Entrapping aliphatic and heterocyclic gaseous amines on copper-exchanged montmorillonite: A straight and green process to reduce air pollution

The capture of a number of aliphatic (APAs) and heterocyclic (HCAs) amines, known as widespread pollutants, by Cu2+-exchanged montmorillonite (Mt-Cu) was studied through elemental analysis diffuse-reflectance ultraviolet-visible and infra-red spectroscopies, X-rays diffraction, thermal analysis coupled with mass spectrometry of the evolved gases, XANES and EXAFS spectroscopy, and solid-state NMR. The investigated APAs and HCAs were: ethylamine (EtNH2), triethylamine (Et3N), ethylenediamine (En) and morpholine (Morph), piperidine (Piper), and pyridine (Py), respectively. Mt-Cu saturation occurred within 25 h at worst, the immobilized amount was relevant and involved the binding of the amino nitrogen to the interlayer Cu2+ ions. While for APAs the entrapped amount changed with the structure of the molecule, for HCAs it did not. The EXAFS and XANES studies showed that the interlayer Cu2+ ions are strongly coordinated to the amino groups. This resulted in the coordination number changing from four to five coordination, with the exception of En for which the CuII ions remained tetra-coordinated as in pristine Mt-Cu. Residual water molecules were found to be bound to the copper also after exposure to the amines. For EtNH2, En, Morph, and Piper the coordination to CuII occurred without the deprotonation of the amino group. NMR measurements showed the presence of physisorbed amines whose amount depended on the structure: while En was mostly bound to CuII (physisorption was negligible), for EtNH2, Et3N, Morph, and Piper the physisorbed amount ranged from 55 to 30% and for Py it was even the 70%. In addition, En was found to be the amine entrapped with the highest strength and covalent character. The obtained results supported the effectiveness of Cu2+-modified layered silicates as an air/gas purification system. The exploitation of devices based on Cu2+-exchanged montmorillonite could therefore become a very appealing future challenge as the interlayer modification was very simple and fast and the entire process turned out to be green and economic.