ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(22), P. 14530 - 14539
Published: Oct. 27, 2023
Photocatalytic
carbon
dioxide
(CO2)
reduction
is
an
emerging
approach
to
synthesizing
monoxide
(CO)
but
still
suffers
from
poor
selectivity
and
low
catalytic
efficiency
because
of
the
high
energy
barrier
toward
*COOH
formation.
Herein,
we
report
selective
high-efficiency
photosynthesis
CO
with
a
boron
(B)-
sulfur
(S)-codoped
graphitic
nitride
(g-C3N4)
catalyst
(B,S-CN),
which
shifts
rate-determining-step
(RDS)
CO2
protonation
adsorption.
This
realized
by
local
mimicking
frustrated
Lewis
pairs
(M-FLPs)
constructed
abundant
electron-deficient
S
electron-rich
N
adjacent
B.
The
"push–pull"
effect
provided
as-designed
metal-free
M-FLP
configuration
allows
spontaneous
formation
*CO
intermediates
through
balancing
adsorption
energy,
as
evidenced
theoretical
calculations
in
situ
characterizations.
In
addition
free-energy
changes,
B
codoping
can
also
promote
separation
transfer
charges
improve
utilization
rate
light.
Strikingly,
B,S-CN
exhibits
100%
average
yield
313.20
μmol
g–1
h–1
(70.7
times
that
bulk
g-C3N4).
study
provides
strategy
for
development
highly
photocatalysts
paves
way
rational
intermediate
regulation
FLP
configuration.
