Developing electrochemical hydrogenation towards industrial application
Chemical Society Reviews,
Год журнала:
2023,
Номер
52(21), С. 7305 - 7332
Опубликована: Янв. 1, 2023
Electrochemical
hydrogenation
reactions
hold
the
promise
of
more
sustainable
production
routes
for
towards
bulk
and
fine
chemicals.
Their
broad
applicability,
reactor
concepts,
achieved
milestones
future
perspectives
are
described
herein.
Язык: Английский
Promoting Electrocatalytic Semihydrogenation of Alkynols to Alkenols over a Bimetallic CuAu Alloy Catalyst
ACS Catalysis,
Год журнала:
2024,
Номер
14(8), С. 5675 - 5684
Опубликована: Апрель 1, 2024
Electrocatalytic
semihydrogenation
of
alkynols
to
alkenols
under
ambient
conditions
using
H2O
as
a
hydrogen
source
is
highly
attractive
in
synthetic
chemistry.
However,
it
still
challenging
achieve
high
Faradaic
efficiency
(FE)
wide
potential
window.
Herein,
we
reported
bimetallic
Cu3Au
alloy
an
efficient
catalyst
for
electrocatalytic
alkenols.
Specifically,
during
2-butyne-1,4-diol
(BYD)
2-butene-1,4-diol
(BED),
the
achieves
12.6-fold
greater
reaction
rate
and
higher
FE
compared
with
pure
Cu
(99
vs
63%).
Moreover,
maintains
>96%
FEs
window
from
−0.19
−0.59
V
RHE.
We
demonstrate
that
competitive
adsorptions
reactive
(H*)
BYD
greatly
influence
processes.
The
presence
Au
facilitates
H*
formation
reduces
adsorption
on
Cu,
thus
enhancing
hydrogenation
performance.
affords
broad
substrate
scope
aromatic
alkynes,
producing
corresponding
alkenes
good
selectivities.
Finally,
coupled
glycerol
oxidation
replace
oxygen
evolution
two-electrode
system,
showing
40%
energy
saving
at
200
mA
BED
production
coproduction
valuable
formate
anode,
demonstrating
economical
manner.
Язык: Английский
A Cosolvent Electrolyte Boosting Electrochemical Alkynol Semihydrogenation
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
147(2), С. 1938 - 1947
Опубликована: Янв. 2, 2025
Green
electricity-driven
alkenol
electrosynthesis
via
electrocatalytic
alkynol
semihydrogenation
represents
a
sustainable
route
to
conventional
thermocatalysis.
Both
the
electrocatalyst
and
electrolyte
strongly
impact
performance.
Despite
significant
progress
in
developing
sophisticated
electrocatalysts,
well-designed
conjunction
with
industrial
catalysts
is
an
attractive
strategy
advance
industrialization
process
of
semihydrogenation,
but
remains
unexplored.
Here,
we
develop
dimethyl
sulfoxide
(DMSO)-H2O
cosolvent
for
semihydrogenation.
At
conversion
about
100%,
DMSO-H2O
compared
DMSO-free
counterpart
enables
selectivity
on
Cu
be
promoted
from
60–70%
over
90%
at
all
measured
current
densities;
meanwhile,
reaction
rate
slightly
decreased
due
inhibited
water
dissociation.
Mechanistic
studies
reveal
that
strong
hydrogen-bond
interactions
between
DMSO
H2O
suppress
dissociation
interfacial
H2O,
leading
H*
coverage
electrode
surface.
The
hinders
overhydrogenation
alkynols
favors
production
alkenols.
Remarkably,
DMSO-induced
enhancement
applicable
set
commercial
various
alkynols.
Eventually,
scaled-up
3
×
100
cm2
electrolyzer
stack
established
achieve
∼96%
∼95%
electrolyte.
This
work
not
only
presents
boosting
electrosynthesis,
also
highlights
possibility
electro-production.
Язык: Английский
Efficient Photocatalytic Semihydrogenation of 2-Butyne-1,4-diol over TiO2 Supported Cu Single Atoms with Near-Unity Conversion and Selectivity
ACS Sustainable Chemistry & Engineering,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 8, 2025
Язык: Английский
Renaissance in Alkyne Semihydrogenation: Mechanism, Selectivity, Functional Group Tolerance, and Applications in Organic Synthesis
Chemical Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 25, 2025
Alkenes
constitute
a
significant
class
of
chemical
compounds
with
applications
in
the
bulk,
pharmaceutical,
or
perfume
industry.
Among
known
methods
olefin
production,
semihydrogenation
C-C
triple
bond
seems
to
be
most
straightforward
one.
Nonetheless,
success
this
reaction
requires
full
control
over
diastereoselectivity,
eradication
parasitic
process
over-reduction
migration
double
formed,
and
achieving
satisfactory
functional-group
compatibility.
The
review
demonstrates
developments
field
alkyne
period
2010-2022,
selected
papers
published
2023
2024,
emphasizing
solutions
above-mentioned
limitations.
We
discuss
mechanistic
aspects
transformation,
including
those
related
unconventional
systems.
includes
examples
organic
synthesis,
confirming
considerable
utility
process.
Finally,
strategies
enhance
catalyst
selectivity
are
summarized.
For
reader's
convenience,
we
provided
graphical
guidebook
catalytic
systems,
illustrating
efficiency
particular
method.
Язык: Английский
Membrane‐Free Selective Semi‐Hydrogenation of Alkynes Over an In Situ Formed Copper Nanoparticle Electrode
Small,
Год журнала:
2024,
Номер
20(33)
Опубликована: Март 26, 2024
Selective
semi-hydrogenation
of
alkynes
is
a
significant
reaction
for
preparing
functionalized
alkenes.
Electrochemical
presents
sustainable
alternative
to
the
traditional
thermal
process.
In
this
research,
affordable
copper
acetylacetonate
employed
as
catalyst
precursor
electrocatalytic
hydrogenation
alkynes,
using
MeOH
hydrogen
source
in
an
undivided
cell.
Good
excellent
yields
both
aromatic
and
aliphatic
internal/terminal
are
obtained
under
constant
current
conditions.
Notably,
up
99%
Z
selectivity
achieved
various
internal
alkynes.
Mechanistic
investigations
revealed
formation
nanoparticles
(NPs)
at
cathode
during
electrolysis,
acting
selective
semireduction
The
NPs
deposited
demonstrated
reusable
further
hydrogenation.
Язык: Английский
Electroplated Electrodes for Continuous and Mass‐Efficient Electrochemical Hydrogenation
Chemistry - A European Journal,
Год журнала:
2023,
Номер
30(18)
Опубликована: Дек. 15, 2023
Abstract
Electrocatalytic
hydrogenations
(ECH)
enable
the
reduction
of
organic
substrates
upon
usage
electric
current
and
present
a
sustainable
alternative
to
conventional
processes
if
green
electricity
is
used.
Opposed
most
protocols
for
electrode
preparation,
this
work
presents
one‐step
binder‐
additive‐free
production
silver‐
copper‐electroplated
electrodes.
Controlled
adjustment
preparation
parameters
allows
tuning
catalyst
morphology
its
electrochemical
properties.
Upon
optimization
deposition
protocol
carbon
support,
high
faradaic
efficiencies
93
%
ECH
Vitamin
A‐
E‐synthon
2‐methyl‐3‐butyn‐2‐ol
(MBY)
are
achieved
that
can
be
maintained
at
densities
240
mA
cm
−2
minimal
loadings
0.2
mg
,
corresponding
an
unmatched
rate
1.47
kg
MBE
g
cat
−1
h
.
For
continuous
hydrogenation
process,
directly
transferred
into
single‐pass
operation
mode
giving
1.38
Subsequently,
substrate
spectrum
was
extended
total
17
different
C−C−,
C−O−
N−O−unsaturated
compounds
revealing
general
applicability
reported
process.
Our
results
lay
important
groundwork
development
reactors
electrodes
able
compete
with
palladium‐based
thermocatalytic
state
art.
Язык: Английский
Thiol treatment tunes interfacial wettability for electrochemical alkynol semi‐hydrogenation
AIChE Journal,
Год журнала:
2024,
Номер
70(12)
Опубликована: Авг. 23, 2024
Abstract
Electrocatalytic
semi‐hydrogenation
of
alkynols
holds
tremendous
advantages
over
conventional
thermocatalysis
process.
However,
the
selectivity‐activity
seesaw
effect
is
a
principal
obstacle
to
its
further
development.
Inspired
by
interfacial
self‐assembled
monolayers,
alkanethiols
with
different
alkyl
chain
lengths
are
employed
modify
Cu
surface
for
controllably
modulating
activity
and
selectivity
in
alkynols.
1‐dodecanethiol‐modified
nanowires
(Cu
NWs)
exhibit
optimal
electrosynthesis
2‐methyl‐3‐buten‐2‐ol
excellent
specific
(above
93%)
2‐methyl‐3‐butyn‐2‐ol.
Mechanistic
studies
reveal
that
proportion
liquid‐like
water
increases
while
isolated
reduces
at
hydrophobic
interface.
Moreover,
we
assemble
larger
3
×
100
cm
2
electrolyzer
stack,
which
can
deliver
single‐pass
alkynol
conversion
rate
95%
an
alkenol
94%
15
A
stack
current.
Eventually,
NWs
catalyst
thiol
treatment
also
applicable
various
unsaturated
Язык: Английский