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Multifunctional catalysts have received considerable attention in the cascade reactions of biomass processing. A cascade (or tandem) reaction is realized when multiple reaction steps that require different catalysts are performed in a one-step process. These reactions require bi- or multifunctional catalysts or catalyst mixtures to serve successfully at each reaction step. In this review article, we discuss the major factors of the catalyst design influencing the structure–property relationships, which could differ depending on the catalyst type. The major factors include the amounts and strengths of acidic and basic sites, interactions between those and metal sites, synergetic effects, nanoparticle sizes and morphology, nanostructures, porosity, etc. The catalysts described in this review are based on zeolites, mesoporous solids, MOFs, and enzymes. The importance of continuous cascade processes is also examined.

Acidic properties of ion-exchanged LTL zeolites have been studied using FTIR spectroscopy, complemented by X-ray powder diffraction, SEM-EDX, XRF and N2 physisorption. Infrared spectra of the ion-exchanged zeolites show the presence of two intense bands of the bridging OH-groups: a narrow band at ~3640 cm−1 that is attributed to Si(OH)Al groups freely vibrating in 12 MR and a broad, intense band at ~3250 cm−1 that is assigned to bridging OH groups forming hydrogen bond with neighbouring oxygen atoms, e.g., in six-membered rings. The former can be selectively removed by caesium or rubidium cations with up to 3 Cs+ or Rb+ per unit cell readily ion-exchanged into the LTL zeolite, replacing an equivalent number of acidic OH-groups or K+ cations within the structure. The cation migration of the larger cation, evaluated by the Rietveld refinement method, occurs mostly via the main 12 MR channels. By contrast, less than 1 Li+ or Na+ cation per unit cell can be introduced under similar conditions. Accordingly, the concentration of Si(OH)Al groups in back-exchanged NH4-K-LTL with smaller cations (Li+, Na+) does not differ considerably from the concentration of Brønsted acid sites in the original NH4-K-LTL. Lower concentrations of acid sites have been detected in the samples back-exchanged with Cs+, Rb+ and K+. In addition, the acidic properties of NH4-LTL samples have been compared with a structurally related NH4-MAZ zeolite.

Crystal size is a key parameter of zeolites applied as catalysts. Herein, ZSM-5 crystals with similar physicochemical and acid properties, few defects, and aluminum exclusively in tetrahedral coordination are synthesized and the influence of the crystal size on the MTO and ETA conversion is investigated. Short olefins are the main products of the MTO conversion, whereas larger olefins and aromatics dominate the products after ETA conversion. In the case of both feeds, an increased crystal size decreases the catalyst’s lifetime. The MTO conversion over larger ZSM-5 altered the product distribution, which was not the case for the ETA conversion. The reason is that the instantly available aromatics during ETA conversion lead to fast coking and zeolite crystals only active in the outer layers. Thus, the different reactivity of different-sized ZSM-5 is direct proof of a different conversion mechanism for both alcohols.

ZSM-5 zeolite is the synthetic counterpart to mutinaite. After thermal activation of the as-synthesized form, the symmetry of the ZSM-5 zeolite is lowered to the monoclinic P21/n. ZSM-5 then undergoes a polymorphic displacive phase transition from the monoclinic P21/n to the orthorhombic Pnma, Pn21a or P212121 space groups, which occurs upon heating. This phase transition can be influenced by factors such as the type and amount of sorbate molecules present in the zeolite channels. ZSM-5 has many applications, including as a catalyst or sorbent in various industries, where high thermal stability is required. In this study, four ZSM-5 zeolites with different Si/Al ratios were investigated by synchrotron X-ray powder diffraction at both room temperature and high temperature conditions to determine the effects of chemical composition on the structural response of the zeolite lattice. The results showed that the ZSM-5 zeolites retained their crystallinity and structural features throughout the thermal treatment, indicating that they could be used as effective acid catalysts. Distortions in the zeolite framework can occur after TPA+ decomposition and thermal activation, affecting thermal regeneration and efficiency. The charge balance in ZSM-5 is achieved by the formation of Brønsted acid sites, and variations in bonding geometries are influenced by the initial Si/Al ratio.

Beta zeolites with Si/Al around 14 were prepared using three new alkali-free synthesis methods based on the application of amorphous aluminosilicate precursor and calcined in ammonia or air. All samples exhibit structural and textural properties of standard beta zeolite. Comprehensive study by 27Al and 29Si MAS NMR, together with FTIR adsorption of d3-acetonitrile and pyridine were used to characterize the influence of both the synthesis and calcination procedure on the framework Al atoms and related Brønsted and Lewis acid sites. While calcination in ammonia preserves all framework Al atoms, calcination in air results in 15% release of framework Al, but without restrictions of the accessibility of the beta zeolite channel system for bulky pyridine molecules. Terminal (SiO)3AlOH groups present in the hydrated zeolites were suggested as a precursor of framework Al-Lewis sites. Surprisingly, the mild dealumination of the air-calcined zeolites result in an increase of the concentration of Brønsted acid sites and a decrease of the total concentration of Lewis sites with the formation of the extra-framework ones.

At the forefront of global development, the chemical industry is being confronted by a growing demand for products and services, but also the need to provide these in a manner that is sustainable in the long-term. In facing this challenge, the industry is being revolutionised by advances in catalysis that allow chemical transformations to be performed in a more efficient and economical manner. To this end, molecular design, facilitated by detailed theoretical and empirical studies, has played a pivotal role in creating highly-active and selective heterogeneous catalysts. In this review, the industrially-relevant Beckmann rearrangement is presented as an exemplar of how judicious characterisation and ab initio experiments can be used to understand and optimise nanoporous materials for sustainable catalysis.