Abstract
TiO2/WO3 heterojunctions are one of the most investigated systems for photocatalytic applications. However, distinct behavior can be found in the literature depending on the pollutant to be degraded and the photocatalyst preparation conditions. Some authors reported improved photocatalytic activities in relation to TiO2, while others a deleterious effect. Different factors have been identified to influence the activity of such systems. In this work, a systematic investigation of TiO2/WO3 samples with different W/Ti ratios (0–100%) was carried out using different pollutants as targets (gaseous NO, acetaldehyde and aqueous methylene blue solutions). A detailed structural investigation along with transient absorption studies and photoelectrochemical measurements allowed the rationalization of some of the previously reported factors that control the TiO2/WO3 photoactivity, i.e. the inability to reduce molecular oxygen, the stabilization of the anatase phase and the adsorption surface properties. The investigations also identified a factor not previously reported: in TiO2/WO3 systems, a fraction of long-lived holes do not take part in the interfacial charge transfer to efficient hole quenchers, such as methanol. This behavior seems to be related to the doping of the TiO2 matrix with W(vi) and plays a key role in the photocatalytic activity.
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J. Low, J. Yu, M. Jaroniec, S. Wageh and A. A. Al-Ghamdi, Heterojunction Photocatalysts, Adv. Mater., 2017, 29, 1601694.
K. Afroz, M. Moniruddin, N. Bakranov, S. Kudaibergenov and N. Nuraje, A heterojunction strategy to improve the visible light sensitive water splitting performance of photocatalytic materials, J. Mater. Chem. A, 2018, 6, 21696–21718.
L. Wei, C. Yu, Q. Zhang, H. Liu and Y.Wang, TiO2-based heterojunction photocatalysts for photocatalytic reduction of CO2 into solar fuels, J. Mater. Chem. A, 2018, 6, 22411–22436.
N. Fajrina and M. Tahir, A critical review in strategies to improve photocatalytic water splitting towards hydrogen production, Int. J. Hydrogen Energy, 2019, 44, 540–577.
A. O. T. Patrocinio, L. F. Paula, R. M. Paniago, J. Freitag and D. W. Bahnemann, Layer-by-Layer TiO2/WO3 Thin Films As Efficient Photocatalytic Self-Cleaning Surfaces, ACS Appl. Mater. Interfaces, 2014, 6, 16859–16866.
Z. DohĿeviĿ-MitroviĿ, S. StojadinoviĿ, L. Lozzi, S. AškrabiĿ, M. RosiĿ, N. TomiĿ, N. PaunoviĿ, S. LazoviĿ, M. G. NikoliĿ and S. Santucci, WO3/TiO2 composite coatings: Structural, optical and photocatalytic properties, Mater. Res. Bull., 2016, 83, 217–224.
A. A. Ismail, I. Abdelfattah, A. Helal, S. A. Al-Sayari, L. Robben and D. W. Bahnemann, Ease synthesis of mesoporous WO3–TiO2 nanocomposites with enhanced photocatalytic performance for photodegradation of herbicide imazapyr under visible light and UV illumination, J. Hazard. Mater., 2016, 307, 43–54.
M. Yan, G. Li, C. Guo, W. Guo, D. Ding, S. Zhang and S. Liu, WO3−x sensitized TiO2 spheres with full-spectrumdriven photocatalytic activities from UV to near infrared, Nanoscale, 2016, 8, 17828–17835.
S. Dominguez, M. Huebra, C. Han, P. Campo, M. N. Nadagouda, M. J. Rivero, I. Ortiz and D. D. Dionysiou, Magnetically recoverable TiO2-WO3 photocatalyst to oxidize bisphenol A from model wastewater under simulated solar light, Environ. Sci. Pollut. Res., 2017, 24, 12589–12598.
J. A. Mendoza, D. H. Lee and J.-H. Kang, Photocatalytic removal of gaseous nitrogen oxides using WO3/TiO2 particles under visible light irradiation: Effect of surface modification, Chemosphere, 2017, 182, 539–546.
C. P. Sajan, A. Naik and H. N. Girish, Hydrothermal fabrication of WO3-modified TiO2 crystals and their efficiency in photocatalytic degradation of FCF, Int. J. Environ. Sci. Technol., 2017, 14, 1513–1524.
T. Xu, Y. Wang, X. Zhou, X. Zheng, Q. Xu, Z. Chen, Y. Ren and B. Yan, Fabrication and assembly of two-dimensional TiO2/WO3·H2O heterostructures with type II band alignment for enhanced photocatalytic performance, Appl. Surf. Sci., 2017, 403, 564–571.
A. Arce-Sarria, F. Machuca-Martínez, C. Bustillo-Lecompte, A. Hernández-Ramírez and J. Colina-Márquez, Degradation and Loss of Antibacterial Activity of Commercial Amoxicillin with TiO2/WO3-Assisted Solar Photocatalysis, Catalysts, 2018, 8, 222.
D. S. Han, R. Elshorafa, S. H. Yoon, S. Kim, H. Park and A. Abdel-Wahab, Sunlight-charged heterojunction TiO2 and WO3 particle-embedded inorganic membranes for nighttime environmental applications, Photochem. Photobiol. Sci., 2018, 17, 491–498.
K. Huang and Z. Cai, Synthesis of Three-dimensionally Ordered Macroporous TiO2 and TiO2/WO3 Composites and Their Photocatalytic Performance, Z. Anorg. Allg. Chem., 2018, 644, 1072–1077.
H. Khan, M. G. Rigamonti, G. S. Patience and D. C. Boffito, Spray dried TiO2/WO3 heterostructure for photocatalytic applications with residual activity in the dark, Appl. Catal., B, 2018, 226, 311–323.
J. A. Mendoza, D. H. Lee, L.-H. Kim, I. H. Kim and J.-H. Kang, Photocatalytic performance of TiO2 and WO3/ TiO2 nanoparticles coated on urban green infrastructure materials in removing nitrogen oxide, Int. J. Environ. Sci. Technol., 2018, 15, 581–592.
S. Prabhu, L. Cindrella, O. J. Kwon and K. Mohanraju, Photoelectrochemical and photocatalytic activity of TiO2- WO3 heterostructures boosted by mutual interaction, Mater. Sci. Semicond. Process., 2018, 88, 10–19.
L. Soares and A. Alves, Photocatalytic properties of TiO2 and TiO2/WO3 films applied as semiconductors in heterogeneous photocatalysis, Mater. Lett., 2018, 211, 339–342.
M. B. Tahir, M. Sagir and K. Shahzad, Removal of acetylsalicylate and methyl-theobromine from aqueous environment using nano-photocatalyst WO3-TiO2 @g-C3N4 composite, J. Hazard. Mater., 2019, 363, 205–213.
J. Hu, L. Wang, P. Zhang, C. Liang and G. Shao, Construction of solid-state Z-scheme carbon-modified TiO2/WO3 nanofibers with enhanced photocatalytic hydrogen production, J. Power Sources, 2016, 328, 28–36.
C. Sotelo-Vazquez, R. Quesada-Cabrera, M. Ling, D. O. Scanlon, A. Kafizas, P. K. Thakur, T.-L. Lee, A. Taylor, G. W. Watson, R. G. Palgrave, J. R. Durrant, C. S. Blackman and I. P. Parkin, Evidence and Effect of Photogenerated Charge Transfer for Enhanced Photocatalysis in WO3/TiO2 Heterojunction Films: A Computational and Experimental Study, Adv. Funct. Mater., 2017, 27, 1605413.
H. Liu, W. Guo, Y. Li, S. He and C. He, Photocatalytic degradation of sixteen organic dyes by TiO2/WO3-coated magnetic nanoparticles under simulated visible light and solar light, J. Environ. Chem. Eng., 2018, 6, 59–67.
H. Tada, A. Kokubu, M. Iwasaki and S. Ito, Deactivation of the TiO2 Photocatalyst by Coupling with WO3 and the Electrochemically Assisted High Photocatalytic Activity of WO3, Langmuir, 2004, 20, 4665–4670.
S. Higashimoto, Y. Ushiroda and M. Azuma, Electrochemically Assisted Photocatalysis of Hybrid WO3/ TiO2 Films: Effect of the WO3 Structures on Charge Separation Behavior, Top. Catal., 2008, 47, 148–154.
C.-F. Lin, C.-H. Wu and Z.-N. Onn, Degradation of 4-chlorophenol in TiO2, WO3, SnO2, TiO2/WO3 and TiO2/SnO2 systems, J. Hazard. Mater., 2008, 154, 1033–1039.
J. Yang, X. Zhang, H. Liu, C. Wang, S. Liu, P. Sun, L. Wang and Y. Liu, Heterostructured TiO2/WO3 porous microspheres: Preparation, characterization and photocatalytic properties, Catal. Today, 2013, 201, 195–202.
L. Yang, Z. Si, D. Weng and Y. Yao, Synthesis, characterization and photocatalytic activity of porous WO3/TiO2 hollow microspheres, Appl. Surf. Sci., 2014, 313, 470–478.
G. Žerjav, M. S. Arshad, P. Djinović, J. Zavašnik and A. Pintar, Electron trapping energy states of TiO2–WO3 composites and their influence on photocatalytic degradation of bisphenol A, Appl. Catal., B, 2017, 209, 273–284.
A. O. T. Patrocinio, E. B. Paniago, R. M. Paniago and N. Y. M. Iha, XPS characterization of sensitized n-TiO2 thin films for dye-sensitized solar cell applications, Appl. Surf. Sci., 2008, 254, 1874–1879.
A. O. T. Patrocinio, A. El-Bachá, E. B. Paniago, R. M. Paniago and N. Y. M. Iha, Influence of the Sol-Gel pH Process and Compact Film on the Efficiency of TiO2-Based Dye-Sensitized Solar Cells, Int. J. Photoenergy, 2012, 2012, 7.
E. P. Barrett, L. G. Joyner and P. P. Halenda, The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms, J. Am. Chem. Soc., 1951, 73, 373–380.
A. O. T. Patrocinio, J. Schneider, M. D. Franca, L. M. Santos, B. P. Caixeta, A. E. H. Machado and D. W. Bahnemann, Charge carrier dynamics and photocatalytic behavior of TiO2 nanopowders submitted to hydrothermal or conventional heat treatment, RSC Adv., 2015, 5, 70536–70545.
K. A. Borges, L. M. Santos, R. M. Paniago, N. M. Barbosa Neto, J. Schneider, D. W. Bahnemann, A. O. T. Patrocinio and A. E. H. Machado, Characterization of a highly efficient N-doped TiO2 photocatalyst prepared via factorial design, New J. Chem., 2016, 40, 7846–7855.
T.-P. Lin and H. K. A. Kan, Calculation of Reflectance of a Light Diffuser with Nonuniform Absorption, J. Opt. Soc. Am., 1970, 60, 1252–1256.
R. W. Kessler, G. Krabichler, S. Uhl, D. Oelkrug, W. P. Hagan, J. Hyslop and F. Wilkinson, Transient Decay Following Pulse Excitation of Diffuse Scattering Samples, Optica Acta: Int. J. Optics, 1983, 30, 1099–1111.
N. O. Balayeva, M. Fleisch and D. W. Bahnemann, Surfacegrafted WO3/TiO2 photocatalysts: Enhanced visible-light activity towards indoor air purification, Catal. Today, 2018, 313, 63–71.
F. Sieland, J. Schneider and D. W. Bahnemann, Photocatalytic activity and charge carrier dynamics of TiO2 powders with a binary particle size distribution, Phys. Chem. Chem. Phys., 2018, 20, 8119–8132.
J. Tschirch, R. Dillert and D. Bahnemann, Photocatalytic degradation of Methylene blue on fixed powder layers: Which limitations are to be considered?, J. Adv. Oxid. Technol., 2008, 11, 193–198.
A. Mills, An overview of the methylene blue ISO test for assessing the activities of photocatalytic films, Appl. Catal., B, 2012, 128, 144–149.
F. Riboni, M. V. Dozzi, M. C. Paganini, E. Giamello and E. Selli, Photocatalytic activity of TiO2-WO3 mixed oxides in formic acid oxidation, Catal. Today, 2017, 287, 176–181.
M. R. Mohammadi, D. J. Fray and A. Mohammadi, Sol–gel nanostructured titanium dioxide: Controlling the crystal structure, crystallite size, phase transformation, packing and ordering, Microporous Mesoporous Mater., 2008, 112, 392–402.
D.-S. Kim, J.-H. Yang, S. Balaji, H.-J. Cho, M.-K. Kim, D.-U. Kang, Y. Djaoued and Y.-U. Kwon, Hydrothermal synthesis of anatase nanocrystals with lattice and surface doping tungsten species, CrystEngComm, 2009, 11, 1621–1629.
M. Horn, C. Schwebdtfeger and E. Meagher, Refinement of the structure of anatase at several temperatures, Z. Kristallogr. –Cryst. Mater., 1972, 136, 273–281.
R. D. Shannon, Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides, Acta Crystallogr., Sect. A: Cryst. Phys., Diffr., Theor. Gen. Crystallogr., 1976, 32, 751–767.
F. Riboni, L. G. Bettini, D. W. Bahnemann and E. Selli, WO3–TiO2 vs. TiO2 photocatalysts: effect of the W precursor and amount on the photocatalytic activity of mixed oxides, Catal. Today, 2013, 209, 28–34.
A. Kubacka, A. Fuerte, A. Martínez-Arias and M. Fernández- García, Nanosized Ti–V mixed oxides: Effect of doping level in the photo-catalytic degradation of toluene using sunlight- type excitation, Appl. Catal., B, 2007, 74, 26–33.
M. Fernández-García, A. Martinez-Arias, A. Fuerte and J. Conesa, Nanostructured Ti− W Mixed-Metal Oxides: Structural and Electronic Properties, J. Phys. Chem. B, 2005, 109, 6075–6083.
G. Tompsett, G. Bowmaker, R. Cooney, J. Metson, K. Rodgers and J. Seakins, The Raman spectrum of brookite, TiO2 (PBCA, Z = 8), J. Raman Spectrosc., 1995, 26, 57–62.
A. Gutiérrez-Alejandre, J. Ramírez and G. Busca, A Vibrational and Spectroscopic Study of WO3/TiO2−Al2O3 Catalyst Precursors, Langmuir, 1998, 14, 630–639.
A. I. Gavrilyuk, Aging of the nanosized photochromic WO3 films and the role of adsorbed water in the photochromism, Appl. Surf. Sci., 2016, 364, 498–504.
Y.-A. Lee, S.-I. Han, H. Rhee and H. Seo, Correlation between excited d-orbital electron lifetime in polaron dynamics and coloration of WO3 upon ultraviolet exposure, Appl. Surf. Sci., 2018, 440, 1244–1251.
I. M. Szilágyi, S. Saukko, J. Mizsei, A. L. Tóth, J. Madarász and G. Pokol, Gas sensing selectivity of hexagonal and monoclinic WO3 to H2S, Solid State Sci., 2010, 12, 1857–1860.
S. Kumar, K. Ojha and A. K. Ganguli, Interfacial Charge Transfer in Photoelectrochemical Processes, Adv. Mater. Interfaces, 2017, 4, 1600981.
J. Schneider, M. Matsuoka, M. Takeuchi, J. Zhang, Y. Horiuchi, M. Anpo and D. W. Bahnemann, Understanding TiO2 Photocatalysis: Mechanisms and Materials, Chem. Rev., 2014, 114, 9919–9986.
A. O. T. Patrocinio, J. Schneider, M. D. França, L. M. Santos, B. P. Caixeta, A. E. H. Machado and D. W. Bahnemann, Charge carrier dynamics and photocatalytic behavior of TiO2 nanopowders submitted to hydrothermal or conventional heat treatment, RSC Adv., 2015, 5, 70536–70545.
G. M. Hasselmann and G. J. Meyer, Diffusion-Limited Interfacial Electron Transfer with Large Apparent Driving Forces, J. Phys. Chem. B, 1999, 103, 7671–7675.
V. Cristino, S. Marinello, A. Molinari, S. Caramori, S. Carli, R. Boaretto, R. Argazzi, L. Meda and C. A. Bignozzi, Some aspects of the charge transfer dynamics in nanostructured WO3 films, J. Mater. Chem. A, 2016, 4, 2995–3006.
S. Corby, L. Francàs, S. Selim, M. Sachs, C. Blackman, A. Kafizas and J. R. Durrant, Water Oxidation and Electron Extraction Kinetics in Nanostructured Tungsten Trioxide Photoanodes, J. Am. Chem. Soc., 2018, 140, 16168–16177.
H. Kisch, Semiconductor Photocatalysis, Wiley-VCH, 2015.
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Electronic supplementary information (ESI) available. See DOI: 10.1039/ c9pp00163h
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Paula, L.F., Hofer, M., Lacerda, V.P.B. et al. Unraveling the photocatalytic properties of TiO2/WO3 mixed oxides†. Photochem Photobiol Sci 18, 2469–2483 (2019). https://doi.org/10.1039/c9pp00163h
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DOI: https://doi.org/10.1039/c9pp00163h