In Situ Scanning Probe Microscopy in Electrochemical Interfaces

In situ scanning probe microscopy (SPM) has emerged as a cornerstone technique for unravelling the dynamic structure and reactivity of solid–liquid interfaces under electrochemical control. By integrating atomic-scale imaging with precise potential regulation, methods such as scanning tunnelling microscopy (STM) and atomic force microscopy (AFM) now permit real-time visualisation of adsorbate ordering, surface reconstruction and ion transport at electrode surfaces. These insights are pivotal for advancing technologies in energy conversion and storage, corrosion prevention and sensor development. In situ SPM reveals how electric fields, co-adsorbed ions and solvent molecules orchestrate interfacial processes, enabling a bridge between macroscopic electrochemical measurements and atomistic mechanisms. Recent methodological innovations include high-speed AFM for video-rate imaging of interface dynamics, conductive AFM under potential control to map local currents, and combined electrochemical STM-spectroscopy for simultaneous structural and electronic characterisation.

Research from Nature Portfolio

Recent studies have employed high-speed electrochemical AFM to capture restructuring events on electrocatalyst surfaces during water-splitting reactions. These experiments visualise the nucleation and growth of oxide islands on metal electrodes under anodic bias, elucidating how transient adsorbates steer catalytic activity. Another advance utilises operando STM to follow the reversible ordering of halide ions on noble-metal surfaces, revealing voltage-dependent phase transitions in the double layer. Concurrent mapping of local tunnelling conductance provides a direct measure of electronic perturbations induced by ion adsorption. A further investigation combines electrochemical AFM with force spectroscopy to quantify the mechanical properties of adsorbed layers, demonstrating how potential modulates the stiffness and thickness of self-assembled organic films at electrode interfaces.

In Situ Scanning Probe Microscopy in Electrochemical Interfaces publication trend

The graph below shows the total number of articles in in situ scanning probe microscopy in electrochemical interfaces across all publications each year (not limited to Nature Index journals).

Technical terms

In situ scanning probe microscopy: Techniques that image surfaces at the nanometre or atomic scale while the sample remains in an operational environment, such as an electrolyte under applied potential.

Electrochemical interface: The boundary region between an electrode and an electrolyte where charge transfer, adsorption and electric double-layer formation occur.

Electric double layer: A structured arrangement of charged species and solvent molecules at an electrified interface, composed of the compact (inner) and diffuse (outer) layers.

Potential of zero charge (PZC): The electrode potential at which the net electrical charge on the surface is zero, marking a balance between adsorbed ions and surface charge.

Underpotential deposition (UPD): The electrochemical deposition of a metal monolayer onto a foreign substrate at potentials more positive than its bulk deposition potential.

Operando: A mode of measurement in which the functional properties of a system are monitored under real operating conditions, combining in situ analysis with performance metrics.

References

1. Significant two-step potential-induced surface reconstruction observed on Au(111) in aqueous sulfuric acid. Electrochemistry Communications (2022).
2. Scanning Tunneling Microscopy Examination of Molecules with Fused Thiophene and Pyrrole Groups Adsorbed on the Electrified Au(111) Interface. The Journal of Physical Chemistry C (2024).