Spectro-electrochemical methods
Electrochemical tip-enhanced Raman scattering nanoscopy EC-TERS is a combination of an electrochemical scanning tunnelling microscope (EC-STM) and a Raman scattering optical platform that simultaneously gathers chemical and electronic information of a solid/liquid interface under reaction conditions Owing to the underlying nearfield optical excitation, the Raman vibrational fingerprint is obtained from a region of interest of a few nm in diameter, thereby providing single-site or even molecule spatial chemical resolution, either at equilibrium potential conditions or while the reaction of interest is proceeding. The Raman chemical fingerprint, spanning a broad energy range that covers vibrational modes of solvent, reagent and interface, can be directly related to the topographic information recorded in parallel with the EC-STM. As such, EC-TERS provides unprecedented nanoscale chemical images that depict solid/liquid interface reactivity on the sub-10 nm scale.
Martín Sabanés, Natalia; Ohto, Tatsuhiko; Andrienko, Denis; Nagata, Yuki; Domke, Katrin F.
Electrochemical TERS Elucidates Potential-Induced Molecular Reorientation of Adenine/Au(111)
In: Angewandte Chemie International Edition, Vol. 56, 2017, Nr. 33, pp. 9796 – 9801
DOI
Martín Sabanés, Natalia; Driessen, Leonie M.A.; Domke, Katrin F.
Versatile Side-Illumination Geometry for Tip-Enhanced Raman Spectroscopy at Solid/Liquid Interfaces
In: Analytical Chemistry, Vol. 88, 2016, Nr. 14, pp. 7108 – 7114
DOI (Open Access)
Broadband coherent anti-Stokes Raman spectro-microscopy b-CARS is a label-free imaging technique in which picosecond laser pulses are combined to simultaneously excite and detect a broad range of molecular vibrations, providing Raman chemical information with 3D sub-micron spatial resolution and tens of millisecond integration time per voxel. A nonlinear analogon of conventional Raman scattering, b-CARS significantly improves imaging speed and sensitivity compared to spontaneous Raman spectroscopy, enabling rapid, label-free and noninvasive chemical mapping of complex samples like biological tissues and materials.
Parekh, Sapun H.; Domke, Katrin F.
Watching Orientational Ordering at the Nanoscale with Coherent AntiāStokes Raman Microscopy
In: Chemistry - A European Journal, Vol. 19, 2013, Nr. 36, pp. 11822 – 11830
DOI
Electrochemical plasmonic break-junction spectroscopy EC-PBJ is a method for studying electron transport at the single-molecule level by mechanically forming and breaking metal-molecule-metal junctions under electrochemical control, often while monitoring plasmonic (optical) properties. This approach enables precise tuning of the molecule-electrode interface and the investigation of phenomena such as quantum interference and redox processes triggered by external electrochemical and/or optical stimuli. EC-PBJ provides direct insights into electron tunneling mechanisms and molecular interactions at solid–liquid (electrified) interfaces in real time. Furthermore, the technique can be coupled with EC-TERS to correlated charge transport behaviour with molecular Raman fingerprints.
Aragonès, Albert C.; Domke, Katrin F.
Nearfield trapping increases lifetime of single-molecule junction by one order of magnitude
In: Cell Reports Physical Science, Vol. 2, 2021, Nr. 4, 100389
DOI (Open Access)
Electrochemical fluorescence microscopy EC-FM combines electrochemical triggers with fluorescence readouts to visualize redox processes in real time. It often uses a fluorogenic or fluorophore-generating pair, where an electrochemical (surface) reaction is coupled to a fluorescence-producing step, enabling imaging of reaction layers, interfaces, or single-molecule events across engineered electrode interfaces. The EC-FM approach provides spatially resolved insight into reaction pathways, kinetics, and heterogeneity at interfaces that are difficult to capture with bulk electrochemistry alone.
Electrochemical scanning tunnelling microscopy EC-STM is an imaging technique that enables high-resolution, real-time observation of electrode surfaces and electrochemical processes at the atomic level in a liquid environment. By independently controlling the potentials of both the sample and the tip against a reference electrode, EC-STM can precisely visualize the effects of reactions and adsorbates at the solid-liquid interface during electrochemical experiments. This capability makes EC-STM crucial for understanding surface structure, dynamics, and interfacial phenomena in fields such as nanotechnology, surface science, and electrochemistry.