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13 figures, 6 tables.-- Supplementary information available. ; Pyrolysis of formamidinium halide salts (FAI, FABr) results in a new type of amorphous carbon nitride materials with a mass fraction of 40–50% nitrogen content. Pyrolysis temperature drives final chemical composition, morphology, optical and electrical properties of the material independently of the halide precursor and identifying triazine ring, instead of typical heptazine unit, as the main building block of this material. We elaborated a temperature dependent mechanism of formation for these materials and foresee its potential value as native passivation layer in the field of perovskite solar cells. ; E.J.J-P acknowledges the funding support from MCIN/AEI/10.13039/501100011033 and European Union NextGenerationEU/PRTR (project grants PID2019-107893RB-I00 and EIN2020-112315, respectively). M.H. acknowledges the funding support from MCIN/AEI/10.13039/501100011033 for the Ramón y Cajal fellowship (RYC-2018-025222-I) and the project PID2019-108247RA-I00. R.A. acknowledges funding from the Spanish MICINN (project grant PID2019-104739 GB-100/AEI/10.13039/501100011033). RA also acknowledge to Government of Aragon (project DGA E13-20R (FEDER, EU)) and European Union H2020 program "ESTEEM3" (823717). A.A-C acknowledges financial support from Spanish MCIN/AEI/10.13039/501100011033 under project PID2019-104272RB-C51/AEI/10.13039/501100011033 and the Diputación General de Aragón under project T03_20R (Grupo Reconocido). ; Peer reviewed

Abstract
The growing concern about the environmental consequences of anthropogenic CO2 emissions significantly stimulated the research of low-cost, efficient, and recyclable solid adsorbents for CO2 capture. In this work, a series of MgO-supported mesoporous carbon nitride adsorbents with different MgO contents (xMgO/MCN) was prepared using a facile process. The obtained materials were tested for CO2 capture from 10 vol% CO2 mixture gas with N2 using a fixed bed adsorber at atmospheric pressure. At 25 ºC, the bare MCN support and unsupported MgO samples demonstrated CO2 capture capacities of 0.99, and 0.74 mmol g−1, respectively, which were lower than those of the xMgO/MCN composites.The incorporation of MgO into the MCN improved the CO2 uptake, and the 20MgO/MCN exhibited the highest CO2 capture capacity of 1.15 mmol g−1 at 25 °C. The improved performance of the 20MgO/MCN nanohybrid can be possibly assigned to the presence of high content of highly dispersed MgO NPs along with its improved textural properties in terms of high specific surface area (215 m2g−1), large pore volume (0.22 cm3g−1), and abundant mesoporous structure. The efffects of temperature and CO2 flow rate were also investigated on the CO2 capture performance of 20MgO/MCN. Temperature was found to have a negative influence on the CO2 capture capacity of the 20MgO/MCN, which decreased from 1.15 to 0.65 mmol g−1with temperature rise from 25 C to 150º C, due to the endothermicity of the process. Similarly, the capture capacity decreased from 1.15 to 0.54 mmol g−1 with the increase of the flow rate from 50 to 200 ml minute−1 respectively. Importantly, 20MgO/MCN showed excellent reusability with consistent CO2 capture capacity over five sequential sorption–desorption cycles, suggesting its suitability for the practical capture of CO2.

Nowadays, the development of highly efficient routes for the low cost synthesis of nitrides is greatly growing. Mechanochemical synthesis is one of those promising techniques which is conventionally employed for the synthesis of nitrides by long term milling of metallic elements under a pressurized N2 or NH3 atmosphere (A. Calka and J. I. Nikolov, Nanostruct. Mater., 1995, 6, 409–412). In the present study, we describe a versatile, room-temperature and low-cost mechanochemical process for the synthesis of nanostructured metal nitrides (MNs), carbonitrides (MCNs) and carbon nitride (CNx). Based on this technique, melamine as a solid nitrogen-containing organic compound (SNCOC) is ball milled with four different metal powders (Al, Ti, Cr and V) to produce nanostructured AlN, TiCxN1−x, CrCxN1−x, and VCxN1−x (x ∼ 0.05). Both theoretical and experimental techniques are implemented to determine the reaction intermediates, products, by-products and finally, the mechanism underling this synthetic route. According to the results, melamine is polymerized in the presence of metallic elements at intermediate stages of the milling process, leading to the formation of a carbon nitride network. The CNx phase subsequently reacts with the metallic precursors to form MN, MCN or even MCN–CNx nano-composites depending on the defect formation energy and thermodynamic stability of the corresponding metal nitride, carbide and C/N co-doped structures. ; S. A. R. would like to thank Birjand University of Technology (project no. RP-95-1005) and IFW Dresden for financial support. D. E. P. V. acknowledges funding by the Foundation of Scientific Research-Flanders (FWO) (project no. 12S3415N). The computational resources and services used in this work were provided by the VSC (Flemish Supercomputer Center), funded by the Research Foundation – Flanders (FWO) and the Flemish Government – department EWI.