Some Questionable Approaches in Interfacial Electrochemistry—The Charged State of Adsorbed Species and Their Involvement in Redox Processes

On the basis of a survey on the relevant literature it can be stated that some views and approaches concerning the charged state of adsorbed species and the charge transfer processes occurring with them are far from being unambiguous even in some respect they contradict fundamental physical and physicochemical principles. The meaning of the electrosorption valency, the misleading formulation of the Gibbs adsorption equation, and the interpretation of redox processes occurring with adsorbed species, is discussed in detail. It has been concluded that although the electrosorption valency of an adsorbed species as usually defined is an extra-thermodynamic and self-contradictory concept, experimental determined formal partial charge numbers can be a useful tool for scientists investigating adsorption phenomena, since the observed deviation between its value and the charge number of the same species in the solution phase unequivocally indicates a non-simple mechanism of the adsorption process, which should be taken into account in theoretical interpretation of the experimental data. It has been emphasized that the evaluation of voltammetric curves obtained in the presence of adsorbed redox partners requires a cautious analysis of the accompanying chemical transformations. In the framework of a critical analysis it is demonstrated that probably one of the most important sources of the misinterpretations and misunderstandings is the inadequate approach to the concept of electrode charge. The possibility of a general and straightforward presentation of the Gibbs adsorption equation has also been discussed.

Probing the charged state of layered positive electrodes in sodium-ion batteries: reaction pathways, stability and opportunities

The complex behaviour of layered oxide cathode materials at high voltages currently limits the energy densities which can be achieved by sodium-ion batteries.

Revisiting McGovern-Fraser: Party Nationalization and the Rhetoric of Reform

The Democratic Party faced a crisis of political legitimacy in the late 1960s as distrust and protest permeated its electoral base. In response, the Democratic National Committee established the Commission on Party Structure and Delegate Selection, tasked with restructuring the party’s presidential nomination process. Contrary to the conventional historical narrative of the McGovern-Fraser Commission that has focused on a supposed displacement of the party’s old guard by radical insurgents, this article instead argues that the main impetus for reform came from national party leaders seeking to build up the legitimacy and authority of the National Committee. Commission Chair George McGovern and the DNC used a particular reform rhetoric that charged state parties with the corruption of the political process, necessitating rescue by an empowered national party. This focus on the nationalizing impulses behind McGovern-Fraser serves to shift our attention away from ideological struggles and toward institutional motives.

Effects of native defects and cerium impurity on the monoclinic BiVO4 photocatalyst obtained via PBE+U calculations

Under O-rich conditions, during the substitution of V by Ce in the single negatively charged state (Ce1−V) for m-BiVO4, no localized state is found within the calculated band gap so as to improve photocatalysis.