纳米铁催化剂在 Fischer-Tropsch 合成低烯烃 (FTO) 中表现出良好的性能,但是,仍然缺乏简单的制备方法。在这项工作中,我们引入了一种简单的胶体沉积 (CD) 方法,使用由氢氧化铁制备的胶体溶液制备二氧化硅负载的 Fe2O3 纳米颗粒。随着 Fe 负载量从 16.3 % 增加到 31.6 %,Fe2O3 粒径从 1.3 nm 增加到 6.1 nm。在 H2/CO 摩尔比为 1 的情况下测试 FTO 中的催化性能。当 Fe 负载量为 30.4 % 时,粒径为 4.7 nm 的催化剂表现出最高的烯烃选择性和最低的 CO2 选择性,优于通过浸渍法制备的类似物。此外,该催化剂在 200 小时的耐久性测试中表现出良好的稳定性,而浸渍的类似物由于严重焦化而迅速失活。据推测,纳米颗粒和生成的碳片之间的有效接触面积在几何上很小,这导致它们之间的范德华力较弱,从而防止前者被后者严重覆盖。此外,从焦化的碳化物分解机理来看,由于中间碳化物纳米颗粒的体积与表面积比相对较低,因此从中释放的碳原子表面浓度较低,从而延缓了焦炭的形成。本研究可能提供一种简单的方法来制备负载型纳米铁催化剂,并为理解 FTO 中的催化剂耐久性提供一些启示。
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Nano-Fe/SiO2 catalysts prepared by facile colloidal deposition: Enhanced durability in Fischer-Tropsch synthesis
Nano-iron catalysts exhibit good performances in the Fischer–Tropsch synthesis to lower olefins (FTO), however, there is still a lack of simple methods for their preparation. In this work, we introduced a facile colloidal deposition (CD) method to fabricate silica-supported Fe2O3 nanoparticles using a colloidal solution readily prepared from ferric hydroxide. With increasing the Fe loading from 16.3 % to 31.6 %, the Fe2O3 particle size increased from 1.3 to 6.1 nm. The catalytic performances in FTO were tested at a H2/CO molar ratio of 1. At a Fe loading of 30.4 %, the catalyst having a particle size of 4.7 nm showed the highest lower olefin selectivity and the lowest CO2 selectivity, outperforming analogs prepared by impregnation method. Furthermore, this catalyst showed good stability in a 200-hour durability test, while the impregnated analogue quickly deactivated due to serious coking. Presumably, the effective contact areas between the nanoparticles and the generated carbon sheets are geometrically small, which results in weak van der Waals forces between them, preventing the former from being heavily covered by the latter. Besides, from the point of view of the carbide decomposition mechanism of coking, due to the relatively low volume to surface area ratios of the intermediate carbide nanoparticles, the surface concentrations of carbon atoms released from them are low, which delays the coke formation. This study may provide a simple method to fabricate supported nano-iron catalysts, and cast some light on understanding catalyst durability in FTO.