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.

Single Crystal Electrochemistry as an In Situ Analytical Characterization Tool

The electrochemical behavior of platinum single crystal surfaces can be taken as a model response for the interpretation of the activity of heterogeneous electrodes. The cyclic voltammogram of a given platinum electrode can be considered a fingerprint characteristic of the distribution of sites on its surface. We start this review by providing some simple mathematical descriptions of the voltammetric response in the presence of adsorption processes. We then describe the voltammogram of platinum basal planes, followed by the response of stepped surfaces. The voltammogram of polycrystalline materials can be understood as a composition of the response of the different basal contributions. Further resolution in the discrimination of different surface sites can be achieved with the aid of surface modification using adatoms such as bismuth or germanium. The application of these ideas is exemplified with the consideration of real catalysts composed of platinum nanoparticles with preferential shapes.

Effects of the Interfacial Structure on the Methanol Oxidation on Platinum Single Crystal Electrodes

Methanol oxidation has been studied on low index platinum single crystal electrodes using methanol solutions with different pH (1–5) in the absence of specific adsorption. The goal is to determine the role of the interfacial structure in the reaction. The comparison between the voltammetric profiles obtained in the presence and absence of methanol indicates that methanol oxidation is only taking place when the surface is partially covered by adsorbed OH. Thus, on the Pt(111) electrode, the onset for the direct oxidation of methanol and the adsorption of OH coincide. In this case, the adsorbed OH species are not a mere spectator, because the obtained results for the reaction order for methanol and the proton concentrations indicate that OH adsorbed species are involved in the reaction mechanism. On the other hand, the dehydrogenation step to yield adsorbed CO on the Pt(100) surface coincides with the onset of OH adsorption on this electrode. It is proposed that adsorbed OH collaborates in the dehydrogenation step during methanol oxidation, facilitating either the adsorption of the methanol in the right configuration or the cleavage of the C—H bond.

Site-specific reactivity of molecules with surface defects—the case of H2 dissociation on Pt

The classic system that describes weakly activated dissociation in heterogeneous catalysis has been explained by two dynamical models that are fundamentally at odds. Whereas one model for hydrogen dissociation on platinum(111) invokes a preequilibrium and diffusion toward defects, the other is based on direct and local reaction. We resolve this dispute by quantifying site-specific reactivity using a curved platinum single-crystal surface. Reactivity is step-type dependent and varies linearly with step density. Only the model that relies on localized dissociation is consistent with our results. Our approach provides absolute, site-specific reaction cross sections.

Method Development for High Temperature In-Situ Neutron Diffraction Measurements of Glass Crystallization on Cooling from Melt

A glass-ceramic borosilicate waste form is being considered for immobilization of waste streams of alkali, alkaline-earth, lanthanide, and transition metals generated by transuranic extraction for reprocessing used nuclear fuel. Waste forms are created by partial crystallization on cooling, primarily of oxyapatite and powellite phases. In-situ neutron diffraction experiments were performed to obtain detailed information about crystallization upon cooling from 1200°C. The combination of high temperatures and reactivity of borosilicate glass with typical containers used in neutron experiments, such as vanadium and niobium, prevented their use here. Therefore, methods using sealed thick-walled silica ampoules were developed for the in-situ studies. Unexpectedly, high neutron absorption, low crystal fraction, and high silica container background made quantification difficult for these high temperature measurements. As a follow-up, proof-of-concept measurements were performed on different potential high-temperature container materials, emphasizing crystalline materials so that residual glass in the waste form sample could be more easily analyzed. Room temperature measurements were conducted with a pre-crystallized sample in ‘ideal’ containers stable at low temperatures (i.e., vanadium and thin-wall silica capillaries) and compared to the same measurements in containers stable at high temperatures (i.e, platinum, single crystal sapphire, and thick-walled silica ampoules). Results suggested that Pt is probably the best choice if suitably sealed to prevent contamination from the sample after neutron activation.