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

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外文摘要：The Zr(Ⅳ)ions are easily hydrolyzed to form oxides,which severely limits the discovery of new struc-tures and applications of Zr-based compounds.In this work,three ferrocene(Fc)-functionalized Zr-oxo clusters(ZrOCs),Zr9Fc6,Zr10Fc6 and Zr12Fc8 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,Zr12Fc8 with the largest number of Zr active sites and Fc groups can achieve＞95％yield for LA-to-γ-valerolactone within 4 h(130 ℃)and＞98％yield for 2,3,6-trimethylphenol-to-2,3,5-trimethyl-p-benzoquinone 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.

外文关键词：

Zirconium-oxo clusterMetal-ligand synergitic thermalcatalysisCrystalline coordination compoundHydrogen transferFenton reagent

作者：

Su-Juan Yao、Jiao-Min Lin、Long-Zhang Dong、Ying-Lin Li、Ning Li、Jiang Liu、Ya-Qian Lan

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作者单位：

School of Chemistry,South China Normal University,Guangzhou 510006,China

基金：

国家重点研发计划国家自然科学基金国家自然科学基金国家自然科学基金国家自然科学基金Excellent Youth Foundation of Jiangsu Natural Science FoundationYoung Top Talents of Pearl River Talent Program of Guangdong ProvinceGuangdong Basic and Applied Basic Research FoundationOpen Fund of Energy and Materials Chemistry Joint Laboratory of South China Normal University and Guangzhou Tinci Materials

项目编号：

2023YFA150720422271104222251092207110922201046BK202115932021QN02L6172023A1515030097SCNU-TINCI-202204

出版年：

2024

DOI：

10.1016/j.scib.2024.02.032

科学通报(英文版)

中国科学院

科学通报(英文版)

CSTPCD

ISSN：1001-6538

年,卷(期)：2024.69(10)

参考文献量49