Mechanochemical synthesis of MAPbBr₃/carbon sphere composites for boosting carrier-involved superoxide species

Lead halide perovskites MAPbX₃ (MA = CH₃NH₃ or Cs; X = I, Br, Cl) are well considered to be potential candidates for photocatalytic reaction due to its excellent photoelectrical properties, but they still suffer from the low charge separation efficiency and slow catalytic reaction dynamics. To tackle the drawbacks, herein, MAPbBr₃/carbon sphere (CS) composite photocatalysts using glucose as the carbon source were elaborately designed and fabricated via a dry mechanochemical grinding process. The interfacial interaction Pb-O-C chemical bonds were constructed between MAPbBr₃ and the carbon sphere surface containing organic functional groups. By optimizing the content of CSs, the enhanced photocatalytic degradation kinetic rate of Malachite Green (MG) pollutants (92% within 20 min) for MAPbBr₃/CS_x (x = 17 wt.%) is about 3.6-fold of that for pristine MAPbBr₃, which is attributed to the corporative adsorption and enhanced carrier transportation and separation of MAPbBr₃/CS_x. Furthermore, the possible degradation mechanism was proposed on basis of the electrochemical, mass spectrometry and optical characterization results. Owing to the robust interfacial interaction, effective electron extraction rate (k_et = 4.6 × 10⁷ sec^-1) from MAPbBr₃ to CS can be established, which driven oxygen activation where superoxide radicals (•O₂^-) played an important role in MG degradation. It is expected that mechanochemistry strategy may provide a new route to design efficient lead halide perovskite-carbon or metal oxide or sulfide composite photocatalysts.