ACS Catalysis,
Год журнала:
2020,
Номер
10(19), С. 10826 - 10846
Опубликована: Авг. 11, 2020
Despite
advances
in
the
development
of
molecular
catalysts
capable
reducing
dinitrogen
to
ammonia
using
proton
donors
and
chemical
reductants,
few
electrocatalysts
have
been
discovered.
This
Perspective
considers
prospects
electrocatalyst
based
on
a
mechanism
featuring
cleavage
N2
into
metal
nitride
complexes.
By
understanding
factors
that
control
reactivity
individual
steps
along
electrochemical
path,
opportunities
for
new
are
identified.
Ligand
design
principles
facile
binding,
formation
bridging
complexes,
thermal
or
photochemical
cleavage,
conversion
ligand
described,
recent
authors'
collaborative
work
rhenium
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(36)
Опубликована: Июль 5, 2022
The
electrocatalytic
nitrogen
reduction
reaction
(NRR)
on
metal-free
catalysts
is
an
attractive
alternative
to
the
industrial
Haber-Bosch
process.
However,
state-of-the-art
electrocatalysts
still
suffer
from
low
Faraday
efficiencies
and
ammonia
yields.
Herein,
we
present
a
molecular
design
strategy
develop
defective
boron
carbon
nitride
(BCN)
catalyst
with
abundant
unsaturated
B
N
atoms
as
Lewis
acid
base
sites,
which
upgrades
single
"Lewis
catalysis"
"frustrated
pairs
(FLPs)
catalysis."
14
N2
/15
exchange
experiments
density
functional
theory
(DFT)
calculations
reveal
that
FLPs
can
adsorb
molecule
form
six-membered
ring
intermediate,
enables
cleavage
of
via
pull-pull
effect,
thereby
significantly
reducing
energy
barrier
-0.28
eV.
Impressively,
BCN
achieves
high
efficiency
18.9
%,
yield
20.9
μg
h-1
mg-1cat.
,
long-term
durability.
Chemical Society Reviews,
Год журнала:
2022,
Номер
51(14), С. 5930 - 5973
Опубликована: Янв. 1, 2022
Radical
species
are
significant
in
modern
chemistry.
Their
unique
chemical
bonding
and
novel
physicochemical
properties
play
roles
not
only
fundamental
chemistry,
but
also
materials
science.
Main
group
element
radicals
usually
transient
due
to
their
high
reactivity.
Highly
stable
often
stabilized
by
π-delocalization,
sterically
demanding
ligands,
carbenes
weakly
coordinating
anions
recent
years.
This
review
presents
the
advances
synthesis,
characterization,
reactivity
physical
of
isolable
main
radicals.
Chemical Reviews,
Год журнала:
2023,
Номер
123(16), С. 10468 - 10526
Опубликована: Авг. 9, 2023
Heteroatom-centered
diradical(oid)s
have
been
in
the
focus
of
molecular
main
group
chemistry
for
nearly
30
years.
During
this
time,
diradical
concept
has
evolved
and
shifted
to
rational
design
specific
applications.
This
review
article
begins
with
some
important
theoretical
considerations
tetraradical
concept.
Based
on
these
considerations,
terms
ligand
choice,
steric,
symmetry,
electronic
situation,
element
reactivity
is
highlighted
examples.
In
particular,
heteroatom-centered
reactions
are
discussed
compared
closed-shell
such
as
pericyclic
additions.
The
comparison
between
reactivity,
which
proceeds
a
concerted
manner,
open-shell
stepwise
fashion,
along
diradical(oid)
design,
provides
understanding
interesting
unusual
class
compounds.
application
diradical(oid)s,
example
small
molecule
activation
or
switches,
also
highlighted.
final
part
application-related
details
spectroscopy
followed
by
an
update
tetraradical(oid)s
published
last
10
years
since
2013.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(8), С. 3896 - 3951
Опубликована: Янв. 1, 2024
This
review
provides
an
overview
of
main
group
carbene
analogues,
covering
recent
advancements,
synthesis
strategies,
and
the
diverse
reactivity
elements
in
groups
13–15
based
on
their
structural
characteristics.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(10), С. 5054 - 5082
Опубликована: Янв. 1, 2024
This
review
summarises
advances
in
the
chemistry
of
low-oxidation
state
and
hydrido
group
2
metal
complexes,
focussing
on
their
use
for
reductive
activation
feed-stock
gaseous
small
molecules,
subsequent
transformation
into
value
added
products.
Journal of the American Chemical Society,
Год журнала:
2019,
Номер
142(1), С. 308 - 317
Опубликована: Дек. 16, 2019
Boron
nitride
(BN),
with
outstanding
stability
and
robustness
in
diverse
polymorphs,
possesses
many
advantageous
properties
for
industrial
applications.
Activation
of
BN
materials
nonmetal
catalysts
is
among
the
most
revolutionary
challenging
tasks.
Taking
advantage
quantum
size
effect
synergistic
effect,
here
we
exploit
boron
nanotubes
(BNNTs)
encapsulating
early
transition
metal
nanowires,
which
experimentally
feasible,
nitrogen
fixation
ammonia
synthesis.
Using
first-principles
calculations
microkinetic
modeling,
show
that
coexisting
occupied
unoccupied
p
states
B
atoms
filled
BNNTs
can
effectively
mimic
d
metal.
They
act
as
electron
reservoirs
tunable
orbital
energies
occupancy,
are
beneficial
associative
N2
adsorption
hydrogenation.
Due
to
competition
between
thermodynamics
gas
kinetics
hydrogenation
reaction,
activity
be
optimized
by
controlling
type
filler
nanotube,
achieving
a
turnover
frequency
competitive
benchmark
Fe
catalyst.
These
results
manifest
universal
strategy
activating
nanomaterials
promising
family
robust
efficient
provide
vital
insights
into
activity-band
structure
relationship
p-block
catalysts.
Advanced Materials,
Год журнала:
2019,
Номер
32(18)
Опубликована: Окт. 1, 2019
Abstract
The
electrocatalytic
conversion
of
earth‐abundant
simple
molecules
into
value‐added
commodity
chemicals
can
transform
current
chemical
production
regimes
with
enormous
socioeconomic
and
environmental
benefits.
For
these
applications,
2D
electrocatalysts
have
emerged
as
a
new
class
high‐performance
electrocatalyst
massive
forward‐looking
potential.
Recent
advances
in
are
reviewed
for
emerging
applications
that
utilize
naturally
existing
H
2
O,
N
,
O
Cl
−
(seawater)
CH
4
(natural
gas)
reactants
nitrogen
reduction
(N
→
NH
3
),
two‐electron
oxygen
(O
chlorine
evolution
(Cl
methane
partial
oxidation
(CH
OH)
reactions
to
generate
OH.
unique
features
effective
approaches
take
advantage
such
create
articulated
emphasis.
To
benefit
the
readers
expedite
future
progress,
challenges
facing
development
each
above
related
perspectives
provided.
