Abstract
Nanozymes
have
recently
gained
attention
for
their
low
cost
and
high
stability.
However,
unlike
natural
enzymes,
they
often
exhibit
multiple
enzyme‐like
activities,
complicating
use
in
selective
bioassays.
Since
H
2
O
are
common
substrates
these
reactions,
controlling
activation—and
thus
reaction
specificity—is
crucial.
Recent
advances
tuning
the
chemical
state
of
cerium
enabled
control
over
activation
pathways
tunable
peroxidase/haloperoxidase‐like
activities.
In
contrast,
on
an
element
oxidase/laccase
nanozymes
impact
its
activities
remains
unexplored.
Herein,
a
facile
one‐pot
method
is
presented
gram‐scale
synthesis
Fe‐based
with
compositions
Fe
3
4
C
by
adjusting
preparation
temperatures.
The
‐containing
samples
superior
laccase‐like
activity,
while
C‐containing
counterparts
demonstrate
better
oxidase‐like
activity.
This
divergent
behavior
linked
to
surface
species:
abundant
reactive
2+
promotes
activity
via
3+
‐superoxo
formation,
whereas
metallic
facilitates
OH
radical
generation
Controlled
improved
sensitivity
corresponding
biomolecule
detection,
which
should
inform
design
enhanced
specificity.
Engineering
the
local
coordination
environment
of
single
metal
atoms
is
an
effective
strategy
to
improve
their
catalytic
activity,
selectivity,
and
stability.
In
this
study,
we
develop
asymmetric
Pd–Ag
diatomic
site
on
surface
g-C3N4
for
selective
electrocatalytic
semihydrogenation
alkynes.
The
Pd
atom
catalyst,
which
has
a
locally
symmetric
coordination,
was
inactive
phenylacetylene
in
1
M
KOH
1,4-dioxane
solution
at
applied
potential
−1.3
V
(vs
RHE).
sharp
contrast,
doping
Ag
sites
into
catalyst
form
paired
with
substantially
enhanced
reaction,
resulting
high
conversion
(>98%)
exceptional
time-independent
selectivity
styrene
under
identical
conditions.
Characterization
theoretical
calculations
reveal
that
introduction
disrupts
symmetry
by
forming
bonds
N2–Pd–Ag–N
configuration,
thereby
modulating
electronic
geometric
structures
sites,
turn
benefits
adsorption
activation
substrate
lowers
energy
barrier
rate-determining
step
semihydrogenation,
ultimately
enhancing
reaction.
This
work
provides
facile
powerful
design
advanced
catalysts
tuning
catalysis.
