Electrocatalytic Methane Functionalization with d Early Transition Metals Under Ambient Conditions.

The undesirable loss of methane (CH ) at remote locations welcomes approaches that ambiently functionalize CH on-site without intense infrastructure investment. Recently, we found that electrochemical oxidation of vanadium(V)-oxo with bisulfate ligand leads to CH activation at ambient conditions. The key question is whether such an observation is a one-off coincidence or a general strategy for electrocatalyst design.

When Fluxionality Beats Size Selection: Acceleration of Ostwald Ripening of Sub-Nano Clusters.

Size selection was demonstrated to suppress Ostwald ripening of supported catalytic nanoparticles. When the supported clusters are subnanometer in size and highly fluxional, such as Pt clusters on the rutile TiO (110) surface, this paradigm breaks down, and the established theory of sintering needs a revision. At temperatures characteristic of catalysis (i.

Ensembles of Metastable States Govern Heterogeneous Catalysis on Dynamic Interfaces.

Heterogeneous catalysis is at the heart of the chemical industry. Being able to tune and design efficient catalysts for processes of interest is of the utmost importance, and for this, a molecular-level understanding of heterogeneous catalysts is the first step and indeed a prime focus of modern catalysis research. For a long time, the single most thermodynamically stable structure of the catalytic interface attained under the reaction conditions had been envisioned as the reactive phase.

Sn-modification of Pt/alumina model catalysts: Suppression of carbon deposition and enhanced thermal stability.

An atomic layer deposition process is used to modify size-selected Pt/alumina model catalysts by Sn addition, both before and after Pt cluster deposition. Surface science methods are used to probe the effects of Sn-modification on the electronic properties, reactivity, and morphology of the clusters. Sn addition, either before or after cluster deposition, is found to strongly affect the binding properties of a model alkene, ethylene, changing the number and type of binding sites, and suppressing decomposition leading to carbon deposition and poisoning of the catalyst.

Dynamics of Subnanometer Pt Clusters Can Break the Scaling Relationships in Catalysis.

Scaling relationships in catalysis impose fundamental limitations on the catalyst maximal performance; therefore, there is a continuous hunt for ways of circumventing them. We show that, at the subnano-scale, scaling relationships can be broken through catalyst dynamics. Oxygen reduction reaction (ORR), which can be catalyzed by Pt nanoparticles, is used as our study case.

Hydroxyl-functionalized 1-(2-hydroxyethyl)-3-methyl imidazolium ionic liquids: thermodynamic and structural properties using molecular dynamics simulations and ab initio calculations.

The influences of hydroxyl functional group (-OH) on the thermodynamic and structural properties of ionic liquids (ILs) composed of 1-(2-Hydroxyethyl)-3-methyl imidazolium ([C2OHmim](+)) cation and the six different conventional anions, including [Cl](-), [NO3](-), [BF4](-), [PF6](-), [TfO](-), and [Tf2N](-) have been extensively investigated using classical molecular dynamics (MD) simulations combined with ab initio calculations over a wide range of temperature (298-550 K). The volumetric thermodynamic properties, enthalpy of vaporization, cohesive energy density, Hildebrand solubility parameter, and heat capacity at constant pressure were estimated at desired temperature. The simulated densities were in good agreement with the experimental data with a slight overestimation.