화학공학소재연구정보센터
Applied Catalysis B: Environmental, Vol.188, 154-168, 2016
Gold catalysts supported on Y-modified ceria for CO-free hydrogen production via PROX
The preferential CO oxidation in the presence of excess hydrogen (PROX) was studied over gold catalysts on yttrium-modified ceria supports synthesized by impregnation (IM) and co-precipitation (CP) methods. In order to avoid oxygen vacancies ordering by heavily yttrium doping, a low extent Y-modification of ceria (up to 7.5 wt.% Y2O3, i.e., 11 at.% Y) was investigated. The samples were characterized by XRD, HRTEM/HAADF, Raman and XP spectroscopy and TPR measurements. At the operating temperature of the fuel cells (80-120 degrees C) the selectivity of the Y-doped gold catalysts was larger than that of Au/CeO2. However, at these temperatures all studied catalysts exhibited quite similar PROX activity and selectivity. This was explained by the similarity in relatively small average size of gold particles (estimated by HRTEM in the 2.1-3.5 nm range) and the reducibility of ceria surface layers. Raman spectroscopy showed a higher extent of bulk defects, O vacancies and interstitials with increasing Y-doping in the supports made by the CP method and-based on sequential spectra obtained under oxidizing and reducing conditions-enabled the assignment of a band at similar to 605 cm(-1) to a vibrational mode within the anionic (oxygen) sub-lattice that involve mobile (detachable) oxygen atoms that can be delivered by the support under suitable conditions. The absence of correlation between CO conversion and yttrium loading could suggest a preferential role played by the surface modification and surface oxygen mobility in PROX. Although under ideal conditions there was not substantial dependence of the behavior in PROX on the preparation method of doped supports, the IM method was more appropriate than the CP method for PROX with CO2 and water addition to the gas feed. The improved tolerance to CO2 could be explained by the lowering of ceria surface basicity due to the nanosized Y2O3, covering ceria grains. (C) 2016 Elsevier B.V. All rights reserved.