Diseño Basado en Datos de Nanoestructuras de CeO₂ con Morfología Controlada y Propiedades Catalíticas Ajustables

B. Trujillo-Navarrete

doi:10.29057/aactm.v13i13.17288

Autores/as

B. Trujillo-Navarrete Tecnológico Nacional de México https://orcid.org/0000-0002-0196-1001

DOI:

https://doi.org/10.29057/aactm.v13i13.17288

Palabras clave:

óxido de cerio, análisis multivariante, UMAP, optimización bayesiana, control morfológico, relaciones estructura-propiedad, ingeniería de defectos

Resumen

Las nanoestructuras de óxido de cerio (CeO₂) con morfologías controladas (esferulitas, nanobarras cortas y nanobarras largas) se sintetizaron mediante un diseño factorial que varió la concentración de octadecilamina (0.01–0.2 M) y la relación etanol/agua (α = 0.3–3.0). A partir de una caracterización exhaustiva, se seleccionaron 15 propiedades fisicoquímicas clave para un análisis multivariante. El análisis de componentes principales reveló una agrupación morfológica: el primer componente principal (55 % de varianza) separó las muestras según la densidad de defectos y el área superficial, mientras que el segundo componente principal (25 % de varianza) lo hizo según la relación de aspecto. La regresión por Mínimos Cuadrados Parciales mostró que los parámetros de síntesis explican más del 90 % de la varianza en las propiedades, siendo la concentración de octadecilamina el factor dominante. El método de K‑medias confirmó tres grupos diferenciados. La proyección uniforme de variedades y aproximación (UMAP) proporcionó una visualización no lineal superior, sugiriendo heterogeneidad dentro de la muestra óptima, consistente con la polidispersidad observada por microscopía electrónica de transmisión (TEM, coeficiente de variación de longitud = 60.3 %). Sin embargo, debido al reducido tamaño muestral (n = 4), no se pueden identificar subpoblaciones estadísticamente fiables; la alta polidispersidad refleja una distribución continua de longitudes. La optimización multiobjetivo identificó a la muestra denominada BB (0.05 M de octadecilamina, α = 1.0) como la condición óptima: área superficial de 79.9 m²/g, contenido de Ce³⁺ de 30.2 %, relación de aspecto de 5.4 y banda prohibida de 3.02 eV, alcanzando una deseabilidad global de 0.913. La optimización bayesiana sugiere explorar valores cercanos a [octadecilamina] = 0.250 M, α = 1.002 (deseabilidad predicha de 0.904). Esta prueba de concepto demuestra el diseño de nanomateriales basado en datos; sin embargo, la capacidad predictiva requiere validación con conjuntos de datos más amplios.

Descargas

Los datos de descargas todavía no están disponibles.

Biografía del autor/a

B. Trujillo-Navarrete, Tecnológico Nacional de México

Dr. Balter Trujillo-Navarrete es profesor e investigador en TecNM/IT. Tijuana. Se especializa en el desarrollo de nanomateriales avanzados como óxidos dopados y perovskitas para aplicaciones ambientales, incluidos sensores de contaminantes y energía limpia.

Citas

Burroughs, P., Hamnett, A., Orchard, A. F., & Thornton, G. (1976). Satellite structure in the X-ray photoelectron spectra of some binary and mixed oxides of lanthanum and cerium. Journal of the Chemical Society, Dalton Transactions, (17), 1686. https://doi.org/10.1039/dt9760001686

Capdevila-Cortada, M., & López, N. (2017). Entropic contributions enhance polarity compensation for CeO2(100) surfaces. Nature Materials, 16(3), 328–334. https://doi.org/10.1038/nmat4804

Choudhary, K., DeCost, B., Chen, C., Jain, A., Tavazza, F., Cohn, R., Park, C. W., Choudhary, A., Agrawal, A., Billinge, S. J. L., Holm, E., Ong, S. P., & Wolverton, C. (2022). Recent advances and applications of deep learning methods in materials science. Npj Computational Materials, 8(1), 59. https://doi.org/10.1038/s41524-022-00734-6

Choung, S., Kim, Y., Jang, M. G., Cho, G. H., Kang, D. G., Lee, T., Lee, D., Han, S., Seo, B., Park, W., Kim, M., Seo, O., Watanabe, T., Kumara, L. S. R., Matsumura, D., Kim, T. Y., Kim, J. H., Kim, J., & Han, J. W. (2026). Hierarchical ceria nanoarchitecture enabling accelerated lattice oxygen activation for efficient redox reactions. Nature Communications. https://doi.org/10.1038/s41467-026-72447-z

Desimpel, S., Dorbec, M., Van Geem, K. M., & Stevens, C. V. (2026). Bayesian optimization for chemical reactions. Chemical Society Reviews, 55(5), 2731–2775. https://doi.org/10.1039/D5CS00962F

Ganduglia-Pirovano, M. V., Hofmann, A., & Sauer, J. (2007). Oxygen vacancies in transition metal and rare earth oxides: Current state of understanding and remaining challenges. Surface Science Reports, 62(6), 219–270. https://doi.org/10.1016/j.surfrep.2007.03.002

Hair, J. F., Black, W. C., Babin, B. J., & Anderson, R. E. (2019). Multivariate Data Analysis. Cengage. https://books.google.com.mx/books?id=0R9ZswEACAAJ

Hao, X., Zhang, S., Xu, Y., Tang, L., Inoue, K., Saito, M., Ma, S., Chen, C., Xu, B., Adschiri, T., & Ikuhara, Y. (2021). Surfactant-mediated morphology evolution and self-assembly of cerium oxide nanocrystals for catalytic and supercapacitor applications. Nanoscale, 13(23), 10393–10401. https://doi.org/10.1039/D1NR01746B

Himanen, L., Geurts, A., Foster, A. S., & Rinke, P. (2019). Data‐Driven Materials Science: Status, Challenges, and Perspectives. Advanced Science, 6(21). https://doi.org/10.1002/advs.201900808

Khan, M. M., Ansari, S. A., Pradhan, D., Han, D. H., Lee, J., & Cho, M. H. (2014). Defect-Induced Band Gap Narrowed CeO2 Nanostructures for Visible Light Activities. Industrial & Engineering Chemistry Research, 53(23), 9754–9763. https://doi.org/10.1021/ie500986n

Konsolakis, M., & Lykaki, M. (2021). Facet-Dependent Reactivity of Ceria Nanoparticles Exemplified by CeO2-Based Transition Metal Catalysts: A Critical Review. Catalysts, 11(4), 452. https://doi.org/10.3390/catal11040452

Kronenberg, K., Rave, H., Ghaffari-Tabrizi-Wizsy, N., Nyckees, D., Elinkmann, M., Freitak, D., Linsen, L., Gonzalez de Vega, R., & Clases, D. (2025). Exploring high-dimensional LA-ICP-TOFMS data with uniform manifold approximation and projection (UMAP). Journal of Analytical Atomic Spectrometry, 40(12), 3473–3484. https://doi.org/10.1039/D5JA00215J

Li, J., Lu, G., Li, H., Wang, Y., Guo, Y., & Guo, Y. (2011). Facile synthesis of 3D flowerlike CeO2 microspheres under mild condition with high catalytic performance for CO oxidation. Journal of Colloid and Interface Science, 360(1), 93–99. https://doi.org/10.1016/j.jcis.2011.04.052

Li, Z.-X., Li, L.-L., Yuan, Q., Feng, W., Xu, J., Sun, L.-D., Song, W.-G., & Yan, C.-H. (2008). Sustainable and Facile Route to Nearly Monodisperse Spherical Aggregates of CeO2 Nanocrystals with Ionic Liquids and Their Catalytic Activities for CO Oxidation. The Journal of Physical Chemistry C, 112(47), 18405–18411. https://doi.org/10.1021/jp807348n

Liu, X., Yang, H., Han, L., Liu, W., Zhang, C., Zhang, X., Wang, S., & Yang, Y. (2013). Mesoporous-shelled CeO2 hollow nanospheres synthesized by a one-pot hydrothermal route and their catalytic performance. CrystEngComm, 15(38), 7769. https://doi.org/10.1039/c3ce40959g

Lookman, T., Balachandran, P. V., Xue, D., & Yuan, R. (2019). Active learning in materials science with emphasis on adaptive sampling using uncertainties for targeted design. Npj Computational Materials, 5(1), 21. https://doi.org/10.1038/s41524-019-0153-8

Mai, H.-X., Sun, L.-D., Zhang, Y.-W., Si, R., Feng, W., Zhang, H.-P., Liu, H.-C., & Yan, C.-H. (2005). Shape-Selective Synthesis and Oxygen Storage Behavior of Ceria Nanopolyhedra, Nanorods, and Nanocubes. The Journal of Physical Chemistry B, 109(51), 24380–24385. https://doi.org/10.1021/jp055584b

McInnes, L., Healy, J., & Melville, J. (2020). UMAP: Uniform Manifold Approximation and Projection for Dimension Reduction. ArXiv Preprint ArXiv:1802.03426. http://arxiv.org/abs/1802.03426

Meher, S. K., & Ranga Rao, G. (2012). Tuning, via Counter Anions, the Morphology and Catalytic Activity of CeO2 Prepared under Mild Conditions. Journal of Colloid and Interface Science, 373(1), 46–56. https://doi.org/10.1016/j.jcis.2011.09.050

Montini, T., Melchionna, M., Monai, M., & Fornasiero, P. (2016). Fundamentals and Catalytic Applications of CeO2 -Based Materials. Chemical Reviews, 116(10), 5987–6041. https://doi.org/10.1021/acs.chemrev.5b00603

Nguyen, T.-D., Dinh, C.-T., Mrabet, D., Tran-Thi, M.-N., & Do, T.-O. (2013). Controlled synthesis of ceria nanoparticles for the design of nanohybrids. Journal of Colloid and Interface Science, 394, 100–107. https://doi.org/10.1016/j.jcis.2012.12.020

Nolan, M., Parker, S. C., & Watson, G. W. (2005). The electronic structure of oxygen vacancy defects at the low index surfaces of ceria. Surface Science, 595(1–3), 223–232. https://doi.org/10.1016/j.susc.2005.08.015

Parsaeifard, B., Sankar De, D., Christensen, A. S., Faber, F. A., Kocer, E., De, S., Behler, J., Anatole von Lilienfeld, O., & Goedecker, S. (2021). An assessment of the structural resolution of various fingerprints commonly used in machine learning. Machine Learning: Science and Technology, 2(1), 015018. https://doi.org/10.1088/2632-2153/abb212

Pyzer-Knapp, E. O., Pitera, J. W., Staar, P. W. J., Takeda, S., Laino, T., Sanders, D. P., Sexton, J., Smith, J. R., & Curioni, A. (2022). Accelerating materials discovery using artificial intelligence, high performance computing and robotics. Npj Computational Materials, 8(1), 84. https://doi.org/10.1038/s41524-022-00765-z

Rajan, K. (2015). Materials Informatics: The Materials “Gene” and Big Data. Annual Review of Materials Research, 45(1), 153–169. https://doi.org/10.1146/annurev-matsci-070214-021132

Shan, W., Guo, H., Liu, C., & Wang, X. (2012). Controllable preparation of CeO2 nanostructure materials and their catalytic activity. Journal of Rare Earths, 30(7), 665–669. https://doi.org/10.1016/S1002-0721(12)60109-4

Snoek, J., Larochelle, H., & Adams, R. P. (2012). Practical Bayesian Optimization of Machine Learning Algorithms. Advances in Neural Information Processing Systems, 4, 2951–2959. http://arxiv.org/abs/1206.2944

Sun, C., Li, H., Zhang, H., Wang, Z., & Chen, L. (2005). Controlled synthesis of CeO2 nanorods by a solvothermal method. Nanotechnology, 16(9), 1454–1463. https://doi.org/10.1088/0957-4484/16/9/006

Szymanski, N. J., Rendy, B., Fei, Y., Kumar, R. E., He, T., Milsted, D., McDermott, M. J., Gallant, M., Cubuk, E. D., Merchant, A., Kim, H., Jain, A., Bartel, C. J., Persson, K., Zeng, Y., & Ceder, G. (2023). An autonomous laboratory for the accelerated synthesis of inorganic materials. Nature, 624(7990), 86–91. https://doi.org/10.1038/s41586-023-06734-w

Tian, J., Zhong, J., Xie, Z., Cai, H., Song, L., Lei, K., Zhong, X., Liu, P., Shang, S., Ren, Q., Huang, H., Chen, L., Fu, M., & Ye, D. (2026). Activating lattice oxygen via self-adaptive Ce4+–O–Ce3+ symmetry-breaking sites in ceria for volatile organic compounds oxidation. Applied Catalysis B: Environment and Energy, 385, 126307. https://doi.org/10.1016/j.apcatb.2025.126307

Trovarelli, A. (1996). Catalytic Properties of Ceria and CeO2 -Containing Materials. Catalysis Reviews, 38(4), 439–520. https://doi.org/10.1080/01614949608006464

Ulugöl, A., Bückmann, J., Yang, R., Hoitink, R., van Blaaderen, A., Smallenburg, F., & Filion, L. (2025). Comparing unsupervised learning methods for local structural identification in colloidal systems. http://arxiv.org/abs/2509.07186

Urbach, F. (1953). The Long-Wavelength Edge of Photographic Sensitivity and of the Electronic Absorption of Solids. Physical Review, 92(5), 1324–1324. https://doi.org/10.1103/PhysRev.92.1324

Wang, X., Jiang, Z., Zheng, B., Xie, Z., & Zheng, L. (2012). Synthesis and shape-dependent catalytic properties of CeO2 nanocubes and truncated octahedra. CrystEngComm, 14(22), 7579. https://doi.org/10.1039/c2ce25333j

Yang, C., Yu, X., Heißler, S., Nefedov, A., Colussi, S., Llorca, J., Trovarelli, A., Wang, Y., & Wöll, C. (2017). Surface Faceting and Reconstruction of Ceria Nanoparticles. Angewandte Chemie International Edition, 56(1), 375–379. https://doi.org/10.1002/anie.201609179

Yang, S., & Gao, L. (2006). Controlled Synthesis and Self-Assembly of CeO2 Nanocubes. Journal of the American Chemical Society, 128(29), 9330–9331. https://doi.org/10.1021/ja063359h

Yao, H., Wang, Y., Jing, Y., & Luo, G. (2018). Ultrafast, Continuous and Shape-Controlled Preparation of CeO2 Nanostructures: Nanorods and Nanocubes in a Microfluidic System. Industrial & Engineering Chemistry Research, 57(22), 7525–7532. https://doi.org/10.1021/acs.iecr.8b01298

Zhang, D., Du, X., Shi, L., & Gao, R. (2012). Shape-controlled synthesis and catalytic application of ceria nanomaterials. Dalton Transactions, 41(48), 14455. https://doi.org/10.1039/c2dt31759a

Zhou, K., Wang, X., Sun, X., Peng, Q., & Li, Y. (2005). Enhanced catalytic activity of ceria nanorods from well-defined reactive crystal planes. Journal of Catalysis, 229(1), 206–212. https://doi.org/10.1016/j.jcat.2004.11.004