用于实现高性能热催化氧化还原反应的二茂铁功能化锆氧簇  

Ferrocene-functionalized zirconium-oxo clusters for achieving high-performance thermocatalytic redox reactions

作　　者：姚苏娟 林焦敏 董龙章 李颖霖 李宁 刘江 兰亚乾 Su-Juan Yao;Jiao-Min Lin;Long-Zhang Dong;Ying-Lin Li;Ning Li;Jiang Liu;Ya-Qian Lan(School of Chemistry,South China Normal University,Guangzhou 510006,China)

机构地区：[1]School of Chemistry,South China Normal University,Guangzhou 510006,China

出　　处：《Science Bulletin》2024年第10期1418-1426,共9页科学通报（英文版）

基　　金：supported by the National Key R&D Program of China(2023YFA1507204);the National Natural Science Foundation of China(22271104,22225109,22071109,and 22201046);the Excellent Youth Foundation of Jiangsu Natural Science Foundation(BK20211593);Young Top Talents of Pearl River Talent Program of Guangdong Province(2021QN02L617);Guangdong Basic and Applied Basic Research Foundation(2023A1515030097);the Open Fund of Energy and Materials Chemistry Joint Laboratory of South China Normal University and Guangzhou Tinci Materials Technology(SCNU-TINCI-202204).

摘　　要：The Zr(Ⅳ)ions are easily hydrolyzed to form oxides,which severely limits the discovery of new structures and applications of Zr-based compounds.In this work,three ferrocene(Fc)-functionalized Zr-oxo clusters(ZrOCs),Zr_(9)Fc_(6),Zr_(10)Fc_(6) and Zr_(12)Fc_(8) were synthesized through inhibiting the hydrolysis of Zr(Ⅳ)ions,which show increased nuclearity and regular structural variation.More importantly,these Fc-functionalized ZrOCs were used as heterogeneous catalysts for the transfer hydrogenation of levulinic acid(LA)and phenol oxidation reactions for the first time,and displayed outstanding catalytic activity.In particular,Zr_(12)Fc_(8) with the largest number of Zr active sites and Fc groups can achieve>95% yield for LAto-c-valerolactone within 4 h(130℃)and>98% yield for 2,3,6-trimethylphenol-to-2,3,5-trimethyl-pbenzoquinone within 30 min(80℃),showing the best catalytic performance.Catalytic characterization combined with theory calculations reveal that in the Fc-functionalized ZrOCs,the Zr active sites could serve as substrate adsorption sites,while the Fc groups could act as hydrogen transfer reagent or Fenton reagent,and thus achieve effectively intramolecular metal-ligand synergistic catalysis.This work develops functionalized ZrOCs as catalysts for thermal-triggered redox reactions.

关 键 词：Zirconium-oxo cluster Metal-ligand synergitic thermalcatalysis Crystalline coordination compound Hydrogen transfer Fenton reagent 

分 类 号：O643.36[理学—物理化学]