A Polycrystalline Pd Surface Studied by Two-Dimensional Surface Optical Reflectance during CO Oxidation: Bridging the Materials Gap.

Industrial catalysts are complex materials systems operating in harsh environments. The active parts of the catalysts are nanoparticles that expose different facets with different surface orientations at which the catalytic reactions occur. However, these facets are close to impossible to study in detail under industrially relevant operating conditions. Instead, simpler model systems, such as single crystals with a well-defined surface orientation, have been successfully used to study gas-surface interactions such as adsorption and desorption, surface oxidation, and oxidation/reduction reactions. To more closely mimic the many facets exhibited by nanoparticles and thereby close the so-called materials gap, there has also been a recent move toward using polycrystalline surfaces and curved crystals. However, these studies are limited either by the pressure or spatial resolution at realistic pressures or by the number of surfaces studied simultaneously. In this work, we demonstrate the use of reflectance microscopy to study a vast number of catalytically active surfaces simultaneously under realistic and identical reaction conditions. As a proof of concept, we have conducted an operando experiment to study CO oxidation over a Pd polycrystal, where the polycrystalline surface acts as a collection of many single-crystal surfaces. Finally, we visualized the resulting data by plotting the reflectivity as a function of surface orientation. We think the techniques and visualization methods introduced in this work will be key toward bridging the materials gap in catalysis.

Formation of Epitaxial PdO(100) During the Oxidation of Pd(100).

The catalytic oxidation of CO and CH4 can be strongly influenced by the structures of oxide phases that form on metallic catalysts during reaction. Here, we show that an epitaxial PdO(100) structure forms at temperatures above 600 K during the oxidation of Pd(100) by gaseous O atoms as well as exposure to O2-rich mixtures at millibar partial pressures. The oxidation of Pd(100) by gaseous O atoms preferentially generates an epitaxial, multilayer PdO(101) structure at 500 K, but initiating Pd(100) oxidation above 600 K causes an epitaxial PdO(100) structure to grow concurrently with PdO(101) and produces a thicker and rougher oxide. We present evidence that this change in the oxidation behavior is caused by a temperature-induced change in the stability of small PdO domains that initiate oxidation. Our discovery of the epitaxial PdO(100) structure may be significant for developing relationships among oxide structure, catalytic activity, and reaction conditions for applications of oxidation catalysis.

Effect of Different In2O3(111) Surface Terminations on CO2 Adsorption.

In2O3-based catalysts have shown high activity and selectivity for CO2 hydrogenation to methanol; however, the origin of the high performance of In2O3 is still unclear. To elucidate the initial steps of CO2 hydrogenation over In2O3, we have combined X-ray photoelectron spectroscopy and density functional theory calculations to study the adsorption of CO2 on the In2O3(111) crystalline surface with different terminations, namely, the stoichiometric, reduced, and hydroxylated surface. The combined approach confirms that the reduction of the surface results in the formation of In adatoms and that water dissociates on the surface at room temperature. A comparison of the experimental spectra and the computed core-level shifts (using methanol and formic acid as benchmark molecules) suggests that CO2 adsorbs as a carbonate on all three surface terminations. We find that the adsorption of CO2 is hindered by hydroxyl groups on the hydroxylated surface.

HAT: a high-energy surface X-ray diffraction analysis toolkit.

This work introduces the high-energy surface X-ray diffraction analysis toolkit (HAT), an open-source cross-platform software package written in Python to allow the extraction and processing of high-energy surface X-ray diffraction (HESXRD) data sets. Thousands of large-area detector images are collected in a single HESXRD scan, corresponding to billions of pixels and hence reciprocal space positions. HAT is an optimized reciprocal space binner that implements a graphical user interface to allow the easy and interactive exploration of HESXRD data sets. Regions of reciprocal space can be selected with movable and resizable masks in multiple views and are projected onto different axes to allow the creation of reciprocal space maps and the extraction of crystal truncation rods. Current and future versions of HAT can be downloaded and used free of charge.

Structure Matters: Asymmetric CO Oxidation at Rh Steps with Different Atomic Packing.

Curved crystals are a simple but powerful approach to bridge the gap between single crystal surfaces and nanoparticle catalysts, by allowing a rational assessment of the role of active step sites in gas-surface reactions. Using a curved Rh(111) crystal, here, we investigate the effect of A-type (square geometry) and B-type (triangular geometry) atomic packing of steps on the catalytic CO oxidation on Rh at millibar pressures. Imaging the crystal during reaction ignition with laser-induced CO2 fluorescence demonstrates a two-step process, where B-steps ignite at lower temperature than A-steps. Such fundamental dissimilarity is explained in ambient pressure X-ray photoemission (AP-XPS) experiments, which reveal partial CO desorption and oxygen buildup only at B-steps. AP-XPS also proves that A-B step asymmetries extend to the active stage: at A-steps, low-active O-Rh-O trilayers buildup immediately after ignition, while highly active chemisorbed O is the dominant species on B-type steps. We conclude that B-steps are more efficient than A-steps for the CO oxidation.

Operando Reflectance Microscopy on Polycrystalline Surfaces in Thermal Catalysis, Electrocatalysis, and Corrosion.

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.

Catalytic Oxidation of CO on a Curved Pt(111) Surface: Simultaneous Ignition at All Facets through a Transient CO-O Complex*.

The catalytic oxidation of CO on transition metals, such as Pt, is commonly viewed as a sharp transition from the CO-inhibited surface to the active metal, covered with O. However, we find that minor amounts of O are present in the CO-poisoned layer that explain why, surprisingly, CO desorbs at stepped and flat Pt crystal planes at once, regardless of the reaction conditions. Using near-ambient pressure X-ray photoemission and a curved Pt(111) crystal we probe the chemical composition at surfaces with variable step density during the CO oxidation reaction. Analysis of C and O core levels across the curved crystal reveals that, right before light-off, subsurface O builds up within (111) terraces. This is key to trigger the simultaneous ignition of the catalytic reaction at different Pt surfaces: a CO-Pt-O complex is formed that equals the CO chemisorption energy at terraces and steps, leading to the abrupt desorption of poisoning CO from all crystal facets at the same temperature.

Combining synchrotron light with laser technology in catalysis research.

High-energy surface X-ray diffraction (HESXRD) provides surface structural information with high temporal resolution, facilitating the understanding of the surface dynamics and structure of the active phase of catalytic surfaces. The surface structure detected during the reaction is sensitive to the composition of the gas phase close to the catalyst surface, and the catalytic activity of the sample itself may affect the surface structure, which in turn may complicate the assignment of the active phase. For this reason, planar laser-induced fluorescence (PLIF) and HESXRD have been combined during the oxidation of CO over a Pd(100) crystal. PLIF complements the structural studies with an instantaneous two-dimensional image of the CO2 gas phase in the vicinity of the active model catalyst. Here the combined HESXRD and PLIF operando measurements of CO oxidation over Pd(100) are presented, allowing for an improved assignment of the correlation between sample structure and the CO2 distribution above the sample surface with sub-second time resolution.