Deganello Giulio, Giannici Francesco, Martorana Antonino, Pantaleo Giuseppe, Prestianni Antonio, Balerna Antonella, Liotta Leonarda F, Longo Alessandro
Dipartimento di Chimica Inorganica e Analitica "Stanislao Cannizzaro", Università di Palermo, viale delle Scienze, I-90128 Palermo, Italy.
J Phys Chem B. 2006 May 4;110(17):8731-9. doi: 10.1021/jp057427i.
The catalyst Pt(1 wt %)/Ce(0.6)Zr(0.4)O(2) is studied by CO-temperature programmed reduction (CO-TPR), isothermal oxygen storage complete capacity (OSCC), X-ray absorption spectroscopy (XAS) at the Pt L(III) edge, and in situ X-ray diffraction (in situ XRD), with the aim of elucidating the role of supported metal in CO oxidation by ceria-based three-way catalysts (TWC). The redox behavior of Pt(1 wt %)/Ce(0.6)Zr(0.4)O(2) is compared to that of bare ceria-zirconia. OSCC of redox-aged Pt/ceria-zirconia is twice that of bare ceria-zirconia, and the maximum of CO consumption occurs at a temperature about 300 K lower than redox-aged ceria-zirconia. XAS analysis allows one to evidence the formation of a platinum-cerium alloy in redox-aged samples and the stability of the metal particles toward oxidation and sintering during high-temperature treatments. Under CO flux at 773 K, bare ceria-zirconia shows a continuous drift of diffraction peaks toward smaller Bragg angles, due to a progressive increase of Ce(III) content. Under the same treatment, the structural rearrangement of Pt-supported ceria-zirconia starts after an induction time and takes place with an abrupt change of the lattice constant. The experimental evidence points to the role of supported Pt in modifying the redox properties of ceria-zirconia with respect to the bare support. It is proposed that the much faster bulk reduction observed by in situ XRD for redox-aged Pt/ceria-zirconia can be attributed to an easier release of reacted CO(2), producing a more effective turnover of reactants at the catalyst surface.
通过一氧化碳程序升温还原(CO-TPR)、等温储氧完全容量(OSCC)、铂L(III)边的X射线吸收光谱(XAS)以及原位X射线衍射(原位XRD)对催化剂Pt(1 wt %)/Ce(0.6)Zr(0.4)O(2)进行了研究,目的是阐明负载型金属在基于二氧化铈的三元催化剂(TWC)催化CO氧化反应中的作用。将Pt(1 wt %)/Ce(0.6)Zr(0.4)O(2)的氧化还原行为与纯二氧化铈-氧化锆的进行了比较。氧化还原老化后的Pt/二氧化铈-氧化锆的OSCC是纯二氧化铈-氧化锆的两倍,并且CO消耗的最大值出现在比氧化还原老化后的二氧化铈-氧化锆低约300 K的温度下。XAS分析表明,在氧化还原老化的样品中形成了铂-铈合金,并且在高温处理过程中金属颗粒对氧化和烧结具有稳定性。在773 K的CO通量下,由于Ce(III)含量的逐渐增加,纯二氧化铈-氧化锆的衍射峰向较小的布拉格角持续漂移。在相同处理下,负载铂的二氧化铈-氧化锆的结构重排在诱导时间后开始,并伴随着晶格常数的突然变化。实验证据表明,负载的Pt相对于纯载体改变了二氧化铈-氧化锆的氧化还原性质。有人提出原位XRD观察到的氧化还原老化后的Pt/二氧化铈-氧化锆更快的体相还原可归因于反应生成的CO(2)更容易释放,从而在催化剂表面产生更有效的反应物周转。