In situ electrochemical pH modulation for the development of electroanalytical tools

The performance of an analytical method is strongly influenced by the nature of the sample considered and its possible fluctuations in its physicochemical properties. In situ pH control is a means of maintaining optimum detection conditions, particularly in the case of electrochemical analyses. We highlight emerging approaches regarding in situ electrochemical pH modulation strategies, from water splitting to proton-pumping systems, implemented across different spatial scales. Particular emphasis is placed on designs and strategies, such as enhanced local control enabled by interdigitated electrode arrays and microdroplet platforms. We discuss miniaturized and flow-based systems, how they work in the presence of interfering agents, and the growing integration of complementary detection modes ( e.g. optodes, electrochemical sensors, generator/collector modes). This review outlines the evolving environment of in situ pH control for future analytical technologies.