Abstract
This
study
explored
the
use
of
amino
acid‐based
ionic
liquids
to
facilitate
conversion
carbon
dioxide
(CO
2
)
into
methanol
through
catalytic
hydrogenation.
Combining
tetrabutylammonium
L‐argininate
(TBA⋅Arg)
with
ruthenium
Ru‐MACHO‐BH
complex
allowed
achieving
significant
yields
under
optimized
conditions,
a
turnover
number
(TON)
up
700.
By
systematically
varying
key
reaction
parameters,
we
demonstrated
that
TBA⋅Arg
liquid
promotes
efficient
hydrogenation
pathway
leading
formation,
thus
offering
sustainable
approach
CO
valorization.
These
findings
underscore
potential
in
catalyzing
transformation
valuable
chemicals,
contributing
mitigation
efforts.
Chemical Society Reviews,
Год журнала:
2022,
Номер
51(11), С. 4386 - 4464
Опубликована: Янв. 1, 2022
The
emerging
field
of
organometallic
catalysis
has
shifted
towards
research
on
Earth-abundant
transition
metals
due
to
their
ready
availability,
economic
advantage,
and
novel
properties.
In
this
case,
manganese,
the
third
most
abundant
transition-metal
in
Earth's
crust,
emerged
as
one
leading
competitors.
Accordingly,
a
large
number
molecularly-defined
Mn-complexes
been
synthesized
employed
for
hydrogenation,
dehydrogenation,
hydroelementation
reactions.
regard,
catalyst
design
is
based
three
pillars,
namely,
metal-ligand
bifunctionality,
ligand
hemilability,
redox
activity.
Indeed,
developed
catalysts
not
only
differ
chelating
atoms
they
possess
but
also
working
principles,
thereby
different
turnover
numbers
product
molecules.
Hence,
critical
assessment
molecularly
defined
manganese
terms
atoms,
reaction
conditions,
mechanistic
pathway,
significant.
Herein,
we
analyze
complexes
catalytic
activity,
versatility
allow
multiple
transformations
routes
convert
substrates
target
This
article
will
be
helpful
get
significant
insight
into
design,
aiding
design.
ACS Catalysis,
Год журнала:
2023,
Номер
13(22), С. 15013 - 15053
Опубликована: Ноя. 6, 2023
Methanol
is
a
fundamental
feedstock
and
widely
used
in
the
chemical
petroleum
industries.
It
can
serve
as
C1
source
to
make
variety
of
C–C
C–N
bond
formation
dehydrogenative
coupling
products,
which
have
important
applications
natural
products
drug
discovery.
A
high
hydrogen
content
(12.5
wt%)
methanol
makes
it
an
effective
H2
donor
for
transfer
hydrogenation
various
reducible
functional
groups.
plethora
transition
metal-based
processes
been
developed
using
methanol.
Notably,
recent
review
articles
focused
on
aspect
However,
more
updated
that
examines
challenges
both
C1-source
H2-source
organic
transformations
contributing
concept
economy
has
not
presented
yet.
This
Review
summarizes
(homogeneous,
heterogeneous,
photo-)
catalyst
system
C-,
N-,
O-methylation
ketones,
alcohols,
amides,
nitriles,
heterocyclic
compounds,
sulfones,
amines,
sulfonamides
direct
N-methylation
nitro
compounds
under
borrowing
strategy
N-formylation
amines
acceptorless
dehydrogenation
source.
also
covers
insights
into
reaction
mechanisms
role
carefully
selected
ligands
metal
catalysis
activation
incorporation
-CD3,
methylation
molecules.
Moreover,
describes
groups
such
aldehydes,
alkynes,
with
detail.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(14), С. 9657 - 9664
Опубликована: Апрель 1, 2024
Hydrogen
production
from
methanol
represents
an
energy-sustainable
way
to
produce
ethanol,
but
it
normally
results
in
heavy
CO2
emissions.
The
selective
conversion
of
into
H2
and
valuable
chemical
feedstocks
offers
a
promising
strategy;
however,
is
limited
by
the
harsh
operating
conditions
low
efficiency.
Herein,
we
realize
efficient
high-purity
CO
coupling
thermocatalytic
dehydrogenation
with
electrocatalytic
hydrogen
oxidation
on
bifunctional
Ru/C
catalyst.
Electrocatalysis
enables
acceleration
C–H
cleavage
reduces
partial
pressure
at
anode,
which
drives
equilibrium
significantly
enhances
dehydrogenation.
Furthermore,
bilayer
+
Pd/C
electrode
designed
mitigate
poisoning
facilitate
oxidation.
As
result,
high
yield
(558.54
mmol
h–1
g–1)
purity
(99.9%)
was
achieved
integrating
applied
cell
voltage
0.4
V
200
°C,
superior
conventional
thermal
processes,
main
product
anode.
This
work
presents
new
avenue
for
together
synthesis
methanol.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(24)
Опубликована: Апрель 8, 2024
The
vast
bulk
of
polystyrene
(PS),
a
major
type
plastic
polymers,
ends
up
in
landfills,
which
takes
to
thousands
years
decompose
nature.
Chemical
recycling
promises
enable
lower-energy
pathways
and
minimal
environmental
impacts
compared
with
traditional
incineration
mechanical
recycling.
Herein,
we
demonstrated
that
methanol
as
hydrogen
supplier
assisted
the
depolymerization
PS
(denoted
PS-MAD)
into
alkylbenzenes
over
heterogeneous
catalyst
composed
Ru
nanoparticles
on
SiO
ACS Catalysis,
Год журнала:
2022,
Номер
12(7), С. 3995 - 4001
Опубликована: Март 15, 2022
Conversion
of
readily
available
feedstocks
to
valuable
platform
chemicals
via
an
eco-friendly
catalytic
pathway
has
always
been
one
the
key
focuses
synthetic
chemists.
In
this
context,
herein,
we
report
selective
transformation
feedstock,
vicinal
glycols,
value-added
α-hydroxycarboxylic
acid
molecules
that
are
prevalent
in
bioactive
and
biodegradable
polymers.
A
bench
stable
Earth-abundant
metal
complex,
{[HN(C2H4PPh2)2]Mn(CO)2Br},
Mn-I
catalyzed
reformation
reaction
at
low
temperature
high
selectivity
with
a
turnover
number
reaching
2400,
surpassing
previously
used
homogeneous
catalysts
for
such
reaction.
Hydrogen
gas
is
evolved
as
byproduct
without
needing
acceptor.
The
developed
protocol
applicable
both
aromatic
aliphatic
delivering
α-substituted
hydroxycarboxylic
acids
yields
selectivities.
Detailed
mechanistic
studies
elucidated
involvements
different
manganese(I)-species
during
acceptorless
dehydrogenation
catalysis.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(51), С. 26500 - 26505
Опубликована: Окт. 1, 2021
The
acceptorless
dehydrogenation
of
methanol
to
carbon
monoxide
and
hydrogen
was
investigated
using
homogeneous
molecular
complexes.
Complexes
ruthenium
manganese
comprising
the
MACHO
ligand
framework
showed
promising
activities
for
this
reaction.
complex
[RuH(CO)(BH4
)(HN(C2
H4
PPh2
)2
)]
(Ru-MACHO-BH)
achieved
up
3150
turnovers
9230
formation
at
150
°C
reaching
pressures
12
bar
when
decomposition
carried
out
in
a
closed
vessel.
Control
experiments
affirmed
that
metal
mediates
initial
fast
formaldehyde
methyl
formate
followed
by
subsequent
slow
decarbonylation.
Depending
on
catalyst
reaction
conditions,
CO/H2
ratio
gas
mixture
thus
varies
over
broad
range
from
almost
pure
stoichiometric
limit
1:2.
Nano Letters,
Год журнала:
2022,
Номер
22(20), С. 8381 - 8388
Опубликована: Сен. 20, 2022
Tandem
catalysis
provides
an
economical
and
energy-efficient
process
for
the
production
of
fine
chemicals.
In
this
work,
we
demonstrate
that
a
rationally
synthesized
carbon-based
catalyst
with
atomically
dispersed
dual
Fe–Al
sites
(ADD-Fe-Al)
achieves
superior
catalytic
activity
one-pot
oxidative
carboxylation
olefins
(conversion
∼97%,
selectivity
∼91%),
where
yield
target
product
over
ADD-Fe-Al
is
at
least
62%
higher
than
monometallic
counterparts.
The
kinetic
results
reveal
excellent
performance
arises
from
synergistic
effect
between
Fe
(oxidation
site)
Al
(cycloaddition
site),
efficient
CO2
cycloaddition
epoxides
in
presence
(3.91
wt
%)
positively
shifts
oxidation
equilibrium
to
olefin
epoxidation
(0.89
%).
This
work
not
only
offers
advanced
but
also
opens
up
avenue
rational
design
multifunctional
catalysts
tandem
reactions
future.
Advanced Energy Materials,
Год журнала:
2022,
Номер
12(46)
Опубликована: Окт. 3, 2022
Abstract
An
efficient
and
selective
heterogeneous
catalyst
is
identified
for
the
condensed‐phase
hydrogenation
of
captured
CO
2
in
presence
an
advanced
water‐lean
post‐combustion
capture
solvent,
(
N
‐(2‐EthoxyEthyl)‐3‐MorpholinoPropan‐1‐Amine),
2‐EEMPA.
The
catalysts
commonly
used
gas‐phase
(e.g.,
Cu/Zn/Al
O
3
)
cause
deactivation
amine
promoters
via
‐methylation
by
CO
cleavage
formamide
intermediates.
A
system
that
suppresses
solvents
identified,
demonstrating
how
Pt,
supported
reducible
metal
oxides
CeO
or
TiO
,
can
be
CN
to
produce
methanol.
This
first
known
demonstration
integrated
low‐temperature
thermocatalytic
conversion
methanol
economically
viable
solvent.
Technoeconomic
analyses
performed
on
state‐of‐technology
suggest
produced
with
a
minimum
selling
price
$4.4/gallon
($1,460/metric
ton)
when
using
from
650
MW
natural
gas
combined
cycle
plant.
Ultimately,
road
map
realistic
achievable
improvements
space
velocity
selectivity
this
process
enable
near
cost
parity
fossil‐derived
methanol,
≈$1.4/gal
($470/metric
ton),
presented.