Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(6), P. 2950 - 3006
Published: Feb. 21, 2023
The
net
rate
of
a
reversible
chemical
reaction
is
the
difference
between
unidirectional
rates
traversal
along
forward
and
reverse
paths.
In
multistep
sequence,
trajectories,
in
general,
are
not
microscopic
one
another;
rather,
each
route
comprised
distinct
rate-controlling
steps,
intermediates,
transition
states.
Consequently,
traditional
descriptors
(e.g.,
orders)
do
reflect
intrinsic
kinetic
information
but
instead
conflate
contributions
determined
by
(i)
occurrence
forward/reverse
reactions
(i.e.,
kinetics)
(ii)
reversibility
nonequilibrium
thermodynamics).
This
review
aims
to
provide
comprehensive
resource
analytical
conceptual
tools
which
deconvolute
kinetics
thermodynamics
disambiguate
trajectories
precisely
identify
rate-
reversibility-controlling
molecular
species
steps
systems.
extrication
mechanistic
from
bidirectional
accomplished
through
equation-based
formalisms
De
Donder
relations)
grounded
principles
interpreted
context
theories
developed
past
25
years.
aggregate
mathematical
detailed
herein
general
thermochemical
electrochemical
encapsulates
diverse
body
scientific
literature
encompassing
physics,
thermodynamics,
kinetics,
catalysis,
modeling.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(14), P. 8404 - 8433
Published: June 30, 2022
As
a
fundamental
step
of
water
splitting
and
stepping
stone
toward
exploring
other
multielectron
transfer
processes,
the
electrocatalytic
hydrogen
evolution
reaction
(HER)
is
an
ideal
model
for
both
understanding
electrocatalyst
design.
Here,
we
review
fundamentals
recent
developments
theoretical
insights
into
HER,
covering
mechanistic
aspects,
key
activity
descriptors,
local
environment
considerations,
advances
beyond
computational
electrode.
Although
it
experimentally
challenging
to
explore
active
sites
mechanisms
in
process,
show
great
potential
identifying
mechanisms.
In
this
Review,
especially
focus
depth
on
revealing
designing
HER.
Major
challenges
ahead
will
also
be
discussed
at
end
Review.
Journal of Chemical Theory and Computation,
Journal Year:
2023,
Volume and Issue:
19(20), P. 6859 - 6890
Published: June 29, 2023
TURBOMOLE
is
a
highly
optimized
software
suite
for
large-scale
quantum-chemical
and
materials
science
simulations
of
molecules,
clusters,
extended
systems,
periodic
solids.
uses
Gaussian
basis
sets
has
been
designed
with
robust
fast
applications
in
mind,
ranging
from
homogeneous
heterogeneous
catalysis
to
inorganic
organic
chemistry
various
types
spectroscopy,
light-matter
interactions,
biochemistry.
This
Perspective
briefly
surveys
TURBOMOLE's
functionality
highlights
recent
developments
that
have
taken
place
between
2020
2023,
comprising
new
electronic
structure
methods
molecules
solids,
previously
unavailable
molecular
properties,
embedding,
dynamics
approaches.
Select
features
under
development
are
reviewed
illustrate
the
continuous
growth
program
suite,
including
nuclear
orbital
methods,
Hartree-Fock-based
adiabatic
connection
models,
simplified
time-dependent
density
functional
theory,
relativistic
effects
magnetic
multiscale
modeling
optical
properties.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(4), P. 2022 - 2055
Published: Jan. 1, 2024
Beyond
conventional
electrocatalyst
engineering,
recent
studies
have
unveiled
the
effectiveness
of
manipulating
local
reaction
environment
in
enhancing
performance
electrocatalytic
reactions.
The
general
principles
and
strategies
environmental
engineering
for
different
processes
been
extensively
investigated.
This
review
provides
a
critical
appraisal
advancements
aiming
to
comprehensively
assess
this
emerging
field.
It
presents
interactions
among
surface
structure,
ions
distribution
electric
field
relation
environment.
Useful
protocols
such
as
interfacial
reactant
concentration,
mass
transport
rate,
adsorption/desorption
behaviors,
binding
energy
are
in-depth
discussed
toward
modifying
Meanwhile,
electrode
physical
structures
cell
configurations
viable
optimization
methods
environments.
In
combination
with
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(46), P. 25264 - 25273
Published: Nov. 8, 2023
Electronic
structure
is
essential
to
understanding
the
catalytic
mechanism
of
metal
single-atom
catalysts
(SACs),
especially
under
electrochemical
conditions.
This
study
delves
into
nuanced
modulation
"frontier
orbitals"
in
SACs
on
nitrogen-doped
graphene
(N-C)
substrates
by
potentials.
We
observe
shifts
Fermi
level
and
changes
d-orbital
occupation
with
alterations
potentials,
emphasizing
a
synergy
between
discretized
atomic
orbitals
metals
continuous
bands
N-C
based
environment.
Using
O2
CO2
as
model
adsorbates,
we
highlight
direct
consequences
these
adsorption
energies,
unveiling
an
intriguing
inversion
energies
Co/N-C
SAC
negative
Such
insights
are
attributed
role
dxz
dz2
orbitals,
pivotal
for
stabilizing
π*
O2.
Through
this
exploration,
our
work
offers
interplay
electronic
structures
behaviors
SACs,
paving
way
enhanced
catalyst
design
strategies
processes.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(14)
Published: Feb. 10, 2023
Proton
transfer
is
crucial
for
electrocatalysis.
Accumulating
cations
at
electrochemical
interfaces
can
alter
the
proton
rate
and
then
tune
electrocatalytic
performance.
However,
mechanism
regulating
remains
ambiguous.
Here,
we
quantify
cation
effect
on
diffusion
in
solution
by
hydrogen
evolution
microelectrodes,
revealing
be
suppressed
more
than
10
times.
Different
from
prevalent
opinions
that
transport
slowed
down
modified
electric
field,
found
water
structure
imposes
a
evident
kinetics.
FTIR
test
path
integral
molecular
dynamics
simulation
indicate
prefers
to
wander
within
hydration
shell
of
rather
hop
rapidly
along
wires.
Low
connectivity
networks
disrupted
corrupts
fast-moving
bulk
water.
This
study
highlights
promising
way
kinetics
via
structure.
JACS Au,
Journal Year:
2023,
Volume and Issue:
3(10), P. 2640 - 2659
Published: Sept. 18, 2023
Structures
of
the
electric
double
layer
(EDL)
at
electrocatalytic
interfaces,
which
are
modulated
by
material
properties,
electrolyte
characteristics
(e.g.,
pH,
types
and
concentrations
ions),
electrode
potential,
play
crucial
roles
in
reaction
kinetics.
Understanding
EDL
effects
electrocatalysis
has
attracted
substantial
research
interest
recent
years.
However,
intrinsic
relationships
between
specific
structures
kinetics
remain
poorly
understood,
especially
on
atomic
scale.
In
this
Perspective,
we
briefly
review
advances
deciphering
mainly
hydrogen
oxygen
through
a
multiscale
approach,
spanning
from
atomistic
scale
simulated
ab
initio
methods
to
macroscale
hierarchical
approach.
We
highlight
importance
resolving
local
environment,
bond
network,
understanding
effects.
Finally,
some
remaining
challenges
outlined,
an
outlook
for
future
developments
these
exciting
frontiers
is
provided.
Small,
Journal Year:
2023,
Volume and Issue:
19(30)
Published: May 16, 2023
Enhancing
alkaline
urea
oxidation
reaction
(UOR)
activity
is
essential
to
upgrade
renewable
electrolysis
systems.
As
a
core
step
of
UOR,
proton-coupled
electron
transfer
(PCET)
determines
the
overall
performance,
and
accelerating
its
kinetic
remains
challenge.
In
this
work,
newly
raised
electrocatalyst
NiCoMoCuOx
Hy
with
derived
multi-metal
co-doping
(oxy)hydroxide
species
during
electrochemical
states
reported,
which
ensures
considerable
UOR
(10/500
mA
cm-2
at
1.32/1.52
V
vs
RHE,
respectively).
Impressively,
comprehensive
studies
elucidate
correlation
between
electrode-electrolyte
interfacial
microenvironment
electrocatalytic
behavior.
Specifically,
featured
dendritic
nanostructure
creates
strengthened
electric
field
distribution.
This
structural
factor
prompts
local
OH-
enrichment
in
electrical
double
layer
(EDL),
so
that
dehydrogenative
catalyst
directly
reinforced
facilitate
subsequent
PCET
kinetics
nucleophilic
urea,
resulting
high
performance.
practical
utilization,
-driven
coupled
cathodic
hydrogen
evolution
(HER)
carbon
dioxide
reduction
(CO2
RR),
harvested
value-added
products
H2
C2
H4
,
respectively.
work
clarifies
novel
mechanism
improve
performance
through
structure-induced
modulation.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(13), P. 8731 - 8751
Published: June 16, 2023
Electrochemically
driven
hydrogen
atom
transfer
(HAT)
catalysis
provides
a
complementary
approach
for
the
transformation
of
redox-inactive
substrates
that
would
be
inaccessible
to
conventional
electron
(ET)
catalysis.
Moreover,
electrochemically
HAT
could
promote
organic
transformations
with
either
abstraction
or
donation
as
key
step.
It
versatile
and
effective
tool
direct
functionalization
C(sp3)–H/Si–H
bonds
hydrofunctionalization
alkenes.
Despite
these
attractive
properties,
has
been
largely
overlooked
due
lack
understanding
both
catalytic
mechanism
how
catalyst
selection
should
occur.
In
this
Review,
we
give
an
overview
applications
in
The
mechanistic
pathways,
physical
properties
mediators,
state-of-the-art
examples
are
described
discussed.