Sabatier's principle suggests, that for hydrogen evolution a plot of the rate constant versus adsorption energy should result in volcano, and several such plots have been presented literature. A thorough examination data shows, there is no volcano once oxide-covered metals are left out. We examine factors govern reaction light our own theory conclude, only one determine rate. With exception nickel cobalt, does not decrease highly exothermic as predicted, because passes through more suitable...

Abstract The transfer coefficient α is a quantity that commonly employed in the kinetic investigation of electrode processes. In 3 rd edition IUPAC Green Book, cathodic c defined as –( RT / nF )( d ln k /d E ), where electroreduction rate constant, applied potential, and R, T , F have their usual significance. This definition equivalent to other, -( ln| j |/d current density corrected for any changes reactant concentration at surface with respect its bulk value. anodic similarly, by simply...

Density functional theory (DFT) by itself is insufficient to model electrochemical reactions, because the interface too large, and there no satisfactory way incorporate electrode potential. In our group we have developed a of electrocatalysis, which combines DFT with for electron transfer, thereby avoids these difficulties. Our explains how metal d band situated near Fermi level can lower energy activation charge transfer reaction. An explicit application hydrogen evolution reaction gives...

We show how a theory for electrocatalysis developed in our group can be combined with density-functional order to obtain free-energy surfaces electrochemical reactions. The is applied the first step hydrogen evolution reaction, which proton transfer from an electrolyte solution metal electrode. Explicit calculations have been performed five metals: Pt, Au, Ag, Cu, and Cd. In accord experimental findings we find high activation energy Cd, medium values coin metals, on Pt occurs little...

Present theories of the capacity metal-electrolyte interface are discussed with particular emphasis on contribution metal. A unified treatment is presented in which potential distribution calculated from nonlocal electrostatics. Two models treated detail: In first model boundary between metal and electrolyte considered as sharp; it shown that such a difficult to reconcile experimental data. The second allows for spill-over electrons into solvent. Rough estimates show this type more line results.

Abstract The transfer coefficient α is a quantity that commonly employed in the kinetic investigation of electrode processes. An unambiguous definition coefficient, independent any mechanistic consideration and exclusively based on experimental data, proposed. cathodic c defined as –( RT / F )(dln| j |/d E ), where current density corrected for changes reactant concentration surface with respect to its bulk value, applied electric potential, R, T , have their usual significance. anodic...

The two faces of gold: reduction oxygen on gold electrodes in alkaline solutions has been investigated theoretically. most favorable reaction leads directly to adsorbed O2−, but the activation energy for a two-step pathway, which first step is an outer-sphere electron transfer give solvated only slightly higher. d-band catalysis, dominates acid media, plays no role. reason why slow media also explained.

A model for the metal/liquid electrolyte interphase is presented, in which metal modelled as jellium, an ensemble of hard spheres. An expression derived interfacial capacity at potential zero charge. Numerical calculations are performed various metal/solvent systems. The gives good results second and third row sp metals, temperature dependence Hg/water interface.

We compare the adsorption energies calculated by Nørskov et al. with data derived from experimental values; except for Ni and Co, which absorb hydrogen strongly, there is a linear relation. discuss model proposed these authors in light of extensive previous work find it overly simplistic.

Abstract The kinetic parameters of the outer sphere redox couple [Ru(NH 3 ) 6 ] 2+/3+ were measured on six different metal electrodes. reaction rate is independent substrate. significance these results for electron transfer theory discussed, and a new model adiabatic reactions outlined.

Abstract Much theoretical effort has been spent on the causes of dendrite formation in lithium metal batteries, but a decisive factor overlooked: Lithium is deposited an electrode which carries sizable negative charge, and this charge not distributed homogeneously surface. We show by explicit model calculations that excess accumulates small protrusions creates strong electric field, attracts Li + ions induces further growth tip finally dendrites. Even consisting few atoms will carry tenth...