水与沸石的相互作用研究进展

D. Resasco, S. Crossley, Bin Wang, Jeffery L. White
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引用次数: 16

摘要

在沸石催化剂的热处理和反应条件下,水是普遍存在的,但潜在的影响是复杂的。不同类型的水与沸石的相互作用对这些重要催化剂的稳定性、结构/组成和反应性有着深远的影响。本文综述了沸石表面水吸附和成核的机理,以及沸石缺陷、阳离子和附加骨架的作用。本文回顾和分析了水与不同Si/Al比、拓扑结构和硅醇缺陷水平的沸石相互作用的实验和计算研究实例。蒸制过程的不同步骤,包括Al-O-Si键水解和随后的结构修饰,如脱铝、介孔形成和非晶化,根据最近的DFT计算、SS NMR和其他光谱研究进行了评估。强调并解释了沸石在气相和液相中水侵蚀机理的差异,以及沸石壁疏水/亲水性质的影响。同时,回顾和讨论了水作为普通沸石以及稀土或磷改性材料的反应性改性剂的各种作用。
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Interaction of water with zeolites: a review
ABSTRACT Water is ubiquitous in many thermal treatments and reaction conditions involving zeolite catalysts, but the potential impacts are complex. The different types of water interaction with zeolites have profound consequences in the stability, structure/composition, and reactivity of these important catalysts. This review analyzes the current knowledge about the mechanistic aspects of water adsorption and nucleation on zeolites surfaces and the concomitant role of zeolite defects, cations and extra framework species. Examples of experimental and computational studies of water interaction with zeolites of varying Si/Al ratios, topologies, and level of silanol defects are reviewed and analyzed. The different steps associated with the process of steaming, including the Al-O-Si bond hydrolysis and subsequent structural modifications, such as dealumination, mesopore formation, and amorphization, are evaluated in light of recent DFT calculations, as well as SS NMR and other spectroscopic studies. Differences between the mechanisms of water attack of the zeolite in vapor or liquid phase are highlighted and explained, as well as the effect of hydrophobic/hydrophilic properties of the zeolite walls. In parallel, the various roles of water as modifier of reactivity are reviewed and discussed, both for plain zeolites as well as rare-earth or phosphorous-modified materials.
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