ZnAl-Hydrotalcite-Catalyzed Aqueous-Phase Rearrangement of Furfuryl Alcohol to 4-Hydroxycyclopent-2-Enone

4-Hydroxycyclopent-2-enone (HCP), a chemical substance with a unique molecular structure and distinct physical properties, is an important intermediate for the synthesis of natural products, chemicals, and liquid fuels, demonstrating exceptionally high application value. This study introduces a novel approach for HCP synthesis via the rearrangement of furfuryl alcohol (FAL). A series of ZnAl-based hydrotalcite (HT) catalysts was prepared and characterized by SEM, XPS, XRD, NH3-TPD, and CO2-TPD. HCP is efficiently synthesized by the rearrangement of furfuryl alcohol in water at a relatively low temperature of 205 °C. Using a 10 wt.% aqueous solution of furfuryl alcohol as the raw material, the yield of HCP remained stable at 80.2% under the selected reaction conditions (ZnAl-HT-1: 1–500 °C as catalyst, 205 °C, and 5 min). It is worth noting that when the concentration of furfuryl alcohol solution was reduced to 5%, the conversion of furfuryl alcohol reached 100%, and the HCP yield reached an excellent 92.5%. The exceptional performance observed can be primarily attributed to several key factors associated with the ZnAl-HT-1: 1–500 °C catalyst: its expansive specific surface area and ample pore volume, the distinctive layered structure inherent to hydrotalcites, and its well-balanced acid–base properties, featuring optimal densities of acid and base sites with a uniform distribution of acidic and basic active centers that cooperate synergistically to promote the reaction.