Abstract
Thanks to aqueous sol–gel chemistry, it is now possible to prepare several phase pure TiO2 brookite colloidal systems that significantly differ on nanoparticles size and shape. This TiO2 polymorph is more difficult to be obtained as phase pure material than anatase or rutile. Here we have prepared a set of four different sol–gel brookite syntheses with particles size ranging from 10 to 500 nm and significantly different morphologies as demonstrated by X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. We have studied their photocatalytic activities in aqueous solution on phenol and formic acid. The brookite sample with higher specific surface displays better activity for both pollutants abatement than anatase and rutile reference samples and very close to the TiO2 P25 commercial reference. Additional experimental characterization of photogenerated charge carriers and their lifetime is performed using time-resolved microwave conductivity. We could then explain why another efficient brookite material is able to compensate a significantly lower specific surface with a higher photon conversion rate. This study involving a broad set of pure phase brookite samples brings back that phase into the TiO2 polymorphs race for light-enhanced applications. It confirms that size/shape–activity correlation already observed for the anatase polymorph is also valid for the brookite phase.
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References
Weir A, Westerhoff P, Fabricius L, Hristovski K, von Goetz N (2012) Titanium dioxide nanoparticles in food and personal care products. Environ Sci Technol 46:2242–2250
Fujishima A, Rao TN, Tryk DA (2000) Titanium dioxide photocatalysis. J Photochem Photobiol C 1:1–21
Bonhôte P, Moser J-E, Humphry-Baker R et al (1999) Long-lived photoinduced charge separation and redox-type photochromism on mesoporous oxide films sensitized by molecular dyads. J Am Chem Soc 121:1324–1336
Lin H-M, Keng C-H, Tung C-Y (1997) Gas-sensing properties of nanocrystalline TiO2. Nanostruct Mater 9:747–750
Croce F, Appetecchi GB, Persi L, Scrosati B (1998) Nanocomposite polymer electrolytes for lithium batteries. Nature 394:456–458
Baudrin E, Cassaignon S, Koesch M, Jolivet JP, Dupont L, Tarascon JM (2007) Structural evolution during the reaction of Li with nano-sized rutile type TiO2 at room temperature. Electrochem Commun 9:337–342
Magne C, Cassaignon S, Lancel G, Pauporte T (2011) Brookite TiO(2) nanoparticle films for dye-sensitized solar cells. ChemPhysChem 12:2461–2467
Reisch M (2001) Paints and coatings. Chem Eng News 79:23–28
Henderson MA (2011) A surface science perspective on TiO(2) photocatalysis. Surf Sci Rep 66:185–297
Di Paola A, Bellardita M, Palmisano L (2013) Brookite, the Least Known TiO2 photocatalyst. Catalysts 3:36–73
Di Paola A, Bellardita M, Palmisano L, Barbierikova Z, Brezova V (2014) Influence of crystallinity and OH surface density on the photocatalytic activity of TiO2 powders, J. Photochem Photobiol A 273:59–67
Le Bahers T, Rérat M, Sautet P (2014) Semiconductors used in photovoltaic and photocatalytic devices: assessing fundamental properties from DFT. J Phys Chem C 118:5997–6008
Dou M, Persson C (2013) Comparative study of rutile and anatase SnO2 and TiO2: band-edge structures, dielectric functions, and polaron effects. J Appl Phys 113:083703
Ozawa K, Emori M, Yamamoto S et al (2014) Electron-hole recombination time at TiO2 single-crystal surfaces: influence of surface band bending. J Phys Chem Lett 5:1953–1957
Mino L, Spoto G, Bordiga S, Zecchina A (2012) Particles morphology and surface properties as investigated by HRTEM, FTIR, and periodic DFT calculations: from pyrogenic TiO2 (P25) to nanoanatase. J Phys Chem C 116:17008–17018
Odling G, Robertson N (2015) Why is anatase a better photocatalyst than rutile? The importance of free hydroxyl radicals. ChemSusChem 8:1838–1840
Lin H, Huang CP, Li W, Ni C, Shah SI, Tseng Y-H (2006) Size dependency of nanocrystalline TiO2 on its optical property and photocatalytic reactivity exemplified by 2-chlorophenol. Appl Catal B 68:1–11
Tachikawa T, Yamashita S, Majima T (2011) Evidence for crystal-face-dependent TIO2 photocatalysis from single-molecule imaging and kinetic analysis. J Am Chem Soc 133:7197–7204
Liu S, Yu J, Jaroniec M (2011) Anatase TiO2 with dominant high-energy 001 Facets: synthesis, properties, and applications. Chem Mater 23:4085–4093
Ohno Y, Tomita K, Komatsubara Y et al (2011) Pseudo-cube shaped brookite (TiO2) nanocrystals synthesized by an oleate-modified hydrothermal growth method. Cryst Growth Des 11:4831–4836
Lin H, Li L, Zhao M et al (2012) Synthesis of high-quality brookite TiO2 Single-crystalline nanosheets with specific facets exposed: tuning catalysts from inert to highly reactive. J Am Chem Soc 134:8328–8331
Zhao M, Xu H, Chen H et al (2015) Photocatalytic reactivity of 121 and 211 facets of brookite TiO2 crystals. J Mater Chem A 3:2331–2337
Cargnello M, Montini T, Smolin SY et al (2016) Engineering titania nanostructure to tune and improve its photocatalytic activity. Proc Natl Acad Sci USA 113:3966–3971
Pourjafari D, Reyes-Coronado D, Vega-Poot A et al (2018) Brookite-based dye-sensitized solar cells: influence of morphology and surface chemistry on cell performance. J Phys Chem C 122:14277–14288
Choi M, Lim J, Baek M, Choi W, Kim W, Yong K (2017) Investigating the unrevealed photocatalytic activity and stability of nanostructured brookite TiO2 film as an environmental photocatalyst. ACS Appl Mater Interfaces 9:16252–16260
Kandiel TA, Feldhoff A, Robben L, Dillert R, Bahnemann DW (2010) Tailored titanium dioxide nanomaterials: anatase nanoparticles and brookite nanorods as highly active photocatalysts. Chem Mater 22:2050–2060
Ismail AA, Kandiel TA, Bahnemann DW (2010) Novel (and better?) titania-based photocatalysts: brookite nanorods and mesoporous structures. J Photochem. Photobiol A 216:183–193
Kobayashi M, Tomita K, Petrykin V et al (2007) Hydrothermal synthesis of nanosized titania photocatalysts using novel water-soluble titanium complexes. Solid State Phenom 124–126:723–726
Stengl V, Bakardjieva S, Murafa N, Subrt J, Mest’ankova H, Jirkovsky J (2007) Preparation, characterization and photocatalytic activity of optically transparent titanium dioxide particles. Mater Chem Phys 105:38–46
Zhao B, Chen F, Huang Q, Zhang J (2009) Brookite TiO2 nanoflowers. Chem Commun 34:5115–5117
Vequizo JJM, Matsunaga H, Ishiku T, Kamimura S, Ohno T, Yamakata A (2017) Trap**-induced enhancement of photocatalytic activity on brookite TiO2 powders: comparison with anatase and rutile TIO2 powders. ACS Catal 7:2644–2651
Monai M, Montini T, Fornasiero P (2017) Brookite: nothing new under the sun? Catalysts 7:304
Yang Z, Wang B, Cui H, An H, Pan Y, Zhai J (2015) Synthesis of crystal-controlled TiO2 nanorods by a hydrothermal method: rutile and brookite as highly active photocatalysts. J Phys Chem C 119:16905–16912
Montoya JF, Velasquez JA, Salvador P (2009) The direct-indirect kinetic model in photocatalysis: a reanalysis of phenol and formic acid degradation rate dependence on photon flow and concentration in TiO2 aqueous dispersions. Appl Catal B 88:50–58
Turki A, Guillard C, Dappozze F, Ksibi Z, Berhault G, Kochkar H (2015) Phenol photocatalytic degradation over anisotropic TiO2 nanomaterials: kinetic study, adsorption isotherms and formal mechanisms. Appl Catal B 163:404–414
Turki A, Guillard C, Dappozze F, Berhault G, Ksibi Z, Kochkar H (2014) Design of TiO2 nanomaterials for the photodegradation of formic acid—adsorption isotherms and kinetics study. J Photochem Photobiol 279:8–16
Quang Duc T, Thi Hang L, Huu Thu H (2017) Amino acid-assisted controlling the shapes of rutile, brookite for enhanced photocatalytic CO2 reduction. CrystEngComm 19:4519–4527
Pottier A, Chanéac C, Tronc E, Mazerolles L, Jolivet J-P (2001) Synthesis of brookite TiO2 nanoparticles by thermolysis of TiCl4 in strongly acidic aqueous media. J Mater Chem 11:1116–1121
Kakihana M, Kobayashi M, Tomita K, Petrykin V (2010) Application of water-soluble titanium complexes as precursors for synthesis of titanium-containing oxides via aqueous solution processes. Bull Chem Soc Jpn 83:1285–1308
Nagase T, Ebina T, Iwasaki T, Hayashi K, Onodera Y, Chatterjee M (1999) Hydrothermal synthesis of brookite. Chem Lett 28:911–912
Pottier A, Chanéac C, Tronc E, Mazerolles L, Jolivet J-P (2001) Synthesis of brookite TiO2 nanoparticles by thermolysis of TiCl4 in strongly acidic aqueous media. J Mater Chem 11:1116–1121
Perego C, Clemençon I, Rebours B, et al (2009) Thermal stability of brookite—TiO2 nanoparticles with controlled size and shape: in situ studies by XRD. In: Mater. Res. Soc. Symp. Proc. 1146: NN04-02
Durupthy O, Bill J, Aldinger F (2007) Bioinspired synthesis of crystalline TiO2: effect of amino acids on nanoparticles structure and shape. Cryst Growth Des 7:2696–2704
Pigeot-Rémy S, Dufour F, Herissan A et al (2017) Bipyramidal anatase TiO2 nanoparticles, a highly efficient photocatalyst? Towards a better understanding of the reactivity. Appl Catal B 203:324–334
Emilio CA, Litter MI, Kunst M, Bouchard M, Colbeau-justin C (2006) Phenol photodegradation on platinized-TiO 2 photocatalysts related to charge-carrier dynamics. Langmuir 22:4943–4950
Tompsett GA, Bowmaker GA, Cooney RP, Metson JB, Rodgers KA, Seakins JM (1995) The Raman spectrum of brookite, TiO2 (Pbca, Z = 8). J Raman Spectrosc 26:57–62
Tran HTT, Kosslick H, Ibad MF et al (2016) Photocatalytic performance of highly active brookite in the degradation of hazardous organic compounds compared to anatase and rutile. Appl Catal B 200:647–658
Lopez-Munoz MJ, Revilla A, Alcalde G (2015) Brookite TiO2-based materials: synthesis and photocatalytic performance in oxidation of methyl orange and As(III) in aqueous suspensions. Catal Today 240:138–145
Deiana C, Fois E, Coluccia S, Martra G (2010) Surface structure of TiO2 P25 nanoparticles: infrared study of hydroxy groups on coordinative defect sites. J Phys Chem C 114:21531–21538
Hurum DC, Agrios AG, Gray KA, Rajh T, Thurnauer MC (2003) Explaining the enhanced photocatalytic activity of degussa P25 mixed-phase TiO2 using EPR. J Phys Chem B 107:4545–4549
Kroeze JE, Savenije TJ, Warman JM (2004) Electrodeless determination of the trap density, decay kinetics, and charge separation efficiency of dye-sensitized nanocrystalline TiO2. J Am Chem Soc 126:7608–7618
Nakajima S, Katoh R (2015) Time-resolved microwave conductivity study of charge carrier dynamics in commercially available TiO2 photocatalysts. J Mater Chem A 3:15466–15472
Kolen’ko YV, Churagulov BR, Kunst M, Mazerolles L, Colbeau-Justin C (2004) Photocatalytic properties of titania powders prepared by hydrothermal method. Appl Catal B 54:51–58
Acknowledgements
The authors thank J.-M. Krafft (LRS, UPMC, France) for its precious help in Raman spectra acquisition and S. Casale (LRS, UPMC, France) for the HRTEM analyses. Funding: This work was supported by the French Agence Nationale de la Recherche (ANR) through the PhotoNorm project.
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This study was funded by the Agence 678 Nationale de la Recherche (ANR Photonorm).
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Pigeot-Rémy, S., Gregori, D., Hazime, R. et al. Size and shape effect on the photocatalytic efficiency of TiO2 brookite. J Mater Sci 54, 1213–1225 (2019). https://doi.org/10.1007/s10853-018-2924-x
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DOI: https://doi.org/10.1007/s10853-018-2924-x