Additive Effects of Rare-Earth Ions in Sodium Aluminoborate Glasses Using ²³Na and ²⁷Al Magic Angle Spinning Nuclear Magnetic Resonance

We conducted structural analysis of xNa2O-yY2O3-5B2O3-3Al2O3 and xNa2O-yLa2O3-5B2O3-3Al2O3 glasses to elucidate the additive effects of rare-earth ions in these sodium aluminoborate glasses, and investigated the local environment surrounding Na+ in them by using 23Na and 27Al magic angle spinning?nuclear magnetic resonance (MAS NMR) spectroscopy. The amount of higher-coordinated Al species ([5]Al and [6]Al) gradually increased in response to an increase in the ratios of Y2O3 to Al2O3 and La2O3 to Al2O3 in each type of glass, respectively. Moreover, the difference in the cation field strength (CFS) between Y3+ and La3+ was observed to affect the generation of [5]Al and [6]Al, especially when the amount of these ions in the glasses increased. In addition to the above, the coordination number of Na+ ions increased with an increase in the number of rare earth ions, confirmed by comparing results with NMR spectra of crystalline Na2Al2B2O7. The latter possibly occurred due to the oxygen concentration on Al[5] and Al[6]. Finally, it was confirmed that the formation of [5]Al and [6]Al decreases molar volume in oxide glasses, which might be partially due to better atomic packing of [5]Al and [6]Al.

Fe doped aluminoborate PKU-1 catalysts for the ketalization of glycerol to solketal: Unveiling the effects of iron composition and boron

An inexpensive Fe doped aluminoborate consisted of 18% Fe in PKU-1 material that exhibits high selectivity of 4-hydroxymethy-2,2-dimethyl^(-1),3-dioxolane (Solketal, 98.3%), considerable activity (TOF 51.7 h-1), and recyclable ability in the ketalization of glycerol to Solketal with acetone at 318 K has been developed. Our study demonstrated that the structure of Fe (less agglomerated iron species vs. FeO clusters) can be tuned by changing Fe loading in the PKU-1 material, which correlated well with experimental observations. Furthermore, the surface boron sites were promoted by iron loading and behaved as Lewis-acid sites to facilitate the reaction process of glycerol ketalization, while the Solketal selectivity was closely related with the structure of iron species in PKU-1, which was proved by kinetic studies, density function theory (DFT) calculations, and a series of spectroscopy studies. This investigation demonstrates that the surface B sites can play important roles in the reaction instead of being spectators.