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Synthesis and characterization of porphyrin-based porous coordination polymers obtained by supercritical CO2 extraction

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Abstract

H2TCP and ZnTCP (TCP = 5,10,15,20-tetra(4-(phenoxy-4-yl)butanoic acid)porphyrin) were synthesized as gelator, reacted with Al(NO3)3·9H2O and Cr(NO3)3·9H2O by solvothermal and sol–gel method to give four organic–inorganic hybrid gels. The intermediate gels were extracted by supercritical CO2 to remove the redundant solvent molecules (DMF, EtOH) and the unreacted M3+ (M = Al, Cr), the final H2TCP-Al (PCP1), H2TCP-Cr (PCP2), ZnTCP-Al (PCP3), ZnTCP-Cr (PCP4) porous coordination polymers (PCPs) were obtained based on aerogels. The PCPs were characterized by FT-TR, UV–Vis, SEM, TEM and PXRD. Thermal stability and BET tests were carried by TGA and nitrogen sorption measurements. Results show that these PCPs exhibit superior thermal stability, tunable porosity and relative high BET surface ranging from 409 to 454 m2 g−1. Dyes adsorption experiments were performed to evaluate the adsorption capacity to dyes and the PCP3 has the best capacity which is 589 mg g−1 for rhodamine B (RhB) and 595 mg g−1 for methylene blue (MB). This work provides a promising method for the preparation of porous materials by supercritical CO2 extraction and exhibits some considerable applications in dyes adsorption.

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References

  1. Guo CC, Li HP, Xu JB (1999) Study of synthesis of µ-oxo-bismanganese (III) porphyrin compounds and their catalysis of cyclohexane oxidation by PhIO. J Catal 185:345–351

    Article  Google Scholar 

  2. Sun Q, Dai ZF, Meng XJ et al (2015) Task-specific design of porous polymer heterogeneous catalysts beyond homogeneous counterparts. ACS Catal 5:4556–4567

    Article  Google Scholar 

  3. Zhang KN, Farha OK, Hupp JT et al (2015) Complete double epoxidation of divinylbenzene using Mn(porphyrin)-based porous organic polymers. ACS Catal 5:4859–4866

    Article  Google Scholar 

  4. Hod I, Sampson MD, Deria P et al (2015) Fe-porphyrin-based metal-organic framework films as high-surface concentration, heterogeneous catalysts for electrochemical reduction of CO2. ACS Catal 5:6302–6309

    Article  Google Scholar 

  5. Wang T, She YB, Fu HY et al (2016) Selective cyclohexane oxidation catalyzed by manganese porphyrins and co-catalysts. Catal Today 264:185–190

    Article  Google Scholar 

  6. Johnson JA, Luo J, Zhang X et al (2015) Porphyrin-metalation-mediated tuning of photoredox catalytic properties in metal-organic frameworks. ACS Catal 5:5283–5291

    Article  Google Scholar 

  7. Shu J, Qiu ZL, Zhuang JY et al (2015) In situ generation of electron donor to assist signal amplification on porphyrin-sensitized titanium dioxide nanostructures for ultrasensitive photoelectrochemical immunoassay. ACS Appl Mater Interfaces 7:23812–23818

    Article  Google Scholar 

  8. Yella A, Lee HW, Tsao HN et al (2011) Porphyrin-sensitized solar cells with cobalt (II/III)-based redox electrolyte exceed 12 percent efficiency. Science 334:629–634

    Article  Google Scholar 

  9. Sivalingam Y, Martinelli E, Catini A et al (2012) Gas-sensitive photoconductivity of porphyrin-functionalized ZnO nanorods. J Phys Chem C 116:9151–9157

    Article  Google Scholar 

  10. Mathew S, Yella A, Gao P et al (2014) Dye-sensitized solar cells with 13% efficiency achieved through the molecular engineering of porphyrin sensitizers. Nat Chem 6:242–247

    Article  Google Scholar 

  11. Gibson LE, Wright DW (2016) Sensitive method for biomolecule detection utilizing signal amplification with porphyrin nanoparticles. Anal Chem 88:5928–5933

    Article  Google Scholar 

  12. Chang KW, Tang Y, Fang XF et al (2016) Incorporation of porphyrin to π-conjugated backbone for polymer-dot-sensitized photodynamic therapy. Biomacromol 17:2128–2136

    Article  Google Scholar 

  13. Pandey RK, Smith KM, Dougherty TJ (1990) Porphyrin dimers as photosensitizers in photodynamic therapy. J Med Chem 33:2032–2038

    Article  Google Scholar 

  14. Schmitt F, Govindaswamy P, Süss-Fink G et al (2008) Ruthenium porphyrin compounds for photodynamic therapy of cancer. J Med Chem 51:1811–1816

    Article  Google Scholar 

  15. Guo CC, Song JX, Chen XB et al (2000) A new evidence of the high-valent oxo-metal radical cation intermediate and hydrogen radical abstract mechanism in hydrocarbon hydroxylation catalyzed by metalloporphyrins. J Mol Catal A Chem 157:31–40

    Article  Google Scholar 

  16. Alkordi MH, Liu YL, Larsen RW et al (2008) Zeolite-like metal-organic frameworks as platforms for applications: on metalloporphyrin-based catalysts. J Am Chem Soc 130:12639–12641

    Article  Google Scholar 

  17. Sun Q, Dai ZF, Meng XJ et al (2015) Porous polymer catalysts with hierarchical structures. Chem Soc Rev 44:6018–6034

    Article  Google Scholar 

  18. Sun Q, Aguila B, Verma G et al (2016) Superhydrophobicity: constructing homogeneous catalysts into super hydrophobic porous frameworks to protect them from hydrolytic degradation. Chem 1:628–639

    Article  Google Scholar 

  19. Sun Q, Dai ZF, Meng XJ et al (2017) Homochiral porous framework as a platform for durability enhancement of molecular catalysts. Chem Mater 29:5720–5726

    Article  Google Scholar 

  20. Ma TY, Li H, Tang AN et al (2011) Ordered, mesoporous metal phosphonate materials with microporous crystalline walls for selective separation techniques. Small 13:1827–1837

    Article  Google Scholar 

  21. Shi L, Chu ZY, Liu Y et al (2014) In situ fabrication of three-dimensional graphene films on gold substrates with controllable pore structures for high-performance electrochemical sensing. Adv Funct Mater 24:7032–7041

    Article  Google Scholar 

  22. Zou C, Zhang TF, Xie MH et al (2013) Four metalloporphyrinic frameworks as heterogeneous catalysts for selective oxidation and aldol reaction. Inorg Chem 52:3620–3626

    Article  Google Scholar 

  23. Feng DW, Gu ZY, Li JR et al (2012) Zirconium-metalloporphyrin PCN-222: mesoporous metal-organic frameworks with ultrahigh stability as biomimetic catalysts. Angew Chem 124:10453–10456

    Article  Google Scholar 

  24. Yoon MY, Srirambalaji R, Kim K (2012) Homochiral metal-organic frameworks for asymmetric heterogeneous catalysis. Chem Rev 112:1196–1231

    Article  Google Scholar 

  25. Wan S, Guo J, Kim J et al (2008) A belt-shaped, blue iuminescent, and semiconducting covalent organic framework. Angew Chem 120:8958–8962

    Article  Google Scholar 

  26. Huh S, Kim SJ, Kim Y (2016) Porphyrinic metal–organic frameworks from custom-designed porphyrins. CrystEngComm 18:345–368

    Article  Google Scholar 

  27. Kaur P, Hupp JT, Nguyen ST (2011) Porous organic polymers in catalysis: opportunities and challenges. ACS Catal 1:819–835

    Article  Google Scholar 

  28. Meng L, Cheng QG, Kim C et al (2012) Crystal engineering of a microporous, catalytically active fcu topology MOF using a custom-designed metalloporphyrin linker. Angew Chem Int Ed 51:10082–10085

    Article  Google Scholar 

  29. Wang KC, Feng DW, Liu TF et al (2014) A series of highly stable mesoporous metalloporphyrin Fe-MOFs. J Am Chem Soc 136:13983–13986

    Article  Google Scholar 

  30. Zhang XT, Sui ZY, Xu B et al (2011) Mechanically strong and highly conductive graphene aerogel and its use as electrodes for electrochemical power sources. J Mater Chem 21:6494–6497

    Article  Google Scholar 

  31. Xiang SL, Li L, Zhang JY et al (2012) Porous organic-inorganic hybrid aerogels based on Cr3+/Fe3+ and rigid bridging carboxylates. J Mater Chem 22:1862–1867

    Article  Google Scholar 

  32. Sato T, Mori W, Kato CN et al (2005) Novel microporous rhodium(II) carboxylate polymer complexes containing metalloporphyrin: syntheses and catalytic performances in hydrogenation of olefins. J Catal 232:186–198

    Article  Google Scholar 

  33. Mori W, Sato T, Kato CN et al (2005) Discovery and development of microporous metal carboxylates. Chem Rec 5:336–351

    Article  Google Scholar 

  34. Zhang ZQ, Su XQ, Yu F et al (2016) Three novel metal–organic frameworks based on flexible porphyrin tetracarboxylic acids as highly effective catalysts. J Solid State Chem 238:53–59

    Article  Google Scholar 

  35. Zhao X, Yuan L, Zhang ZQ et al (2016) Synthetic methodology for the fabrication of porous porphyrin materials with metal-organic-polymer aerogels. Inorg Chem 55:5287–5296

    Article  Google Scholar 

  36. Sun S, Yu Q, Zhang W et al (2017) Metalloporphyrin-based porous coordination polymers: synthesis, served as heterogenous catalysts and dye scavengers. Catal Lett 147:228–239

    Article  Google Scholar 

  37. Maiti NC, Mazumdar S, Periasamy N (1998) J- and H-aggregates of porphyrin-surfactant complexes: time-resolved fluorescence and other spectroscopic studies. J Phys Chem B 102:1528–1538

    Article  Google Scholar 

  38. D’Urso A, Fragalà ME, Purrello R (2012) From self-assembly to noncovalent synthesis of programmable porphyrins’ arrays in aqueous solution. Chem Commun 48:8165–8176

    Article  Google Scholar 

  39. Sun ZC, She YB, Zhou Y (2011) Synthesis, characterization and spectral properties of substituted tetraphenylporphyrin iron chloride complexes. Molecules 16:2960–2970

    Article  Google Scholar 

  40. Yao L, He JH, Li T et al (2016) Novel SiO2/H2Ti2O5 H2O-nanochain composite with high UV-visible photocatalytic activity for supertransparent multifunctional thin films. Langmuir 32:13611–13619

    Article  Google Scholar 

  41. Liu XM, Sigen A, Zhang YW et al (2014) A porphyrin-linked conjugated microporous polymer with selective carbon dioxide adsorption and heterogeneous organocatalytic performances. RSC Adv 4:6447–6453

    Article  Google Scholar 

  42. Groen JC, Peffer LAA, Pérez-Ramírez J (2003) Pore size determination in modified micro-and Mesoporous materials. Pitfalls and limitations in gas adsorption data analysis. Micropor Mesopor Mat 60:1–17

    Article  Google Scholar 

  43. Zhu WC, Cui XL, Liu XF (2013) Hydrothermal evolution, optical and electrochemical properties of hierarchical porous hematite nanoarchitectures. Nanoscale Res Lett 8:2

    Article  Google Scholar 

  44. Ren Y, Hardwick LJ, Bruce PG (2010) Lithium intercalation into mesoporous anatase with an ordered 3D pore structure. Angew Chem 122:2624–2628

    Article  Google Scholar 

Download references

Acknowledgements

The authors gratefully acknowledge the National Natural Science Foundation of China (Grant nos. 21671158, 21271148 and 21773184) for financial support of this work.

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Correspondence to Ning Wang or Jun Li.

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Xu, Y., Yu, Q., Zhao, D. et al. Synthesis and characterization of porphyrin-based porous coordination polymers obtained by supercritical CO2 extraction. J Mater Sci 53, 10534–10542 (2018). https://doi.org/10.1007/s10853-018-2305-5

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  • DOI: https://doi.org/10.1007/s10853-018-2305-5

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