Great interest has arisen in the past years in the development of hierarchical zeolites, having at least two levels of porosities. Hierarchical zeolites show an enhanced accessibility, leading to improved catalytic activity in reactions suffering from steric and/or diffusional limitations. Moreover, the secondary porosity offers an ideal space for the deposition of additional active phases and for functionalization with organic moieties. However, the secondary surface represents a discontinuity of the crystalline framework, with a low connectivity and a high concentration of silanols. Consequently, hierarchical zeolites exhibit a less “zeolitic behaviour” than conventional ones in terms of acidity, hydrophobic/hydrophilic character, confinement effects, shape-selectivity and hydrothermal stability. Nevertheless, this secondary surface is far from being amorphous, which provides hierarchical zeolites with a set of novel features. A wide variety of innovative strategies have been developed for generating a secondary porosity in zeolites. In the present review, the different synthetic routes leading to hierarchical zeolites have been classified into five categories: removal of framework atoms, surfactant-assisted procedures, hard-templating, zeolitization of preformed solids and organosilane-based methods. Significant advances have been achieved recently in several of these alternatives. These include desilication, due to its versatility, dual templating with polyquaternary ammonium surfactants and framework reorganization by treatment with surfactant-containing basic solutions. In the last two cases, the materials so prepared show both mesoscopic ordering and zeolitic lattice planes. Likewise, interesting results have been obtained with the incorporation of different types of organosilanes into the zeolite crystallization gels, taking advantage of their high affinity for silicate and aluminosilicate species. Crystallization of organofunctionalized species favours the formation of organic–inorganic composites that, upon calcination, are transformed into hierarchical zeolites. However, in spite of this impressive progress in novel strategies for the preparation of hierarchical zeolites, significant challenges are still ahead. The overall one is the development of methods that are versatile in terms of zeolite structures and compositions, capable of tuning the secondary porosity properties, and being scaled up in a cost-effective way. Recent works have demonstrated that it is possible to scale-up easily the synthesis of hierarchical zeolites by desilication. Economic aspects may become a significant bottleneck for the commercial application of hierarchical zeolites since most of the synthesis strategies so far developed imply the use of more expensive procedures and reagents compared to conventional zeolites. Nevertheless, the use of hierarchical zeolites as efficient catalysts for the production of high value-added compounds could greatly compensate these increased manufacturing costs.

Research activities and recent developments in the area of three-dimensional zeolites and their two-dimensional analogues are reviewed.

This article reviews the recent advances in the development of zeolite catalysts for biomass valorization processes to produce both biofuels and/or bio-based chemicals, which is an emerging and fast expanding field. The work deals with different types of feedstocks, including vegetable oils, lignocellulose and sugars, as well as with a number of relevant intermediates and platform molecules. Transformation of biomass into valuable products is hindered by a number of factors, mainly related to its complex composition, as biomass typically consists of bulky molecules with high oxygen content. Accordingly, biomass processing usually requires the combination of multiple steps and severe conditions, hence concepts like atom efficiency, product selectivity, and catalyst deactivation become of special relevance. A great progress has been achieved in the past years engineering the properties of zeolites for being adapted to the challenges associated to biomass valorization. The possibility of tailoring the main physicochemical properties of zeolites has become now a reality, being the major reason that explains the success achieved by this class of materials in a growing variety of biomass conversion pathways, as those described in this work: catalytic cracking and pyrolysis, hydrotreatments, with special relevance for hydrodeoxygenation processes, as well as in a high number of condensation, isomerization, and dehydration reactions. Thus, the development of hierarchical zeolites, exhibiting enhanced accessibility, and the possibility of introducing and combining in a controlled way different types of active sites (Brønsted and Lewis acid centers, basic sites, and metal phases) are the main basis of the excellent performance of zeolites in numerous biomass conversion routes.