Exploring the Adsorption Site Coordination as a Strategy to Tune Copper Catalysts for CO2 Electro-reduction

The electrochemical reduction of CO2 is a promising technology to reach a carbon-neutral economy. However, among other challenges, the design of active and selective catalysts still bottlenecks such advances. Herein,...

Quantitative structure determination of adsorbed formate and surface hydroxyls on Fe3O4(001)

Quantitative determination of the adsorption site of hydroxyl and formate species formed during the adsorption of formic acid on Fe3O4(001).

Atomistic Descriptions of Gas–Surface Interactions on Tin Dioxide

Historically, in gas sensing literature, the focus on “mechanisms” has been on oxygen species chemisorbed (ionosorbed) from the ambient atmosphere, but what these species actually represent and the location of the adsorption site on the surface of the solid are typically not well described. Recent advances in computational modelling and experimental surface science provide insights on the likely mechanism by which oxygen and other species interact with the surface of SnO2, providing insight into future directions for materials design and optimisation. This article reviews the proposed models of adsorption and reaction of oxygen on SnO2, including a summary of conventional evidence for oxygen ionosorption and recent operando spectroscopy studies of the atomistic interactions on the surface. The analysis is extended to include common target and interfering reducing gases, such as CO and H2, cross-interactions with H2O vapour, and NO2 as an example of an oxidising gas. We emphasise the importance of the surface oxygen vacancies as both the preferred adsorption site of many gases and in the self-doping mechanism of SnO2.

Argon Adsorption on Cationic Gold Clusters Aun+ (n ≤ 20)

The interaction of Aun+ (n ≤ 20) clusters with Ar is investigated by combining mass spectrometric experiments and density functional theory calculations. We show that the inert Ar atom forms relatively strong bonds with Aun+. The strength of the bond strongly varies with the cluster size and is governed by a fine interplay between geometry and electronic structure. The chemical bond between Aun+ and Ar involves electron transfer from Ar to Au, and a stronger interaction is found when the Au adsorption site has a higher positive partial charge, which depends on the cluster geometry. Au15+ is a peculiar cluster size, which stands out for its much stronger interaction with Ar than its neighbors, signaled by a higher abundance in mass spectra and a larger Ar adsorption energy. This is shown to be a consequence of a low-coordinated Au adsorption site in Au15+, which possesses a large positive partial charge.

Oxygen adsorption on (100) surfaces in Fe–Cr alloys

The adsorption of oxygen on bcc Fe–Cr(100) surfaces with two different alloy concentrations is studied using ab initio density functional calculations. Atomic-scale analysis of oxygen–surface interactions is indispensable for obtaining a comprehensive understanding of macroscopic surface oxidation processes. Up to two chromium atoms are inserted into the first two surface layers. Atomic geometries, energies and electronic properties are investigated. A hollow site is found to be the preferred adsorption site over bridge and on-top sites. Chromium atoms in the surface and subsurface layers are found to significantly affect the adsorption properties of neighbouring iron atoms. Seventy-one different adsorption geometries are studied, and the corresponding adsorption energies are calculated. Estimates for the main diffusion barriers from the hollow adsorption site are given. Whether the change in the oxygen affinity of iron atoms can be related to the chromium-induced charge transfer between the surface atoms is discussed. The possibility to utilize the presented theoretical results in related experimental research and in developing semiclassical potentials for simulating the oxidation of Fe–Cr alloys is addressed.