Abstract
Three new CuPp–TiO2 composite materials were prepared by impregnating copper(II) porphyrin with different peripheral substituent (–OH, –COOC2H5, and –COOH) onto the surface of polycrystalline TiO2 at room temperature and characterized by SEM, energy-dispersive X-ray spectrometry, X-ray diffraction, FT-IR, UV–Vis DRS, and photoluminescence. The effects of metalloporphyrins on the surface of TiO2 have been detected by the photodegradation of 4-nitrophenol (4-NP) and rhodamine B (RhB). The loading of metalloporphyrins onto TiO2 results in strong visible light absorption by the composite and, more importantly, a 1.47–2.47 times increase in visible light photocatalytic activity in the degradation of RhB. The metalloporphyrins dispersed on the TiO2 surface can act as a small-band-gap semiconductor to absorb visible light, giving rise to electron–hole separation. What’s more, these CuPp–TiO2 with different peripheral substituent (–OH, –COOC2H5, and –COOH) in meso-sites of porphyrin ring displayed different catalytic activities in the degradation of 4-NP and RhB, the CuPp containing –OH and –COOH showed better catalytic activity due to their strong interaction with TiO2. A possible mechanism of these higher photocatalytic efficiencies was proposed based on the relative experiments.
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Breslow R, Yang J, Yan JM (2002) Biomimetic hydroxylation of saturated carbons with artificial cytochrome P-450 enzymes-liberating chemistry from the tyranny of functional groups. Tetrahedron 58:653–659
Ambroise A, Li JZ, Yu LH, Lindsey JS (2000) A self-assembled light-harvesting array of seven porphyrins in a wheel and spoke architecture. Org Lett 2:2563–2566
Qiu WG, Li ZF, Bai GM, Meng SN, Dai HX, He H (2007) Study on the inclusion behavior between meso-tetrakis [4-(3-pyridiniumpropoxy) phenyl] prophyrin tetrakis-bromide and b-cyclodextrin derivatives in aqueous solution. Spectrochim Acta A Mol Biomol Spectrosc 66:1189–1193
Matthews RW (1991) Photooxidative degradation of coloured organics in water using supported catalysts TiO2 on sand. Water Res 25:1169–1176
Chen HY, Jin HX, Dong B (2012) Preparation of magnetically supported chromium and sulfur co-doped TiO2 and use for photocatalysis under visible light. Res Chem Intermed 38:2335–2342
Isimjan TT, Kazemian H, Rohani S, Ray AjayK (2010) Photocatalytic activities of Pt/ZIF-8 loaded highly ordered TiO2 nanotubes. J Mater Chem 20:10241–10245
Yang Y, Zhong H, Tian CX (2011) Photocatalytic mechanisms of modified titania under visible light. Res Chem Intermed 37:91–102
Jang JH, Jeon KS, Oh S, Kim HJ, Asahi T, Masuhara H, Yoon M (2007) Synthesis of Sn-porphyrin-intercalated trititanate nanofibers: optoelectronic properties and photocatalytic activities. Chem Mater 19:1984–1991
Kim W, Park J, Jo HJ, Kim HJ, Choi W (2008) Visible light photocatalysts based on homogeneous and heterogenized tin porphyrins. J Phys Chem C 112:491–499
Wang C, Li J, Mele G, Yang GM, Zhang FX, Palmisano L, Vasapollo G (2007) Efficient degradation of 4-nitrophenol by using functionalized porphyrin-TiO2 photocatalysts under visible irradiation. Appl Catal B 76:218–226
Campbell WM, Burrell AK, Officer DL, Jolley KW (2004) Porphyrins as light harvesters in the dye-sensitised TiO2 solar cell. Coord Chem Rev 248:1363–1379
Odobel F, Blart E, Lagrée M, Villieras M, Boujtita H, Murr NE, Caramori S, Bignozzi CA (2003) Porphyrin dyes for TiO2 sensitization. J Mater Chem 13:502–510
Mele G, Ciccarella G, Vasapollo G, García-López E, Palmisano L, Schiavello M (2002) Photocatalytic degradation of 4-nitrophenol in aqueous suspension by using polycrystalline TiO2 Samples impregnated with Cu(II)-phthalocyanine. Appl Catal B38:309–319
Mele G, Sole RD, Vasapollo G, García-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
Mele G, Sole RD, Vasapollo G, García-López E, Palmisano L, Mazzetto SE, Attanasi OA, Filippone P (2004) Polycrystalline TiO2 impregnated with cardanol-based porphyrins for the photocatalytic degradation of 4-nitrophenol. Green Chem 6:604–608
Wang C, Yang GM, Li J, Mele G, Słota R, Broda MA, Duan MY, Vasapollo G, Zhang XF, Zhang FX (2009) Novel meso-substituted porphyrins: synthesis, characterization and photocatalytic activity of their TiO2-based composites. Dyes Pigm 80:321–328
Granados-Oliveros G, Páez-Mozo EA, Ortega FM, Ferronato C, Chovelon JM (2009) Degradation of atrazine using metalloporphyrins supported on TiO2 under visible light irradiation. Appl Catal B 89:448–454
Sun WJ, Li J, Yao GP, Zhang FX (2011) Surface-modification of TiO2 with new metalloporphyrins and their photocatalytic activity in the degradation of 4-notrophenol. Appl Surf Sci 258:940–945
Sun WJ, Li J, Yao GP, Jiang M, Zhang FX (2011) Efficient photodegradation of 4-nitrophenol by using new CuPp–TiO2 photocatalyst under visible light irradiation. Catal Commun 16:90–93
Ishibashi K, Fujishima A, Watanabe T, Hashimoto K (2000) Detection of active oxidative species in TiO2 photocatalysis using the fluorescence technique. Electrochem Commun 2:207–210
Bai SL, Li HY, Guan YJ, Jiang ST (2011) The enhanced photocatalytic activity of CdS/TiO2 nanocomposites by controlling CdS dispersion on TiO2 nanotubes. Appl Surf Sci 257:6406–6409
Cherian S, Wamser CC (2000) Adsorption and photoactivity of tetra (4-carboxyphenyl) porphyrin (TCPP) on nanoparticulate TiO2. J Phys Chem B 104:3624–3629
Li XQ, Liu LF, Kang SZ et al (2012) Titanate nanotubes co-sensitized with cadmium sulfide nanoparticles and porphyrin zinc: preparation and enhanced photocatalytic activity under visible light. Catal Commun V17:136–139
Kathiravan A, Renganathan R (2009) Effect of anchoring group on the photosensitization of colloidal TiO2 nanoparticles with porphyrins. J Colloid Interface Sci 331:401–407
Ma TL, Inoue K, Noma H, Yao K, Abe E (2002) Effect of functional group on photochemical properties and photosensitization of TiO2 electrode sensitized by porphyrin derivatives. J Photochem Photobiol A 152:207–212
Ma TL, Inoue K, Noma H, Yao K, Abe E et al (2002) Photoelectrochemical properties of TiO2 electrodes sensitized by porphyrin derivatives with different numbers of carboxyl groups. J Electroanal Chem 537:31–38
Chen DM, Yang D, Geng JQ, Zhu JH, Jiang ZY (2008) Improving visible-light photocatalytic activity of N-doped TiO2 nanoparticles via sensitization by Zn porphyrin. Appl Surf Sci 255:2879–2884
Su BT, Liu XH, Peng XX, Xiao T, Su ZX (2003) Preparation and characterization of the TiO2/polymer complex nanomaterial. Mater Sci Eng A349:59–62
Su BT, Ma ZY, Min SX, She SX, Wang ZY (2007) Preparation of TiO2/PS complex nanoparticles. Mater Sci Eng A 458:44–47
Wang YX, Li XY, Lu G, Quan X, Chen GH (2008) Highly oriented 1-D ZnO nanorod arrays on zinc foil: direct growth from substrate, optical properties and photocatalytic activities. J Phys Chem C112:7332–7336
Baiju KV, Zachariah A, Shukla S, Biju S, Reddy MLP, Warrier KGK (2009) Correlating photoluminescence and photocatalytic activity of mixed-phase nanocrystalline titania. Catal Lett 130:130–136
Li XQ, Liu LF, Kang SZ, Mu J, Li GD (2011) Differences between Zn-porphyrin-coupled titanate nanotubes with various anchoring modes: thermostability, spectroscopic, photocatalytic and photoelectronic properties. Appl Surf Sci 257:5950–5956
Yao HT, Chien HK (2011) Photocatalytic degradation of dye and NOx using visible-light-responsive carbon-containing TiO2. Catal Today 174:114–120
Li XZ, Chen CC, Zhao JC (2001) Mechanism of photodegradation of H2O2 on TiO2 surfaces under visible light irradiation. Langmuir 17:4118–4122
Salvador P (2007) On the nature of photogenerated radical species active in the oxidative degradation of dissolved pollutants with TiO2 Aqueous suspensions: a revision in the light of the electronic structure of adsorbed water. J Phys Chem C 111:17038–17043
Souza FD, Deviprasad GR, El-Khouly ME, Fujitsuka M, Ito O (2001) Probing the donor-acceptor proximity on the physicochemical properties of porphyrin-fullerene dyads: “tail-on” and “tail-off” binding approach. J Am Chem Soc 123:5277–5284
Salzner U, Lagowski JB, Pickup PG, Poirier RA (1998) Comparison of geometries and electronic structures of polyacetylene, polyborole, polycyclopentadiene, polypyrrole, polyfuran, polysilole, polyphosphole, polythiophene, polyselenophene and polytellurophene. Synth Met 96:177–189
Snook JH, Samuelson LA, Kumar J, Kim YG, Whitten JE (2005) Ultraviolet photoelectron spectroscopy of nanocrystalline TiO2 films sensitized with (2,2′-bipyridyl)ruthenium(II) dyes for photovoltaic applications. Org Electron 6:55–64
Li TB, Chen G, Zhou C, Shen ZY, Jin RC, Sun JX (2011) New photocatalyst BiOCl/BiOI composites with highly enhanced visible light photocatalytic performances. Dalton Trans 40:6751–6758
Rao YF, Chu W (2009) Reaction mechanism of linuron degradation in TiO2 suspension under visible light irradiation with the assistance of H2O2. Environ Sci Technol 43:6183–6189
Hilal HS, Majjad LZ, Zatar N, El-Hamouz A (2007) Dye-effect in TiO2 catalyzed contaminant photodegradation: sensitization vs. charge-transfer formalism. Solid State Sci 9:9–15
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The authors acknowledge the research grant provided by the National Nature Science Foundation of China (21271148) and The Educational Committee Foundation of Shaanxi Province (12JK0637) that resulted in this article.
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Yu, Mm., Li, J., Sun, Wj. et al. Preparation, characterization, and photocatalytic properties of composite materials of copper(II) porphyrin/TiO2 . J Mater Sci 49, 5519–5528 (2014). https://doi.org/10.1007/s10853-014-8132-4
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DOI: https://doi.org/10.1007/s10853-014-8132-4