Advanced Functional Materials,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 30, 2024
Abstract
Metal–organic
framework
(MOF)
catalysts
promise
selective
hydrogenation
of
C═O
bonds,
a
process
that
is
thermodynamically
unfavorable
because
the
presence
C─O,
C═C,
and
C─C
bonds
within
furan
rings.
However,
reactivity
stability
MOF
are
often
impeded
in
catalytic
reactions
by
structural
collapse
or
phase
transition
stemming
from
commonly
employed
strategies
such
as
defect
engineering.
The
present
work
investigates
novel
strategy
for
designing
highly
active
Co₁Ni₁@UiO‐66‐NH₂
embedding
Co₁Ni₁
UiO‐66‐NH₂
framework.
This
approach
facilitates
efficient
charge
transfer
between
reactants
catalysts,
thereby
preserving
both
integrity.
turnover
frequency
Co
1
Ni
@UiO‐66‐NH
2
430
h⁻¹,
contrast
to
18
h⁻¹
UiO‐66‐NH
,
demonstrating
activity
24
times
greater
than
.
More
importantly,
reaction
rate
achieves
7.27
mol
g⁻¹
with
furfuryl
alcohol
(FOL)
yield
100%,
catalyst
retains
its
excellent
even
after
eight
cycles
applications.
Density
functional
theory
calculations
indicate
that,
comparison
UiO‐66‐NH₂,
Co‐
Ni@UiO‐66‐NH₂,
exhibits
relatively
strong
interactions
significant
exchanges
catalysts.
These
not
only
facilitate
dehydrogenation
isopropanol
but
also
enhance
furfural.
Furthermore,
density
states
reveals
number
near
Fermi
level
compared
Ni@UiO‐66‐NH
substantial
performance
ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
unknown, P. 1206 - 1216
Published: Jan. 6, 2025
Aqueous-phase
tandem
reactions,
as
a
fundamental
aspect
of
green
chemistry,
hold
crucial
position
in
the
contemporary
synthesis
fine
chemicals,
wherein
advancement
high-performance
heterogeneous
catalysts
remains
formidable
challenge.
Herein,
we
report
Pt1Con
single-atom
alloy
(SAA)
catalyst
which
Pt
single
atoms
are
immobilized
onto
surface
Co
nanoparticles
through
Pt–Co
coordination.
The
SAA
exhibits
high
chemoselectivity
for
aqueous-phase
hydrogenation–rearrangement
reaction
furfural
(FAL)
to
cyclopentanol
(CPL)
(yield:
>93%,
considering
carbon
loss),
with
TOF
value
2257
h–1
(based
on
Pt).
A
joint
investigation
based
dynamics,
isotope-label
tracing
experiments,
EPR,
and
situ
FT-IR
verifies
five-step
consecutive
pathway
formation
CPL.
Notably,
during
reaction,
rapid
exchange
hydrogen
would
occur
between
activated
species
water
solvent.
Furthermore,
molecule
does
not
serve
H-donor
but
is
involved
rearrangement
side
chain
furan
ring.
Kinetic
studies
combined
DFT
calculations
substantiate
that
interface
sites
effectively
lower
energy
barrier
cyclopentanone
(CPO)
hydrogenation
step
via
facilitating
activation
adsorption
carbonyl
group,
accounting
largely
enhanced
catalytic
behavior.
This
study
sheds
light
highly
efficient
stable
biomass
upgrading
aqueous
phase.
AIChE Journal,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 8, 2025
Abstract
Catalytic
hydrogenative
rearrangement
of
furanic
aldehydes
is
crucial
for
producing
biomass‐derived
cyclopentanone
fine
chemicals.
However,
designing
highly
selective
catalysts
remains
challenging
due
to
the
interplay
among
tandem
hydrogenation,
ring‐opening,
aldol
condensation,
dehydration,
and
parallel
ring‐hydrogenation.
Here,
we
employ
a
single
self‐assembly
step
by
depositing
phosphonic
acids
(PAs)
on
conventional
Ni
introduce
tunable
interfacial
Brønsted
acid
sites
(BAS),
resulting
in
an
unprecedented
3‐hydroxymethyl‐cyclopentanone
yield
95.8%
from
hydroxymethylfurfural.
Kinetic
studies
reveal
one‐order‐of‐magnitude
increase
ring‐opening
rates—the
slow
rearrangement—after
PAs
modification,
accompanied
drop
apparent
activation
energy
154.1
105.4
kJ
mol
−1
.
In
contrast,
ring‐hydrogenation
side
reaction
almost
unchanged.
Theoretical
calculations
suggest
that
BAS
synergize
with
adjacent
lower
C–O
cleavage
barrier
providing
protons
attack
hydroxymethyl
oxygen
atom,
which
key
initiate
ring‐opening.
