Microstructural evolution of nickel nanoparticle catalysts supported on gadolinium-doped ceria during autothermal reforming of iso-octane

Abstract

The microstructure and composition of a nanoparticle Ni catalyst supported on gadolinium-doped ceria (Ce1−xGdxO(4−x)/2) were studied using transmission electron microscopy (TEM), x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS). The support of the fresh catalyst exhibits a homogenous aggregation of crystalline grains, with sizes ranging between 20 nm and 50 nm. The crystalline structure of the fresh catalyst support is of the CeO2 phase, in which gadolinium atoms exist in a solid solution of CeO2. Nickel in the fresh catalyst is highly dispersed and forms granular crystals that are 5–30 nm in size on the surface of the ceria support. The support of the used catalyst exhibits a bimodal distribution of grains in which smaller grains have similar structure and morphology as those in the fresh catalyst, while the larger sized grains appear dull and exhibit nonfaceted crystal morphology resulting either from the sintering of a number of CeO2 grains or by the occupation of highly defective crystals of Ce2O3 and CeO phases. A thin amorphous layer of carbon also covers most of the larger grains in the used catalyst. The Ni particles could not be imaged by TEM in the used catalyst, but energy dispersive x-ray spectroscopy (EDX) detected their presence. The XPS analysis of the catalyst samples suggests the participation of lattice O atoms from the ceria support in the catalytic reaction. The XPS data also show the presence of carbonate species and a higher hydrocarbon concentration in the used catalyst.