南京师范大学兰亚乾团队报道了实现高性能热催化氧化还原反应的二茂铁功能化氧化锆团簇。相关研究成果于2024年2月27日发表在国际顶尖学术期刊《科学通报》。

Zr（IV）离子很容易水解形成氧化物，这严重限制了Zr基化合物新结构的发现和应用。

该文中，通过抑制Zr（IV）离子的水解，合成了三种二茂铁（Fc）功能化的Zr-氧簇合物（ZrOCs），Zr₉Fc₆、Zr₁₀Fc₆和Zr₁₂Fc₈，它们显示出增加的核酸性和规则的结构变化。更重要的是，这些Fc功能化的ZrOCs首次被用作乙酰丙酸（LA）转移加氢和苯酚氧化反应的多相催化剂，并显示出优异的催化活性。特别是，具有最多Zr活性位点和Fc基团的Zr₁₂Fc₈可以在4小时（130℃）内实现LA对-γ-戊内酯>95%的产率，在30分钟（80℃）内达到2,3,6-三甲基苯酚对2,3,5-三甲基对苯醌>98%的产率，显示出最佳的催化性能。

催化表征与理论计算相结合表明，在Fc功能化的ZrOCs中，Zr活性位点可以作为底物吸附位点，而Fc基团可以作为氢转移试剂或Fenton试剂，从而实现有效的分子内金属配体协同催化。

该项工作开发了功能化的ZrOCs作为热触发氧化还原反应的催化剂。

附：英文原文

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

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

Issue&Volume: 2024/02/27

Abstract: 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), 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 oC) and >98% yield for 2,3,6-trimethylphenol-to-2,3,5-trimethyl-p-benzoquinone within 30 min (80 oC), 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.

DOI: 10.1016/j.scib.2024.02.032

Source: https://www.sciencedirect.com/science/article/abs/pii/S2095927324001348