J. Phys. Chem. C., vol. 114, Issue 20

1H, 29Si, and 27Al MAS NMR as a Tool to Characterize Volcanic Tuffs and Assess Their Suitability for Industrial Applications

Piero Ciccioli†, Paolo Plescia‡ and Donatella Capitani*§

J. Phys. Chem. C, 2010, 114 (20), pp 9328–9343
DOI: 10.1021/jp103082h
Publication Date (Web): April 29, 2010

Abstract: The type and quality of the information provided by the direct analysis of volcanic tuffs by 1H, 29Si, and 27Al NMR were investigated. At this aim, five tuffs, characterized by different origin, bonding mechanism, and clast composition, were used as test materials. Results consistent with the different nature of the tuff matrix and mineral composition were obtained. While the relative content of Al in the crystal and amorphous phase was determined by 27Al MAS and 3Q MAS NMR, the prevalent glassy or zeolitic nature of the matrix was assessed by 29Si and 1H MAS NMR. Zeolites present at levels as low as 15% w/w were detected by 29Si MAS NMR, and in some tuffs, identification of their framework type was performed together with the determination of the Si/Al ratio and, for the first time, of their configurational entropy. Data obtained were coherent with those provided by X-ray fluorescence (XRF), X-ray powder diffraction (XPRD), thermogravimetric analysis (TGA), differential thermal gravimetry (DTG), cation exchange capacity (CEC) determinations, and scanning electron microscopy, used in both backscattering imaging mode (SEM) and for elemental analysis (SEM-EDS). Results show that, under favorable conditions, solid state NMR techniques can provide a comprehensive view of the chemical and physicochemical behavior of a tuff. A combined use of these techniques is suitable for characterization of tuffs on a routine basis, and can be particularly useful to decide if a material is suitable for industrial applications.




The Comparison in Dehydrogenation Properties and Mechanism between MgCl2(NH3)/LiBH4 and MgCl2(NH3)/NaBH4 Systems

L. Gao†, Y. H. Guo†, Q. Li‡ and X. B. Yu*†

J. Phys. Chem. C, 2010, 114 (20), pp 9534–9540
DOI: 10.1021/jp103012t
Publication Date (Web): May 5, 2010

Abstract: The dehydrogenation properties and mechanism of MgCl2(NH3)/MBH4 (here, M is Li or Na) were investigated by thermogravimetric analysis and mass spectrometry, X-ray diffraction (XRD), solid-state 11B NMR, Fourier transform infrared, and differential scanning calorimetry (DSC). As for the MgCl2(NH3)/LiBH4 system, it was found that a new phase, namely, MgCl2(NH3)·LiBH4, to which the following dehydrogenation relates, is formed after ball milling. Judging from the reaction products, it is confirmed that MgCl2 is inclined to work as an ammonia carrier, and the ligand NH3, transferring from MgCl2, is able to combine with the LiBH4 to release H2 with a trace of ammonia at ca. 240 °C. With the increase of LiBH4 content in the mixture, the emission of ammonia was totally suppressed, and Mg(BH4)2 was produced by the decomposition reaction of MgCl2 with the excessive LiBH4 after the ligand NH3 was exhausted, resulting in an improved dehydrogenation in the whole system. As for the MgCl2(NH3)/NaBH4 system, no new phases are detected by XRD after ball milling. The MgCl2 works as a BH4− acceptor, and the ligand NH3 stays with Mg2+ to combine with the BH4−, which transfers from NaBH4 to Mg2+, resulting in a totally different decomposition route and thermal effects as compared with the MgCl2(NH3)/LiBH4 system. DSC results revealed that the decomposition of MgCl2(NH3)/LiBH4 presented an exothermic reaction with an enthalpy of −3.8 kJ mol−1 H2, while the MgCl2(NH3)/NaBH4 showed two apparent endothermic peaks associated with its two-step dehydrogenation with enthalpies of 8.6 and 2.2 kJ mol−1 H2, respectively. Moreover, the MS profiles of the MgCl2(NH3)/2NaBH4, with excessive BH4−, still released a trace of NH3, indicating that the NaBH4 is not so effective in suppressing the emission of NH3 as LiBH4 did.