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Abstract:

Mesoporous titania thin films (MTTF) with p6mm pore array are currently attracting a great interest because of their 2D-hexagonal arrangement of close-packed cylindrical pores, but they are difficult to synthesize. This work seeks to understand such apparent elusiveness of the p6mm phase for MTTF. To that end, a wide variety of MTTF were prepared using different precursors, templates, aging and stabilization conditions, according to procedures reported in the literature and several variations thereof. Initially, the obtained MTTF were cross-characterized by ex situ transmission electron microscopy, two-dimensional small-angle X-ray scattering (2D-SAXS), and grazing incidence SAXS, with no clear evidence of a well-organized p6mm pore structure in the final system. In view of the difficulty of obtaining the desired pore array, the mesophase evolution was monitored during the synthesis, aging, stabilization, and calcination stages, resorting to in situ 2D-SAXS experiments. The performed experiments indicate that the key parameters that affect the ordering in these systems are the humidity of conservation but, mainly, the thermal treatment. Among the different strategies rehearsed, the desired mesophase was finally obtained by a combination of high humidity aging, exposure to NH3 vapors, and a thermal treatment at low temperature, followed by ethanol extraction of the template. However, even resorting to such mild treatments, the obtained MTTF presented an ordered p6mm structure combined with disordered regions, as determined by electron microscopy and porosimetry measurements. Thus, the obtained results stress that considering the mesophase obtained only at initial or intermediate synthesis stages as the one that survives in the template-free system is not a safe assumption. Moreover, complementary experimental techniques should be used to determine mesoporous structures in the final systems. Finally, this work shows the strength of in situ 2D-SAXS measurements as a technique to design new synthetic procedures, in order to obtain specific properties of the final material. © 2017 American Chemical Society.

Registro:

Documento: Artículo
Título:2D-SAXS in Situ Measurements as a Tool to Study Elusive Mesoporous Phases: The Case of p6mm TiO2
Autor:Gonzalez Solveyra, E.; Fuertes, M.C.; Soler-Illia, G.J.A.A.; Angelomé, P.C.
Filiación:Departamento de Química Inorgánica, Analítica y Química Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón II, Ciudad Universitaria, Buenos Aires, C1428EHA, Argentina
Gerencia Química, Centro Atómico Constituyentes, Comisión Nacional de Energía Atómica, CONICET, Av. Gral Paz 1499, San-Martín, Buenos Aires, B1650KNA, Argentina
Instituto Sabato, UNSAM, CNEA, Av. Gral. Paz 1499, San-Martín, Buenos Aires, B1650KNA, Argentina
Instituto de Nanosistemas, UNSAM, CONICET, Av. 25 de Mayo y Francia, San-Martín, Buenos Aires, 1650, Argentina
Department of Biomedical Engineering, Chemistry of Life Processes Institute, Northwestern University, Evanston, IL 60208, United States
Palabras clave:Electron microscopy; Heat treatment; High resolution transmission electron microscopy; Stabilization; Temperature; Transmission electron microscopy; X ray scattering; Close-packed cylindrical pores; Different precursors; Experimental techniques; In-situ measurement; Mesoporous structures; Mesoporous titania thin film; Synthetic procedures; Thermal treatment at low temperatures; Mesoporous materials
Año:2017
Volumen:121
Número:6
Página de inicio:3623
Página de fin:3631
DOI: http://dx.doi.org/10.1021/acs.jpcc.6b12112
Título revista:Journal of Physical Chemistry C
Título revista abreviado:J. Phys. Chem. C
ISSN:19327447
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_19327447_v121_n6_p3623_GonzalezSolveyra

Referencias:

  • Schneider, J., Matsuoka, M., Takeuchi, M., Zhang, J., Horiuchi, Y., Anpo, M., Bahnemann, D.W., Understanding TiO2 Photocatalysis: Mechanisms and Materials (2014) Chem. Rev., 114, pp. 9919-9986
  • Ismail, A.A., Bahnemann, D.W., Mesoporous Titania Photocatalysts: Preparation, Characterization and Reaction Mechanisms (2011) J. Mater. Chem., 21, pp. 11686-11707
  • Wu, K.C.W., Jiang, X., Yamauchi, Y., New Trend on Mesoporous Films: Precise Controls of One-Dimensional (1d) Mesochannels toward Innovative Applications (2011) J. Mater. Chem., 21, pp. 8934-8939
  • Zhou, W., Fu, H., Mesoporous TiO2: Preparation, Doping, and as a Composite for Photocatalysis (2013) ChemCatChem, 5, pp. 885-894
  • Pan, J.H., Zhao, X.S., Lee, W.I., Block Copolymer-Templated Synthesis of Highly Organized Mesoporous TiO2-Based Films and Their Photoelectrochemical Applications (2011) Chem. Eng. J., 170, pp. 363-380
  • Zhang, R., Elzatahry, A.A., Al-Deyab, S.S., Zhao, D., Mesoporous Titania: From Synthesis to Application (2012) Nano Today, 7, pp. 344-366
  • Yun, H.S., Miyazawa, K., Zhou, H.S., Honma, I., Kuwabara, M., Synthesis of Mesoporous Thin TiO2 Films with Hexagonal Pore Structures Using Triblock Copolymer Templates (2001) Adv. Mater., 13, pp. 1377-1380
  • Grosso, D., Balkenende, A.R., Albouy, P.A., Ayral, A., Amenitsch, H., Babonneau, F., Two-Dimensional Hexagonal Mesoporous Silica Thin Films Prepared from Block Copolymers: Detailed Characterization and Formation Mechanism (2001) Chem. Mater., 13, pp. 1848-1856
  • Li, W., Wu, Z., Wang, J., Elzatahry, A.A., Zhao, D., A Perspective on Mesoporous TiO2 Materials (2014) Chem. Mater., 26, pp. 287-298
  • Soler-Illia, G.J.A.A., Angelomé, P.C., Fuertes, M.C., Grosso, D., Boissiere, C., Critical Aspects in the Production of Periodically Ordered Mesoporous Titania Thin Films (2012) Nanoscale, 4, pp. 2549-2566
  • Brinker, C.J., Lu, Y., Sellinger, A., Fan, H., Evaporation-Induced Self-Assembly: Nanostructures Made Easy (1999) Adv. Mater., 11, pp. 579-585
  • Angelomé, P.C., Andrini, L., Calvo, M.E., Requejo, F.G., Bilmes, S.A., Soler-Illia, G.J.A.A., Mesoporous Anatase Tio2 Films: Use of Ti K Xanes for the Quantification of the Nanocrystalline Character and Substrate Effects in the Photocatalysis Behavior (2007) J. Phys. Chem. C, 111, pp. 10886-10893
  • Crepaldi, E.L., Soler-Illia, G.J.A.A., Grosso, D., Cagnol, F., Ribot, F., Sánchez, C., Controlled Formation of Highly Organized Mesoporous Titania Thin Films: From Mesostructured Hybrids to Mesoporous Nanoanatase TiO2 (2003) J. Am. Chem. Soc., 125, pp. 9770-9786
  • Wei, T.-C., Hillhouse, H.W., Mass Transport and Electrode Accessibility through Periodic Self-Assembled Nanoporous Silica Thin Films (2007) Langmuir, 23, pp. 5689-5699
  • Carreon, M.A., Choi, S.Y., Mamak, M., Chopra, N., Ozin, G.A., Pore Architecture Affects Photocatalytic Activity of Periodic Mesoporous Nanocrystalline Anatase Thin Films (2007) J. Mater. Chem., 17, pp. 82-89
  • Das, S., Wu, Q., Garlapalli, R.K., Nagpure, S., Strzalka, J., Jiang, Z., Rankin, S.E., In Situ Gisaxs Investigation of Pore Orientation Effects on the Thermal Transformation Mechanism in Mesoporous Titania Thin Films (2014) J. Phys. Chem. C, 118, pp. 968-976
  • Das, S., Nagpure, S., Garlapalli, R.K., Wu, Q., Islam, S.Z., Strzalka, J., Rankin, S.E., Pore Orientation Effects on the Kinetics of Mesostructure Loss in Surfactant Templated Titania Thin Films (2016) Phys. Chem. Chem. Phys., 18, pp. 2896-2905
  • Ceratti, D.R., Faustini, M., Sinturel, C., Vayer, M., Dahirel, V., Jardat, M., Grosso, D., Critical Effect of Pore Characteristics on Capillary Infiltration in Mesoporous Films (2015) Nanoscale, 7, pp. 5371-5382
  • Lowell, S., Shields, J.E., Thomas, M.A., Thommes, M., (2004) Characterization of Porous Solids and Powders: Surface Area, Pore Size and Density, , Springer: Berlin
  • Thommes, M., Cychosz, K.A., Physical Adsorption Characterization of Nanoporous Materials: Progress and Challenges (2014) Adsorption, 20, pp. 233-250
  • Cimino, R., Cychosz, K.A., Thommes, M., Neimark, A.V., Experimental and Theoretical Studies of Scanning Adsorption-Desorption Isotherms (2013) Colloids Surf., A, 437, pp. 76-89
  • Miyata, H., Fukushima, Y., Okamoto, K., Takahashi, M., Watanabe, M., Kubo, W., Komoto, A., Kuroda, K., Remarkable Birefringence in a TiO2-SiO2 Composite Film with an Aligned Mesoporous Structure (2011) J. Am. Chem. Soc., 133, pp. 13539-13544
  • Miyata, H., Fukushima, Y., Kanno, Y., Hayase, S., Hara, S., Watanabe, M., Kitamura, S., Kuroda, K., Mesoporous Tio2 Films with Regularly Aligned Slit-Like Nanovoids (2015) J. Mater. Chem. C, 3, pp. 3869-3875
  • Zhao, D., Yang, P., Margolese, D.I., Stucky, G.D., Synthesis of Continuous Mesoporous Silica Thin Films with Three-Dimensional Accessible Pore Structures (1998) Chem. Commun., pp. 2499-2500
  • Klotz, M., Albouy, P.-A., Ayral, A., Ménager, C., Grosso, D., Van Der Lee, A., Cabuil, V., Guizard, C., The True Structure of Hexagonal Mesophase-Templated Silica Films as Revealed by X-Ray Scattering: Effects of Thermal Treatments and of Nanoparticle Seeding (2000) Chem. Mater., 12, pp. 1721-1728
  • Alberius, P.C.A., Frindell, K.L., Hayward, R.C., Kramer, E.J., Stucky, G.D., Chmelka, B.F., General Predictive Syntheses of Cubic, Hexagonal, and Lamellar Silica and Titania Mesostructured Thin Films (2002) Chem. Mater., 14, pp. 3284-3294
  • Choi, S.Y., Mamak, M., Coombs, N., Chopra, N., Ozin, G.A., Thermally Stable Two-Dimensional Hexagonal Mesoporous Nanocrystalline Anatase, Meso-Nc-TiO2: Bulk and Crack-Free Thin Film Morphologies (2004) Adv. Funct. Mater., 14, pp. 335-344
  • Koganti, V.R., Dunphy, D., Gowrishankar, V., McGehee, M.D., Li, X., Wang, J., Rankin, S.E., Generalized Coating Route to Silica and Titania Films with Orthogonally Tilted Cylindrical Nanopore Arrays (2006) Nano Lett., 6, pp. 2567-2570
  • Yang, P., Zhao, D., Margolese, D.I., Chmelka, B.F., Stucky, G.D., Generalized Syntheses of Large-Pore Mesoporous Metal Oxides with Semicrystalline Frameworks (1998) Nature, 396, pp. 152-155
  • Yang, P., Zhao, D., Margolese, D.I., Chmelka, B.F., Stucky, G.D., Block Copolymer Templating Syntheses of Mesoporous Metal Oxides with Large Ordering Lengths and Semicrystalline Framework (1999) Chem. Mater., 11, pp. 2813-2826
  • Nagpure, S., Das, S., Garlapalli, R.K., Strzalka, J., Rankin, S.E., In Situ Gisaxs Investigation of Low-Temperature Aging in Oriented Surfactant-Mesostructured Titania Thin Films (2015) J. Phys. Chem. C, 119, pp. 22970-22984
  • Innocenzi, P., Malfatti, L., Kidchob, T., Costacurta, S., Falcaro, P., Piccinini, M., Marcelli, A., Amenitsch, H., Time-Resolved Simultaneous Detection of Structural and Chemical Changes during Self-Assembly of Mesostructured Films (2007) J. Phys. Chem. C, 111, pp. 5345-5350
  • Grosso, D., Babonneau, F., Sanchez, C., Soler-Illia, G.J.A.A., Crepaldi, E.L., Albouy, P.A., Amenitsch, H., Brunet-Bruneau, A., A First Insight in the Mechanisms Involved in the Self-Assembly of 2d-Hexagonal Templated SiO2 and TiO2 Mesostructured Films during Dip-Coating (2003) J. Sol-Gel Sci. Technol., 26, pp. 561-565
  • Doshi, D.A., Gibaud, A., Goletto, V., Lu, M., Gerung, H., Ocko, B., Han, S.M., Brinker, C.J., Peering into the Self-Assembly of Surfactant Templated Thin-Film Silica Mesophases (2003) J. Am. Chem. Soc., 125, pp. 11646-11655
  • Grosso, D., Cagnol, F., Soler-Illia, G.J.A.A., Crepaldi, E.L., Amenitsch, H., Brunet-Bruneau, A., Bourgeois, A., Sanchez, C., Fundamentals of Mesostructuring through Evaporation-Induced Self-Assembly (2004) Adv. Funct. Mater., 14, p. 309
  • Grosso, D., Soler-Illia, G.J.A.A., Crepaldi, E.L., Cagnol, F., Sinturel, C., Bourgeois, A., Brunet-Bruneau, A., Sanchez, C., Highly Porous TiO2 Anatase Optical Thin Films with Cubic Mesostructure Stabilized at 700°C (2003) Chem. Mater., 15, pp. 4562-4570
  • Boissiere, C., Grosso, D., Lepoutre, S., Nicole, L., Bruneau, A.B., Sanchez, C., Porosity and Mechanical Properties of Mesoporous Thin Films Assessed by Environmental Ellipsometric Porosimetry (2005) Langmuir, 21, pp. 12362-12371
  • Grosso, D., Soler-Illia, G.J.A.A., Babonneau, F., Sanchez, C., Albouy, P.A., Brunet-Bruneau, A., Balkenende, A.R., Highly Organized Mesoporous Titania Thin Films Showing Mono-Oriented 2d Hexagonal Channels (2001) Adv. Mater., 13, pp. 1085-1090
  • Wu, Q.L., Rankin, S.E., Tuning the Wall Thickness and Pore Orientation in Mesoporous Titania Films Prepared with Low-Temperature Aging (2011) J. Sol-Gel Sci. Technol., 60, pp. 81-90
  • Angelomé, P.C., Fuertes, M.C., Soler-Illia, G.J.A.A., Multifunctional, Multilayer, Multiscale: Integrative Synthesis of Complex Macro and Mesoporous Thin Films with Spatial Separation of Porosity and Function (2006) Adv. Mater., 18, pp. 2397-2402
  • Bagshaw, S.A., Prouzet, E., Pinnavaia, T.J., Templating of Mesoporous Molecular-Sieves by Nonionic Polyethylene Oxide Surfactants (1995) Science, 269, pp. 1242-1244
  • Fan, H., Hartshorn, C., Buchheit, T., Tallant, D., Assink, R., Simpson, R., Kissel, D.J., Brinker, C.J., Modulus-Density Scaling Behaviour and Framework Architecture of Nanoporous Self-Assembled Silicas (2007) Nat. Mater., 6, pp. 418-423
  • Violi, I.L., Perez, M.D., Fuertes, M.C., Soler-Illia, G.J.A.A., Highly Ordered, Accessible and Nanocrystalline Mesoporous Tio2 Thin Films on Transparent Conductive Substrates (2012) ACS Appl. Mater. Interfaces, 4, pp. 4320-4330
  • Innocenzi, P., Malfatti, L., Kidchob, T., Enzo, S., Ventura, G.D., Schade, U., Marcelli, A., Correlative Analysis of the Crystallization of Sol-Gel Dense and Mesoporous Anatase Titania Films (2010) J. Phys. Chem. C, 114, pp. 22385-22391
  • Richman, E.K., Brezesinski, T., Tolbert, S.H., Vertically Oriented Hexagonal Mesoporous Films Formed through Nanometre-Scale Epitaxy (2008) Nat. Mater., 7, pp. 712-717
  • Sing, K.S.W., Reporting Physisorption Data for Gas/Solid Systems with Special Reference to the Determination of Surface Area and Porosity (1985) Pure Appl. Chem., 57, pp. 603-619

Citas:

---------- APA ----------
Gonzalez Solveyra, E., Fuertes, M.C., Soler-Illia, G.J.A.A. & Angelomé, P.C. (2017) . 2D-SAXS in Situ Measurements as a Tool to Study Elusive Mesoporous Phases: The Case of p6mm TiO2. Journal of Physical Chemistry C, 121(6), 3623-3631.
http://dx.doi.org/10.1021/acs.jpcc.6b12112
---------- CHICAGO ----------
Gonzalez Solveyra, E., Fuertes, M.C., Soler-Illia, G.J.A.A., Angelomé, P.C. "2D-SAXS in Situ Measurements as a Tool to Study Elusive Mesoporous Phases: The Case of p6mm TiO2" . Journal of Physical Chemistry C 121, no. 6 (2017) : 3623-3631.
http://dx.doi.org/10.1021/acs.jpcc.6b12112
---------- MLA ----------
Gonzalez Solveyra, E., Fuertes, M.C., Soler-Illia, G.J.A.A., Angelomé, P.C. "2D-SAXS in Situ Measurements as a Tool to Study Elusive Mesoporous Phases: The Case of p6mm TiO2" . Journal of Physical Chemistry C, vol. 121, no. 6, 2017, pp. 3623-3631.
http://dx.doi.org/10.1021/acs.jpcc.6b12112
---------- VANCOUVER ----------
Gonzalez Solveyra, E., Fuertes, M.C., Soler-Illia, G.J.A.A., Angelomé, P.C. 2D-SAXS in Situ Measurements as a Tool to Study Elusive Mesoporous Phases: The Case of p6mm TiO2. J. Phys. Chem. C. 2017;121(6):3623-3631.
http://dx.doi.org/10.1021/acs.jpcc.6b12112