Camacho, Luis

Jodlowski, Alexander Davis

Luque, Rafael

Martín-Romero, M.T.

Miguel, Gustavo de

Pérez-Morales, M.

Yépez, Alfonso

English

Repositorio Institucional de la Universidad de Córdoba

Benign-by-design solventless mechanochemical synthesis of 3-, 2- and 1-dimensional hybrid perovskitesOrganic-inorganic hybrid perovskites have recently attracted significant attention in the scientific community due to their extraordinary optoelectronic propertieswith applications in the fields of solar energy, lighting, photodetectors and lasing. The rational design of these hybrid materials is a key factor to optimize theirperformance in perovskite-based devices. In this work, a mechanochemical approach is proposed as highly efficient, simple and reproducible methodology for thepreparation of four types of hybrid perovskites obtaining large amounts of polycrystalline powders with high purity. The synthesis of two archetypal three-dimensional (3D) perovskites (MAPbI3 and FAIPbI3) was accomplished, together with a bidimensional (2D) perovskite (Gua)2PbI4) and a “double-chain” perovskite(GuaPbI3), whose structure has been elucidated for the first time by using X-ray diffraction.IntroductionUV-vis diffuse-reflectancespectroscopyTGAThermal analysisMechanosynthesis of  hybrid PerovskitePbI2Organic Cation*  +•Simple•Faster•Reproducible•Highly efficient•Solventless*Metilammonium Iodide (MAI) , Formamidinium Iodide (FAI) and Guanidinium Iodide (GuaI)350 rpm10 minMAPbI3FAPbI33D perovskitesGuaPbI31D perovskite(Gua)2PbI42D perovskite160ºCLarge size of synthesized crystals. Positive effect on potential applications of these materials.Scanning Electron MicroscopyConclusionIn conclusion, the proposed mechanochemical synthesis offers a simple, efficient and highly reproducible approach for the design of advanced hybridperovskites, including 3D, 2D and 1D materials. This solventless synthetic method is expected to pave the way for further discoveries and design of novelperovskite materials with innovative properties. Additionally, the facile and cost-efficient preparation of large quantities of the perovskite materials (ca. 5-10 g perbatch) remarkably simplifies their use in unexplored strategies for optoelectronics applications.Alexander Davis Jodlowski1, Alfonso Yépez2, María Teresa Martín Romero 1, Marta Pérez Morales 1, Rafael Luque2, Luis Camacho1and Gustavo de Miguel11 Institute of Fine Chemistry and Nanochemistry, Department of Physical Chemistry and Applied Thermodynamics,University of Cordoba,Campus Universitario de Rabanales,Edificio Marie Curie, Córdoba, 14014 (Spain).2Department of Organic Chemistry, University of Córdoba, Campus Universitario de Rabanales, Edificio Marie Curie, Córdoba, 14014 (Spain).       e-mail:q82dajoa@uco.esTopic E2 abstract number 80210 20 30 40 50-10010203040Intensity / a.u.2Tetragonal I4/mcma = b = 8.8792330  c =  12.6629650 MAPbI3 at 30 ºC 10 20 30 40 50-100102030405060MAPbI3 at 100 ºC Cubic Pm3ma = b = c = 6.34296441 Intensity / a.u.210 20 30 40 500255075100 Hexagonal P63mca = b = 8.68379816c = 7.93056611Intensity / a.u.2FAPbI3 at 30 ºC10 20 30 40 50-1001020304050FAPbI3 at 160 ºCTrigonal P3m1a = b = 9.04934455c = 11.06894215Intensity / a.u.2Pawley fits of the XRD patterns with very good agreement with the simulated ones           Crystallinity and no impurities or precursorsX-ray Structural studiesCrystal structure of GuaPbI3. NEW PEROVSKITE WAS BORN!!!10 20 30 40-1001020304050 2Intensity / a.u.Orthorhombic Pna21a = 11.990 b = 20.880c = 4.476 GuaPbI3An excellent agreement could beobserved between both patterns with noresidual reflection peaks from any otherconcurrent structure.Acknowledge the Ministry of Economy and Competitivenessfor financial support (CTQ2014-56422-P).Acknowledgements400 500 600 700 800 900 10000.00.20.40.60.81.0 MaPbI3 FaPbI3 Gua2PbI4 GuaPbI3Absorption / a.u.Wavelength / nmLarge blue shift of the absorption band in GuaPbI3Associated to the disruption of the 3D network of PbI6-octaedraNo significant weight loss. Good stability.ReferencesC. Xua, S. De, A.M. Balu, M. Ojeda, R. Luque Chem. Commun. 2015, 51, 6698-6713.T. Baikie, Y. Fang, J.M. Kadro, M. Schreyer, F. Wei, S.G. Mhaisalkar, M. Graetzel, T.J. White J. Mater.Chem. A 2013.B. Sarapov, D. Mitzi Chem. Rev. 2016, 116, 4558-4596; b) K. Meng, S. Gao, L. Wu, G. Wang, X. Liu,G. Chen, Z. Liu, G. Chen Nano Lett. 2016, 16, 4166-4173.1D perovskite

Benign-by-design solventless mechanochemical synthesis of 3-, 2- and 1-dimensional hybrid perovskites

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Benign-by-design solventless mechanochemical synthesis of 3-, 2- and 1-dimensional hybrid perovskites

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