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Issue 2, 2014
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Hierarchical high-silica zeolites as superior base catalysts

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Abstract

For more than four decades, the design of zeolite base catalysts has relied on the application of aluminium-rich frameworks exchanged with alkali metal cations (preferably Cs+). However, moderate activity associated with access and diffusion limitations, and high manufacturing costs associated with high caesium content (typically over 30%) have hampered their industrial implementation so far. Herein, we have discovered that high-silica USY zeolites outperform their Al-rich counterparts in a variety of base-catalysed reactions of relevance in the fine chemical industry, as well as in the upgrading of biofuels. The benefits of this class of materials are amplified upon the alleviation of diffusion constraints through the introduction of a network of intracrystalline mesopores by post-synthetic modification. For example, the resulting cation-free hierarchical USY provides an up to 30-fold Knoevenagel condensation activity compared to the benchmark Cs–X, and similar observations were made upon application in liquid-phase (nitro)aldol reactions. Moreover, in the gas-phase aldol condensation of propanal, high-silica zeolites provide superior activity, selectivity, and lifetime compared to caesium-containing zeolites and even a strong solid base such as MgO. We decouple the complex interplay between mesoporosity and intrinsic zeolitic properties such as crystallinity, and quantify the increase in catalyst effectiveness upon hierarchical structuring as a function of reactant size. The obtained results are a major step to resolve the drawbacks of zeolites catalysis and thereby revitalise their potential for industrial application.

Graphical abstract: Hierarchical high-silica zeolites as superior base catalysts

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Publication details

The article was received on 10 Jul 2013, accepted on 15 Oct 2013 and first published on 16 Oct 2013


Article type: Edge Article
DOI: 10.1039/C3SC51937F
Chem. Sci., 2014,5, 677-684

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    Hierarchical high-silica zeolites as superior base catalysts

    T. C. Keller, S. Isabettini, D. Verboekend, E. G. Rodrigues and J. Pérez-Ramírez, Chem. Sci., 2014, 5, 677
    DOI: 10.1039/C3SC51937F

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