RESUMEN

Nano-confined spaces in nanoporous materials enable anomalous physicochemical phenomena. While most nanoporous materials including metal-organic frameworks are mechanically hard, graphene-based nanoporous materials possess significant elasticity and behave as nanosponges that enable the force-driven liquid-gas phase transition of guest molecules. In this work, we demonstrate force-driven liquid-gas phase transition mediated by nanosponges, which may be suitable in high-efficiency heat management. Compression and free-expansion of the nanosponge afford cooling upon evaporation and heating upon condensation, respectively, which are opposite to the force-driven solid-solid phase transition in shape-memory metals. The present mechanism can be applied to green refrigerants such as H2O and alcohols, and the available latent heat is at least as high as 192 kJ kg-1. Cooling systems using such nanosponges can potentially achieve high coefficients of performance by decreasing the Young's modulus of the nanosponge.

RESUMEN

The development of hydrogen-based energy sources as viable alternatives to fossil-fuel technologies has revolutionized clean energy production using fuel cells. However, to date, the slow rate of the hydrogen oxidation reaction (HOR) in alkaline environments has hindered advances in alkaline fuel cell systems. Here, we address this by studying the trends in the activity of the HOR in alkaline environments. We demonstrate that it can be enhanced more than fivefold compared to state-of-the-art platinum catalysts. The maximum activity is found for materials (Ir and Pt0.1Ru0.9) with an optimal balance between the active sites that are required for the adsorption/dissociation of H2 and for the adsorption of hydroxyl species (OHad). We propose that the more oxophilic sites on Ir (defects) and PtRu material (Ru atoms) electrodes facilitate the adsorption of OHad species. Those then react with the hydrogen intermediates (Had) that are adsorbed on more noble surface sites.

Asunto(s)

Conservación de los Recursos Energéticos , Fuentes Generadoras de Energía , Hidrógeno/química , Radical Hidroxilo/química , Adsorción , Catálisis , Electroquímica , Electrodos , Oro/química , Iridio/química , Oxidación-Reducción , Platino (Metal)/química , Rutenio/química

RESUMEN

Improving the sluggish kinetics for the electrochemical reduction of water to molecular hydrogen in alkaline environments is one key to reducing the high overpotentials and associated energy losses in water-alkali and chlor-alkali electrolyzers. We found that a controlled arrangement of nanometer-scale Ni(OH)(2) clusters on platinum electrode surfaces manifests a factor of 8 activity increase in catalyzing the hydrogen evolution reaction relative to state-of-the-art metal and metal-oxide catalysts. In a bifunctional effect, the edges of the Ni(OH)(2) clusters promoted the dissociation of water and the production of hydrogen intermediates that then adsorbed on the nearby Pt surfaces and recombined into molecular hydrogen. The generation of these hydrogen intermediates could be further enhanced via Li(+)-induced destabilization of the HO-H bond, resulting in a factor of 10 total increase in activity.