Models of Electron Transfer at Different Electrode Materials

Abstract

Electron transfer is the most important electrochemical process. In this review, we present elements of various aspects of electron transfer theory from the early work of Marcus and Hush to recent developments. The emphasis is on the role of the electronic, and to a lesser extent the geometrical, properties of the electrode. A variety of experimental works are discussed in light of these theoretical concepts. Because the field of electron transfer is so vast, this review is far from comprehensive; rather, we focus on systems that offer a special interest and illuminate aspects of the theory.

Solvation–Reduction Coupling in Ca2+ Electroactivity in Glyme‐Based Electrolytes: A First Principles Study

“…[50] For some cations such as Zn 2+ , the reduction reaction can occur while the cation is in the fully solvated state. [51,52] On the other hand, a partial desolvation and an adsorption on the electrode surface is required for the reduction to occur, as for Fe 2+ . [51] Nevertheless, the proposed concept was derived from a rigorous theoretical approach by considering the simplified electrodeelectrolyte interface and the surface electron transfer process.…”

Ice‐Templating: Integrative Ice Frozen Assembly to Tailor Pore Morphology of Energy Storage and Conversion Devices

“…[70,[97][98][99][100] The geometric characteristics of porous materials play a significant role in demonstrating both outstanding electrochemical performance and excellent structural stability in terms of the specific surface area, the pore volume, and the pore size distribution. [11,44,101] For exerting the synergistic effect of monomer materials on the stabilization of electrochemical performance, it is necessary to develop an assembling method for the as-designed functional nanomaterials that enables the morphology and dimension of the hierarchical architecture to be precisely controlled for optimizing charge transfer, ion/mass transport. Integrative ice frozen assembly is considered a highly efficient technology to control the inner microstructure and outer macromorphology, which is favorable for preparing porous materials with high energy density, high power density, and strong tolerance (Table 1).…”

Anomalous Interfacial Electron-Transfer Kinetics in Twisted Trilayer Graphene Caused by Layer-Specific Localization

“…Electron-transfer (ET) reactions at electrode–electrolyte interfaces are fundamental to electrochemical energy conversion. − The collective of microscopic theories and models for interfacial ET, inclucing the Marcus–Gerischer formalism, − the so-called Marcus–Hush–Chidsey (MHC) model, , and the density of states (DOS)–incorporated MHC (MHC–DOS) model, highlight the importance of the electronic structure of an electrode on heterogeneous electrochemical rates. These frameworks motivate the discovery of new approaches to manipulate the band structure of electrodes as a means of controlling the performance limits of energy conversion and storage devices.…”