Heterostructural Mixed Oxides Prepared via ZnAlLa LDH or ex-ZnAl LDH Precursors—Effect of La Content and Its Incorporation Route

The effect of La content and its incorporation route on physicochemical properties of ZnO/Zn(Al,La)2O4 or La2O3–ZnO/ZnAl2O4 mixed oxides with a spinel structure obtained from ZnAlLa Layered double hydroxides (LDHs) or ex-ZnAl LDH materials was investigated. The heterostructural nanocomposites with the similar Zn/Al molar ratio and varied La content were prepared by two techniques: via co-precipitation and thermal treatment of ZnAlLa LDHs at 500 °C or via incipient wetness impregnation of ex-ZnAl LDHs with aqueous solutions of lanthanum nitrate and subsequent thermal treatment. The obtained series of materials were characterized by the following techniques: X-ray fluorescence (XRF), N2 adsorption (BET), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis with evolved gas analysis (TG/DTG/EGA), scanning transmission electron microscopy (STEM) energy-dispersive X-ray spectroscopy (EDS), high-resolution transmission electron microscopy (HRTEM) and Fourier-transform infrared spectroscopy (FFT). The evaluation of activity toward the high-temperature water gas shift (HT-WGS) within the temperature range of 350–420 °C was carried out on the basis of rate constant measurements in the kinetic mode using a differential reactor. The co-precipitation technique allowed for a better distribution of La in bulk and on the spinel surface than in case of lanthanum incorporation via impregnation. ZnO/Zn(Al,La)2O4 or La2O3–ZnO/ZnAl2O4 mixed oxides were characterized by moderate activity in the HT-WGS reaction. The results reveal that introduction of lanthanum oxide over 2.4–2.8 wt% induces the phase separation of the ZnAl2O4 spinel, forming ZnO on the ZnAl2O4 spinel surface.

Study of ZnAl2O4 spinel nanoparticles synthesized using gelatin as organic precursor

In this work, zinc aluminate spinel powders were prepared by a fast, simple, eco-friendly and low-cost modified Pechini method using commercial gelatin as the organic precursor. The materials were calcinated at 600, 700 and 800 °C and characterized by thermogravimetric analysis, in situ and ex situ X-ray diffraction (XRD), N2-adsorption/desorption isotherms and scanning electron microscopy. The results showed that single phase ZnAl2O4 particles with spinel structure were successfully obtained resulting in a high purity, nanometric, homogeneous and mesoporous materials. The in situ XRD results showed that the crystalline spinel structure of ZnAl2O4 started forming at a temperature lower than 600 °C, revealing powders with crystallite size smaller than 40 nm, which increased with increasing the temperature (91% of increase between 600 and 800 °C). The effect of calcination time showed that the materials calcinated at 600 °C for 3 h presented the higher percentage of crystallite growth due to the increase of crystallinity. The ZnAl2O4 samples retained their pore size up to 700 °C.