Primary
amines
represent
highly
privileged
chemicals
for
synthesis
of
polymers,
pharmaceuticals,
agrochemicals,
coatings,
etc.
Consequently,
the
development
efficient
and
green
methodologies
production
primary
are
great
importance
in
chemical
industry.
Owing
to
advantages
low
cost
ease
availability,
ammonia
is
considered
as
a
feasible
nitrogen
source
N-containing
compounds.
Thus,
transformation
into
has
received
much
attention.
In
this
review,
commonly
applied
synthetic
routes
produce
from
were
summarized,
including
reductive
amination
carbonyl
compounds,
hydrogen
transfer
alcohols,
hydroamination
olefins
arylation
with
ammonia,
which
catalytic
performance
recent
heterogeneous
catalysts
discussed.
Additionally,
various
strategies
modulate
surface
properties
outlined
conjunction
analysis
reaction
mechanism.
Particularly,
biomass-derived
substrates
highlighted,
could
provide
competitive
industry
stimulate
sustainable
catalysis
future.
Ultimately,
perspectives
challenges
opportunities
N-resource
Green Chemistry,
Год журнала:
2024,
Номер
26(19), С. 9957 - 9992
Опубликована: Янв. 1, 2024
This
review
highlights
recent
advancements
in
the
selective
conversion
of
biomass-derived
furfural
to
high-value
platform
chemicals
over
various
heterogeneous
catalytic
systems.
Green Chemistry,
Год журнала:
2024,
Номер
26(22), С. 11019 - 11060
Опубликована: Янв. 1, 2024
Recent
advances
in
the
amination
of
biomass-derived
molecules
to
generate
valuable
nitrogenous
chemicals
by
employing
thermocatalysis,
electrocatalysis
and
photocatalysis
strategies
are
reviewed.
ACS Catalysis,
Год журнала:
2023,
Номер
13(19), С. 12835 - 12847
Опубликована: Сен. 18, 2023
Hydrogen
spillover
has
provided
great
insights
for
elevating
catalytic
performance
in
hydrogen-involved
heterogeneous
processes,
which
is
normally
promoted
by
the
reducible
oxide
support.
However,
it
seems
powerless
some
cases
when
unreducible
desired
to
play
role
activating
another
molecular
reactant,
and
thus
competition
needs
be
reconciled.
Herein,
taking
tandem
reductive
amination
of
furfural
as
an
example,
we
constructed
Ru/Ga2O3/MgAlGaOx
catalyst,
metallic
Ru
sites
Al3+
take
responsibility
H2
dissociation
intermediate
Schiff
base
activation,
respectively.
More
attractively,
nanosized
Ga2O3
atomic
distributed
Ga3+
MgAlGaOx
can
considered
dual
scale
hydrogen
transfer
bridges
break
deadlock.
As
dissociated
H*
efficient
site
timely,
facilitating
vital
step
hydrogenolysis
furfurylamine,
as-synthesized
catalysts
achieved
satisfactory
performance,
universality,
cycling
stability
(93%
yield,
80.43
gFAM·gRu–1·h–1
product
formation
rate,
broad
scope
14
substrates,
recycling
5
times)
under
both
mild
pressure
extremely
low
NH3
feeding
conditions.
Through
designed
in/ex-situ
experiments
DFT
calculations,
such
a
promotional
effect
was
revealed.
This
work
opens
strategy
avenue
other
complex
reactions
presents
prospective
catalyst
biomass
upgrading
condition.
Catalysts,
Год журнала:
2023,
Номер
13(3), С. 528 - 528
Опубликована: Март 5, 2023
Bio-based
furanic
oxygenates
represent
a
well-known
class
of
lignocellulosic
biomass-derived
platform
molecules.
In
the
presence
H2
and
different
nitrogen
sources,
these
versatile
building
blocks
can
be
transformed
into
valuable
amine
compounds
via
reductive
amination
or
hydrogen-borrowing
mechanisms,
yet
they
still
face
many
challenges
due
to
co-existence
side-reactions,
such
as
direct
hydrogenation,
polymerization
cyclization.
Hence,
catalysts
with
specific
structures
functions
are
required
achieve
satisfactory
yields
target
amines.
recent
years,
heterogeneous
catalytic
synthesis
amines
from
bio-based
has
received
extensive
attention.
this
review,
we
summarize
discuss
significant
progress
in
generation
useful
sources
over
catalysts,
according
various
raw
materials
reaction
pathways.
The
key
factors
affecting
performances,
active
metals,
supports,
promoters,
solvents
conditions,
well
possible
routes
mechanisms
studied
discussed
depth.
Special
attention
is
paid
structure–activity
relationship,
which
would
helpful
for
development
more
efficient
stable
catalysts.
Moreover,
future
research
direction
trend
prospected.
Green Chemistry,
Год журнала:
2023,
Номер
26(3), С. 1610 - 1626
Опубликована: Дек. 13, 2023
A
bimetallic
Ru(
ii
)
complex
efficiently
catalyzes
reductive
amination
of
diverse
substrates
in
water
with
the
highest
reported
TONs
and
TOFs.
Experimental
DFT
calculations
point
to
a
cooperative
effect
for
increased
efficiency
at
low
catalyst
loading
(0.05
mol%).
Abstract
Phenol
amination
to
various
valuable
amines
has
attracted
considerable
attention
in
heterogeneous
catalysis,
but
limited
studies
have
focused
on
non‐noble
metal
catalysts.
This
study
reports
a
bifunctional
catalyst
(Ni/SiO
2
‐AE)
containing
nickel
nanoparticles
and
Lewis
acid
sites
derived
from
phyllosilicates
for
efficient
of
phenol
cyclohexylamine.
The
Ni/SiO
‐AE
resulted
89.4%
conversion
86.0%
selectivity
cyclohexylamine
at
160
°C
h,
which
outperforms
the
catalysts
by
conventional
deposition‐precipitation
‐DP)
wetness‐impregnation
‐WI).
turnover
frequencies
based
actual
exposed
surface
area
‐AE,
‐DP,
‐WI
are
calculated
as
71.7,
49.0,
8.7
h
−1
,
respectively.
Results
demonstrate
that
Ni
exsoluted
participate
activation
dihydrogen
molecules,
stemmed
coordination
unsaturated
2+
serve
adsorb
activate
phenol.
synergistic
effect
dual‐functions
intensifies
amination.
