Advanced Materials,
Journal Year:
2023,
Volume and Issue:
36(14)
Published: Sept. 27, 2023
Hydrogenation
reactions
play
a
critical
role
in
the
synthesis
of
value-added
products
within
chemical
industry.
Electrocatalytic
hydrogenation
(ECH)
using
water
as
hydrogen
source
has
emerged
an
alternative
to
conventional
thermocatalytic
processes
for
sustainable
and
decentralized
under
mild
conditions.
Among
various
ECH
catalysts,
copper-based
(Cu-based)
nanomaterials
are
promising
candidates
due
their
earth-abundance,
unique
electronic
structure,
versatility,
high
activity/selectivity.
Herein,
recent
advances
application
Cu-based
catalysts
upgrading
valuable
chemicals
systematically
analyzed.
The
properties
initially
introduced,
followed
by
design
strategies
enhance
activity
selectivity.
Then,
typical
on
presented
detail,
including
carbon
dioxide
reduction
multicarbon
generation,
alkyne-to-alkene
conversion,
selective
aldehyde
ammonia
production
from
nitrogen-containing
substances,
amine
organic
nitrogen
compounds.
In
these
catalyst
composition
nanostructures
toward
different
is
focused.
co-hydrogenation
two
substrates
(e.g.,
CO
Advanced Materials,
Journal Year:
2023,
Volume and Issue:
35(48)
Published: Sept. 21, 2023
Ammonia
(NH3
),
known
as
one
of
the
fundamental
raw
materials
for
manufacturing
commodities
such
chemical
fertilizers,
dyes,
ammunitions,
pharmaceuticals,
and
textiles,
exhibits
a
high
hydrogen
storage
capacity
≈17.75%.
Electrochemical
nitrate
reduction
(NO3
RR)
to
valuable
ammonia
at
ambient
conditions
is
promising
strategy
facilitate
artificial
nitrogen
cycle.
Herein,
copper-doped
cobalt
selenide
nanosheets
with
selenium
vacancies
are
reported
robust
highly
efficient
electrocatalyst
ammonia,
exhibiting
maximum
Faradaic
efficiency
≈93.5%
an
yield
rate
2360
µg
h-1
cm-2
-0.60
V
versus
reversible
electrode.
The
in
situ
spectroscopical
theoretical
study
demonstrates
that
incorporation
Cu
dopants
Se
into
efficiently
enhances
electron
transfer
from
Co
atoms
via
bridging
atoms,
forming
electron-deficient
structure
sites
accelerate
NO3-
dissociation
stabilize
*NO2
intermediates,
eventually
achieving
selective
catalysis
entire
NO3
RR
process
produce
efficiently.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(35)
Published: May 4, 2024
Abstract
Directly
electrochemical
conversion
of
nitrate
(NO
3
−
)
is
an
efficient
and
environmentally
friendly
technology
for
ammonia
(NH
production
but
challenged
by
highly
selective
electrocatalysts.
High‐entropy
alloys
(HEAs)
with
unique
properties
are
attractive
materials
in
catalysis,
particularly
multi‐step
reactions.
Herein,
we
first
reported
the
application
HEA
(FeCoNiAlTi)
electrocatalytic
NO
reduction
to
NH
(NRA).
The
bulk
active
NRA
limited
unsatisfied
yield
0.36
mg
h
−1
cm
−2
Faradaic
efficiency
(FE)
82.66
%.
Through
effective
phase
engineering
strategy,
uniform
intermetallic
nanoparticles
introduced
on
increase
surface
area
charge
transfer
efficiency.
resulting
nanostructured
(n‐HEA)
delivers
enhanced
performance
terms
(0.52
FE
(95.23
%).
Further
experimental
theoretical
investigations
reveal
that
multi‐active
sites
(Fe,
Co,
Ni)
dominated
electrocatalysis
over
n‐HEA.
Notably,
typical
Co
exhibit
lowest
energy
barrier
*NH
2
as
rate‐determining
step.
Advanced Materials,
Journal Year:
2023,
Volume and Issue:
35(32)
Published: May 26, 2023
Renewable
electricity-powered
nitrate
(NO3-
)
reduction
reaction
(NO3
RR)
offers
a
net-zero
carbon
route
to
the
realization
of
high
ammonia
(NH3
productivity.
However,
this
suffers
from
low
energy
efficiency
(EE,
with
half-cell
EE
commonly
<36%),
since
overpotentials
are
required
overcome
weak
NO3-
binding
affinity
and
sluggish
NO3
RR
kinetics.
To
alleviate
this,
rational
catalyst
design
strategy
that
involves
linear
assembly
sub-5
nm
Cu/Co
nanophases
into
sub-20
thick
nanoribbons
is
suggested.
The
theoretical
experimental
studies
show
Cu-Co
nanoribbons,
similar
enzymes,
enable
strong
adsorption
rapid
tandem
catalysis
NH3
,
owing
their
richly
exposed
binary
phase
boundaries
adjacent
sites
at
distance.
In
situ
Raman
spectroscopy
further
reveals
applied
overpotentials,
rapidly
activated
subsequently
stabilized
by
specifically
designed
redox
polymer
in
scavenges
intermediately
formed
highly
oxidative
nitrogen
dioxide
(NO2
).
As
result,
stable
current
density
≈450
mA
cm-2
achieved,
Faradaic
>97%
for
formation
an
unprecedented
≈42%.
Advanced Materials,
Journal Year:
2023,
Volume and Issue:
36(14)
Published: Sept. 27, 2023
Hydrogenation
reactions
play
a
critical
role
in
the
synthesis
of
value-added
products
within
chemical
industry.
Electrocatalytic
hydrogenation
(ECH)
using
water
as
hydrogen
source
has
emerged
an
alternative
to
conventional
thermocatalytic
processes
for
sustainable
and
decentralized
under
mild
conditions.
Among
various
ECH
catalysts,
copper-based
(Cu-based)
nanomaterials
are
promising
candidates
due
their
earth-abundance,
unique
electronic
structure,
versatility,
high
activity/selectivity.
Herein,
recent
advances
application
Cu-based
catalysts
upgrading
valuable
chemicals
systematically
analyzed.
The
properties
initially
introduced,
followed
by
design
strategies
enhance
activity
selectivity.
Then,
typical
on
presented
detail,
including
carbon
dioxide
reduction
multicarbon
generation,
alkyne-to-alkene
conversion,
selective
aldehyde
ammonia
production
from
nitrogen-containing
substances,
amine
organic
nitrogen
compounds.
In
these
catalyst
composition
nanostructures
toward
different
is
focused.
co-hydrogenation
two
substrates
(e.g.,
CO
