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.

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A facile and ingenious method to chemical etching-coordinating a metal-organic framework (MOF) followed by an annealing treatment was proposed to prepare Co3O4 nanoparticles uniformly dispersed in rational porous carbon nano-boxes (Co3O4@CNBs), which was further used to detect H2O2 released from living cells. The Co3O4@CNBs H2O2 sensor delivers much higher sensitivity than non-etching/coordinating Co3O4, offering a limit of detection of 2.32 nM. The wide working range covers 10 nM-359 μM H2O2, while possessing good selectivity and excellent reproducibility. Moreover, this biosensor was used to successfully real-time detect H2O2 released from living cells, including both healthy and tumor cells. The excellent performance holds great promise for Co3O4@CNBs’s applications in electrochemical biomimetic sensing, particularly real-time monitor H2O2 released from living cells.

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Rapid determination of cysteine in aqueous solution is important for the diagnosis and treatment of some diseases.