Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Авг. 24, 2024
Abstract
The
thermodynamically
and
kinetically
sluggish
electrocatalytic
C−N
coupling
from
CO
2
NO
3
−
is
inert
to
initially
take
place
while
typically
occurring
after
protonation,
which
severely
dwindles
urea
efficiency
carbon
atom
economy.
Herein,
we
report
a
single
O‐philic
adsorption
strategy
facilitate
initial
of
*OCO
subsequent
protonation
over
dual‐metal
hetero‐single‐atoms
in
N
−Fe−(N−B)
−Cu−N
coordination
mode
(FeN
4
/B
CuN
@NC),
greatly
inhibits
the
formation
C‐containing
byproducts
facilitates
electrosynthesis
an
unprecedented
C‐selectivity
97.1
%
with
yield
2072.5
μg
h
−1
mg
cat.
71.9
Faradaic
efficiency,
outperforming
state‐of‐the‐art
electrodes.
carbon‐directed
antibonding
interaction
Cu−B
elaborated
benefit
rather
than
conventional
C‐end
or
bridging
O,O‐end
modes,
can
accelerate
kinetics
initiated
protonation.
Theoretical
results
indicate
that
O‐monodentate
pathway
benefits
thermodynamics
*NO
rate‐determining
step,
markedly
direct
This
oriented
manipulating
reactant
patterns
initiate
specific
step
universal
moderate
oxophilic
transition
metals
offers
kinetic‐enhanced
path
for
multiple
conversion
processes.
ACS Nano,
Год журнала:
2024,
Номер
18(43), С. 29856 - 29863
Опубликована: Окт. 16, 2024
Urea
electrosynthesis
from
the
coelectrolysis
of
NO3–
and
CO2
(UENC)
presents
a
fascinating
approach
for
simultaneously
migrating
pollutants
producing
valuable
urea.
In
this
study,
isolated
Rh-alloyed
copper
(Rh1Cu)
is
explored
as
highly
active
selective
catalyst
toward
UENC.
Combined
in
situ
spectroscopic
analysis
theoretical
calculations
reveal
relay
catalysis
Rh1
site
Cu
to
promote
UENC
energetics,
which
activates
form
*NH2
while
*CO.
The
formed
*CO
then
migrated
substrate
nearby
site,
promotes
C–N
coupling
urea
formation.
Prominently,
Rh1Cu
achieves
an
exceptional
performance
flow
cell,
exhibiting
highest
urea-Faradaic
efficiency
67.10%
yield
rate
50.36
mmol
h–1
g–1
at
−0.6
V
versus
RHE.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(26)
Опубликована: Апрель 10, 2024
Abstract
Oxime
ethers
are
attractive
compounds
in
medicinal
scaffolds
due
to
the
biological
and
pharmaceutical
properties,
however,
crucial
widespread
step
of
industrial
oxime
formation
using
explosive
hydroxylamine
(NH
2
OH)
is
insecure
troublesome.
Herein,
we
present
a
convenient
method
ether
synthesis
one‐pot
tandem
electrochemical
system
magnesium
based
metal‐organic
framework‐derived
oxide
anchoring
self‐supporting
carbon
nanofiber
membrane
catalyst
(MgO‐SCM),
situ
produced
NH
OH
from
nitrogen
oxides
electrocatalytic
reduction
coupled
with
aldehyde
produce
4‐cyanobenzaldoxime
selectivity
93
%
Faraday
efficiency
up
65.1
%,
which
further
reacted
benzyl
bromide
directly
give
precipitate
purity
97
by
filtering
separation.
The
high
was
attributed
ultrafine
MgO
nanoparticles
MgO‐SCM,
effectively
inhibiting
hydrogen
evolution
reaction
accelerating
production
OH,
rapidly
attacked
carbonyl
aldehydes
form
oximes,
but
hardly
crossed
hydrogenation
barrier
forming
amines,
thus
leading
yield
when
coupling
nucleophilic
reaction.
This
work
highlights
importance
kinetic
control
complex
electrosynthetic
organonitrogen
demonstrates
green
safe
alternative
for
organic
drug
molecules.
Physical Chemistry Chemical Physics,
Год журнала:
2024,
Номер
26(26), С. 18016 - 18020
Опубликована: Янв. 1, 2024
Arylnitrenium
ions
generated
by
plasma
discharge
play
a
key
role
in
the
selectivity
of
process
C–N
coupling
directly
with
N
2
,
which
may
have
profound
implications
for
direct
conversion
into
value-added
organics.
This
study
presents
a
facile
tandem
strategy
for
improving
the
efficiency
of
glycine
electrosynthesis
from
oxalic
acid
and
nitrate.
In
this
electrocatalytic
process,
is
first
reduced
to
glyoxylic
acid,
while
nitrate
hydroxylamine.
Subsequent
coupling
these
two
precursors
results
in
formation
C-N
bond,
producing
intermediate
oxime,
which
further
situ
glycine.
Here
we
show,
using
only
simple
Pb
foil
electrode,
that
maximizing
yield
step
transformation
(i.e.
reduction
acid)
prior
allows
an
unprecedented
selectivity
conversion
be
achieved.
Overall,
maximum
faradaic
(FE)
59
%
achieved
at
-300
mA
cm-2
high
partial
current
density
-232
production
rate
0.82
mmol
h-1
are
attained
400
cm-2,
thereby
paving
way
energy
economically
efficient
electrochemical
synthesis
Abstract
Nitrogen
oxide
(NO
x
)
is
an
attractive
nitrogen
source.
Electrocatalytic
NO
reduction
coupled
with
the
conversion
of
carbon
source
molecules
offers
a
potential
route
for
sustainable
synthesis
valuable
nitrogenous
organics.
This
review
discusses
recent
progress
on
electrocatalytic
organonitrogen
compounds
(such
as
oximes,
amino
acids,
amines,
amides
and
urea)
via
C−N
coupling
from
The
performance,
catalyst
structure
especially
reaction
mechanism
are
discussed.
Current
challenges,
design
principles,
understanding
mechanisms,
well
possible
strategies
improving
selectivity
activity
proposed,
which
will
guide
future
researches
in
ACS Catalysis,
Год журнала:
2024,
Номер
14(21), С. 16127 - 16139
Опубликована: Окт. 17, 2024
The
electrocatalytic
oxidation
of
5-hydroxymethylfurfural
(HMF)
provides
a
viable
pathway
for
the
efficient
utilization
biomass
resources.
However,
designing
and
regulating
activity
selectivity
corresponding
electrocatalysts
remain
significant
challenge.
Spinel
compounds
show
great
potential
as
catalysts
due
to
their
adjustable
electronic
structures
notable
catalytic
properties,
but
intrinsic
low
conductivity
has
limited
further
application.
Herein,
lignin-based
carbon
fiber
(LCF)
embedded
CuFe2O4
catalyst
(CuFe2O4/LCF)
is
successfully
constructed
using
an
electrospinning
technique.
can
efficiently
selectively
synthesize
2,5-furandicarboxylic
acid
(FDCA)
at
relatively
potential.
experimental
results
theoretical
simulations
demonstrate
that
introduction
lignin
significantly
optimize
pregraphitic
turbine
microstructure
fibers
facilitate
rapid
electron
transfer
between
layer.
Furthermore,
ATd–O–BOh
interactions
on
surface
spinel
structure
enhance
adsorption
capacity
substrates
OH–
species,
effectively
promoting
reaction.
findings
hope
provide
unique
perspective
improve
stability
value-added
mechanism.
