Single-atom
catalysis is mainly focused on its dispersed high-density
catalytic sites, but delicate designs to realize a unique catalysis
mechanism in terms of target reactions have been much less investigated.
Herein an iron single atomic site catalyst anchored on 2-D N-doping
graphene (Fe-SASC/G) was synthesized and further employed as a biomimetic
sensor to electrochemically detect hydrogen peroxide, showing an extremely
high sensitivity of 3214.28 μA mM–1 cm–2, which is much higher than that (6.5 μA mM–1 cm–2) of its dispersed on 1-D carbon
nanowires (Fe-SASC/NW), ranking the best sensitivity among all reported
Fe based catalyst at present. The sensor was also used to successfully in situ monitor H2O2 released from
A549 living cells. The mechanism was further systematically investigated.
Results interestingly indicate that the distance between adjacent
single Fe atomic catalytic sites on 2-D graphene of Fe-SASC/G matches
statistically well with the outer length of bioxygen of H2O2 to promote a bridge adsorption of −O–O–
for simultaneous 2-electron transfer, while the single Fe atoms anchored
on distant 1-D nanowires in Fe-SASC/NW only allow an end-adsorption
of oxygen atoms for 1-electron transfer. These results demonstrate
that Fe-SASC/G holds great promise as an advanced electrode material
in selective and sensitive biomimetic sensor and other electrocatalytic
applications, while offering scientific insights in deeper single
atomic catalysis mechanisms, especially the effects of substrate dimensions
on the mechanism.