Electrochemistry in a Cage: How Steps, Defects and Molecular Confinement Drives the Solid–Liquid Interface Reactions

Electrochemistry is usually described through macroscopic observables: current, potential, charge transfer and reaction rates. Yet the elementary events that decide whether an electrode remains stable, reconstructs, corrodes, intercalates ions or activates catalytic pathways often take place in a far less ideal world: atomic steps, defects, nanocavities, molecular cages and buried interfacial regions. In this talk, I will argue that nanoscale physical confinement is not a geometrical detail of the electrode surface, but an active variable of electrochemical processes .

Starting from in situ and operando scanning probe microscopy studies at electrified solid–liquid interfaces, I will discuss how EC-AFM, EC-STM and complementary spectroscopies can reveal local transformations that are invisible to spatially averaged electrochemical measurements. Highly oriented pyrolytic graphite will be presented as a model system where anion intercalation, gas evolution, blister formation and subsurface oxidation challenge the classical picture of uniform and reversible graphite intercalation. The same conceptual framework will then be extended to vicinal metal surfaces and molecularly modified electrodes, where steps and terraces can be used to separate chemical driving forces from physical confinement effects.

The broader message is that the next generation of interface science should move beyond simply “imaging electrochemistry” toward engineering the local boundary conditions under which electrochemistry occurs . By combining nanomicroscopy, spectroscopy and controlled interfacial architecture, solid–liquid interfaces can become laboratories where reactivity, degradation and protection are not only observed, but spatially programmed.

Cookie categories	Purpose of cookie
Essential Cookies	To provide you with the Service you have requested. Without these cookies, Services that you have asked for cannot be provided. For example, essential cookies enable us to remember the items you place in the shopping basket so that you can order products.
Performance Cookies (Audience measurement)	Advertising CoTo analyze the use, performance and design of our Services, detect errors and improve user experience. For example, this type of cookie enables us to understand how often you are using our Services, to recognize that you have visited our websites before and to identify which parts of our Services and which sections of our website are most popular, for example by allowing us to see which pages visitors access most frequently and how much time visitors spend on each page.okies (Behavioral advertising)
Functional Cookies (Content customization)	To deliver a better user experience, and build up customer usage patterns and profiles. For example, this type of cookie ensures that the information displayed when you use our Services (e.g. on your next visit to our website) will match up with your user preferences (such as language preferences, font size or auto-fill options).
Advertising Cookies (Behavioral advertising)	To personalize our website, deliver customized advertisements to you, or contact you directly where you have separately consented to such communications, in a way which is relevant to you and which matches your interests by, for example, using information about products you have browsed or ordered on our website.