Theoretical and experimental evidence for rGO-4-PP Nc as a metal-free Fenton-like catalyst by tuning the electron distribution.

The application of the classical Fenton reaction has long been limited by several problems, such as metallic sludge and narrow pH range, which derived from the metal components in the catalyst. Developing a metal-free Fenton catalyst may efficiently address these problems. Here, we firstly perform a density functional theory (DFT) study to explore the possibility of developing the 4-phenoxyphenol molecule-doped reduced graphene oxide nanocomposite (rGO-4-PP Nc) as a metal-free Fenton-like catalyst by tuning the electron distribution. The theoretical calculation results reveal that rGO-4-PP Nc can act as an efficient Fenton-like catalyst for H 2 O 2 activation and pollutant degradation through formation of electron-rich O and electron-deficient C centers on the C-O-C bridge. The actual rGO-4-PP Nc is also prepared via a surface complexation and copolymerization process. The experimental evidence, such as that gained from XRD, FIIR and EPR analysis, confirm the theoretical models and the dual-reaction-center Fenton-like mechanism. This work provides a basis for theoretical calculation to guide the actual synthesis and prediction of catalytic activity of the Fenton-like catalysts, and also offers a creative perspective to develop new generation metal-free Fenton catalysts by tuning the electron distribution using organic polymers.