Abstract
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.
基金项目
国家重点研发计划(2023YFA1507204)
国家自然科学基金(22271104)
国家自然科学基金(22225109)
国家自然科学基金(22071109)
国家自然科学基金(22201046)
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)
Open Fund of Energy and Materials Chemistry Joint Laboratory of South China Normal University and Guangzhou Tinci Materials (SCNU-TINCI-202204)
NETL
NSTL
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