▎ 摘　　要

Here we present a new method to fabricate enzyme-mimic metal-free catalysts for electrochemical detection of superoxide anion (O-2(center dot-)) by introducing phosphate groups into graphene-based foam. Through a template-free hydrothermal process, graphene oxide (GO) was treated with different amount of phytic acid (PA) to obtain 3D porous graphene-based foam (PAGF). Characterizations demonstrate that phosphate groups were successfully modified on the surface and inter layer structure of PAGF materials and the defects and disorder degree of PAGF could be controlled by adjusting the addition of PA precursors. Meanwhile, the synthesized PAGF was successfully immobilized on screen printed carbon electrodes (SPCEs) and employed in O-2(center dot-) detection. With PA treated on graphene structure, the resulted PAGF/SPCEs exhibit distinct characteristic redox peaks, showing enzyme-mimic catalytic activity toward O-2(center dot-) dismutation. Also, the amount of modified phosphate groups has caused a considerable variety on the performance of PAGF-based electrodes. Apart from high sensitivity, wide liner range, low detection limit, good selectivity and long-term stability, our sensors also present satisfying performance in the real-time monitoring of drug-induced O-2(center dot-) released from Hela cells. The reliability of the biological measurement was further demonstrated via electron paramagnetic resonance (EPR) to characterize the released O-2(center dot-) from stimulated cells by using 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPOL) to trap the transient O-2(center dot-). The above results indicate that our established sensors hold potential application in the real-time detection of O-2(center dot-) in biological samples.