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揭示CuO在流化床反应器中用于O直接丙烯环氧化的CuO/TiO光催化剂中的作用。

Unraveling the Role of CuO in CuO/TiO Photocatalyst for the Direct Propylene Epoxidation With O in a Fluidized Bed Reactor.

作者信息

Morante Nicola, Tammaro Olimpia, Monzillo Katia, Sannino Diana, Battiato Alfio, Vittone Ettore, Castellino Micaela, Esposito Serena, Vaiano Vincenzo

机构信息

Department of Industrial Engineering, University of Salerno, Via Giovanni Paolo II 132, 84084, Fisciano (SA), Italy.

Department of Applied Science and Technology, INSTM Unit of Torino - Politecnico, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129, Torino, Italy.

出版信息

ChemSusChem. 2025 Apr 14;18(8):e202401546. doi: 10.1002/cssc.202401546. Epub 2024 Dec 6.

DOI:10.1002/cssc.202401546
PMID:39589077
Abstract

Propylene epoxidation in mild conditions using molecular O is a highly desirable reaction that represents a significant challenge in the field of heterogeneous catalysis for the synthesis of oxygenated organic compounds of industrial interest. In this work, CuO/TiO composites with different mominal CuO loadings (in the range of 0.5-8.4 wt %) were used to promote the photocatalytic epoxidation of propylene with molecular oxygen under UV-A irradiation in a fluidized bed system. The photocatalysts were prepared by a straightforward method consisting of thermal annealing of physical mixtures between copper acetate and sol-gel-derived TiO. Different characterization techniques were employed to assess the influence of CuO content on the physical-chemical properties of the CuO/TiO composites. The best combination in terms of propylene conversion and selectivity towards propylene oxide (18.1 % and 72 %, respectively) was obtained with CuO/TiO at 1.1 wt % CuO, as shown by photocatalytic tests. The high propylene oxide selectivity is due to the ability of CuO in the CuO/TiO composite to transform molecular O into hydrogen peroxide that, in turn, is able to directly oxidize propylene to propylene oxide. By using a UV-A light intensity of 297.2 mW cm, the propylene conversion and the epoxide yield were 31.5 and 22.2 %, respectively, significantly higher than that reported in the literature. Moreover, the energy consumption of the reaction system employed in this paper was significantly lower than that of photocatalytic systems studied in the literature dealing with selective propylene epoxidation.

摘要

在温和条件下使用分子氧进行丙烯环氧化是一个非常理想的反应,但在多相催化领域中,对于合成具有工业价值的含氧化合物而言,这是一项重大挑战。在这项工作中,使用了具有不同名义CuO负载量(在0.5 - 8.4 wt%范围内)的CuO/TiO复合材料,以促进在流化床系统中紫外-A辐射下丙烯与分子氧的光催化环氧化反应。通过一种简单的方法制备光催化剂,该方法包括对醋酸铜和溶胶-凝胶法制备的TiO之间的物理混合物进行热退火。采用不同的表征技术来评估CuO含量对CuO/TiO复合材料物理化学性质的影响。光催化测试表明,在CuO负载量为1.1 wt%的CuO/TiO复合材料中,就丙烯转化率和对环氧丙烷的选择性而言(分别为18.1%和72%),获得了最佳组合。环氧丙烷的高选择性归因于CuO/TiO复合材料中的CuO能够将分子氧转化为过氧化氢,而过氧化氢又能够直接将丙烯氧化为环氧丙烷。在紫外-A光强度为297.2 mW/cm²的条件下,丙烯转化率和环氧化物产率分别为31.5%和22.2%,显著高于文献报道的值。此外,本文所采用的反应系统的能量消耗明显低于文献中研究的选择性丙烯环氧化光催化系统。

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