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Enhanced photocatalytic activity in porphyrin-sensitized TiO2 nanorods

  • Wei Zhang (a1), Chen Wang (a2), Xiao Liu (a1) and Jun Li (a1)

Two novel porphyrins (5,10,15,20-tetra(3-(carboethoxymethyleneoxy)phenyl)porphyrin, H2TEPp and 5,10,15,20-tetra(3-(carboxymethyleneoxy)phenyl)porphyrin, H2TCPp) and their copper(II) porphyrins (CuTEPp, CuTCPp) were synthesized. With these porphyrins, four new porphyrin-sensitized TiO2 nanorod composites (H2TEPp/TiO2, H2TCPp/TiO2, CuTEPp/TiO2, and CuTCPp/TiO2) were prepared and characterized by methods of XRD, SEM, TEM, FT-IR, UV-vis DRS, nitrogen adsorption–desorption and fluorescence spectra. Besides, the photocatalytic activity and stability of the composites were assessed in the degradation of 4-nitrophenol (4-NP). The results indicate that the morphologies and structures of these composites are less influenced by the loaded porphyrins or copper porphyrins compared with the nanorods TiO2 (anatase). The porphyrin or copper porphyrin molecules are confirmed to bond on the surface of TiO2 through carboxyl group, which is beneficial to the electron transfer between porphyrin and TiO2. All composites exhibit enhanced photoactivities compared with the bare TiO2 nanorods. The possible reason is that the recombination of photoproduced electron–hole has been controlled effectively in these composites, which can be seen from their decreased fluorescence emission. The stability results of composites show that they still hold considerable photocatalytic activities after six cycling experiments.

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Contributing Editor: Xiaobo Chen

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1. Lin, Z-Y., Li, L-H., Yu, L-L., Li, W-G., and Yang, G-W.: Modifying photocatalysts for solar hydrogen evolution based on the electron behavior. J. Mater. Chem. A 5, 5235 (2017).
2. Liu, X-Q., Iocozzia, J., Wang, Y., Cui, X., Chen, Y-H., Zhao, S-Q., Li, Z., and Lin, Z-Q.: Noble metal–metal oxide nanohybrids with tailored nanostructures for efficient solar energy conversion, photocatalysis and environmental remediation. Energy Environ. Sci. 10, 402 (2017).
3. Huang, H-W., Xiao, K., Yu, S-X., Dong, F., Zhang, T-R., and Zhang, Y-H.: Iodide surface decoration: A facile and efficacious approach to modulating the band energy level of semiconductors for high-performance visible-light photocatalysis. Chem. Commun. 52, 354 (2016).
4. Wenderich, K. and Mul, G.: Methods, mechanism, and applications of photodeposition in photocatalysis: A review. Chem. Rev. 116, 14587 (2016).
5. Muuronen, M., Parker, S.M., Berardo, E., Le, A., Zwijnenburg, M.A., and Furche, F.: Mechanism of photocatalytic water oxidation on small TiO2 nanoparticles. Chem. Sci. 8, 2179 (2017).
6. Schneider, J., Matsuoka, M., Takeuchi, M., Zhang, J-L., Horiuchi, Y., Anpo, M., and Bahnemann, D.W.: Understanding TiO2 photocatalysis: Mechanisms and materials. Chem. Rev. 114, 9919 (2014).
7. Ma, Y., Wang, X-L., Jia, Y-S., Chen, X-B., Han, H-X., and Li, C.: Titanium dioxide-based nanomaterials for photocatalytic fuel generations. Chem. Rev. 114, 9987 (2014).
8. Dahl, M., Liu, Y-D., and Yin, Y-D.: Composite titanium dioxide nanomaterials. Chem. Rev. 114, 9853 (2014).
9. Jiménez, J.M., Bourret, G.R., Berger, T., and McKenna, K.P.: Modification of charge trapping at particle/particle interfaces by electrochemical hydrogen doping of nanocrystalline TiO2 . J. Am. Chem. Soc. 138, 15956 (2016).
10. Asahi, R., Morikawa, T., Ohwaki, T., Aoki, K., and Taga, Y.: Visible-light photocatalysis in nitrogen-doped titanium oxides. Science 293, 269 (2001).
11. Yang, H-G., Sun, C-H., Qiao, S-Z., Zou, J., Liu, G., Smith, S.C., Cheng, H-M., and Lu, G-Q.: Anatase TiO2 single crystals with a large percentage of reactive facets. Nature 453, 638 (2008).
12. Yu, J-G., Low, J-X., Xiao, W., Zhou, P., and Jaroniec, M.: Enhanced photocatalytic CO2-reduction activity of anatase TiO2 by coexposed {001} and {101} facets. J. Am. Chem. Soc. 136, 8839 (2014).
13. Pan, L., Zou, J-J., Zhang, X-W., and Wang, L.: Water-mediated promotion of dye sensitization of TiO2 under visible light. J. Am. Chem. Soc. 133, 10000 (2011).
14. Urbani, M., Grätzel, M., Nazeeruddin, M.K., and Torres, T.: Meso-substituted porphyrins for dye-sensitized solar cells. Chem. Rev. 114, 12330 (2014).
15. Wen, P-H., Itoh, H., Tang, W-P., and Feng, Q.: Transformation of layered titanate nanosheets into nanostructured porous titanium dioxide in polycation solution. Microporous Mesoporous Mater. 116, 147 (2008).
16. Pan, J., Wu, X., Wang, L-Z., Liu, G., Lu, G-Q., and Cheng, H-M.: Synthesis of anatase TiO2 rods with dominant reactive {010} facets for the photoreduction of CO2 to CH4 and use in dye-sensitized solar cells. Chem. Commun. 47, 8361 (2011).
17. Wen, P-H., Itoh, H., Tang, W-P., and Feng, Q.: Single nanocrystals of anatase-type TiO2 prepared from layered titanate nanosheets: Formation mechanism and characterization of surface properties. Langmuir 23, 11782 (2007).
18. Morris, A.J., Marton, A., and Meyer, G.J.: Halide coordination to zinc porphyrinsensitizers anchored to nanocrystalline TiO2 . Inorg. Chem. 47, 7681 (2008).
19. Ren, X-B., Chen, M., and Qian, D-J.: Pd(II)-mediated triad multilayers with zinc tetrapyridylporphyrin and pyridine-functionalized nano-TiO2 as linkers: Assembly, characterization, and photocatalytic properties. Langmuir 28, 7717 (2012).
20. Zhao, X., Liu, X., Yu, M-M., Wang, C., and Li, J.: The highly efficient and stable Cu, Co, Zn-porphyrine TiO2 photocatalysts with heterojunction by using fashioned one-step method. Dyes Pigm. 136, 648 (2017).
21. Sun, W-J., Li, J., , X-F., and Zhang, F-X.: Preparation, characterization and photocatalytic activity of metalloporphyrins-modified TiO2 composites. Res. Chem. Intermed. 39, 1447 (2013).
22. Wang, C., Yang, G-M., Li, J., Mele, G., Slota, R., Broda, M.A., Duan, M-Y., Vasapollo, G., Zhang, X-F., and Zhang, F-X.: Novel meso-substituted porphyrins: Synthesis, characterization and photocatalytic activity of their TiO2-based composites. Dyes Pigm. 80, 321 (2009).
23. Yu, M-M., Li, J., Sun, W-J., Jiang, M., and Zhang, F-X.: Preparation, characterization, and photocatalytic properties of composite materials of copper(II) porphyrin/TiO2 . J. Mater. Sci. 49, 5519 (2014).
24. Yao, G-P., Li, J., Luo, Y., and Sun, W-J.: Efficient visible photodegradation of 4-nitrophenol in the presence of H2O2 by using a new copper(II) porphyrin–TiO2 photocatalyst. J. Mol. Catal. A: Chem. 361–362, 29 (2012).
25. Wang, C., Li, J., Mele, G., Duan, M-Y., , X-F., Palmisano, L., Vasapollo, G., and Zhang, F-X.: The photocatalytic activity of novel, substituted porphyrin/TiO2-based composites. Dyes Pigm. 84, 183 (2010).
26. Cochran, F.V., Wu, S.P., Wang, W., Nanda, V., Saven, J.G., Therien, M.J., and DeGrado, W.F.: Computational de novo design and characterization of a four-helix bundle protein that selectively binds a nonbiological cofactor. J. Am. Chem. Soc. 127, 1346 (2005).
27. Duncan, T.V., Wu, S.P., and Therien, M.J.: Ethyne-bridged (porphinato) zinc(II)–(porphinato) iron(III) complexes: Phenomenological dependence of excited-state dynamics upon (porphinato) iron electronic structure. J. Am. Chem. Soc. 128, 10423 (2006).
28. Adler, A.D., Longo, F.R., and Shergails, W.: Mechanistic investigations of porphyrin syntheses. I. Preliminary studies on ms-tetraphenylporphin. J. Am. Chem. Soc. 86, 3145 (1964).
29. Das, T., Chakraborty, S., Sarma, H.D., Banerjee, S., and Venakatesh, M.: A novel 177 Lu-labeled porphyrin for possible use in targeted tumor therapy. Nucl. Med. Biol. 37, 655 (2010).
30. Li, B-B., Zhao, Z-B., Gao, F., Wang, X-Z., and Qiu, J-S.: Mesoporous microspheres composed of carbon-coated TiO2 nanocrystals with exposed {001} facets for improved visible light photocatalytic activity. Appl. Catal., B 147, 958 (2014).
31. Wang, Y-X., Li, X-Y., Lu, G., Quan, X., and Chen, G-H.: Highly oriented 1-D ZnO nanorod arrays on zinc foil: Direct growth from substrate, optical properties and photocatalytic activities. J. Phys. Chem. C 112, 7332 (2008).
32. Baiju, K.V., Zachariah, A., Shukla, S., Biju, S., Reddy, M.L.P., and Warrier, K.G.K.: Correlating photoluminescence and photocatalytic activity of mixed-phase nanocrystalline titania. Catal. Lett. 130, 130 (2009).
33. Su, X-Q., Li, J., Zhang, Z-Q., Yu, M-M., and Yuan, L.: Cu(II) porphyrins modified TiO2 photocatalysts: Accumulated patterns of Cu(II) porphyrin molecules on the surface of TiO2 and influence on photocatalytic activity. J. Alloys Compd. 626, 252 (2015).
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