Density-Based Descriptors of Redox Reactions Involving Transition Metal Compounds as a Reality-Anchored Framework: A Perspective

Molecules

Daniel Koch¹  Mohamed Chaker¹  Sergei Manzhos²  Manabu Ihara² 

[1] Centre Énergie Matériaux Télécommunications, Institut National de la Recherche Scientifique, 1650 Boulevard Lionel-Boulet, Varennes, QC J3X 1S2, Canada;School of Materials and Chemical Technology, Tokyo Institute of Technology, Ookayama 2-12-1, Meguro-ku, Tokyo 152-8552, Japan;

关键词: oxidation;    transition metal compounds;    density functional theory;    charge self-regulation;    oxygen redox;   

DOI  :  10.3390/molecules26185541

来源: DOAJ

【 摘 要 】

Description of redox reactions is critically important for understanding and rational design of materials for electrochemical technologies, including metal-ion batteries, catalytic surfaces, or redox-flow cells. Most of these technologies utilize redox-active transition metal compounds due to their rich chemistry and their beneficial physical and chemical properties for these types of applications. A century since its introduction, the concept of formal oxidation states (FOS) is still widely used for rationalization of the mechanisms of redox reactions, but there exists a well-documented discrepancy between FOS and the electron density-derived charge states of transition metal ions in their bulk and molecular compounds. We summarize our findings and those of others which suggest that density-driven descriptors are, in certain cases, better suited to characterize the mechanism of redox reactions, especially when anion redox is involved, which is the blind spot of the FOS ansatz.

【 授权许可】

Unknown