How palladium inhibits CO poisoning during electrocatalytic formic acid oxidation and carbon dioxide reduction

Development of reversible and stable catalysts for the electrochemical reduction of CO2 is of great interest. Here, we elucidate the atomistic details of how a palladium electrocatalyst inhibits CO poisoning during both formic acid oxidation to carbon dioxide and carbon dioxide reduction to formic acid. We compare results obtained with a platinum single-crystal electrode modified with and without a single monolayer of palladium. We combine (high-scan-rate) cyclic voltammetry with density functional theory to explain the absence of CO poisoning on the palladium-modified electrode. We show how the high formate coverage on the palladium-modified electrode protects the surface from poisoning during formic acid oxidation, and how the adsorption of CO precursor dictates the delayed poisoning during CO2 reduction. The nature of the hydrogen adsorbed on the palladium-modified electrode is considerably different from platinum, supporting a model to explain the reversibility of this reaction. Our results help in designing catalysts for which CO poisoning needs to be avoided.

Toward a quantitative theoretical method for infrared and Raman spectroscopic studies on single-crystal electrode/liquid interfaces

An integrated approach for quantitatively predicting the electrochemical-infrared and electrochemical-Raman spectra and STM images of Pt(111)(2 × 2)-3CO adstructures has been developed.

Mechanism of surface reactions and dissolution of fluorite surface in an aqueous electrolyte solution

Environmental contextSolubility and dissolution rates of mineral surfaces depend on both the surface properties of the mineral and the composition of the aqueous solution. We investigated the link between the interfacial reactions and dissolution of a fluorite crystal. The study provides a detailed microscopic picture of the dissolution phenomena at the fluorite surface, and the results have wider application to general mineral dissolution processes taking place in the environment. AbstractDissolutions of the fluorite (111) crystallographic plane and fluorite (CaF2) colloidal particles were studied as a function of pH. The process was examined by measuring the concentration of released fluoride and calcium ions by ion-selective electrodes. Additionally, electrokinetic and inner surface potentials were measured by means of electrophoresis and a fluorite single crystal electrode respectively. The rate of fluorite dissolution was analysed assuming a reaction mechanism with a series of elementary steps, which included the reaction of surface groups with H+ ions, the formation of F− vacancies, the dissociation of surface groups and the release of calcium and fluoride ions into the interfacial region as well as the diffusion of ions from the interfacial region. The proposed reaction mechanism indicates that H+ ions play a necessary role in allowing the dissolution to take place, a concept not possible to confirm by looking at the overall equation of fluorite dissolution. The order of the total reaction with respect to H+ ions was found to be 0.37, which is in good accordance with the value derived from the reaction mechanism (1/3). The experimentally determined rate coefficient of fluorite dissolution was found to be kdis=9×10−6mol2/3dmm−2s−1.

Ordered SiO2 cavity promoted formation of gold single crystal nanoparticles towards an efficient electrocatalytic application

A [111] facet dominated gold single crystal electrode with improved electrocatalytic ability for the oxidation of ethanol and nitrite.