Synthesis of metal-free lightweight materials with sequence-encoded properties

[EN] A high-temperature solid-state synthesis is a widespread tool for the construction of metal-free materials, owing to its simplicity and scalability. However, no method is currently available for the synthesis of metal-free materials, which enables control over the atomic ratio and spatial organization of several heteroatoms. Here we report a general and large-scale synthesis of phosphorus-nitrogen-carbon (PNC) materials with highly controllable elemental composition and structural, electronic, and thermal stability properties. To do so, we designed four different crystals consisting of melamine and phosphoric acid with different monomers sequences as the starting precursors. The monomer sequence of the crystals is preserved upon calcination (up to 800 degrees C) to an unprecedented degree, which leads to precise control over the composition of the final PNC materials. The latter exhibit a remarkable stability up to 970 degrees C in air, positioning them as sustainable, lightweight supports for catalysts in high-temperature reactions as well as halogen-free fire-retardant materials.The authors would like to thank Dr Volodiya Ezersky, Dr Natalya Froumin, Dr Anna Milionshchik, Dr Radion Vainer, Dr Einat Nativ-Roth, and Mr Nitzan Shauloff for analytical HRTEM, XPS, TGA, SC-XRD, HRSEM, and technical support, respectively. This research was partly funded by the following: the Planning & Budgeting Committee/Israel Council for Higher Education (CHE) and Fuel Choice Initiative (Prime Minister Office of Israel), within the framework of "Israel National Research Center for Electrochemical Propulsion" (INREP); the Minerva Center No. 117873; the Spanish Ministerio de Economia y Competitividad (MAT2016-77608-C3-1-P, MAT2016-75883-C2-2-P); J. A. and H. G. also gratefully acknowledges financial support from the Spanish Ministry of Economy and Competitiveness (Severo Ochoa SEV2016-0683 and RTI2018-89023-CO2-R1) and by the Generalitat Valenciana (Prometeo 2017-083). This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 Research and Innovation Programme (grant agreement No. [849068]). NMR spectroscopic calculations were performed using HPC resources from GENCI-IDRIS (Grant 097535). The French Region Ile de France-SESAME program is acknowledged for financial support (700 MHz spectrometer).Azoulay, A.; Barrio, J.; Tzadikov, J.; Volokh, M.; Albero-Sancho, J.; Gervais, C.; Amo-Ochoa, P.... (2020). Synthesis of metal-free lightweight materials with sequence-encoded properties. Journal of Materials Chemistry A. 8(17):8752-8760. https://doi.org/10.1039/d0ta03162c87528760817Paraknowitsch, J. P., & Thomas, A. (2013). 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