Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(28)
Опубликована: Май 5, 2022
Cu-based
metal-organic
frameworks
have
attracted
much
attention
for
electrocatalytic
CO2
reduction,
but
they
are
generally
instable
and
difficult
to
control
the
product
selectivity.
We
report
flexible
Cu(I)
triazolate
as
efficient,
stable,
tunable
electrocatalysts
reduction
C2
H4
/CH4
.
By
changing
size
of
ligand
side
groups,
selectivity
ratio
can
be
gradually
tuned
inversed
from
11.8
:
1
2.6,
giving
,
CH4
hydrocarbon
selectivities
up
51
%,
56
77
respectively.
After
long-term
electrocatalysis,
retain
structures/morphologies
without
formation
inorganic
species.
Computational
simulations
showed
that
coordination
geometry
changed
triangular
tetrahedral
bind
reaction
intermediates,
two
adjacent
cooperated
C-C
coupling
form
Importantly,
groups
controlled
catalyst
flexibility
by
steric
hindrance
mechanism,
pathway
is
more
sensitive
than
one.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(32)
Опубликована: Июнь 8, 2022
Heteroatom-doping
in
metal-nitrogen-carbon
single-atom
catalysts
(SACs)
is
considered
a
powerful
strategy
to
promote
the
electrocatalytic
CO2
reduction
reaction
(CO2
RR),
but
origin
of
enhanced
catalytic
activity
still
elusive.
Here,
we
disclose
that
sulfur
doping
induces
an
obvious
proton-feeding
effect
for
RR.
The
model
SAC
catalyst
with
second-shell
FeN4
(Fe1
-NSC)
was
verified
by
X-ray
absorption
spectroscopy
and
aberration-corrected
scanning
transmission
electron
microscopy.
Fe1
-NSC
exhibits
superior
RR
performance
compared
sulfur-free
most
reported
Fe-based
SACs,
maximum
CO
Faradaic
efficiency
98.6
%
turnover
frequency
1197
h-1
.
Kinetic
analysis
situ
characterizations
confirm
accelerates
H2
O
activation
feeds
sufficient
protons
promoting
conversion
*COOH,
which
also
corroborated
theoretical
results.
This
work
deepens
understanding
mechanism
based
on
catalysts.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
61(4)
Опубликована: Ноя. 12, 2021
The
exploitation
of
highly
efficient
carbon
dioxide
reduction
(CO2
RR)
electrocatalyst
for
methane
(CH4
)
electrosynthesis
has
attracted
great
attention
the
intermittent
renewable
electricity
storage
but
remains
challenging.
Here,
N-heterocyclic
carbene
(NHC)-ligated
copper
single
atom
site
(Cu
SAS)
embedded
in
metal-organic
framework
is
reported
(2Bn-Cu@UiO-67),
which
can
achieve
an
outstanding
Faradaic
efficiency
(FE)
81
%
CO2
to
CH4
at
-1.5
V
vs.
RHE
with
a
current
density
420
mA
cm-2
.
FE
our
catalyst
above
70
within
wide
potential
range
and
achieves
unprecedented
turnover
frequency
(TOF)
16.3
s-1
σ
donation
NHC
enriches
surface
electron
Cu
SAS
promotes
preferential
adsorption
CHO*
intermediates.
porosity
facilitates
diffusion
2Bn-Cu,
significantly
increasing
availability
each
catalytic
center.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(48), С. 25485 - 25492
Опубликована: Сен. 17, 2021
Herein,
an
effective
tandem
catalysis
strategy
is
developed
to
improve
the
selectivity
of
CO2
RR
towards
C2
H4
by
multiple
distinct
catalytic
sites
in
local
vicinity.
An
earth-abundant
elements-based
electrocatalyst
PTF(Ni)/Cu
constructed
uniformly
dispersing
Cu
nanoparticles
(NPs)
on
porphyrinic
triazine
framework
anchored
with
atomically
isolated
nickel-nitrogen
(PTF(Ni))
for
enhanced
produce
.
The
Faradaic
efficiency
reaches
57.3
%
at
-1.1
V
versus
reversible
hydrogen
electrode
(RHE),
which
about
6
times
higher
than
non-tandem
catalyst
PTF/Cu,
produces
CH4
as
major
carbon
product.
operando
infrared
spectroscopy
and
theoretic
density
functional
theory
(DFT)
calculations
reveal
that
high
concentration
CO
generated
PTF(Ni)
can
facilitate
C-C
coupling
form
nearby
NP
sites.
work
offers
avenue
design
electrocatalysts
highly
selective
multicarbon
products
via
a
route.
Accounts of Chemical Research,
Год журнала:
2022,
Номер
55(20), С. 2978 - 2997
Опубликована: Сен. 26, 2022
ConspectusThe
continuing
increase
of
the
concentration
atmospheric
CO2
has
caused
many
environmental
issues
including
climate
change.
Catalytic
conversion
using
thermochemical,
electrochemical,
and
photochemical
methods
is
a
potential
technique
to
decrease
simultaneously
obtain
value-added
chemicals.
Due
high
energy
barrier
however,
this
method
still
far
from
large-scale
applications
which
requires
activity,
selectivity,
stability.
Therefore,
development
efficient
catalysts
convert
different
products
urgent.
With
their
well-engineered
pores
chemical
compositions,
surface
area,
elevated
adsorption
capability,
adjustable
active
sites,
porous
crystalline
frameworks
metal-organic
(MOFs)
covalent
organic
(COFs)
are
materials
for
catalytic
conversion.
Here,
we
summarize
our
recent
work
on
MOFs
COFs
thermocatalytic,
electrocatalytic,
photocatalytic
describe
structure-activity
relationships
that
could
guide
design
effective
catalysts.The
first
section
paper
describes
imidazolium-functionalized
MOFs,
liquid
cationic
with
nucleophilic
halogen
ions,
can
promote
thermocatalytically
cycloaddition
reaction
epoxides
toward
cyclic
carbonates
at
one
bar
pressure.
A
MOF
takes
role
reservoir
tackle
low
local
concentrations
in
gas-liquid-solid
heterogeneous
reactions.
Imidazolium-functionalized
ions
avoid
use
cocatalysts,
leads
milder
more
facile
experimental
conditions
separation
processes.In
dealing
electrocatalytic
reduction
(CO2RR),
developed
series
conductive
framework
fast
electron
transmission
capabilities,
afford
current
densities
outperform
traditional
COF
have
been
reported.
The
intrinsically
two-dimensional
2D
nanosheets
based
fully
π-conjugated
phthalocyanine
motif
excellent
transport
capability
were
prepared,
strong
transporters
also
integrated
into
metalloporphyrin-based
CO2RR.
Cu2O
quantum
dots
Cu
nanoparticles
(NPs)
be
uniformly
dispersed
MOFs/COFs
synergistic
and/or
tandem
electrocatalysts,
achieve
highly
selective
production
CH4
or
C2H4
CO2RR.A
third
efforts
facilitate
electron-hole
photocatalysis.
Our
focus
regulation
coordination
spheres
fabrication
architecture
heterojunctions,
engineering
films
reduction.Finally,
discuss
several
problems
associated
studies
consider
some
prospects
ACS Nano,
Год журнала:
2022,
Номер
16(2), С. 1759 - 1780
Опубликована: Янв. 20, 2022
A
highly
effective
electrocatalyst
is
the
central
component
of
advanced
electrochemical
energy
conversion.
Recently,
two-dimensional
conjugated
metal-organic
frameworks
(2D
c-MOFs)
have
emerged
as
a
class
promising
electrocatalysts
because
their
advantages
including
2D
layered
structure
with
high
in-plane
conjugation,
intrinsic
electrical
conductivity,
permanent
pores,
large
surface
area,
chemical
stability,
and
structural
diversity.
In
this
Review,
we
summarize
recent
advances
c-MOF
for
First,
introduce
design
principles
synthetic
strategies
reported
c-MOFs,
well
functional
electrocatalysis.
Subsequently,
present
representative
in
various
reactions,
such
hydrogen/oxygen
evolution,
reduction
reactions
oxygen,
carbon
dioxide,
nitrogen.
We
highlight
property
tuning
to
boost
catalytic
performance,
offer
our
perspectives
regard
challenges
be
overcome.
Deleted Journal,
Год журнала:
2022,
Номер
1, С. e9120021 - e9120021
Опубликована: Июль 4, 2022
With
the
disruptive
carbon
cycle
being
blamed
for
global
warming,
plausible
electrocatalytic
CO2
reduction
reaction
(CO2RR)
to
form
valuable
C2+
hydrocarbons
and
feedstock
is
becoming
a
hot
topic.
Cu-based
electrocatalysts
have
been
proven
be
excellent
CO2RR
alternatives
high
energy
value-added
products
in
this
regard.
However,
selectivity
of
via
catalysts
suffers
from
overpotential,
slow
kinetics,
low
selectivity.
This
review
attempts
discuss
various
cutting-edge
strategies
understanding
catalytic
design
such
as
catalyst
surface
engineering,
tuning
Cu
bandgap
alloying,
nanocatalysis,
effect
electrolyte
pH
on
morphology.
The
most
recent
advances
in
situ
spectroscopy
computational
techniques
are
summarized
fully
comprehend
mechanisms,
structural
transformation/degradation
crystal
facet
loss
with
subsequent
effects
activity.
Furthermore,
approaches
interactions
discussed
four
key
perspectives:
single-atom
catalysts,
interfacial
metal-organic
frameworks,
polymer-incorporated
materials,
which
provide
new
insights
into
products.
Finally,
major
challenges
outlined,
potential
prospects
rational
robust
proposed.
integration
mechanistic
step
forward
promising
advancement
technology
industrial
applications.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(11), С. 6339 - 6348
Опубликована: Март 9, 2023
Electrocatalytic
CO2
reduction
reaction
(CO2RR)
is
one
of
the
most
promising
routes
to
facilitate
carbon
neutrality.
An
alkaline
electrolyte
typically
needed
promote
production
valuable
multi-carbon
molecules
(such
as
ethylene).
However,
between
and
OH-
consumes
a
significant
quantity
CO2/alkali
causes
rapid
decay
CO2RR
selectivity
stability.
Here,
we
design
catalyst-electrolyte
interface
with
an
effective
electrostatic
confinement
in
situ
generated
improve
ethylene
electrosynthesis
from
neutral
medium.
In
Raman
measurements
indicate
direct
correlation
intensities
surface
Cu-CO
Cu-OH
species,
suggesting
promoted
C-C
coupling
enrichment
OH-.
Thus,
report
CO2-to-ethylene
Faradaic
efficiency
(FE)
70%
partial
current
density
350
mA
cm-2
at
-0.89
V
vs
reversible
hydrogen
electrode.
Furthermore,
system
demonstrated
50
h
stable
operation
300
average
FE
∼68%.
This
study
offers
universal
strategy
tune
micro-environment,
significantly
improved
64.5%
was
obtained
even
acidic
electrolytes
(pH
=
2).