The photoelectrochemical response and catalytic efficiency towards phenol photooxidation of mesoporous titania particles with spherical morphology have been explored. The catalysts were synthesized in two different arrangements using carbon spheres in a dual role as support and morphology director: hollow spherical titania particles and dense structures where the titania shell is surrounding a carbon core. Although the synthesized titania hollow spheres exhibited a similar photoelectrochemical behavior and optical properties than commercial P25, they showed a better photocatalytic response towards phenol photo-oxidation in terms of pollutant mineralization. This behavior cannot be explained in terms of the crystallinity (found to be higher for P25) and has been attributed to both confinement effects in the mesoporosity of these catalysts as well as to the spherical morphology of titania particles. The spherical arrangement of the titania surface would favor the fast motion of the charge carriers and minimize recombination processes. On the other hand, no clear contribution of the carbon phase to the enhanced photocatalytic response, since quite similar performance is observed for the hollow spheres and the core/shell composite. However, separation and filtration of the catalysts become easier for the carbon/titania composite, thereby improving the so-called practical efficiency. 1. Introduction Triggered by the rising interest in the development of advanced oxidation processes (AOP) for wastewater remediation, heterogeneous photocatalysis has received much attention in the last years [1, 2]. Particularly, extensive research is being carried out on the development of novel synthetic routes to improve the photocatalytic activity of conventional semiconductors—mostly TiO2 and ZnO—and ideally achieving the complete degradation (mineralization) of recalcitrant pollutants both in liquid and gas phase. The low efficiency of AOP based on heterogeneous photocatalysis is mainly due to high surface recombination rates of the charge carriers, low efficiency under visible light, separation (filtration), and recovery and reutilization of the fine photocatalyst powders [3, 4]. To overcome all these issues, different approaches are being considered such as doping with transition metal and nonmetal ions, surface sensitization of dyes, design of nanostructured photocatalysts with controlled morphology, or immobilization on appropriate substrates [2, 5–8]. In this regard, the enhanced photocatalytic performance of carbon/semiconductor composites has been reported over a
References
[1]
D. F. Ollis and H. Al-Elkabi, Photocatalytic Purification and Treatment of Water and Air, Elsevier, Amsterdam, The Netherlands, 1993.
[2]
M. A. Henderson, “A surface science perspective on TiO2 photocatalysis,” Surface Science Reports, vol. 66, no. 6-7, pp. 185–297, 2011.
[3]
N. Serpone and E. Pelizzetti, Photocatalysis: Fundamental and Applications, Wiley-Interscience, New-York, NY, USA, 1983.
[4]
A. L. Linsebigler, G. Lu, and J. T. Yates, “Photocatalysis on TiO2 surfaces: principles, mechanisms, and selected results,” Chemical Reviews, vol. 95, no. 3, pp. 735–758, 1995.
[5]
M. I. Litter and J. A. Navío, “Photocatalytic properties of iron-doped titania semiconductors,” Journal of Photochemistry and Photobiology A, vol. 98, no. 3, pp. 171–181, 1996.
[6]
S. Sakthivel and H. Kisch, “Daylight photocatalysis by carbon-modified titanium dioxide,” Angewandte Chemie—International Edition, vol. 42, no. 40, pp. 4908–4911, 2003.
[7]
Y. Cho, W. Choi, C. H. Lee, T. Hyeon, and H. I. Lee, “Visible light-induced degradation of carbon tetrachloride on dye-sensitized TiO2,” Environmental Science and Technology, vol. 35, no. 5, pp. 966–970, 2001.
[8]
A. Fernández, G. Lassaletta, V. M. Jiménez et al., “Preparation and characterization of TiO2 photocatalysts supported on various rigid supports (glass, quartz and stainless steel). Comparative studies of photocatalytic activity in water purification,” Applied Catalysis B: Environmental, vol. 7, no. 1-2, pp. 49–63, 1995.
[9]
R. Leary and A. Westwood, “Carbonaceous nanomaterials for the enhancement of TiO2 photocatalysis,” Carbon, vol. 49, no. 3, pp. 741–772, 2011.
[10]
J. L. Faria and W. H. Wang, “Carbon materials in photocatalysis,” in Carbon Materials for Catalysis, P. Serp and J. L. Figueiredo, Eds., chapter 13, John Wiley & Sons, New York, NY, USA, 2009.
[11]
J. Matos, J. Laine, and J. M. Herrmann, “Synergy effect in the photocatalytic degradation of phenol on a suspended mixture of titania and activated carbon,” Applied Catalysis B, vol. 18, no. 3-4, pp. 281–291, 1998.
[12]
L. F. Velasco, J. B. Parra, and C. O. Ania, “Role of activated carbon features on the photocatalytic degradation of phenol,” Applied Surface Science, vol. 256, no. 17, pp. 5254–5258, 2010.
[13]
L. F. Velasco, I. M. Fonseca, J. B. Parra, J. C. Lima, and C. O. Ania, “Photochemical behavior of activated carbons under UV irradiation,” Carbon, vol. 50, no. 1, pp. 249–258, 2012.
[14]
M. Inagaki, N. Kondo, R. Nonaka et al., “Structure and photoactivity of titania derived from nanotubes and nanofibers,” Journal of Hazardous Materials, vol. 161, no. 2-3, pp. 1514–1521, 2009.
[15]
W. Shen, Y. Zhu, X. Dong, J. Gu, and J. Shi, “A new strategy to synthesize TiO2-hollow spheres using carbon spheres as template,” Chemistry Letters, vol. 34, no. 6, pp. 840–841, 2005.
[16]
R. B. Zheng, X. W. Meng, and F. Q. Tang, “A general protocol to coat titania shell on carbon-based composite cores using carbon as coupling agent,” Journal of Solid State Chemistry, vol. 182, no. 5, pp. 1235–1240, 2009.
[17]
J. Matos, A. García, L. Zhao, and M. M. Titirici, “Solvothermal carbon-doped TiO2 photocatalyst for the enhanced methylene blue degradation under visible light,” Applied Catalysis A, vol. 390, no. 1-2, pp. 175–182, 2010.
[18]
J. Liu, G. Zhang, W. Ao, K. Yang, S. Peng, and C. Müller-Goymann, “Hollow mesoporous titania microsphere with low shell thickness/diameter ratio and high photocatalysis,” Applied Surface Science, vol. 258, no. 20, pp. 8083–8089, 2012.
[19]
Y. H. Ao, J. J. Xu, D. G. Fu, and C. W. Yuan, “Visible-light responsive C,N-codoped Titania hollow spheres for X-3B dye photodegradation,” Microporous and Mesoporous Materials, vol. 118, no. 1-3, pp. 382–386, 2009.
[20]
X. Wang, H. He, Y. Chen, J. Zhao, and X. Zhang, “Anatase TiO2 hollow microspheres with exposed {001} facets: facile synthesis and enhanced photocatalysis,” Applied Surface Science, vol. 258, no. 15, pp. 5863–5868, 2012.
[21]
J. S. Noh and J. A. Schwarz, “Estimation of the point of zero charge of simple oxides by mass titration,” Journal of Colloid And Interface Science, vol. 130, no. 1, pp. 157–164, 1989.
[22]
X. Sun and Y. Li, “Colloidal carbon spheres and their core/shell structures with noble-metal nanoparticles,” Angewandte Chemie—International Edition, vol. 43, no. 5, pp. 597–601, 2004.
[23]
M. Sevilla and A. B. Fuertes, “Chemical and structural properties of carbonaceous products obtained by hydrothermal carbonization of saccharides,” Chemistry—A European Journal, vol. 15, no. 16, pp. 4195–4203, 2009.
[24]
R. López and R. Gómez, “Band gap energy estimation from diffuse reflectance measurements on sol-gel and commercial TiO2: a comparative study,” Journal of Sol-Gel Science and Technology, vol. 61, no. 1, pp. 1–7, 2012.
[25]
J. Ara?a, J. M. Do?a-Rodríguez, E. Tello Rendón et al., “TiO2 activation by using activated carbon as a support: part II. Photoreactivity and FTIR study,” Applied Catalysis B, vol. 44, no. 2, pp. 153–160, 2003.
[26]
L. F. Velasco, J. B. Parra, and C. O. Ania, “Phenol adsorption and photo-oxidation on porous carbon/titania composites,” Adsorption Science and Technology, vol. 28, no. 8-9, pp. 727–738, 2010.
[27]
M. Yang, L. H. Li, S. Q. Zhang, G. Y. Li, and H. J. Zhao, “Preparation, characterisation and sensing application of inkjet-printed nanostructured TiO2 photoanode,” Sensors and Actuators B, vol. 147, no. 2, pp. 622–628, 2010.
[28]
D. L. Jiang, H. J. Zhao, S. Q. Zhang, and R. John, “Characterization of photoelectrocatalytic processes at nanoporous TiO2 film electrodes: photocatalytic oxidation of glucose,” Journal of Physical Chemistry B, vol. 107, no. 46, pp. 12774–12780, 2003.
[29]
T. Lana-Villarreal, Y. B. Mao, S. S. Wong, and R. Gómez, “Photoelectrochemical behaviour of anatase nanoporous films: effect of the nanoparticle organization,” Nanoscale, vol. 2, no. 9, pp. 1690–1698, 2010.
[30]
J. G. Yu, X. J. Zhao, and Q. N. Zhao, “Effect of film thickness on the grain size and photocatalytic activity of the sol-gel derived nanometer TiO2 thin films,” Journal of Materials Science Letters, vol. 19, no. 12, pp. 1015–1017, 2000.
[31]
S. C. Jung, S. J. Kim, N. Imaishi, and Y. I. Cho, “Effect of TiO2 thin film thickness and specific surface area by low-pressure metal-organic chemical vapor deposition on photocatalytic activities,” Applied Catalysis B, vol. 55, no. 4, pp. 253–257, 2005.
[32]
E. B. Azevedo, A. R. T?rres, F. R. A. Neto, and M. Dezotti, “TiO2-photocatalyzed degradation of phenol in saline media in an annular reactor: hydrodynamics, lumped kinetics, intermediates, and acute toxicity,” Brazilian Journal of Chemical Engineering, vol. 26, no. 1, pp. 75–87, 2009.
[33]
R. Ocampo-Pérez, M. Sánchez-Polo, J. Rivera-Utrilla, and R. Leyva-Ramos, “Enhancement of the catalytic activity of TiO2 by using activated carbon in the photocatalytic degradation of cytarabine,” Applied Catalysis B, vol. 104, no. 1-2, pp. 177–184, 2011.
[34]
T. Berger, T. Lana-Villarreal, D. Monllor-Satoca, and R. Gómez, “An electrochemical study on the nature of trap states in nanocrystalline rutile thin films,” Journal of Physical Chemistry C, vol. 111, no. 27, pp. 9936–9942, 2007.
[35]
M. Kaneko, S. Suzuki, H. Ueno, J. Nemoto, and Y. Fujii, “Photoelectrochemical decomposition of bio-related compounds at a nanoporous semiconductor film photoanode and their photocurrent-photovoltage characteristics,” Electrochimica Acta, vol. 55, no. 9, pp. 3068–3074, 2010.
[36]
A. Syoufian, O. H. Satriya, and K. Nakashima, “Photocatalytic activity of titania hollow spheres: photodecomposition of methylene blue as a target molecule,” Catalysis Communications, vol. 8, no. 5, pp. 755–759, 2007.
[37]
J. G. Yu and J. Zhang, “A simple template-free approach to TiO2 hollow spheres with enhanced photocatalytic activity,” Dalton Transactions, vol. 39, no. 25, pp. 5860–5867, 2010.
[38]
J. G. Yu and X. X. Yu, “Hydrothermal synthesis and photocatalytic activity of zinc oxide hollow spheres,” Environmental Science and Technology, vol. 42, no. 13, pp. 4902–4907, 2008.
[39]
J. G. Yu and G. H. Wang, “Hydrothermal synthesis and photocatalytic activity of mesoporous titania hollow microspheres,” Journal of Physics and Chemistry of Solids, vol. 69, no. 5-6, pp. 1147–1151, 2008.
[40]
H. Bala, Y. H. Yu, and Y. H. Zhang, “Synthesis and photocatalytic oxidation properties of titania hollow spheres,” Materials Letters, vol. 62, no. 14, pp. 2070–2073, 2008.