Tailoring Electronic Properties of Porphyrin Manganese on Boron Nitride for Enhancing Aerobic Oxidative Desulfurization at Room Temperature

Abstract

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 the electronic properties of TPPMnCl on h-BN for enhancing aerobic oxidative desulfurization at room temperature.

In Situ Implanting of Single Tungsten Sites into Defective UiO‐66(Zr) by Solvent‐Free Route for Efficient Oxidative Desulfurization at Room Temperature

“…[7][8][9] Several works have focused on the fabrication of ODS catalyst based on ionic liquid, [10,11] metalorganic frameworks (MOFs), [12,13] polyoxometalates, [4,14] metal oxide [3,15] or metal cluster [16] for removing sulfur compounds at low temperature.U nfortunately,t he unevenly dispersed large pieces of active species easily block the pore of supports thus preventing contact with reactant or can only remove dibenzothiophene (DBT), which limit their ODS performance. [17,18] Fort his,t he development of highly active ODS catalysts with rich porosity and atomic scale active sites at ambient temperature has been strongly pursued.…”

Aerobic Oxidative Desulfurization by Nanoporous Tungsten Oxide with Oxygen Defects

“…Hence, WO 3 suffers from some problems such as a low mass transfer rate and a pore structure that is easily blocked in the ODS process. Meanwhile, strong steric hindrance around the sulfur atom could also significantly hinder the oxidation of alkyl-substituted dibenzothiophene in the ODS process. − Although the immobilization of tungsten oxide nanoparticles onto a support with a high specific surface could enhance the reaction interface, , the reaction system still faced some problems such as aggregation and leaching of active species.…”

Oxygen Vacancy Engineering of Molybdenum Oxide Nanobelts by Fe Ion Intercalation for Aerobic Oxidative Desulfurization

“…Due to the limitless abundance and environmental friendliness of oxygen (O 2 ), research on robust aerobic oxidation catalysts for the eco-friendly conversion of chemicals has attracted widespread attention for sustainable development. − An important example is aerobic oxidative desulfurization (AODS), an emerging desulfurization technology of fuels. − In the AODS process, thiophenic sulfides in fuels are oxidized selectively for yielding sulfones with strong polarity and then deeply removed by solvent extraction so as to eliminate the environmental hazards generated from the use of sulfur-containing fuels. − Compared with the currently adopting hydrodesulfurization (HDS) method, AODS promises a carbon-neutral process by realizing sulfur removal at mild conditions . However, ground-state O 2 is a triplet, making it chemically inert to singlet substrates, which therefore requires a high-performance catalyst to overcome the barrier in activating O 2 at mild temperatures. , So far, a variety of catalysts have been suggested for AODS, such as metal–organic frameworks, , supported noble-metal catalysts, − metal oxides, − polyoxometalates, − metal-free materials, , etc . However, the current catalysts still suffer from some problems such as high cost, limited activity, or poor stability.…”