
full
increasing
selectivity
formation
rate
toward
C–C
coupled
with
additional
emphasis
stability
catalysts.
Finally,
through
combined
experimental
research,
future
outlooks
offered
further
develop
over
isolated
atoms
sub‐nanometal
clusters.
ACS Sustainable Chemistry & Engineering,
Год журнала:
2025,
Номер
13(1), С. 151 - 164
Опубликована: Янв. 2, 2025
The
production
of
urea
predominantly
relies
on
the
energy-intensive
Bosch–Meiser
process,
which
operates
at
temperatures
ranging
from
150
to
200
°C
and
pressures
approximately
250
bar.
More
sustainable
approaches
synthesis
under
milder
conditions
remain
a
significant
challenge.
Herein,
we
demonstrate
that
can
be
synthesized
via
mechanochemical
method
using
ammonia–water
CO2
an
ambient
environment.
Without
extra
catalysts,
ZrO2
texture
jar
grinding
balls
has
crucial
mechanocatalytic
effect
direct
synthesis.
Experimental
data
coupled
with
theoretical
calculation
results
indicate
mechano-induced
oxygen
vacancies
(OV)
within
(101)
crystal
plane
play
pivotal
role
in
formation.
These
notably
reduce
energy
barrier
for
generation
*NH2
subsequent
decomposition
NH2COOH,
thereby
facilitating
more
energy-efficient
process.
This
work
presents
novel
synthesizing
mild
conditions,
offering
potential
cost-effective
alternatives
production.
Advanced Functional Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 16, 2025
Abstract
Despite
recent
achievements
in
the
co‐reduction
electrosynthesis
of
urea
from
nitrogen
wastes
and
CO
2
,
selectivity
yield
products
remain
fairly
average
because
competition
NITRR,
RR,
HER.
Here,
a
strategy
involving
FeNC
catalysts
disperse
with
oxygen‐vacancy‐rich
CeO
(FeNC‐Ce)
is
illustrated,
which
reversible
hydrogenation
defects,
bimetallic
catalytic
centers
enable
spontaneous
switching
between
reduction
paths
NO
3
−
.
The
FeNC‐Ce
electrocatalyst
exhibits
an
extremely
high
Faraday
efficiency
(FE)
20969.2
µg
mg
−1
h
89.3%,
respectively,
highly
superior
to
most
reported
values
(maximum
200–2300
FE
max
11.5%–83.4%).
study
findings,
rationalize
by
situ
spectroscopy
theoretical
calculations,
are
rooted
evolution
dynamic
NITRR
RR
protons,
alleviating
overwhelming
single‐system
reactants
thereby
minimizing
formation
by‐products.
