RESUMEN
Organic functionalization of graphene is successfully performed via 1,3-dipolar cycloaddition of azomethine ylide in the liquid phase. The comparison between 1-methyl-2-pyrrolidinone and N,N-dimethylformamide as dispersant solvents, and between sonication and homogenization as dispersion techniques, proves N,N-dimethylformamide and homogenization as the most effective choice. The functionalization of graphene nanosheets and reduced graphene oxide is confirmed using different techniques. Among them, energy-dispersive X-ray spectroscopy allows to map the pyrrolidine ring of the azomethine ylide on the surface of functionalized graphene, while micro-Raman spectroscopy detects new features arising from the functionalization, which are described in agreement with the power spectrum obtained from ab initio molecular dynamics simulation. Moreover, X-ray photoemission spectroscopy of functionalized graphene allows the quantitative elemental analysis and the estimation of the surface coverage, showing a higher degree of functionalization for reduced graphene oxide. This more reactive behavior originates from the localization of partial charges on its surface due to the presence of oxygen defects, as shown by the simulation of the electrostatic features. Functionalization of graphene using 1,3-dipolar cycloaddition is shown to be a significant step towards the controlled synthesis of graphene-based complex structures and devices at the nanoscale.
RESUMEN
[This corrects the article DOI: 10.1039/D1NA00335F.].
RESUMEN
Every time a chemical reaction occurs, an energy exchange between reactants and the environment takes place, which is defined as the enthalpy of the reaction. During the last few decades, research has resulted in an increasing number of devices at the micro- or nano-scale. Sensors, catalyzers, and energy storage systems are more and more developed as nano-devices which represent the building blocks for commercial "macroscopic" objects. A general method for the direct evaluation of the energy balance of such systems is not available at present. Calorimetry is a powerful tool to investigate energy exchange, but it usually requires macroscopic sample quantities. Here, we report on the development of an original experimental setup able to detect temperature variations as low as 10 mK in a sample of â¼10 ng using a thermometer device having physical dimensions of 5 × 5 mm2. This technique has been utilized to measure the enthalpy release during the adsorption process of H2 on titanium-decorated monolayer graphene. The sensitivity of these thermometers is high enough to detect a hydrogen uptake of â¼10-10 moles, corresponding to â¼0.2 ng, with an enthalpy release of about 23 µJ. The experimental setup allows, in perspective, scalability to even smaller sizes.