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Synchrotron Radiation X-ray Fluorescence at Grazing Incident Angle (SR-GIXRF) and Total-Reflection (SR-TXRF) of Ormosil Films Containing TiO2 and Phosphotungstates

In 2011-2013 during the experiments performed at LNLS (Brazilian Synchrotron Light Laboratory) based on Grazing Incident Angle X-ray Fluorescence analysis assisted by Synchrotron Radiation (SR-GIXRF) of Ormosil (Organic Modified Silicates) films containing Phosphotungstates ([PW12O40]3-) was obtained an image (Figure 8 in this article), which can be explained by different hypotheses based on physical and chemical phenomena. In 2021 the same author of this present investigation reported the possibility of to generate the conditions for the production of Maser-rays based on Total Reflection X-ray Fluorescence assisted by Synchrotron Radiation (SR-TXRF) measurements of ormosil films. Devices based on Maser-rays can extend their corresponding range of frequencies at microwave, radio, infrared, optical, ultraviolet, and X-ray regions possibly also (as was mentioned above). In this opportunity, the results of GIXRF measurements are presented. GIXRF is an XRF analysis mode in shallow incidence angles. Nonetheless, unlike of TXRF condition, GIXRF not only addresses Total Reflection phenomena, but also phenomena based on Partial Reflection (of secondary and primary X-rays), and X-ray Refraction. Thus, under these conditions, it was possible generate Molecular Fluorescence at visible region from Synchrotron Radiation X-ray Fluorescence (SR-XRF). We proposed models of Fluorescence at Molecular scale and Multiscale (from nanometer to millimeter size level) based on Luminescence phenomena, whose are result of the Interactions (physical and chemical) of Synchrotron Radiation with the matter. These Interactions can be based on the linear-polarization of relativistic electron beams generated from this X-ray source, which exhibits coherence of the rays produced. At molecular scale, the model of Fluorescence is based on the interaction of the molecular and ionic species of TiO2 with the atomic and molecular groups of Oxygen (—O=O—) present in PWA structure, which by the chemical resonance effects of the double bonds in diene structure conjugated (.......=O—W=O—W=O—) can enable luminescence phenomena, via electronic displacements. At Multiscale level of size (result of the summation of the fluorescence model mentioned above) play an important role the Van der Waals forces, taking in consideration the contact between the great surfaces of PWA clusters and the different TiO2 molecular and ionic species (TiO2, TiOH2+, and TiO) in intramolecular and intermolecular configurations of PWA. SR-TXRF demonstrated be a suitable method for identification of Titanium and Tungsten in ormosil films.

Synchrotron Radiation (SR), Grazing Incident Angle X-ray Fluorescence (GIXRF), Ormosil, Phosphotungstates ([PW12O40]3-), Titanium Dioxide (TiO2)

Orlando Elguera Ysnaga. (2023). Synchrotron Radiation X-ray Fluorescence at Grazing Incident Angle (SR-GIXRF) and Total-Reflection (SR-TXRF) of Ormosil Films Containing TiO2 and Phosphotungstates. American Journal of Physics and Applications, 11(3), 55-79.

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1. L. Valgas de Souza. Filmes de ormosils contendo polioxometalatos e seu fotoreatividade frente a lipídeos e proteínas de adesão. 2014.130f. Tese de Doutorado em Físico-Química- Instituto de Química de São Carlos. São Carlos, São Paulo-Brasil: Universidade de São Paulo (IQSC-USP), 2014. Unpublished.
2. Hench, L., West J. The Sol-Gel Process. Chem. Rev. 1990. 90 (1): 33–72.
3. J. Steed, J. Atwood. Supramolecular Chemistry, 2nd Edition. February 2009, 1216 pages ISBN: 978-0-470-51234-0.
4. Ajay Kumar Manna, "Supramolecular Chemistry-Concepts and Applications", International Journal of Science and Research (IJSR). 2015. 4 (4): 892-899.
5. Jean-Marie Lehn. "Supramolecular Chemistry-Scope and Perspectives. Molecules-Supermolecules-Molecular Devices". Nobel lecture, December 8, 1987. Angewandte Chemie. 1988. 27 (1): 89-112.
6. Resnati G, Boldyreva E, Bombicz P, Kawano M. Supramolecular interactions in the solid state. IUCrJ. 2015. 2 (6): 675–690. ISSN: 2052-2525 6
7. Guido Kickelbick (2007). Hybrid Materials: Synthesis, Characterization, and Applications. Wiley-VCH Verlag GmbH & Co. KGaA. Print ISBN: 9783527312993, DOI: 10.1002/9783527610495.
8. O. A. Elguera Ysnaga. Métodos de Análise de Materiais Híbridos: Um Estudo Comparativo Entre Fluorescência de Raios-X Com Detecção Dispersiva em Energia Usando Fonte Tradicional e Luz Síncrotron. [Doctor of Science in Analytical and Inorganic Chemistry, Thesis]. Instituto de Química de São Carlos. São Carlos, São Paulo-Brasil: Universidade de São Paulo (IQSC-USP), 2015. Pp. 159-163. Unpublished.
9. L. P. Gonçalves. Nanopartículas de Titânio como aditivos em materiais híbridos inorgânicos fotocrômicos baseados em fosfotungstatos. 2011.138f. Dissertação de Mestrado (Mestrado em Engenharia de Materiais) -Instituto de Química de São Carlos. São Carlos, São Paulo-Brasil: Universidade de São Paulo (IQSC-USP), 2011. Unpublished.
10. L. Gonçalves, E. Ferreira-Neto, S. Ullah, et al. "Enhanced Photochromic Response of Ormosil–Phosphotungstate Nanocomposite Coatings Doped with TiO2 Nanoparticles". J. Sol-Gel Sci. Technol. 2015. 76 (2): 386–394. DOI 10.1007/s10971-015-3787-0, Online ISSN 0928-0707, Publisher: Springer US.
11. Baoling, W.; Hu, L. “Study of hybrid TiO2/ormosil films doped with laser dyes”. Journal of Molecular Structure. 2005. 748 (1–3): 177-181. ISSN 0022-2860.
12. Shyam Tripathi, V.; Babu Kandimalla, V.; Ju, H. “Preparation of ormosil and its applications in the immobilizing biomolecules”. Sensors and Actuators B: Chemical. 2006. 114 (2): 1071–1082. ISSN0925-4005.
13. Laranjo, M.; Stefani, V.; Benvenutti, E.; Costa, T.; Ramminger, G.; Gallas, M. “Synthesis of ormosil silica/rhodamine 6G: Powders and compacts. Journal of Non-Crystalline Solids”. 2007. 353 (1): 24-30. DOI: 10.1016/j.jnoncrysol.2006.09.029. ISSN 0022-3093.
14. F. Silva De Carvalho. Efeito da Matriz no Comportamento Fotocrômico de Ormosils de Fosfotungstato. 2008.104f. Dissertação de Mestrado (Mestrado em Ciências (Físico-Química)) – Instituto de Química de São Carlos. São Carlos, São Paulo-Brasil: Universidade de São Paulo (IQSC-USP), 2008. Unpublished.
15. De Oliveira, M., Lopes de Souza, A., Rodrigues Filho, U. P., Schneider, J. “Local Structure and Photochromic Response in Ormosils Containing Dodecatungstophosphoric Acid”. Journal of Materials Chemistry, 23 (4): 953-963, 2011.
16. Heng, H., Gan, Q., Meng, P., Liu, X. "The visible-light-driven type III heterojunction H3PW12O40/TiO2-In2S3: A photocatalysis composite with enhanced photocatalytic activity". Journal of Alloys and Compounds. 2017. 696: 51-59. ISSN 0925-8388.
17. Yao, F., Fu, W., Ge, X., Wang, L., Wang, J., Zhong, W. “Preparation and characterization of a Copper phosphotungstate/Titanium dioxide (Cu-H3PW12O40/TiO2) composite and the photocatalytic oxidation of high-concentration ammonia nitrogen”, Science of The Total Environment. 2020. 727: 138425, ISSN 0048-9697,
18. Rengifo-Herrera, J., Blanco, M., Wist, J., Florian, P., Pizzio, L. "TiO2 modified with polyoxotungstates should induce visible-light absorption and high photocatalytic activity through the formation of surface complexes". Applied Catalysis B: Environmental, 2016. 189 (1): 99-109, ISSN 0926-3373,
19. Orlando Elguera Ysnaga. “Maser-rays Based on Synchrotron Radiation-Total Reflection X-ray Fluorescence (SR-TXRF)”. Engineering Physics. 2021. 5 (2): 40-53. doi: 10.11648/j.ep.20210502.13.
20. Klockenkämper, R., Von Bohlen, A. “Survey of sampling techniques for solids suitable for microanalysis by Total-Reflection X-ray Fluorescence Spectrometry”. J. Anal. At. Spectrom. 1999. 14 (4): 571–576.
21. Compton, A. “CXVII. The Total Reflection of X-Rays”. Philosophical Magazine Series 1, vol. 45, p1121-1131, 1923.
22. Parratt, L. G. “Surface Studies of Solids by Total Reflection of X-rays”. Physical Reviews. 1954. 95 (2): 359-369.
23. Yoneda, Y; Horiuchi, T. “Optical flats for use in X-ray Spectrochemical Microanalysis”. The Review of Scientific Instruments: 1971. 42 (7): 169-70.
24. Wobrauschek, P; Aiginger, H. “Total-Reflection X-ray Fluorescence Spectrometric Determination of Elements in Nanogram Amounts”. Analytical Chemistry. 1975.47 (6): 852–855.
25. Ladisich, W.; Rieder, R.; Wobrauschek, P.; Aiginger, H. “Total Reflection X-ray Fluorescence analysis with monoenergetic excitation and full spectrum excitation using rotating anode X-ray tubes”. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment. 1993. 330 (3): 501-506. ISSN 0168-9002.
26. R. Klockenkämper, A. Von Bohlen. "Efficiency and Evaluation". In: M. F. Vitha, editor. Total Reflection X-ray Fluorescence Analysis and Related Methods. New York: John Wiley, 1997. Chap. 6, Pp. 221–230.
27. R. Klockenkämper, A. Von Bohlen. "Efficiency and Evaluation". In: M. F. Vitha, editor. Total Reflection X-ray Fluorescence Analysis and Related Methods. New York: John Wiley, 2015. Chap. 7, Pp. 434-438.
28. Pérez, C., Radtke, M., Sánchez, H., Tolentino, H., Neuenshwander, R., Barg, W., Rubio, M., Silveira Bueno, M., Raimundo, I., Rohwedder. "Synchrotron radiation X-Ray fluorescence at the LNLS: beamline instrumentation and experiments". X-ray Spectrometry. 1999. 28 (5): 320–326.<320::AID-XRS359>3.0.CO;2-1
29. Elguera Ysnaga Orlando. “Grazing Incidence and Total Reflection X-ray Fluorescence Analyses of Ormosil Thin Films”. LNLS 2013 Activity Report. Brazilian Synchrotron Light Laboratory. 2013.
30. F. Y. Xie, L. Gong, X. Liu, Y. T. Tao, W. H. Zhang, S. H. Chen, H. Meng, J. Chen. "XPS studies on surface reduction of tungsten oxide nanowire film by Ar+ bombardment”. Journal of Electron Spectroscopy and Related Phenomena. 2012. 185 (3–4): 112-118, ISSN 0368-2048.
31. H. Zhang, C. Cheng, H. Zhang, R. Chen, B. Huang, H. Chen, W. Peiab. "Physical mechanism for the synapse behavior of WTiOx-based memristors”. Phys. Chem. Chem. Phys. 2019. 21 (42): 23758-23763.
32. Breckenridge, R., Hosler, W. "Electrical Properties of Titanium Dioxide semiconductors”. Phys. Rev. 1953. 91 (4): 793-802. doi = {10.1103/PhysRev.91.793}.
33. Becker, K. H., Haaks, D. and Schürgers, M. "Notizen: Fluorescence by the Vacuum-UV Photolysis of Acetylene”. Zeitschrift für Naturforschung A, 1971, 26 (10): 1770-1771.
34. Jiang, J., Saladrigas, C., Erickson, T., Keenan, C., Field. R. "Probing the predissociated levels of the S1 state of acetylene via H-atom fluorescence and photofragment fluorescence action spectroscopy”. J Chem Phys. 2018 Nov 7; 149 (17): 174309.
35. Brus, L. "Acetylene fluorescence”. Journal of Molecular Spectroscopy. 1979.75 (2): 245-250. ISSN 0022-2852.
36. Cuylle, S., Zhao, D., Strazzulla, G., Linnartz, H. "Vacuum ultraviolet photochemistry of solid acetylene: a multispectral approach”. Astronomy & Astrophysics. 2014. 570, A&A, A83. DOI: 10.1051/0004-6361/201424379.
37. Okabe, H. "Photochemistry of acetylene”. 1983, Can. J. Chem. 61, 850-855.
38. Kočišek, J., Fedor, J., Poterya, V., Pysanenko, A., O. Votava, M. Fárník. "UV Photodissociation of Acetylene in Various Environments”. WDS'11 Proceedings of Contributed Papers, Part II, 241–246, 2011. ISBN 978-80-7378-185-9 © MATFYZPRESS.
39. Tanimoto, H., Nagao, T., Fujiwara, T., Kakuta, T., Tanaka, K., Chujo, Y. and Kakiuchi, K. "Fluorescence and phosphorescence study of germanium–acetylene polymers and germa [N] pericyclynes”. Polym. Chem., 2015, 6 (43) 7495-7499.
40. Byzynski, G., Ribeiro, C., Longo, E. "Blue to Yellow Photoluminescence Emission and Photocatalytic Activity of Nitrogen Doping in TiO2 Powders". International Journal of Photoenergy. 2015. Volume 2015, Article ID 831930, 12 pages.
41. Liu, Y., Claus, R. O. "Blue Light Emitting Nanosized TiO2 Colloids”. J. Am. Chem. Soc. 1997, 119 (22): 5273–5274.
42. Hayyan, M., Hashim, M., AlNashef, I. "Superoxide Ion: Generation and Chemical Implications”. DOI: 10.1021/acs.chemrev.5b00407 Chem. Rev. 2016, 116, 5, 3029−3085.
43. Mayeda, E. A., Bard, A. J. "Singlet oxygen. Suppression of its production in dismutation of superoxide ion by superoxide dismutase”. J. Am. Chem. Soc. 1974, 96 (12): 4023–4024.
44. Zent, A., Ichimura, A., Quinn, R., Harding, H. "The formation and stability of the superoxide radical (O2-) on rock-forming minerals: Band gaps, hydroxylation state, and implications for Mars oxidant chemistry”. Journal of Geophysical Research, Vol. 113, E09001, 2008.
45. Farley J, Hough S (2003). "Single Bubble Sonoluminsescence". APS Northwest Section Meeting Abstracts: D1.007.
46. Frenzel, H. and Schultes, H. "Luminescenz im ultraschallbeschickten Wasser". Zeitschrift für Physikalische Chemie International Journal of Research in Physical Chemistry and Chemical Physics. 1934. 27B (1): 421-424. Published Online: 2017-01-12.
47. Didenko Y, McNamara W, Suslick K. "Effect of Noble Gases on Sonoluminescence Temperatures during Multibubble Cavitation". Physical Review Letters. 2000, 84 (4): 777–780.
48. Jarman, P. “Sonoluminescence: A discussion”. The Journal of the Acoustical Society of America. 1960, 32 (11): 1459–1462. ISSN 0001-4966. doi: 10.1121/1.1907940.
49. Suslick, K. “The chemical effects of ultrasound,” Scientific American, 1989, 260 (2), 80-86.
50. A Star in a Jar!.......... SOUND Can Produce LIGHT........ Sonoluminescence.
51. Klockenkämper, R. Total Reflection X-ray Fluorescence Analysis. Chemical analysis A series of monographs on analytical chemistry and its applications, v. 140, New York: John Wiley, 1997. 246 p.
52. F. F. Beijer. (1998). "Cooperative Multiple Hydrogen Bonding in Supramolecular Chemistry". ISBN 90-386-0698-2. Cip-Data Library Technische Universiteit Eindhoven.
53. Egerton, T., Purnama, H. “Does hydrogen peroxide really accelerate TiO2 UV-C photocatalyzed discoloration of azo-dyes such as Reactive Orange 16?”. Dyes and Pigments. 2014. 101: 280-285. ISSN: 0143-7208. DOI: 10.1016/j.dyepig.2013.10.019.
54. D. Huang, Y. Wang, L. Yang, G. Luo. “Direct synthesis of mesoporous TiO2 modified with phosphotungstic acid under template-free condition”. Microporous and Mesoporous Materials. 2006. 96 (1–3): 301–306. ISSN 1387-1811,
55. Javidi, J., Esmaeilpour, M., Rahiminezhad, Z. et al. “Synthesis and Characterization of H3PW12O40 and H3PMo12O40”. Nanoparticles by a Simple Method. J Clust Sci. 2014. 25: 1511–1524.
56. Zhou, Y., Yang, J., Su, H., Zeng, J., Ping-Jiang, S., Goddard. W. “Insight into Proton Transfer in Phosphotungstic Acid Functionalized Mesoporous Silica-Based Proton Exchange Membrane Fuel Cells”. Journal of the American Chemical Society. 2014. 136 (13): 4954-4964.
57. Liu, Y., Lu, Y., Haragirimana, A., Buregeya, I., Li, N., Hu, Z., Chen, S. “Immobilized phosphotungstic acid for the construction of proton exchange nanocomposite membranes with excellent stability and fuel cell performance”. International Journal of Hydrogen Energy. 2020. 45 (35): 17782-17794. ISSN 0360-3199.
58. Ternov, I. M. Synchrotron Radiation and Its Applications. Translated from Russian by S. J. Amoretty. New York: Harwood Academic Publishers, 1985. 379p.