Abstract
The
Co@NC
catalyst
exhibits
significant
protic
solvent
preference
for
hydrogenation
of
nitriles
to
primary
amines.
However,
the
effect
mixed
solvents
on
catalytic
has
received
little
attention.
Herein,
synergetic
been
proposed
accelerate
adiponitrile
(ADN)
hexamethylenediamine
through
H
2
O‐ethanol
hydrogen
bond
networks
catalyst.
Experimental
screenings
showed
that
ADN
conversion
in
was
1.6
~
5.1
times
greater
than
single
solvents.
Kinetic
models
O/ethanol
(
v
W
=
0.6),
O,
and
ethanol
effected
transformation
dominated
reaction.
Isotope
labelling
kinetic
experiments
revealed
O
acted
as
co‐catalysts
exchanging
transferring
via
hydroxyl
groups.
Density
functional
theory
calculations
confirmed
energy
barrier
proton
transfer
mediated
by
H₂O–ethanol
reduced
0.18
eV
compared
H₂O–H₂O
dimers.
Abstract
Optimizing
kinetic
barriers
of
hydrogen
spillover
for
selective
hydrogenation
on
supported
catalysts
with
dual‐active
sites
faces
a
significant
challenge
due
to
inherent
contradiction
between
H
2
activation
and
*H
transformation
from
metal
support.
Herein,
the
adsorption
energy
(
E
ad
(H))
has
been
demonstrated
as
viable
descriptor
understanding
WO
3
surface
single‐atom
metals
oxygen
vacancies.
Theoretical
simulations
rationalize
optimized
value
(H)
−2.49
eV
these
sites.
Furthermore,
absolute
(|Δ
(H)|)
was
calculated
directly
explore
catalytic
activity
M
1
/NR‐WO
.
Among
them,
Pt
lowest
|Δ
(H)|
exhibited
weakened
enabled
efficient
activation,
resulting
in
TOF
170,480
h
−1
>99.9%
selectivity
p
‐chloronitrobenzene
‐chloroaniline.
These
findings
provide
new
insights
into
spillover‐promoted
hydrogenation.
Abstract
Multimetallic
metal–organic
framework
(MOF)
nanoparticles
have
been
regarded
as
promising
electrocatalysts
for
the
oxygen
evolution
reaction
(OER)
due
to
their
small
size,
porous
structure,
and
synergistic
active
metal
site.
However,
limitations
such
stringent
preparation
conditions,
long
times,
low
yields
restrict
further
application.
Herein,
an
instantaneous
continuous
approach
is
proposed
synthesize
multimetallic
MOF
utilizing
high
gravity
technology.
With
greatly
enhanced
mixing
mass
transfer
in
rotating
packed
bed
reactor,
instantaneously
synthesized
bimetallic/trimetallic
show
smaller
particle
sizes,
higher
surface
areas,
OER
performance
compared
with
corresponding
stirred
tank
reactor
products.
Density
functional
theory
calculations
elucidate
intrinsic
activity
regulation
mechanism
of
bimetallic
MOFs.
This
study
not
only
proposes
efficient
strategy
MOFs
but
also
can
achieve
scaled‐up
ultra‐high
space–time
yield
(43,700
kg
m
−3
day
−1
),
promoting
practical
application
electrocatalysis.
Abstract
The
selective
hydrogenation
of
5‐(hydroxymethyl)furfural
(HMF)
into
2,5‐bis‐(hydroxymethyl)tetrahydrofuran
(BHMTHF)
in
flow
reactor
using
water
as
a
green
solvent,
has
been
achieved
on
non‐noble
metal
catalyst
based
monodispersed
CoNi
alloy
nanoparticles
covered
by
thin
carbon
layer.
alloyed
containing
(molar
ratio
1
:
1)
was
prepared
one‐step
synthesis
following
hydrothermal
method.
Total
conversion
HMF
with
91
%
selectivity
to
BHMTHF
achieved.
reaction
network
stablished,
which
the
carbonyl
group
is
first
reduced
alcohol
giving
2,5‐bis‐(hydroxymethyl)furan
(BHMF)
an
apparent
activation
energy
25
KJ/mol,
and
then
double
bonds
furan
ring
are
hydrogenated
(apparent
Ea=31
KJ/mol).
Formation
byproducts,
mainly
proceed
from
opening
rearrangement
processes
BHMF,
promoted
water.
resulted
compound
highly
stable
under
conditions.
fixed
bed
maintained
operational
for
65
h
without
observing
any
loss
catalytic
activity
selectivity.
Abstract
It
is
still
a
challenge
to
develop
electrocatalyst
for
the
efficient
adsorption
and
conversion
of
organic
molecule
in
aqueous
media.
Herein,
hetero‐interface
structure
based
on
CuO@Ni(OH)
2
rationally
designed
enhance
performance
benzyl
alcohol
oxidation
benzoic
acid.
A
high
Faradaic
efficiency
99%
yield
3.09
mmol
cm
−2
h
−1
are
achieved
at
1.70
V
versus
reversible
hydrogen
electrode,
outperforming
previously
reported
electrocatalysts.
Furthermore,
membrane‐free
flow
electrolyzer
was
assembled
hetero‐interface,
exhibiting
much
yielding
acid
(6.73
)
(0.35
L
with
excellent
stability.
Both
experimental
data
density
functional
theory
calculations
verify
that
electron
tend
accumulate
thus
accelerating
reactant
intermediate
reducing
energy
barrier
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 22, 2024
Abstract
The
selective
hydrogenation
of
5‐hydroxymethylfurfural
(HMF)
to
2,5‐bishydroxymethyltetrahydrofuran
(BHMTHF),
a
vital
fuel
precursor
and
solvent,
is
crucial
for
biomass
refining.
Herein,
we
report
highly
stable
PdNi
nanoalloy
catalysts
this
deep
process.
A
CO
2
‐assisted
green
method
was
developed
the
controllable
synthesis
various
bimetallic
monometallic
catalysts.
PdNi/SBA‐15
with
Pd/Ni
ratios
exhibited
volcano‐like
trend
between
BHMTHF
yield
ratio.
Among
all
tested,
Pd
Ni
1
/SBA‐15
achieved
best
performance,
converting
99.0
%
HMF
96.0
selectivity,
surpassing
previously
reported
Additionally,
catalyst
maintained
excellent
stability
even
after
five
recycling
runs.
Catalyst
characterizations
(e.
g.,
HAADF‐STEM)
density
functional
theory
(DFT)
calculations
confirmed
successful
formation
alloy
structure
electron
transfer
Pd,
which
accounts
remarkable
performance
catalyst.
This
work
paves
way
developing
valorization.
ACS Applied Nano Materials,
Год журнала:
2024,
Номер
7(8), С. 9195 - 9209
Опубликована: Апрель 10, 2024
The
hydrogenation
of
nitrogen-containing
heterocyclic
compounds
and
their
derivatives
to
obtain
the
corresponding
valuable
products
is
great
practical
significance.
In
this
work,
a
highly
active
selective
Ni/NC
catalyst
was
developed
by
utilizing
melamine-modified
high-specific
surface
carbon
(NC)
as
carrier
for
nickel
nanoparticles
(NPs),
which
showed
excellent
catalytic
activity
in
methyl
nicotinate,
where
first
used
reaction
(selective
nicotinate).
It
found
that
nitrogen
species
on
NC
significantly
promoted
decomposition
precursor
high
dispersion
nano-Ni,
effectively
affected
agglomeration
metal,
resulting
distribution
metal
with
smaller
particle
size.
nicotinate
under
mild
conditions
(130
°C,
3
h),
conversion
reached
optimal
over
10%
Ni/NC-1-M-I-300,
98.5%
selectivity
methylpiperidine-3-carboxylate
97.2%.
After
5
recycles,
maintained
95.4%
nicotinate.
has
good
substrate
adaptability
N-heterocyclic
carboxylate,
O-heterocyclic
aromatic
carboxylate.
