Edge-Hydrogenated Germanene by Electrochemical Decalcification-Exfoliation of CaGe₂: Germanene-Enabled Vapor Sensor

Two-dimensional germanene has been recently explored for applications in sensing, catalysis, and energy storage. The potential of this van der Waals material lies in its optoelectronic and chemical properties. However, pure free-standing germanene cannot be found in nature, and the synthesis methods are hindering the potentially fascinating properties of germanene. Herein, we report a single-step synthesis of few-layer germanene by electrochemical exfoliation in a nonaqueous environment. As a result of simultaneous decalcification and intercalation of the electrolyte's active ions, we achieved low-level hydrogenation of germanene that occurs at the edges of the material. The obtained edge-hydrogenated germanene flakes have a lateral size of several micrometers and possess a cubic structure. We have pioneered the potential application of edge-hydrogenated germanene for vapor sensing and demonstrated its specific sensitivity to methanol and ethanol. Furthermore, we have shown a selective behavior of the germanene-based sensor that appears to increase the electrical resistance in the vapors where methanol prevails. We anticipate that these results can provide an approach for emerging layered materials with the potential utility in advanced gas sensing.