Single-atom
catalysis efficiently exposes the catalytic sites to
reactant molecules while rendering opportunity to investigate the
catalysis mechanisms at atomic levels for scientific insights. Here,
for the first time, atomically dispersed Co atoms are synthesized
as biomimetic “enzymes” to monitor superoxide anions
(O2
•–), delivering ultraordinary
high sensitivity (710.03 μA·μM–1·cm–2), low detection limit (1.5 nM), and
rapid response time (1.2 s), ranking the best among all the reported
either bioenzymatic or biomimetic O2
•– biosensors. The sensor is further successfully employed to real-time
monitor O2
•– released from living
cells. Moreover, theoretical calculation and analysis associated with
experimental results discover that a mode of end adsorption of the
negatively charged O2
•– on the
Co3+ atom rather than a bridge or/and side adsorption of
the two atoms of O2
•– on two Co3+ atoms, respectively, plays an important role in the single-atomic
catalysis toward O2
•– oxidation,
which not only facilitates faster electron transfer but also offers
better selectivity. This work holds great promise for an inexpensive
and sensitive atomic biomimetic O2
•– sensor for bioresearch and clinic diagnosis, while revealing that
the adsorption mode plays a critical role in single-atom catalysis
for a fundamental insight.