High-efficiency palladium/halloysite nanotubes catalyst for toluene catalytic oxidation: Characterization, performance and reaction mechanism

Abstract

In this study, the halloysite treated with nitric acid was designed as a functionalized support material for favoring surface availability and dispersion of nanometric palladium (Pd) nanoparticles. The prepared supported catalysts were characterized by X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), H2 temperature-programmed reduction (H2-TPR), and O2 temperature-programmed desorption (O2-TPD). The catalytic performance and reaction mechanism of toluene oxidation were evaluated and proposed. Scanning and transmission electron microscopy images showed that 4–5 nm diameter Pd nanoparticles were uniformly dispersed on the external and edge surfaces of the A-Hal nanotubes and no obvious aggregations observed. The Pd nanoparticles were mainly present in the zero-valent state. The ratio of metallic Pd to Pd oxide species and adsorbed (Oads) to lattice (Olatt) presented a maximum value of 2.54 and 23.0, respectively, when the Pd loading was 0.5%. The prepared support catalysts exhibited a satisfactory catalytic performance and cycling stability for toluene conversion. Among the analyzed samples, the 0.5% Pd/A-Hal catalyst exhibited the highest catalytic activity for toluene oxidation, stability, and water resistance. Toluene conversions of 50% and 90% were obtained at 167 and 185 °C, respectively. In situ diffuse reflection Fourier transform spectroscopy measurements confirmed the intermediates generated during toluene oxidation and revealed that toluene oxidation occurred via the benzyl alcohol → benzaldehyde → benzoic acid → maleic anhydride reaction pathway over the obtained catalysts. These results were attributed to the high content of metal Pd species, abundant Oads species, and low-temperature reducibility. These results indicate that Hal support catalysts are promising materials for application in environmental protection.