Energetics and Kinetics of Hydrogen Electrosorption on a Graphene-Covered Pt(111) Electrode.

The Angstrom-scale space between graphene and its substrate provides an attractive playground for scientific exploration and can lead to breakthrough applications. Here, we report the energetics and kinetics of hydrogen electrosorption on a graphene-covered Pt(111) electrode using electrochemical experiments, in situ spectroscopy, and density functional theory calculations. The graphene overlayer influences the hydrogen adsorption on Pt(111) by shielding the ions from the interface and weakening the Pt-H bond energy. Analysis of the proton permeation resistance with controlled graphene defect density proves that the domain boundary defects and point defects are the pathways for proton permeation in the graphene layer, in agreement with density functional theory (DFT) calculations of the lowest energy proton permeation pathways. Although graphene blocks the interaction of anions with the Pt(111) surfaces, anions do adsorb near the defects: the rate constant for hydrogen permeation is sensitively dependent on anion identity and concentration.

Predoped Oxygenated Defects Activate Nitrogen-Doped Graphene for the Oxygen Reduction Reaction.

The presence of defects and chemical dopants in metal-free carbon materials plays an important role in the electrocatalysis of the oxygen reduction reaction (ORR). The precise control and design of defects and dopants in carbon electrodes will allow the fundamental understanding of activity-structure correlations for tailoring catalytic performance of carbon-based, most particularly graphene-based, electrode materials. Herein, we adopted monolayer graphene - a model carbon-based electrode - for systematical introduction of nitrogen and oxygen dopants, together with vacancy defects, and studied their roles in catalyzing ORR. Compared to pristine graphene, nitrogen doping exhibited a limited effect on ORR activity. In contrast, nitrogen doping in graphene predoped with vacancy defects or oxygen enhanced the activities at 0.4 V vs the reversible hydrogen electrode (RHE) by 1.2 and 2.0 times, respectively. The optimal activity was achieved for nitrogen doping in graphene functionalized with oxygenated defects, 12.8 times more than nitrogen-doped and 7.7 times more than pristine graphene. More importantly, oxygenated defects are highly related to the 4e- pathway instead of nitrogen dopants. This work indicates a non-negligible contribution of oxygen and especially oxygenated vacancy defects for the catalytic activity of nitrogen-doped graphene.

Contactless Spin Switch Sensing by Chemo-Electric Gating of Graphene.

Direct electrical probing of molecular materials is often impaired by their insulating nature. Here, graphene is interfaced with single crystals of a molecular spin crossover complex, [Fe(bapbpy)(NCS)2 ], to electrically detect phase transitions in the molecular crystal through the variation of graphene resistance. Contactless sensing is achieved by separating the crystal from graphene with an insulating polymer spacer. Next to mechanical effects, which influence the conductivity of the graphene sheet but can be minimized by using a thicker spacer, a Dirac point shift in graphene is observed experimentally upon spin crossover. As confirmed by computational modeling, this Dirac point shift is due to the phase-dependent electrostatic potential generated by the crystal inside the graphene sheet. This effect, named as chemo-electric gating, suggests that molecular materials may serve as substrates for designing graphene-based electronic devices. Chemo-electric gating, thus, opens up new possibilities to electrically probe chemical and physical processes in molecular materials in a contactless fashion, from a large distance, which can enhance their use in technological applications, for example, as sensors.