Increasing demand for sustainable chemicals and fuels has pushed academia and industry to search for alternative feedstocks replacing crude oil in traditional refineries. As a result, an immense academic attention has focused on the valorisation of biomass (components) and derived intermediates to generate valuable platform chemicals and fuels. Zeolite catalysis plays a distinct role in many of these biomass conversion routes. This contribution emphasizes the progress and potential in zeolite catalysed biomass conversions and relates these to concepts established in existing petrochemical processes. The application of zeolites, equipped with a variety of active sites, in Brønsted acid, Lewis acid, or multifunctional catalysed reactions is discussed and generalised to provide a comprehensive overview. In addition, the feedstock shift from crude oil to biomass involves new challenges in developing fields, like mesoporosity and pore interconnectivity of zeolites and stability of zeolites in liquid phase. Finally, the future challenges and perspectives of zeolites in the processing of biomass conversion are discussed.

A novel catalyst design for the conversion of mono- and disaccharides to lactic acid and its alkyl esters was developed. The design uses a mesoporous silica, here represented by MCM-41, which is filled with a polyaromatic to graphite-like carbon network. The particular structure of the carbon-silica composite allows the accommodation of a broad variety of catalytically active functions, useful to attain cascade reactions, in a readily tunable pore texture. The significance of a joint action of Lewis and weak Brønsted acid sites was studied here to realize fast and selective sugar conversion. Lewis acidity is provided by grafting the silica component with Sn(IV), while weak Brønsted acidity originates from oxygen-containing functional groups in the carbon part. The weak Brønsted acid content was varied by changing the amount of carbon loading, the pyrolysis temperature, and the post-treatment procedure. As both catalytic functions can be tuned independently, their individual role and optimal balance can be searched for. It was thus demonstrated for the first time that the presence of weak Brønsted acid sites is crucial in accelerating the rate-determining (dehydration) reaction, that is, the first step in the reaction network from triose to lactate. Composite catalysts with well-balanced Lewis/Brønsted acidity are able to convert the trioses, glyceraldehyde and dihydroxyacetone, quantitatively into ethyl lactate in ethanol with an order of magnitude higher reaction rate when compared to the Sn grafted MCM-41 reference catalyst. Interestingly, the ability to tailor the pore architecture further allows the synthesis of a variety of amphiphilic alkyl lactates from trioses and long chain alcohols in moderate to high yields. Finally, direct lactate formation from hexoses, glucose and fructose, and disaccharides composed thereof, sucrose, was also attempted. For instance, conversion of sucrose with the bifunctional composite catalyst yields 45% methyl lactate in methanol at slightly elevated reaction temperature. The hybrid catalyst proved to be recyclable in various successive runs when used in alcohol solvent.

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Lewis acid Snβ-type zeolites with varying amounts of Brønsted acid Al in the framework were synthesized using a simple two-step procedure comprising partial dealumination of β zeolite under action of acid, followed by grafting with SnCl4·5H2O in dry isopropanol. Characterization of the thus-prepared Al-containing Snβ (Sn/pDeAlβ) zeolites with ICP, (pyridine probed) FTIR, and 27Al MAS NMR demonstrates the presence of Brønsted acid framework AlIII. Tetrahedral Lewis acidic SnIV is present, as ascertained by a combination of techniques such as EPMA, 119Sn Möβbauer, XPS, (pyridine probed) FTIR, and UV–vis. A closed SnIV configuration was implied by comparing of 119Sn solid-state MAS NMR and deuterated acetonitrile probed FTIR spectra with literature. The catalytic activity of the Al-containing Snβ was tested for the conversion of 1,3-dihydroxyacetone (DHA) into ethyl lactate (ELA), proceeding via pyruvic aldehyde (PAL). Despite the difference in synthesis between the classic hydrothermal Snβ reference and Sn/pDeAlβ, the activity of Sn for the Lewis acid-catalyzed hydride shift of PAL to ELA is similar. Yet, the overall reaction rate of DHA into ELA is faster with Sn/pDeAlβ because Brønsted acidity of the remaining framework AlIII facilitates the rate-determining dehydration of DHA into PAL. Materials containing moderate amounts of Al (0.3 wt % Al) show the highest ELA productivities, leading to a record value of 2113 g ELA·kg catalyst–1·h–1 at 363 K. The cooperative effect of Lewis SnIV and Brønsted AlIII acid sites is verified by comparing catalytic data with physical mixtures of partially dealuminated β zeolite and Al-free Snβ.

α‐Hydroxy acids (AHAs) such as lactic acid are considered platform molecules in the biorefinery concept and have high‐end applications in solvents and biodegradable polyester plastics. The synthesis of AHAs with a four‐carbon backbone structure is a recently emerging field. New biomass‐related routes towards their production could stimulate their practical use in new polyester plastics. Herein, we report the unique catalytic activity of soluble tin metal salts for converting tetroses, namely erythrulose and erythrose, into new four‐carbon‐backbone AHAs such as methyl vinylglycolate and methyl‐4‐methoxy‐2‐hydroxybutanoate. An in situ NMR study together with deuterium labeling experiments and control experiments with intermediates allowed us to propose a detailed reaction pathway.