Fink, Michael F.Michael F.FinkSchönfeld, SophieSophieSchönfeldSchreck, ConstantinConstantinSchreckHörner, GeraldGeraldHörnerWeber, BirgitBirgitWeber2023-08-012023-08-012023-06-23https://publica.fraunhofer.de/handle/publica/44635610.1002/elan.202300154Electrochemistry and its analytics are essential in a variety of scientific and technological fields where properties related to reduction-oxidation reactions, so-called redox properties, are to be explored. While methodological standards for experiments are well established at room temperature, this is still untrue at sub-zero/cryogenic temperatures, the conditions required for the survey of (ultra-)rapid processes and their intermediates. Problems due to "hand-waving" temperature regulation/conditioning and common usage of pseudo-reference electrodes renders cryo-electrochemistry a great challenge. Herein, we describe a robust setup for performing reliable cryo-electrochemical experiments down to -80 °C. It combines highly stable but flexible temperature conditioning with gas-tight sealing of the electrochemical cell setup. Modification of a commercial palladium hydride reference electrode (PdH RE) allows for rapid temperature cycling under cryogenic conditions in aprotic organic solvents. Validation of the setup with the well-known Ferrocene|Ferrocenium (Fc|Fc+) redox couple gave good compliance with literature data at room temperature in a range of organic solvent-based electrolytes. Evaluation of temperature-dependent diffusion kinetic parameters, such as diffusion coefficients (D) and diffusional activation energies (Ea,D) from CVs at multiple potential scan-rates and temperature levels emphasize the reliability of the presented cryo-electrochemical setup.encryo-electrochemistrydiffusion coefficientdiffusional activation energyFerrocene1journal article