Synthesis of Porous Clay Heterostructures Modified with SiO₂–ZrO₂ Nanoparticles for the Valorization of Furfural in One‐Pot Process

Abstract The layered structure of two smectites (montmorillonite and saponite) are modified by the insertion of SiO₂–ZrO₂ nanoparticles, with a Si/Zr molar ratio of 5, to form porous clay heterostructures (PCHs). These PCHs exhibit a clear improvement of the textural and acid properties in comparison to the starting clays, due to the formation of a pillared structure and the presence of Zr species, which provide an increase in the amount of Lewis acid sites. These materials are studied in one‐pot catalytic processes to transform furfural into valuable products, such as furfuryl alcohol, alkyl furfuryl ethers, alkyl levulinates or γ‐valerolactone, depending on the experimental conditions. Thus, the use of milder reaction temperature (110 °C) favors the formation of furfuryl alcohol and alkyl furfuryl ethers, while higher temperatures (170 °C) promote the formation of alkyl levulinate and γ‐valerolactone, as well as an increase in nondetected products associated to the formation of humins due to the polymerization of furfural and/or furfuryl alcohol.