Spatial Precision Tailoring the Catalytic Activity of Graphene Monolayers for Designing Janus Swimmers.

Graphene monolayers have interesting applications in many fields due to their intrinsic physicochemical properties, especially when they can be postmodified with high precision. Herein, we describe the highly site-selective functionalization of freestanding graphene monolayers with platinum (Pt) clusters by bipolar electrochemistry. The deposition of such metal spots leads to catalytically active hybrid two-dimensional (2D) nanomaterials. Their catalytic functionality is illustrated by the spatially controlled decomposition of hydrogen peroxide, inducing motion at the water/air interface due to oxygen bubble evolution. A series of such 2D Janus structures with Pt deposition at predefined positions (corners and edges) is studied with respect to the generation of autonomous motion. The type and speed of motion can be fine-tuned by controlling the deposition time and location of the Pt clusters. These proof-of-principle experiments indicate that this type of hybrid 2D object opens up interesting perspectives in terms of applications, such as environmental detection or remediation.

Wireless Imaging of Transient Redox Activity Based on Bipolar Light-Emitting Electrode Arrays.

Bipolar electrochemistry (BE) is a wireless electrochemical technique, which enables asymmetric electroactivity on the surface of conducting objects. This technique has been extensively studied for different electrochemical applications, including synthesis, separation, sensing, and surface modification. Here, we employ BE for imaging the transient electrochemical activity of different redox species with high accuracy via an array of light-emitting diodes having different lengths. Such a gradient allows the differentiation of redox systems due to their intrinsic difference in thermodynamic potential and the evaluation of their diffusional behavior based on the intensity of light emission. The result is an instantaneous optical readout of analytical information, equivalent to classic electrochemical scanning techniques, such as linear sweep voltammetry.

Wireless electrochemical light emission in ultrathin 2D nanoconfinements.

Spatial confinement of chemical reactions or physical effects may lead to original phenomena and new properties. Here, the generation of electrochemiluminescence (ECL) in confined free-standing 2D spaces, exemplified by surfactant-based air bubbles is reported. For this, the ultrathin walls of the bubbles (typically in the range of 100-700 nm) are chosen as a host where graphene sheets, acting as bipolar ECL-emitting electrodes, are trapped and dispersed. The proposed system demonstrates that the required potential for the generation of ECL is up to three orders of magnitude smaller compared to conventional systems, due to the nanoconfinement of the potential drop. This proof-of-concept study demonstrates the key advantages of a 2D environment, allowing a wireless activation of ECL at rather low potentials, compatible with (bio)analytical systems.