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<p>A nanoarchitectured eggshell-like Co/W bimetallic metal-organic framework (Co<sub><i>x</i></sub>W<sub><i>y</i></sub>-ZIF) nanoreactor was synthesized <i>via</i> a dissolution-regrowth process using ZIF-67 as a sacrificial template. The morphological evolution from rhombic dodecahedra to flower-like aggregates and finally to hollow eggshell-like nanocages was systematically controlled by tuning the Co/W ratio. Among the prepared catalysts, Co<sub>71.56</sub>W<sub>28.44</sub>-ZIF featured a well-defined eggshell-like architecture with a large pore size of 9.50&#xa0;nm. XPS analysis revealed that its bimetallic shell is composed of Co(OH)<sub>2</sub> and CoWO<sub>4</sub> phases, which originate from the coordinated etching and regrowth process. This unique hollow structure not only facilitates mass transfer and enhances substrate accessibility but also provides abundant and stable redox-active sites due to the synergistic coexistence of Co and W species. In the catalytic oxidation of cyclohexene (CHE) using acetonitrile as solvent and H<sub>2</sub>O<sub>2</sub> as oxidant, Co<sub>71.56</sub>W<sub>28.44</sub>-ZIF achieved 76.5% CHE conversion and an outstanding 79.5% selectivity to 2-cyclohexen-1-one (2-one), outperforming catalysts with higher surface areas but less favorable pore architectures. Moreover, the catalyst demonstrated good recyclability and structural stability over four consecutive runs, as confirmed by XRD, FT-IR, and SEM. These results highlight that the synergy between morphological control and compositional engineering is key to overcoming the trade-off between activity and selectivity in alkene oxidation.</p> Graphical Abstract <p></p>

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Nanoarchitectured Eggshell-Like Co/W Bimetallic MOF as a Selective Catalyst for Cyclohexene Oxidation

  • 期刊论文

  • 发表日期：

    2026年7月11日

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  • Xiaonan Shi,
  • Weiru Liu,
  • Ruigang Feng,
  • Haikun Zhai,
  • Xin Zhang,
  • Yujing Jia,
  • Guodong Liu,
  • Chongdian Si,
  • Gongguo Zhang,
  • Qingtao Niu,
  • Manman Jin

摘要

A nanoarchitectured eggshell-like Co/W bimetallic metal-organic framework (CoxWy-ZIF) nanoreactor was synthesized via a dissolution-regrowth process using ZIF-67 as a sacrificial template. The morphological evolution from rhombic dodecahedra to flower-like aggregates and finally to hollow eggshell-like nanocages was systematically controlled by tuning the Co/W ratio. Among the prepared catalysts, Co71.56W28.44-ZIF featured a well-defined eggshell-like architecture with a large pore size of 9.50 nm. XPS analysis revealed that its bimetallic shell is composed of Co(OH)2 and CoWO4 phases, which originate from the coordinated etching and regrowth process. This unique hollow structure not only facilitates mass transfer and enhances substrate accessibility but also provides abundant and stable redox-active sites due to the synergistic coexistence of Co and W species. In the catalytic oxidation of cyclohexene (CHE) using acetonitrile as solvent and H2O2 as oxidant, Co71.56W28.44-ZIF achieved 76.5% CHE conversion and an outstanding 79.5% selectivity to 2-cyclohexen-1-one (2-one), outperforming catalysts with higher surface areas but less favorable pore architectures. Moreover, the catalyst demonstrated good recyclability and structural stability over four consecutive runs, as confirmed by XRD, FT-IR, and SEM. These results highlight that the synergy between morphological control and compositional engineering is key to overcoming the trade-off between activity and selectivity in alkene oxidation.

Graphical Abstract