Tuning the Structure of Platinum Particles on Ceria In†Situ for Enhancing the Catalytic Performance of Exhaust Gas Catalysts.

A dynamic structural behavior of Pt nanoparticles on the ceria surface under reducing/oxidizing conditions was found at moderate temperatures (<500 °C) and exploited to enhance the catalytic activity of Pt/CeO2 -based exhaust gas catalysts. Redispersion of platinum in an oxidizing atmosphere already occurred at 400 °C. A protocol with reducing pulses at 250-400 °C was applied in a subsequent step for controlled Pt-particle formation. Operando X-ray absorption spectroscopy unraveled the different extent of reduction and sintering of Pt particles: The choice of the reductant allowed the tuning of the reduction degree/particle size and thus the catalytic activity (CO>H2 >C3 H6 ). This dynamic nature of Pt on ceria at such low temperatures (250-500 °C) was additionally confirmed by in situ environmental transmission electron microscopy. A general concept is proposed to adjust the noble metal dispersion (size, structure), for example, during operation of an exhaust gas catalyst.

Preparation and electrochemical behavior of PtRu(111) alloy single-crystal surfaces.

The electrochemical behavior of a PtRu(111) single crystal with 1:1 bulk atomic ratio is investigated for the first time by means of cyclic voltammetry and scanning tunneling microscopy (STM). The electrode surfaces are enriched with either Ru or Pt, depending on the cooling conditions after inductive heating. Analysis of the surfaces by STM shows a typical topography with smooth terraces separated by monoatomic high steps. The voltammetric characterization of PtRu(111) in acid media clearly reveals an altered electrochemical behavior of the Pt and Ru surfaces compared to Pt(111) and Ru(0001), respectively. Systematic changes are observed for hydrogen adsorption and underpotential deposition of copper as test reactions. Based on theoretical calculations in the literature, it is experimentally verified that the Pt-rich and the Ru-rich surfaces of the PtRu(111) single-crystal alloy bind adsorbates such as hydrogen significantly weaker and stronger than the pure single-crystal electrode surfaces. Such changes in surface reactivity can be crucial for electrocatalytic reactions.