Aghmasheh Masomeh, Rezvani Mohammad Ali, Jafarian Vahab, Aghasadeghi Zahra
Department of Chemistry, Faculty of Science, University of Zanjan, 451561319 Zanjan, Iran.
Inorg Chem. 2023 Apr 10;62(14):5468-5478. doi: 10.1021/acs.inorgchem.2c04415. Epub 2023 Mar 29.
From the environmental protection and human health perspectives, the design and synthesis of efficient and reusable oxidative desulfurization nanocatalysts has always been sought after by scientists and industries. In this regard, a new heterogeneous nanocatalyst (V-SPM@PANI@CH) was synthesized by immobilizing Keggin-type vanadium-substituted phosphomolybdate ([PVMoO]) (named V-SPM) clusters on the surface of polyaniline (PANI) and chitosan (CH) polymers. The features of the assembled nanocatalyst were detected by Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, X-ray diffraction (XRD), scanning electron microscopy, and energy-dispersive X-ray spectroscopy techniques in detail. The XRD studies indicated that the average crystallite size of V-SPM@PANI@CH was estimated to be about 36 nm. The catalytic performance of V-SPM@PANI@CH was investigated in the extractive and catalytic oxidation desulfurization (ECOD) procedure of real and thiophenic model gasoline by HO/AcOH (volume proportion of 2:1) as an oxidizing system. The optimal desulfurization conditions for ECOD reactions were as follows: 50 mL of model/real gasoline, 0.1 g of V-SPM@PANI@CH, reaction time of 60 min, and reaction temperature of 35 °C. Under the experimental conditions outlined above and the designed ECOD system, the content of sulfur in real gasoline could decline from 0.4985 to 0.0193 wt %, which corresponds to an efficiency of 96%. Moreover, the removal percentage of aromatic hydrocarbons, including thiophene (Th), benzothiophene (BT), and di-benzothiophene (DBT) as model fuels decreases in the order of DBT ≥ BT > Th under identical operating conditions. High catalytic activity was maintained with only a slight loss during five cycles. This work offers the ECOD system (V-SPM@PANI@CH/AcOH/HO) for the desulfurization of liquid fuels, which had a great repercussion on the ECOD efficiency.
从环境保护和人类健康的角度来看,高效且可重复使用的氧化脱硫纳米催化剂的设计与合成一直是科学家和工业界所追求的。在这方面,通过将Keggin型钒取代磷钼酸盐([PVMoO])(命名为V-SPM)簇固定在聚苯胺(PANI)和壳聚糖(CH)聚合物表面,合成了一种新型多相纳米催化剂(V-SPM@PANI@CH)。通过傅里叶变换红外光谱、紫外可见光谱、X射线衍射(XRD)、扫描电子显微镜和能量色散X射线光谱技术详细检测了组装纳米催化剂的特性。XRD研究表明,V-SPM@PANI@CH的平均微晶尺寸估计约为36nm。以HO/AcOH(体积比2:1)作为氧化体系,研究了V-SPM@PANI@CH在实际和噻吩类模型汽油的萃取和催化氧化脱硫(ECOD)过程中的催化性能。ECOD反应的最佳脱硫条件如下:50mL模型/实际汽油、0.1g V-SPM@PANI@CH、反应时间60min和反应温度35℃。在上述实验条件和设计的ECOD体系下,实际汽油中的硫含量可从0.4985降至0.0193wt%,脱硫效率达96%。此外,在相同操作条件下,作为模型燃料的芳烃(包括噻吩(Th)、苯并噻吩(BT)和二苯并噻吩(DBT))去除率的降低顺序为DBT≥BT>Th。在五个循环中仅略有损失的情况下仍保持了高催化活性。这项工作为液体燃料脱硫提供了ECOD体系(V-SPM@PANI@CH/AcOH/HO),对ECOD效率产生了重大影响。