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Photocatalysis by tetraphenylporphyrin of the decomposition of chloroform

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Abstract

Irradiation of solutions of tetraphenylporphyrin (H2TPP) in chloroform causes decomposition of the chloroform at UV wavelengths higher than those that decompose chloroform directly. The catalytic cycle involves photooxidation of the porphyrin followed by thermal reduction. Photocatalysis continues after H2TPP has been completely protonated by the HCl produced during decomposition, and the rate of HCl production accelerates as a second pathway, in which CCl3OOH oxidizes the porphyrin, becomes important.

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Notes and references

  1. Z. Gasyna, W. R. Browett and M. J. Stillman, One-electron photooxidation of porphyrins at low temperature, Inorg. Chim. Acta, 1984, 92, 37–42.

    Article  CAS  Google Scholar 

  2. Z. Gasyna, W. R. Browett and M. J. Stillman, One-electron, visible-light photooxidation of porphyrins in alkyl chloride solutions, Inorg. Chem., 1984, 23, 382–384.

    Article  CAS  Google Scholar 

  3. Z. Gasyna, W. R. Browett and M. J. Stillman, p-Cation-radical formation following visible light photolysis of porphyrins in frozen solution using alkyl chlorides or quinones as electron acceptors, Inorg. Chem., 1985, 24, 2440–2447.

    Article  CAS  Google Scholar 

  4. Z. Gasyna, W. R. Browett and M. J. Stillman, Quenching of low-lying excited states in porphyrins by electron acceptors in rigid matrixes, ACS Symp. Ser., 1986, 321, 298–308.

    Article  CAS  Google Scholar 

  5. V. V. Gurinovich and M. P. Tsvirko, Quantum efficiency of photooxidation of porphyrins by halomethanes in solutions, J. Appl. Spectrosc. (Translation of Zhurnal Prikladnoi Spektroskopii), 2001, 68, 110–117.

    CAS  Google Scholar 

  6. S. Radzki and C. Giannotti, Photochemical reactions of gadolinium(iii) tetraphenylporphyrin in toluene solution containing an electron acceptor or donor, J. Photochem. Photobiol., A, 1994, 80, 257–264.

    Article  CAS  Google Scholar 

  7. G. S. S. Saini, N. K. Chaudhury and A. L. Verma, Photooxidation and electron-transfer processes in free-base tetraphenylporphin probed by resonance Raman spectroscopy, Photochem. Photobiol., 1992, 55, 815–822.

    Article  CAS  Google Scholar 

  8. G. Varani, A. Maldotti and C. Bartocci, Catalytic reduction of carbon tetrachloride by a meso-tetraphenylporphyrin excited state in benzene/ethanol mixed solvent, New J. Chem., 1992, 16, 827–831.

    CAS  Google Scholar 

  9. M. Benaglia, T. Danelli, F. Fabris, D. Sperandio and G. Pozzi, Poly(ethylene glycol)-supported tetrahydroxyphenylporphyrin: A convenient, recyclable catalyst for photooxidation reactions, Org. Lett., 2002, 4, 4229–4232.

    Article  CAS  PubMed  Google Scholar 

  10. S. Funyu, T. Isobe, S. Takagi, D. A. Tryk and H. Inoue, Highly efficient and selective epoxidation of alkenes by photochemical oxygenation sensitized by a ruthenium(ii) porphyrin with water as both electron and oxygen donor, J. Am. Chem. Soc., 2003, 125, 5734–5740.

    Article  CAS  PubMed  Google Scholar 

  11. H. J. Harmon, Photocatalytic demethylation of 2,4,6-trinitrotoluene (TNT) by porphyrins, Chemosphere, 2006, 63, 1094–1097.

    Article  CAS  PubMed  Google Scholar 

  12. A. Maldotti, C. Bartocci, R. Amadelli and V. Carassiti, Photocatalytic reactions in the 2,3,7,8,12,13,17,18-octaethylporphyrinatoiron(iii)-ethanol-carbon tetrachloride system, J. Chem. Soc., Dalton Trans., 1989, 1197–1201.

    Google Scholar 

  13. A. Maldotti, A. Molinari and G. Varani, Biomimetic photocatalysis: iron porphyrins in heterogeneous and organized systems, Int. J. Med., Biol. Environ., 2001, 29, 7–17.

    CAS  Google Scholar 

  14. J. Rosenthal, T. D. Luckett, J. M. Hodgkiss and D. G. Nocera, Photocatalytic oxidation of hydrocarbons by a bis-iron(iii)-µ-oxo pacman porphyrin using O2 and visible light, J. Am. Chem. Soc., 2006, 128, 6546–6547.

    Article  CAS  PubMed  Google Scholar 

  15. T. Shiragami, J. Matsumoto, H. Inoue and M. Yasuda, Antimony porphyrin complexes as visible-light driven photocatalyst, J. Photochem. Photobiol., C, 2005, 6, 227–248.

    Article  CAS  Google Scholar 

  16. M. Trytek, J. Fiedurek and S. Radzki, A novel porphyrin-based photocatalytic system for terpenoids production from (R)-(+)-limonene, Biotechnol. Prog., 2007, 23, 131–137.

    Article  CAS  PubMed  Google Scholar 

  17. G. Wu, M. Hu and H. Leung, Sensitized photoredox reactions. Part IX. Thermodynamic factors in the porphyrin-sensitized photoreduction of methyl viologen, J. Photochem. Photobiol., A, 1991, 62, 141–150.

    Article  CAS  Google Scholar 

  18. J. S. Lindsey, Photochem CAD, spectra recorded by Junzhong Li and Richard W. Wagner, http://omlc.ogi.edu/spectra/PhotochemCAD/html/index.html.

  19. H. Du, R.-C. A. Fuh, J. Li, L. A. Corkan and J. S. Lindsey, Photochem CAD: a computer-aided design and research tool in photochemistry, Photochem. Photobiol., 1998, 68, 141–142.

    CAS  Google Scholar 

  20. A. Stone and E. B. Fleischer, The molecular and crystal structure of porphyrin diacids, J. Am. Chem. Soc., 1968, 90, 2735–2748.

    Article  CAS  Google Scholar 

  21. E. Solis Montiel, J. A. H. Solano, Spectrophotometric analysis for chlorine by the extraction of triiodide formed in chloroform solution of tetrabutylammonium perchlorate, Ingenieria y Ciencia Quimica, 1986, 10, 45–48.

    Google Scholar 

  22. R. Cooper, J. B. Cumming, S. Gordon and W. A. Mulac, The reactions of the halomethyl radicals CCl3 and CF3 with oxygen, Radiat. Phys. Chem., 1980, 16, 169–174.

    CAS  Google Scholar 

  23. S. Hautecloque, On the photooxidation of gaseous trichloromethane and chlorosyl radical formation, J. Photochem., 1980, 14, 157–165.

    Article  CAS  Google Scholar 

  24. S. Mosseri, Z. B. Alfassi and P. Neta, Absolute rate constants for hydrogen abstraction from hydrocarbons by the trichloromethylperoxy radical, Int. J. Chem. Kinet., 1987, 19, 309–317.

    Article  CAS  Google Scholar 

  25. Z. B. Alfassi, A. Harriman, S. Mosseri and P. Neta, Rates and mechanisms of oxidation of ZnTPP by CCl3O2 radicals in various solvents, Int. J. Chem. Kinet., 1986, 18, 1315–1321.

    Article  CAS  Google Scholar 

  26. D. Brault and P. Neta, Reactions of iron(iii) porphyrins with peroxyl radicals derived from halothane and halomethanes, J. Phys. Chem., 1984, 88, 2857–2862.

    Article  CAS  Google Scholar 

  27. J. Grodkowski and P. Neta, One-electron oxidation in irradiated carbon tetrachloride solutions of ZnTPP, TMPD, and phenols, J. Phys. Chem., 1984, 88, 1205–1209.

    Article  CAS  Google Scholar 

  28. R. E. Huie, D. Brault and P. Neta, Rate constants for one-electron oxidation by the trifluoromethylperoxy, trichloromethylperoxy, tribromomethylperoxy radicals in aqueous solutions, Chem.–Biol. Interact., 1987, 62, 227–235.

    Article  CAS  PubMed  Google Scholar 

  29. G. Merenyi, J. Lind and L. Engman, One- and two-electron reduction potentials of peroxyl radicals and related species, J. Chem. Soc., Perkin Trans. 2, 1994, 2551–2553.

    Google Scholar 

  30. J. Moenig, D. Bahnemann and K. D. Asmus, One electron reduction of carbon tetrachloride in oxygenated aqueous solutions: a trichloromethyldioxy-free radical mediated formation of chloride and carbon dioxide, Chem.–Biol. Interact., 1983, 47, 15–27.

    Article  CAS  Google Scholar 

  31. J. E. Packer, R. L. Wilson, D. Bahnemann and K. D. Asmus, Electron transfer reactions of halogenated aliphatic peroxyl radicals: measurement of absolute rate constants by pulse radiolysis, J. Chem. Soc., Perkin Trans. 2, 1980, 296–299.

    Google Scholar 

  32. X. Shen, J. Lind, T. E. Eriksen and G. Merenyi, Reactivity of the trichloromethylperoxo radical: evidence for a first-order transformation, J. Phys. Chem., 1989, 93, 553–557.

    Article  CAS  Google Scholar 

  33. S. Gaeb and W. V. Turner, Photooxidation of chloroform: isolation and characterization of trichloromethyl hydroperoxide, Angew. Chem., 1985, 97, 48.

    Article  CAS  Google Scholar 

  34. J. K. Kochi, Oxidation-reduction reactions of free radicals and metal complexes, Free Radicals, 1973, 1, 591–683.

    CAS  Google Scholar 

  35. T. J. Wallington, W. F. Schneider, I. Barnes, K. H. Becker, J. Sehested and O. J. Nielson, Stability and infrared spectra of mono-, di-, and trichloromethanol, Chem. Phys. Lett., 2000, 322, 97–102.

    Article  CAS  Google Scholar 

  36. R. Mertens, C. von Sonntag, J. Lind and G. Merenyi, Pulse-radiolysis study of the kinetics of phosgene hydrolysis in aqueous solution, Angew. Chem., 1994, 106, 1320–1322.

    Article  CAS  Google Scholar 

  37. C. A. Taatjes, L. K. Christensen, M. D. Hurley and T. J. Wallington, Absolute and site-specific abstraction rate coefficients for reactions of Cl with CH3CH2OH, CH3CD2OH, and CD3CH2OH between 295 and 600 K, J. Phys. Chem. A, 1999, 103, 9805–9814.

    Article  CAS  Google Scholar 

  38. X. Zhang, J. Wu and Y. Zhou, The reaction of a-hydroxyethyl radical in aqueous solution and ethyl alcohol, Radiat. Phys. Chem., 1994, 43, 335–338.

    Article  CAS  Google Scholar 

  39. C. Inisan, J.-Y. Saillard, R. Guilard, A. Tabard, Y. Le Mest, Electrooxidation of porphyrin free bases: fate of the p-cation radical, New J. Chem., 1998, 22, 823–830.

    Article  CAS  Google Scholar 

  40. P. Wardman, Reduction potentials of one-electron couples involving free radicals in aqueous solution, J. Phys. Chem. Ref. Data, 1989, 18, 1637–1755.

    Article  CAS  Google Scholar 

  41. M. C. Richoux, P. Neta, P. A. Christensen and A. Harriman, Formation and decay of zinc tetrakis(N-methyl-3-pyridyl)porphine p-radical cation in water, J. Chem. Soc., Faraday Trans. 2, 1986, 82, 235–249.

    Article  CAS  Google Scholar 

  42. M. C. Richoux, P. Neta and A. Harriman, One- and two-electron oxidation of lead(ii) tetrakis(N-methylpyridyl)porphyrins in aqueous solution, J. Chem. Soc., Faraday Trans. 2, 1986, 82, 201–207.

    Article  CAS  Google Scholar 

  43. A. Harriman, P. Neta and M. C. Richoux, Reactions of magnesium porphyrin radical cations in water. Disproportionation, oxygen production, and comparison with other metalloporphyrins, J. Phys. Chem., 1986, 90, 3444–3448.

    Article  CAS  Google Scholar 

  44. P. Neta, M. C. Richoux, A. Harriman and L. R. Milgrom, Resonance stabilization of zinc porphyrin p-radical cations, J. Chem. Soc., Faraday Trans. 2, 1986, 82, 209–217.

    Article  CAS  Google Scholar 

  45. P. Neta and A. Harriman, Zinc porphyrin p-radical cations in aqueous solution. Formation, spectra, and decay kinetics, J. Chem. Soc., Faraday Trans. 2, 1985, 81, 123–138.

    Article  CAS  Google Scholar 

  46. P. B. Amama, K. Itoh and M. Murabayashi, Photocatalytic oxidation of trichloroethylene in humidified atmosphere, J. Mol. Catal. A: Chem., 2001, 176, 165–172.

    Article  CAS  Google Scholar 

  47. C. Walling, Limiting rates of hydrocarbon autoxidations, J. Am. Chem. Soc., 1969, 91, 7590–7594.

    Article  CAS  Google Scholar 

  48. V. Catoire, R. Lesclaux, W. F. Schneider and T. J. Wallington, Kinetics and mechanisms of the self-reactions of CCl3O2 and CHCl2O2 radicals and their reactions with HO2, J. Phys. Chem., 1996, 100, 14356–14371.

    Article  CAS  Google Scholar 

  49. H. Eyring, F. W. Cagle Jr., The significance of isotopic reactions in rate theory, J. Phys. Chem., 1952, 56, 889–892.

    Article  CAS  Google Scholar 

  50. S. Hautecloque, Kinetics of the reactions CCl3 + H2(D2) and CCl3 + CH4(CD4). Isotope effect, J. Chim. Phys. Phys.-Chim. Biol., 1970, 67, 771–776.

    Article  CAS  Google Scholar 

  51. S. Hautecloque, Reactions of trichloromethyl radicals with ethane and perdeuterioethane. Isotope effect, C. R. Seances Acad. Sci., Ser. C, 1971, 272, 2094–2097.

    CAS  Google Scholar 

  52. S. Hautecloque, Reactions of trichloromethyl radicals with bromomethanes and deuterobromomethanes. Primary isotope effect, J. J. Chim. Phys. Phys.-Chim. Biol., 1974, 71, 13–17.

    Article  CAS  Google Scholar 

  53. S. Hautecloque, Reactions of trichloromethyl radicals with bromoethanes and deuterated bromoethanes, C. R. Seances Acad. Sci., Ser. C, 1975, 280, 701–704.

    CAS  Google Scholar 

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Authors and Affiliations

  1. Department of Chemistry, Santa Clara University, Santa Clara, 95053, California, USA

    Zulmarie Muñoz, Allison S. Cohen, Linh M. Nguyen, Ted A. McIntosh & Patrick E. Hoggard

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  1. Zulmarie Muñoz
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  2. Allison S. Cohen
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Muñoz, Z., Cohen, A.S., Nguyen, L.M. et al. Photocatalysis by tetraphenylporphyrin of the decomposition of chloroform. Photochem Photobiol Sci 7, 337–343 (2008). https://doi.org/10.1039/b713270k

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