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
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(13)
Published: Feb. 3, 2023
We
demonstrate
the
great
feasibility
of
MBenes
as
a
new
class
tandem
catalysts
for
electrocatalytic
nitrate
reduction
to
ammonia
(NO3
RR).
As
proof
concept,
FeB2
is
first
employed
model
MBene
catalyst
NO3
RR,
showing
maximum
NH3
-Faradaic
efficiency
96.8
%
with
corresponding
yield
25.5
mg
h-1
cm-2
at
-0.6
V
vs.
RHE.
Mechanistic
studies
reveal
that
exceptional
RR
activity
arises
from
catalysis
mechanism,
is,
B
sites
activate
NO3-
form
intermediates,
while
Fe
dissociate
H2
O
and
increase
*H
supply
on
promote
intermediate
hydrogenation
enhance
-to-NH3
conversion.
Advanced Functional Materials,
Journal Year:
2023,
Volume and Issue:
33(12)
Published: Jan. 15, 2023
Abstract
Electrochemical
reduction
of
nitrate
to
ammonia
(NO
3
RR)
holds
a
great
promise
for
attaining
both
NH
electrosynthesis
and
wastewater
purification.
Herein,
single‐atom
Bi
alloyed
Pd
metallene
(Bi
1
Pd)
is
reported
as
highly
effective
NO
RR
catalyst,
showing
near
100%
‐Faradaic
efficiency
with
the
corresponding
yield
33.8
mg
h
−1
cm
−2
at
−0.6
V
versus
RHE,
surpassing
those
almost
all
ever
catalysts.
In‐depth
theoretical
operando
spectroscopic
investigations
unveil
that
electronically
couples
its
neighboring
atoms
synergistically
activate
−
destabilize
*NO
on
Pd,
leading
reduced
energy
barrier
potential‐determining
step
(*NO→*NOH)
enhanced
protonation
energetics
‐to‐NH
pathway.
Advanced Materials,
Journal Year:
2023,
Volume and Issue:
36(17)
Published: June 9, 2023
Natural
nitrogen
cycle
has
been
severely
disrupted
by
anthropogenic
activities.
The
overuse
of
N-containing
fertilizers
induces
the
increase
nitrate
level
in
surface
and
ground
waters,
substantial
emission
oxides
causes
heavy
air
pollution.
Nitrogen
gas,
as
main
component
air,
used
for
mass
ammonia
production
over
a
century,
providing
enough
nutrition
agriculture
to
support
world
population
increase.
In
last
decade,
researchers
have
made
great
efforts
develop
processes
under
ambient
conditions
combat
intensive
energy
consumption
high
carbon
associated
with
Haber-Bosch
process.
Among
different
techniques,
electrochemical
reduction
reaction
(NO
Chemical Society Reviews,
Journal Year:
2023,
Volume and Issue:
52(5), P. 1723 - 1772
Published: Jan. 1, 2023
Defective
two-dimensional
(2D)
materials
show
huge
potential
for
energy-related
fields.
This
review
overviews
the
formation/evolution
mechanisms
and
engineering
strategies
of
defects
in
2D
materials,
which
enable
enhanced
electrode
reaction
kinetics.
Advanced Materials,
Journal Year:
2023,
Volume and Issue:
35(31)
Published: Feb. 23, 2023
Single/dual-metal
atoms
supported
on
carbon
matrix
can
be
modulated
by
coordination
structure
and
neighboring
active
sites.
Precisely
designing
the
geometric
electronic
uncovering
structure-property
relationships
of
single/dual-metal
confront
with
grand
challenges.
Herein,
this
review
summarizes
latest
progress
in
microenvironment
engineering
single/dual-atom
sites
via
a
comprehensive
comparison
single-atom
catalyst
(SACs)
dual-atom
catalysts
(DACs)
term
design
principles,
modulation
strategy,
theoretical
understanding
structure-performance
correlations.
Subsequently,
recent
advances
several
typical
electrocatalysis
process
are
discussed
to
get
general
reaction
mechanisms
finely-tuned
SACs
DACs.
Finally,
full-scaled
summaries
challenges
prospects
given
for
This
will
provide
new
inspiration
development
atomically
dispersed
electrocatalytic
application.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(39)
Published: July 22, 2023
The
electrochemical
conversion
of
nitrate
pollutants
into
value-added
ammonia
is
a
feasible
way
to
achieve
artificial
nitrogen
cycle.
However,
the
development
electrocatalytic
nitrate-to-ammonia
reduction
reaction
(NO3-
RR)
has
been
hampered
by
high
overpotential
and
low
Faradaic
efficiency.
Here
we
develop
an
iron
single-atom
catalyst
coordinated
with
phosphorus
on
hollow
carbon
polyhedron
(denoted
as
Fe-N/P-C)
NO3-
RR
electrocatalyst.
Owing
tuning
effect
atoms
breaking
local
charge
symmetry
single-Fe-atom
catalyst,
it
facilitates
adsorption
ions
enrichment
some
key
intermediates
during
process.
Fe-N/P-C
exhibits
90.3
%
efficiency
yield
rate
17980
μg
h-1
mgcat-1
,
greatly
outperforming
reported
Fe-based
catalysts.
Furthermore,
operando
SR-FTIR
spectroscopy
measurements
reveal
pathway
based
observed
under
different
applied
potentials
durations.
Density
functional
theory
calculations
demonstrate
that
optimized
free
energy
ascribed
asymmetric
atomic
interface
configuration,
which
achieves
optimal
electron
density
distribution.
This
work
demonstrates
critical
role
atomic-level
precision
modulation
heteroatom
doping
for
RR,
providing
effective
strategy
improving
catalytic
performance
single
atom
catalysts
in
reactions.
Environmental Science & Technology,
Journal Year:
2022,
Volume and Issue:
56(20), P. 14797 - 14807
Published: Sept. 29, 2022
The
conversion
of
nitrate
to
ammonia
can
serve
two
important
functions:
mitigating
pollution
and
offering
a
low
energy
intensity
pathway
for
synthesis.
Conventional
synthesis
from
electrocatalytic
reduction
reactions
(NO3RR)
is
often
impeded
by
incomplete
conversion,
sluggish
kinetics,
the
competition
hydrogen
evolution
reactions.
Herein,
atomic
Cu
sites
anchored
on
micro-/mesoporous
nitrogen-doped
carbon
(Cu
MNC)
with
fine-tuned
hydrophilicity,
channels,
abundant
Cu(I)
were
synthesized
selective
ammonia,
achieving
ambient
temperature
pressure
hydrogenation
nitrate.
Laboratory
experiments
demonstrated
that
catalyst
has
an
yield
rate
per
active
site
5466
mmol
gCu-1
h-1
transformed
94.8%
in
wastewater
containing
100
mg-N
L-1
near
drinking
water
standard
(MCL
5
L-1)
at
-0.64
V
vs
RHE.
Extended
X-ray
absorption
fine
structure
(EXAFS)
theoretical
calculations
showed
coordination
environment
(Cu(I)-N3C1)
localizes
charge
around
central
atoms
adsorbs
*NO3
*H
onto
neighboring
C
balanced
adsorption
energy.
Cu(I)-N3C1
moieties
reduce
activation
rate-limiting
steps
(*HNO3
→
*NO2,
*NH2
*NH3)
compared
conventional
Cu(II)-N4
lead
thermodynamically
favorable
process
NH3.
as-prepared
cell
run
continuously
84
h
(14
cycles)
produce
21.7
mgNH3
only
5.64
×
10-3
kWh
consumption,
suitable
decentralized
removal
nitrate-containing
wastewater.
Advanced Functional Materials,
Journal Year:
2023,
Volume and Issue:
33(43)
Published: June 25, 2023
Abstract
Ammonia
as
an
irreplaceable
chemical
has
been
widely
demanded
to
keep
the
sustainable
development
of
modern
society.
However,
its
industrial
production
consumes
huge
energy
and
releases
extraordinary
green‐house
gases,
leading
various
environmental
issues.
To
achieve
green
ammonia
is
a
great
challenge
that
extensively
pursued
recently.
In
review,
most
promising
strategy,
electrochemical
nitrate
reduction
reaction
(e‐NO
3
RR)
for
purpose
comprehensively
investigated
give
full
understanding
mechanism
provide
guidance
future
directions.
Particularly,
electrocatalysts
focused
realize
high
yield
rate
Faraday
efficiency
applications.
The
recent‐developed
catalysts,
including
noble
metallic
materials,
alloys,
metal
compounds,
single‐metal‐atom
metal‐free
are
systematically
discussed
review
effects
factors
on
catalytic
performance
in
e‐NO
RR.
Accordingly,
strategies,
defects
engineering,
coordination
environment
modulating,
surface
controlling,
hybridization,
carefully
improve
performance,
such
intrinsic
activity
selectivity.
Finally,
perspectives
challenges
given
out.
This
shall
insightful
advanced
systems
efficiently
industry.
Inorganic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(12), P. 3489 - 3514
Published: Jan. 1, 2023
Ammonia
(NH3)
is
an
essential
raw
material
in
the
production
of
fertilizers
and
a
promising
carbon-free
energy
carrier,
however,
its
synthesis
still
depends
on
energy-
capital-intensive
Haber–Bosch
process.
Recently,
electrochemical
N2
reduction
reaction
has
attracted
significant
interest
as
emerging
method
for
NH3
under
ambient
conditions.
However,
limited
solubility
aqueous
electrolyte
strong
NN
bonds
result
low
yield
rate,
inferior
faradaic
efficiency
unsatisfactory
selectivity,
impeding
further
practical
application.
Considering
high
water
nitrate
(NO3−),
NO3−
(NO3−RR)
become
fascinating
route
achieving
sustainable
NH3,
enormous
progress
been
made
this
field.
As
consequence,
review
discusses
mechanism
systematically
summarizes
recent
development
electrocatalysts
NO3−RR,
including
noble-metal-based
materials,
single-atom
metal
catalysts,
transition-metal-based
catalysts.
Diverse
design
strategies
catalysts
to
boost
NO3−RR
performance,
such
defect
engineering,
rational
structure
design,
strain
engineering
constructing
heterostructures,
are
discussed.
This
followed
by
illustration
how
robust
understanding
optimization
affords
fundamental
insights
into
efficiency,
selectivity
electrocatalysts.
Finally,
we
conclude
with
future
perspectives
critical
issues,
challenges
research
directions
high-efficiency
selective
NH3.