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Micro/mesoporous conjugated fluorinated iron-porphyrin polymer: porosity and heterogeneous catalyst for oxidation

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Abstract

A conjugated micro/mesoporous polymer based on fluorinated iron-porphyrin, FCMP-1, has been prepared via Sonogashira-Hagihara coupling polymerization. The BET-specific surface area of FCMP-1 is about 440 m2 g−1, and its pore sizes are mainly distributed in 0.81 nm and the range of 2.9–3.4 nm, which show that FCMP-1 is the micro/mesoporous polyporphyrin. The polymer shows moderate uptake for methane (4.23 wt%, 273 K) and toluene (615 mg g−1, 298 K). It was also studied as the heterogeneous oxidation catalyst for the oxidative transformation of substituted toluene to corresponding benzoic acid as well as Baeyer–Villiger oxidation using dioxygen as an oxidant. The yields of substituted benzoic acid are ranged from 77 to 88% by employing FCMP-1 as catalyst. Particularly, the yields of the reactions for producing ε-caprolactone (more than 99% selectivity) are ranged from 85 to 98%. The channels derived from the porous structure of Fe-porphyrin network are advantageous for the reactive molecules to contact with the catalytic sites and accelerate the diffusion of reactant and product. When compared with the polymer analogue without fluorinated substituents, FCMP-1 with fluorinated phenyl substituents demonstrates the better catalytic performance and cyclic utilization. The fluorinated phenyl moieties linked to Fe-porphyrins facilitate the transformation, due to their stabilizing effect on porphyrin to restrain the breakdown of the catalyst.

Micro/mesoporous conjugated fluorinated iron-porphyrin polymer FCMP-1 was synthesized. Its uptake performance and catalytic activity for oxidation were also studied.

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Acknowledgements

Qi Chen is also grateful to the selfless support from Prof. Dr. Bao-Hang Han in the National Center for Nanoscience and Technology, China.

Funding

Financial support was from the National Natural Science Foundation of China (Grants 21574031, 51873053, 61761016 and 51775152), the Key Research and Development Plan of Hainan Province (Grant ZDYF2018004), and the Science and Technology Cooperation Project of Guizhou Province (Grant QKHLHZ-2015-7564).

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Authors and Affiliations

  1. State Key Laboratory of Marine Resource Utilization in South China Sea, Hainan University, Haikou, 570228, China

    Anwang Dong, Dongxu Wang, Tingting Dai, Qi Chen & Ning Wang

  2. CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, National Center for Nanoscience and Technology, Beijing, 100190, China

    Qi Chen

  3. Department of Bioengineering, Zunyi Medical College (Zhuhai Compus), Zhuhai, 519041, China

    Lijuan Feng

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  1. Anwang Dong
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Correspondence to Qi Chen, Lijuan Feng or Ning Wang.

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Dong, A., Wang, D., Dai, T. et al. Micro/mesoporous conjugated fluorinated iron-porphyrin polymer: porosity and heterogeneous catalyst for oxidation. Adv Compos Hybrid Mater 1, 696–704 (2018). https://doi.org/10.1007/s42114-018-0063-0

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