dibenzothiophenes such as 4,6-dimethyldibenzothiophene
are a kind of typical refractory sulfur compound in fuel oil. Herein,
three-dimensional ordered macro–mesoporous (3DOM) tungsten
oxide catalysts were successfully prepared for aerobic oxidative desulfurization
of 4,6-dimethyldibenzothiophene. The experimental results indicated
that the as-prepared material 3DOM WO
-400 not only contained a hexagonal packed nanoporous structure but
also abundant oxygen defects on its skeleton, exhibiting aerobic oxidative
desulfurization of over 99% in 4 h. Moreover, sulfur removal could
still reach 99% after recycling five times. Through free radical capture
experiments, the superoxide radical is reasonably proposed in the
mechanism. This work would provide a feasible route to develop highly
efficient nanoporous materials for desulfurization of fuels.
Boron nitride (BN) is a two‐dimensional ceramic material that has been widely applied in various catalysis reactions. However, endowing the BN material with adequate reactive centers remains to be a considerable challenge. Herein, we propose a tunable boron and nitride dual vacancies strategy to generate highly active oxygen‐doping BN (BNO) material via heat treatment in vacuum. Experimental results indicate that the vacuum treatment fabricates boron and nitride dual vacancies on the BNO. The as‐prepared vacuum treated BNO (V‐BNO) was applied as the initiator to accelerate the aerobic oxidative desulfurization (ODS) of fuel. The boosted aerobic ODS system achieves 100 % sulfur removal in 6 h, and it can be recycled 6 times without any significant performance loss. Meanwhile, the density functional theory (DFT) reveals the reaction pathway on the V‐BNO, ensuring the contribution of boron and nitride dual vacancies to the initiation of the reaction. This work highlights the vital role of dual vacancies as initiating sites for the enhanced aerobic ODS.
Refining the Lewis acid of boron nitride (BN) can construct new adsorptive sites and improve the adsorptive capacity and selectivity in adsorption desulfurization of diesel. Herein, we outline a strategy via introducing Ce(III) to anchor strong Lewis acid sites on bundlelike BN adsorbent. The strong Lewis acid sites on BN can bring a dramatic development to the adsorption by enhancing the Lewis acid−base interaction. Meanwhile, an additional microporous structure is built in the optimized BN adsorbent to reinforce the adsorptive performance further. As a result, the optimal bundlelike BN adsorbent shows an excellent adsorptive capacity of up to 48.4 mg S/g adsorbent. Moreover, demonstrated by both experimental and theoretical results, the strong Lewis acid sites in BN adsorbent can also alleviate the adsorption of aromatic hydrocarbons, leading to an improvement to the selectivity of the dibenzothiophene.
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.
scite is a Brooklyn-based startup that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.