Tailoring electronic properties of porphyrin manganese on boron nitride for enhancing aerobic oxidative desulfurization at room temperature

Tailoring electronic properties of the central metal atom of metalloporphyrin has emerged as a practical approach to acquire a high catalytic performance. Herein, 5,10,15,20-tetraphenylporphyrin manganese chloride (TPPMnCl) was immobilized on hexagonal boron nitride (h-BN) and employed as a catalyst to achieve ultradeep aerobic oxidative desulfurization of diesel at room temperature. The interfacial electronic effect on the TPPMnCl induced by the h-BN was embraced, leading to an electron transfer from Mn to h-BN. The resulting high-valence Mn could facilitate the generation of reactive oxygen species from the reduction of oxygen. As a result, 99.2% of refractory aromatic sulfur removal for model diesel could be achieved at 30 °C using immobilized TPPMnCl and oxygen as the catalyst and oxidant, respectively. Besides, the catalytic mechanism was studied in detail, and the peroxyacid was found to be generated on the immobilized TPPMnCl as the active species. This study provides a strategy toward tailoring th...