Chemical Papers

, Volume 72, Issue 9, pp 2327–2337 | Cite as

Dependence of morphology, substrate and thickness of iron phthalocyanine thin films on the photocatalytic degradation of rhodamine B dye

  • Jing Xu
  • Lele Zhao
  • Wenlong Hou
  • Huiyun Guo
  • Haiquan Zhang
Original Paper


The photocatalytic activity of thin film mainly depended on the morphology of thin film and lifetime of photo-generated charges. Here, we reported the effect of morphology adjusted through solvent vapor treatment (SVT) and different substrates on the photocatalytic activity of iron phthalocyanine (FePc) thin films. The FePc thin films on indium tin oxide (ITO) glass, copper (Cu), and quartz glass were prepared by vacuum evaporation, and their morphologies untreated and treated with solvent vapor such as benzene, petroleum ether, N,N-dimethylformamide for different time intervals; time intervals (0, 24, 36, 48, 72 h) were characterized by ultraviolet–visible spectroscopy, field-emission scanning electron microscopy, and X-ray diffractometer. The effects of thickness and substrate on photocatalytic activity of the FePc thin film were characterized accordingly. SVT could effectively adjust morphology (nanorods and nanosheets) of the FePc thin film and improve its photocatalytic activity for Rhodamine B (RhB) degradation under visible light irradiation. In addition, the thickness (10, 20, and 50 nm) and substrate (ITO, Cu, Quartz glass) of the FePc thin film also affected its photocatalytic activity. The degradation rate of RhB with the optimized FePc thin film on ITO substrate was reached 70.0%. We proposed that the morphology treated by SVT could increase the active sites of the FePc thin film and further improve its photocatalytic activity. The thickness and substrate of the FePc thin film were also discussed.


Photocatalyst Iron phthalocyanine Solvent vapor treatment Morphology Substrate Photocatalytic activity 



This work was supported by the National Natural Science Foundation of China (No: 51173155 and 51472214), and the Colleges and Universities Science and Technology Research Project of Hebei Province (No: QN2016130).

Supplementary material

11696_2018_453_MOESM1_ESM.doc (770 kb)
Supplementary material 1 (DOC 770 kb)


  1. Abbaspour A, Norouz-sarvestani F, Mirahmadi E (2012) Electrocatalytic behavior of carbon paste electrode modified with metal phthalocyanines nanoparticles toward the hydrogen evolution. Electrochim Acta 76:404–409. CrossRefGoogle Scholar
  2. Alves W, Ribeiro AO, Pinheiro MVB, Krambrock K, Haber FE, Froyer G, Chauvet O, Ando RA, Souza FL, Alves WA (2011) Quenching of photoactivity in phthalocyanine copper(II)-titanate nanotube hybrid systems. J Phys Chem C 115:12082–12089. CrossRefGoogle Scholar
  3. Angelucci M, Gargiani P, Mariani C, Betti MG (2011) Potassium-doped FePc thin-film on metal surfaces: observation of different empty state occupation. J Nanopart Res 13:5967–5973. CrossRefGoogle Scholar
  4. Avelino CC (1997) From microporous to mesoporous molecular sieve materials and their use in catalysis. Chem Rev 97:2373–2419. CrossRefGoogle Scholar
  5. Biswas S, Shalev O, Pipe KP, Shtein M (2015) Chemical vapor jet deposition of parylene polymer films in air. Macromolecules 48:5550–5556. CrossRefGoogle Scholar
  6. Camp PJ, Jones AC, Neely RK, Speirs NM (2002) Aggregation of copper(II) tetrasulfonated phthalocyanine in aqueous salt solutions. J Phys Chem A 106:10725–10732. CrossRefGoogle Scholar
  7. Cantau C, Pigot T, Dupin JC, Lacombe S (2010) N-doped TiO2 by low temperature synthesis: stability, photo-reactivity and singlet oxygen formation in the visible range. J Photoch Photobio A 216:20–208. CrossRefGoogle Scholar
  8. Cho SW, Piper FJ, DeMasi A, Preston ARH, Smith KE (2010) Soft X-ray spectroscopy of C60/copper phthalocyanine/MoO3 interfaces: role of reduced MoO3 on energetic band alignment and improved performance. J Phys Chem C 114:18252–18257. CrossRefGoogle Scholar
  9. Colomban C, Kudrik EV, Afanasiev P, Sorokin AB (2014) Degradation of chlorinated phenols in water in the presence of H2O2 and water-solubleμ-nitrido diiron phthalocyanine. Catal Today 235:14–19. CrossRefGoogle Scholar
  10. Damascelli A, Gabetta G, Lumachi A, Fini L, Parmigiani F (1996) Multiphoton electron emission from Cu and W: an angle-resolved study. J Am Phys Soc 9:603–6034. CrossRefGoogle Scholar
  11. Ebrahimian A, Zanjanchi MA, Noei H, Arvand M, Wang Y (2014) TiO2 nanoparticles containing sulphonated cobalt phthalocyanine: preparation, characterization and photocatalytic performance. J Chem Eng 2:484–494. CrossRefGoogle Scholar
  12. Gottfried JM (2015) Surface chemistry of porphyrins and phthalocyanines. Surf Sci Rep 70:259–379. CrossRefGoogle Scholar
  13. Gredig T, Colesniuc CN, Crooker SA, Schuller IK (2012) Substrate-controlled ferromagnetism in iron phthalocyanine films due to one-dimensional iron chains. Phys Rev B 86:0144091–0144096. CrossRefGoogle Scholar
  14. Huang KJ, Hsiao YS, Whang WT (2011) Selective growth and enhanced field emission properties of micropatterned iron phthalocyanine nanofiber arrays. Org Electron 12:1826–1834. CrossRefGoogle Scholar
  15. Huang Z, Bao H, Yao Y, Lu W, Chen W (2014) Novel green activation processes and mechanism of peroxymonosulfate based on supported cobalt phthalocyanine catalyst. Appl Cata B Environ 154:36–43. CrossRefGoogle Scholar
  16. Kresge CT, Leonowicz ME, Roth WJ, Vartuli JC, Beck JS (1992) Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism. Nature 22:710–712. CrossRefGoogle Scholar
  17. Kroger M, Hamwi S, Meyer J, Riedl T, Kowalsky W, Kahn A (2009) Role of the deep-lying electronic states of MoO3 in the enhancement of hole-injection in organic thin films. Appl Phys Lett 95:1233011–1233013. CrossRefGoogle Scholar
  18. Lee S, Lee SK, Kang CG, Cho C, Lee YG, Jung U, Lee BH (2015) Graphene transfer in vacuum yielding a high quality graphene. Carbon 93:286–294. CrossRefGoogle Scholar
  19. Li N, Lu W, Pei K, Yao Y, Chen W (2014) Ordered-mesoporous-carbon-bonded cobalt phthalocyanine: a bioinspired catalytic system for controllable hydrogen peroxide activation. Acs Appl Mater Inter 6:5869–5876. CrossRefGoogle Scholar
  20. Li N, Lu W, Pei K, Yao Y, Chen W (2015) Formation of high-valent cobalt-oxo phthalocyanine species in a cellulose matrix for eliminating organic pollutants. Appl Catal B Environ 163:105–112. CrossRefGoogle Scholar
  21. Liu LY, Wan L, Cao L, Han YY, Zhang WH, Chen TX, Guo PP, Wang K, Xu FQ (2013) Assistance of partially reduced MOO3 interlayer to hole-injection at iron phthalocyanine/ITO interface evidenced by photoemission study. Appl Surf Sci 271:352–356. CrossRefGoogle Scholar
  22. Liu Z, Zhang L, Gao X, Zhang L, Zhang Q, Chen J (2016) A theoretical design and investigation on Zn-porphyrin-polyoxometalate hybrids with different π-linkers for searching high performance sensitizers of P-type dye-sensitized solar cells. Dyes Pigments 127:155–160. CrossRefGoogle Scholar
  23. Lliev V, Lleva A, Bilyarska J (1997) Photooxidation of phenols in aqueous solution, catalyzed by mononuclear and polynuclear metal phthalocynine complexes. Mol Catal Chem A 2:99–108. CrossRefGoogle Scholar
  24. Lu W, Chen W, Li N, Xu M, Yao Y (2009a) Oxidative removal of 4-nitrophenol using activated carbon fiber and hydrogen peroxide to enhance reactivity of metallophthalocyanine. Appl Catal B Environ 87:146–151. CrossRefGoogle Scholar
  25. Lu W, Li N, Chen W, Yao Y (2009b) The role of multiwalled carbon nanotubes in enhancing the catalytic activity of cobalt tetraaminophthalocyanine for oxidation of conjugated dyes. Carbon 47:3337–3345. CrossRefGoogle Scholar
  26. Lu W, Li N, Bao S, Chen W, Yao Y (2011) The coupling of metallophthalocyanine with carbon nanotubes to produce a nanomaterial-based catalyst for reaction-controlled interfacial catalysis. Carbon 49:169–1709. CrossRefGoogle Scholar
  27. Ma R, Bando Y, Sasaki T (2003) Nanotubes of lepidocrocite titanates. Chem Phys Lett 380:577–582. CrossRefGoogle Scholar
  28. Mahmiani Y, Sevim AM, Gül A (2016) Photocatalytic degradation of 4-chlorophenol under visible light by using TiO2 catalysts impregnated with Co(II) and Zn(II) phthalocyanine derivatives. J Photoch Photobio A 321:24–32. CrossRefGoogle Scholar
  29. Mele G, Del Sole R, Vasapollo G, Garcı́a-López E, Palmisano L, Schiavello M (2003) Photocatalytic degradation of 4-nitrophenol in aqueous suspension by using polycrystalline TiO2 impregnated with functionalized Cu(II)-porphyrin or Cu(II)-phthalocyanine. J Catal 217:334–342. CrossRefGoogle Scholar
  30. Peisert H, Uihlein J, Petraki F, Chassé T (2015) Charge transfer between transition metal phthalocyanines and metal substrates: the role of the transition metal. J Electron Spectrosc 204:49–60. CrossRefGoogle Scholar
  31. Qian H, Jiang L, Ateeq Ur R, Zhang H, Li H, He P, Bao S (2012) The electronic properties at the iron-phthalocyanine/Ag(110) interface. Chem Phys Lett 537:53–57. CrossRefGoogle Scholar
  32. Ren L, Mao M, Li Y, Lan L, Zhang Z, Zhao X (2016) Novel photothermocatalytic synergetic effect leads to catalytic activity and excellent durability of anatase TiO2 nanosheets with dominant 001 facets for benzene abament. Appl Catal B Environ 198:303–310. CrossRefGoogle Scholar
  33. Rengifo-Herrera JA, Pierzchała K, Sienkiewicz A, Forró L, Kiwi J, Pulgarin C (2010) Abatement of organics and escherichia coli by N, S Co-doped TiO2 under UV and visible light. Implications of the formation of singlet oxygen (1O2) under visible light. Appl Catal B Environ 88:398–406. CrossRefGoogle Scholar
  34. Rihter BD, Bohorquez MD, Rodgers MAJ, Kenney ME (1992) Two new sterically hindered phthalocyanines: synthetic and photodynamic aspects. Photochem Photobiol 5:677–680. CrossRefGoogle Scholar
  35. Sharma GD, Kumar R, Roy MS (2006) Investigation of charge transport, photo generated electron transfer and photovoltatic response of iron phthalocyanine (FePc): TiO2 thin films. Sol Energy Mat Sol C 90:32–45. CrossRefGoogle Scholar
  36. Shen X, Lu W, Feng G, Yao Y, Chen W (2009) Preparation and photoactivity of a novel water-soluble, polymerizable zinc phthalocyanine. J Mol Catal Chem A 298:17–22. CrossRefGoogle Scholar
  37. Sorokin AB (2013) Phthalocyanine metal complexes in catalysis. Chem Rev 113:8152–8191. CrossRefPubMedGoogle Scholar
  38. Souza JS, Pinheiro MVB, Krambrock K, Alves WA (2016) Dye degradation mechanisms using nitrogen doped and copper (II) phthalocyanine tetracarboxylate sensitized titanate and TiO2 nanotube. J Phys Chem C 120:11561–11571. CrossRefGoogle Scholar
  39. Stefan E, Markus S (1999) Immobilization and catalytic properties of perfluorinated ruthenium phthalocyanine complexes in MCM-41-type molecular sieves. Micropor Mesopor Mat 27:355–363. CrossRefGoogle Scholar
  40. Tatar B, Demiroğlu D (2015) Electrical properties of FePc organic semiconductor thin films obtained by CSP technique for photovoltaic applications. Mat Sci Semicon Proc 31:644–650. CrossRefGoogle Scholar
  41. Thompson L, Yates JT (2006) Surface science studies of the photoactivation of TiO2-new photochemical processes. Chem Rev 10:4428–4453. CrossRefGoogle Scholar
  42. Vacus J, Simon J (1995) Luminescence and anti-aggregative properties of polyoxyethylene-substituted phthalocyanine complexes. Adv Mater 9:737–800. CrossRefGoogle Scholar
  43. Vargas E, Vargas R, Núñez O (2014) A TiO2 surface modified with copper(II) phthalocyanine-tetrasulfonic acid tetrasodium salt as a catalyst during photoinduced dichlorvos mineralization by visible solar light. Appl Catal B Environ 157:8–14. CrossRefGoogle Scholar
  44. Wang Y, Liang D (2010) Solvent-stabilized photoconductive metal phthalocyanine nanoparticles: preparation and application in single-layered photoreceptor. Adv Mater 22:1521–1525. CrossRefPubMedGoogle Scholar
  45. Wang Q, Wu W, Chen J, Chu G, Ma K, Zou H (2012) Novel synthesis of ZnPc/TiO2 composite particles and carbon dioxide photo-catalytic reduction efficiency study under simulated solar radiation conditions. Colloid Surface A 409:118–125. CrossRefGoogle Scholar
  46. Wang H, Gonzalez-Pedro V, Kubo T, Fabregat-Santiago F, Bisquert J, Sanehira Y, Nakazaki J, Segawa H (2015) Enhanced carrier transport distance in colloidal Pbs quantum-dot-based solar cells using ZnO nanowires. J Phys Chem C 119:27265–27274. CrossRefGoogle Scholar
  47. Wu H, Zhang T, Wu C, Guan W, Yan L, Su Z (2016) A theoretical design and investigation on Zn-porphyrin-polyoxometalate hybrids with different π-linkers for searching high performance sensitizers of P-type dye-sensitized solar cells. Dyes Pigments 130:168–175. CrossRefGoogle Scholar
  48. Yang JL, Schumann S, Jones TS (2011) Tuning the morphology and molecular orientation of copper hexadecafluorophthalocyanine thin films by solvent annealing. Thin Solid Films 519:3709–3715. CrossRefGoogle Scholar
  49. Yang M, Liu J, Lee S, Zugic B, Huang J, Allard LF, Flytzani-Stephanopoulos M (2015) A common single-site Pt(II)-O(OH)x-species stabilized by sodium on “active” and “inert” supports catalyzes the water-gas shift reaction. J Am Chem Soc 137:3470–3473. CrossRefPubMedGoogle Scholar
  50. Yi Y, Cho SW, Kang SJ (2010) Observation of space-charge-limited current due to charge generation at interface of molybdenum dioxide and organic layer. Appl Phys Lett 97:0161011–0161012. CrossRefGoogle Scholar
  51. Zanjanchi MA, Ebrahimian A, Arvand M, Hazard J (2010) Sulphonated cobalt phthalocyanine-MCM-41: an active photocatalysts for degradation of 2,4-dichlorophenol. Mater 175:992–1000. CrossRefGoogle Scholar
  52. Zhao D, Ke W, Grice CR, Cimaroli AJ, Tan X, Yang M, Collins RW, Zhang H, Zhu K, Yan Y (2016) Annealing-Free efficient vacuum-deposited planar perovskite solar cells with evaporated fullerenes as electron-selective layers. Nano Energy 19:88–97. CrossRefGoogle Scholar

Copyright information

© Institute of Chemistry, Slovak Academy of Sciences 2018

Authors and Affiliations

  • Jing Xu
    • 1
    • 2
  • Lele Zhao
    • 1
  • Wenlong Hou
    • 1
  • Huiyun Guo
    • 1
  • Haiquan Zhang
    • 1
  1. 1.State Key Laboratory of Metastable Materials Science and TechnologyYanshan UniversityQinhuangdaoPeople’s Republic of China
  2. 2.Northeast Petroleum UniversityQinhuangdaoPeople’s Republic of China

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