Graphene electrodes and deep eutectic solvents (DESs) are two emerging material systems that have individually shown highly promising properties in electrochemical applications. To date, however, it has not been tested whether the combination of graphene and DESs can yield synergistic effects in electrochemistry. We therefore study the electrochemical behavior of a defined graphene monolayer of centimeter-scale, which was produced by chemical vapor deposition and transferred onto insulating SiO 2 /Si supports, in the common DES choline chloride/ethylene glycol (12CE) under typical electrochemical conditions. We measure the graphene potential window in 12CE and estimate the apparent electron transfer kinetics of an outer-sphere redox couple. We further explore the applicability of the 12CE electrolyte to fabricate nanostructured metal (Zn) and metalloid (Ge) hybrids with graphene by electrodeposition. By comparing our graphene electrodes with common bulk glassy carbon electrodes, a key finding we make is that the two-dimensional nature of the graphene electrodes has a clear impact on DES-based electrochemistry. Thereby, we provide a first framework toward rational optimization of graphene–DES systems for electrochemical applications.

A single crystal of SrTiO3 doped with 0.5 wt% niobium (Nb-STO) was irradiated with 200 MeV Au32+ ions at grazing incidence to characterize the irradiation-induced hillock chains. Exactly the same hillock chains are observed by using atomic force microscopy (AFM) and scanning electron microscopy (SEM) to study the relation between irradiation-induced change of surface topography and corresponding material property changes. As expected, multiple hillocks as high as 5-6 nm are imaged by AFM observation in tapping mode. It is also found that the regions in between the adjacent hillocks are not depressed, and in many cases they are slightly elevated. Line-like contrasts along the ion paths are found in both AFM phase images and SEM images, indicating the formation of continuous ion tracks in addition to multiple hillocks. Validity of preexisting models for explaining the hillock chain formation is discussed based on the present results. In order to obtain new insights related to the ion track formation, cross-sectional transmission electron microscopy (TEM) observation was performed. The ion tracks in the near-surface region are found to be relatively large, whereas buried ion tracks in the deeper region are relatively small. The results suggest that recrystallization plays an important role in the formation of small ion tracks in the deep region, whereas formation of large ion tracks in the near-surface region is likely due to the absence of recrystallization. TEM images also show shape deformation of ion tracks in the near-surface region, suggesting that material transport towards the surface is the reason for the absence of recrystallization.

The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/smll.202207263.

We present a direct way to generate hillock-like nanostructures on CaF2(111) ionic crystals by kinetic energy deposition upon Au-cluster irradiation. In the past, the formation of similar nanostructures has been observed for both slow highly charged ions and swift heavy ions. However, in these cases, potential energy deposition of highly charged ions or the electronic energy loss of fast heavy ions, respectively, first leads to strong electronic excitation of the target material before the excitation energy is transferred to the lattice by efficient electron-phonon coupling. We now show that the kinetic energy deposited by slow single Au-clusters directly in the lattice of CaF2(111) leads to the production of nano-hillocks very similar to those found with slow highly charged and swift heavy ions, with heights between 1 and 2 nm. Our results are in good agreement with previous cluster irradiation studies regarding energy deposition and hence nano-structuring of surfaces, and we present Au-cluster irradiation as novel tool to fine-tune nanostructure formation.