The interaction of ultrathin single-crystalline IrO 2 (110) films with the gas phase proceeds via the coordinatively unsaturated sites (cus), in particular Ir cus , the undercoordinated oxygen species on-top O (O ot ) that are coordinated to Ir cus , and bridging O (O br ). With the combination of different experimental techniques, such as thermal desorption spectroscopy, scanning tunneling microscopy (STM), high-resolution core-level spectroscopy (HRCLS), infrared spectroscopy, and first-principles studies employing density functional theory calculations, we are able to elucidate surface properties of single-crystalline IrO 2 (110). We provide spectroscopic fingerprints of the active surface sites of IrO 2 (110). The freshly prepared IrO 2 (110) surface is virtually inactive toward gas-phase molecules. The IrO 2 (110) surface needs to be activated by annealing to 500−600 K under ultrahigh vacuum (UHV) conditions. In the activation step, Ir cus sites are liberated from on-top oxygen (O ot ) and monoatomic Ir metal islands are formed on the surface, leading to the formation of a bifunctional model catalyst. Vacant Ir cus sites of IrO 2 (110) allow for strong interaction and accommodation of molecules from the gas phase. For instance, CO can adsorb atop on Ir cus and water forms a strongly bound water layer on the activated IrO 2 (110) surface. Single-crystalline IrO 2 (110) is thermally not very stable although chemically stable. Chemical reduction of IrO 2 (110) by extensive CO exposure at 473 K is not observed, which is in contrast to the prototypical RuO 2 (110) system.

We have developed a microscope with a spatial resolution of 5 μm, which can be used to image the two-dimensional surface optical reflectance (2D-SOR) of polycrystalline samples in operando conditions. Within the field of surface science, operando tools that give information about the surface structure or chemistry of a sample under realistic experimental conditions have proven to be very valuable to understand the intrinsic reaction mechanisms in thermal catalysis, electrocatalysis, and corrosion science. To study heterogeneous surfaces in situ , the experimental technique must both have spatial resolution and be able to probe through gas or electrolyte. Traditional electron-based surface science techniques are difficult to use under high gas pressure conditions or in an electrolyte due to the short mean free path of electrons. Since it uses visible light, SOR can easily be used under high gas pressure conditions and in the presence of an electrolyte. In this work, we use SOR in combination with a light microscope to gain information about the surface under realistic experimental conditions. We demonstrate this by studying the different grains of three polycrystalline samples: Pd during CO oxidation, Au in electrocatalysis, and duplex stainless steel in corrosion. Optical light-based techniques such as SOR could prove to be a good alternative or addition to more complicated techniques in improving our understanding of complex polycrystalline surfaces with operando measurements.

We have developed an electrochemical cell for in situ 2-Dimensional Surface Optical Reflectance (2D-SOR) studies during anodization and cyclic voltammetry. The 2D-SOR signal was recorded from electrodes made of polycrystalline Al, Au(111), and Pt(100) single crystals. The changes can be followed at a video rate acquisition frequency of 200 Hz and demonstrate a strong contrast between oxidizing and reducing conditions. Good correlation between the 2D-SOR signal and the anodization conditions or the cyclic voltammetry current is also observed. The power of this approach is discussed, with a focus on applications in various fields of electrochemistry. The combination of 2D-SOR with other techniques, as well as its spatial resolution and sensitivity, has also been discussed.

We have combined three techniques, High Energy Surface X-Ray Diffraction (HESXRD), Surface Optical Reflectance, and Planar Laser Induced Fluorescence in an operando study of CO oxidation over a Pd(100) catalyst. We show that these techniques provide useful new insights such as the ability to verify that the finite region being probed by techniques such as HESXRD is representative of the sample surface as a whole. The combination is also suitable to determine when changes in gas composition or surface structure and/or morphology occur and to subsequently correlate them with high temporal resolution. In the study, we confirm previous results which show that the Pd(100) surface reaches high activity before an oxide can be detected. Furthermore, we show that the single crystal catalyst surface does not behave homogeneously, which we attribute to the surface being exposed to inhomogeneous gas conditions in mass transfer limited scenarios.

The catalytic oxidation of CO on transition metals, such as Pt, is commonly viewed as asharp transition from the CO-inhibited surface to the active metal, covered with O. However,w ef ind that minor amounts of Oa re present in the CO-poisoned layer that explain why,surprisingly,COdesorbs at stepped and flat Pt crystal planes at once,r egardless of the reaction conditions.Using near-ambient pressure X-ray photoemission and ac urved Pt(111) crystal we probe the chemical composition at surfaces with variable step density during the CO oxidation reaction. Analysis of Cand Ocore levels across the curved crystal reveals that, right before light-off,subsurface Ob uilds up within (111) terraces.T his is key to trigger the simultaneous ignition of the catalytic reaction at different Pt surfaces:aCO-Pt-O complex is formed that equals the CO chemisorption energy at terraces and steps,l eading to the abrupt desorption of poisoning CO from all crystal facets at the same temperature.