ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(22), P. 13969 - 13979
Published: Oct. 31, 2022
Hydrogenolysis
of
C–C
bonds
over
Ru-based
catalysts
has
emerged
as
a
deconstruction
strategy
to
convert
single-use
polyolefin
waste
liquid
alkanes
at
relatively
mild
conditions,
but
this
approach
exhibits
limitations,
including
methane
formation
resulting
from
terminal
bond
scission.
In
study,
variety
were
investigated
for
the
reductive
polyethylene
(PE)
and
polypropylene
(PP)
identify
supports
that
promote
nonterminal
We
found
Ru
nanoparticles
supported
on
Brønsted-acidic
zeolites
with
faujasite
(FAU)
Beta
(BEA)
topologies
highly
active
cleavage
in
PE
PP,
exhibiting
improved
yields
suppressed
formation.
For
PE,
supporting
ruthenium
(5
wt
%)
FAU
increased
67%
compared
33%
an
inert
silica
support
%
Ru/SiO2)
200
°C,
16
h,
under
30
bar
H2.
A
dramatic
selectivity
enhancement
toward
hydrocarbons
was
also
observed
PP
Ru/FAU
Ru/BEA
Ru/SiO2.
To
understand
origin
improvement,
combination
ex
situ
operando
characterization
techniques
used
reveal
both
catalyst
structure
acidity
play
key
roles
conversion.
Operando
X-ray
absorption
spectroscopy
studies
model
polyolefins
Ru-supported
varying
levels
revealed
local
chemical
environment
Ru[0]
during
reaction
is
consistent
across
multiple
acidic
supports,
although
onset
reduction
synthesis
varies
different
supports.
These
results,
combined
reactivity
data,
demonstrate
importance
acid-noble
metal
cooperativity
promoting
selective
scission
shifts
mechanism
hydrogenolysis
ideal
hydrocracking.
Science,
Journal Year:
2022,
Volume and Issue:
378(6616), P. 207 - 211
Published: Oct. 13, 2022
Mixed
plastics
waste
represents
an
abundant
and
largely
untapped
feedstock
for
the
production
of
valuable
products.
The
chemical
diversity
complexity
these
materials,
however,
present
major
barriers
to
realizing
this
opportunity.
In
work,
we
show
that
metal-catalyzed
autoxidation
depolymerizes
comingled
polymers
into
a
mixture
oxygenated
small
molecules
are
advantaged
substrates
biological
conversion.
We
engineer
robust
soil
bacterium,
Pseudomonas
putida,
funnel
compounds
single
exemplary
product,
either
β-ketoadipate
or
polyhydroxyalkanoates.
This
hybrid
process
establishes
strategy
selective
conversion
mixed
useful
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(9), P. 5612 - 5701
Published: March 14, 2023
Plastics
are
everywhere
in
our
modern
way
of
living,
and
their
production
keeps
increasing
every
year,
causing
major
environmental
concerns.
Nowadays,
the
end-of-life
management
involves
accumulation
landfills,
incineration,
recycling
to
a
lower
extent.
This
ecological
threat
environment
is
inspiring
alternative
bio-based
solutions
for
plastic
waste
treatment
toward
circular
economy.
Over
past
decade,
considerable
efforts
have
been
made
degrade
commodity
plastics
using
biocatalytic
approaches.
Here,
we
provide
comprehensive
review
on
recent
advances
enzyme-based
biocatalysis
design
related
processes
recycle
or
upcycle
plastics,
including
polyesters,
polyamides,
polyurethanes,
polyolefins.
We
also
discuss
scope
limitations,
challenges,
opportunities
this
field
research.
An
important
message
from
that
polymer-assimilating
enzymes
very
likely
part
solution
reaching
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(11), P. 6144 - 6155
Published: Feb. 17, 2023
Transformation
of
biomass
and
plastic
wastes
to
value-added
chemicals
fuels
is
considered
an
upcycling
process
that
beneficial
resource
utilization.
Electrocatalysis
offers
a
sustainable
approach;
however,
it
remains
huge
challenge
increase
the
current
density
deliver
market-demanded
with
high
selectivity.
Herein,
we
demonstrate
electrocatalytic
strategy
for
glycerol
(from
biodiesel
byproduct)
lactic
acid
ethylene
glycol
polyethylene
terephthalate
waste)
glycolic
acid,
both
products
being
as
valuable
monomers
biodegradable
polymer
production.
By
using
nickel
hydroxide-supported
gold
electrocatalyst
(Au/Ni(OH)2),
achieve
selectivities
(77
91%,
respectively)
densities
at
moderate
potentials
(317.7
mA/cm2
0.95
V
vs
RHE
326.2
1.15
RHE,
respectively).
We
reveal
can
be
enriched
Au/Ni(OH)2
interface
through
their
adjacent
hydroxyl
groups,
substantially
increasing
local
concentrations
thus
densities.
As
proof
concept,
employed
membrane-free
flow
electrolyzer
triglyceride
PET
bottles,
attaining
11.2
g
coupled
9.3
L
H2
13.7
9.4
H2,
respectively,
revealing
potential
coproduction
fuel
from
in
fashion.
Science,
Journal Year:
2023,
Volume and Issue:
381(6658), P. 666 - 671
Published: Aug. 10, 2023
Conversion
of
plastic
wastes
to
fatty
acids
is
an
attractive
means
supplement
the
sourcing
these
high-value,
high-volume
chemicals.
We
report
a
method
for
transforming
polyethylene
(PE)
and
polypropylene
(PP)
at
~80%
conversion
with
number-average
molar
masses
up
~700
670
daltons,
respectively.
The
process
applicable
municipal
PE
PP
their
mixtures.
Temperature-gradient
thermolysis
key
controllably
degrading
into
waxes
inhibiting
production
small
molecules.
are
upcycled
by
oxidation
over
manganese
stearate
subsequent
processing.
ꞵ-scission
produces
more
olefin
wax
yields
higher
acid-number
than
does
ꞵ-scission.
further
convert
large-market-volume
surfactants.
Industrial-scale
technoeconomic
analysis
suggests
economic
viability
without
need
subsidies.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(11)
Published: Jan. 19, 2023
Electro-reforming
of
Polyethylene-terephthalate-derived
(PET-derived)
ethylene
glycol
(EG)
into
fine
chemicals
and
H2
is
an
ideal
solution
to
address
severe
plastic
pollution.
Here,
we
report
the
electrooxidation
EG
glycolic
acid
(GA)
with
a
high
Faraday
efficiency
selectivity
(>85
%)
even
at
industry-level
current
density
(600
mA
cm-2
1.15
V
vs.
RHE)
over
Pd-Ni(OH)2
catalyst.
Notably,
stable
electrolysis
200
h
can
be
achieved,
outperforming
all
available
Pd-based
catalysts.
Combined
experimental
theoretical
results
reveal
that
1)
OH*
generation
promoted
by
Ni(OH)2
plays
critical
role
in
facilitating
EG-to-GA
oxidation
removing
poisonous
carbonyl
species,
thereby
achieving
activity
stability;
2)
Pd
downshifted
d-band
center
oxophilic
Ni
synergistically
facilitate
rapid
desorption
transfer
GA
from
active
sites
inactive
sites,
avoiding
over-oxidation
thus
selectivity.
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(8), P. 5139 - 5219
Published: April 9, 2023
Combustion
is
a
reactive
oxidation
process
that
releases
energy
bound
in
chemical
compounds
used
as
fuels─energy
needed
for
power
generation,
transportation,
heating,
and
industrial
purposes.
Because
of
greenhouse
gas
local
pollutant
emissions
associated
with
fossil
fuels,
combustion
science
applications
are
challenged
to
abandon
conventional
pathways
adapt
toward
the
demand
future
carbon
neutrality.
For
design
efficient,
low-emission
processes,
understanding
details
relevant
transformations
essential.
Comprehensive
knowledge
gained
from
decades
fossil-fuel
research
includes
general
principles
establishing
validating
reaction
mechanisms
models,
relying
on
both
theory
experiments
suite
analytic
monitoring
sensing
techniques.
Such
can
be
advantageously
applied
extended
configure,
analyze,
control
new
systems
using
different,
nonfossil,
potentially
zero-carbon
fuels.
Understanding
impact
its
links
chemistry
needs
some
background.
The
introduction
therefore
combines
information
exemplary
cultural
technological
achievements
nature
effects
emissions.
Subsequently,
methodology
described.
A
major
part
devoted
followed
by
discussion
selected
applications,
illustrating
future.