Construction Of Zirconium Sulfonate Catalyst And Its Application In Catalytic Transfer Hydrogenation Of Carbonyl Compounds

Hydrogenation of carbonyl compounds from biomass to alcohols is an important way to synthesize high value-added chemicals.Among various hydrogenation strategies of carbonyl compounds,Meerwein-Ponndorf-Verley（MPV）reaction with alcohol as hydrogen source is one of the most important reaction routes.Herein,the effects of zirconium-based catalysts with different ligands on the catalytic activity of MPV reaction were studied and it was found that zirconium based catalysts coordinated with sulfonic acid could efficiently catalyze MPV reduction of carbonyl compounds.The main research contents of this dissertation are as below:（1）Using 2,6-naphthalenedisulfonic acid disodium salt（NDA）and ZrCl₄ as raw materials,a kind of MOF-like zirconium sulfonate organic-inorganic hybrid material（Zr-NDA）was successfully prepared by hydrothermal method.Zr-NDA was used to catalyze transfer hydrogenation of ethyl levulinate（EL）toγ-valerolactone（GVL）using isopropanol as hydrogen source,and showed good catalytic activity.Then the conditions required for the reaction（such as:solvent,reaction temperature,reaction time,etc.）were optimized.Under the reaction condition of 200 mg Zr-NDA,10 mL isopropanol,160℃and 12 h,the yield of GVL was up to 97%.At the same time,recycle tests and filtration experiments showed that Zr-NDA catalyst has good stability and can be reused for five times without decreasing catalytic activity.（2）A new sulfonate coordinated Zr（Ⅳ）catalyst was prepared by the coordination of Zr（Ⅳ）onto the sulfonate groups of Amberlyst-15.The Zr-AIER catalyst showed good catalytic activity in the hydrogen transfer of EL to GVL in the presence of isopropanol as hydrogen source.Then,the catalytic activities of zirconium based catalysts with different ligands（Zr-PhyA,Zr-CA,Zr-Tannin and Zr-Chitosan）were systematically studied.The results showed that Zr-AIER exhibited the best catalytic activity among the above catalysts.At the same time,the catalyst can be used in the catalytic transfer hydrogenation of a series of carbonyl compounds,and shows good substrate universality and selectivity.The recycle tests,filtration experiments and ICP-AES tests showed that the Zr-AIER had good stability and reusability.Finally,detail mechanistic investigations reveal that the catalytic performance of the catalyst can be attributed to the synergetic effect between Zr⁴⁺and sulfonate group,and the porous structure with high surface area.