RESUMO
Designing highly active and robust earth abundant trifunctional electrocatalysts for energy storage and conversion applications remain an enormous challenge. Herein, we report a trifunctional electrocatalyst (CrCo/CoN4@CNT-5), synthesized at low calcination temperature (550 °C), which consists of Co-N4 single atom and CrCo alloy nanoparticles and exhibits outstanding electrocatalytic performance for the hydrogen evolution reaction, oxygen evolution reaction, and oxygen reduction reaction. The catalyst is able to deliver a current density of 10 mA cm-2 in an alkaline electrolytic cell at a very low cell voltage of â¼1.60 V. When the catalyst is equipped in a liquid rechargeable Zn-air battery, it endowed a high open-circuit voltage with excellent cycling durability and outperformed the commercial Pt/C+IrO2 catalytic system. Furthermore, the Zn-air battery powered self-driven water splitting system is displayed using CrCo/CoN4@CNT-5 as sole trifunctional catalyst, delivering a high H2 evolution rate of 168 µmol h-1. Theoretical calculations reveal synergistic interaction between Co-N4 active sites and CrCo nanoparticles, favoring the Gibbs free energy for H2 evolution. The presence of Cr not only enhances the H2O adsorption and dissociation but also tunes the electronic property of CrCo nanoparticles to provide optimized hydrogen binding capacity to Co-N4 sites, thus giving rise to accelerated H2 evolution kinetics. This work highlights the importance of the presence of small quantity of Cr in enhancing the electrocatalytic activity as well as robustness of single-atom catalyst and suggests the design of the multifunctional robust electrocatalysts for long-term H2 evolution application.
RESUMO
Transition metal chalcogenides (TMCs) are a large family of 2D materials that are currently attracting intense interest. TMCs with 3d transition metals provide opportunities for introducing magnetism and strong correlations into the material with manganese standing out as a particularly attractive option due to its large magnetic moment. Here we report on the successful synthesis of monolayer manganese selenide on a NbSe2 substrate. Using scanning tunneling microscopy and spectroscopy experiments and global structure prediction calculations at the density functional theory level, we identify the atomic structure and magnetic and electronic properties of the layered Mn2Se2 phase. The structure is similar to the layered bulk phase of CuI or a buckled bilayer of h-BN. Interestingly, our results suggest that the monolayer is antiferromagnetic, but with an unusual out-of-plane ordering that results in two ferromagnetic planes.
RESUMO
Doping of materials beyond the dopant solubility limit remains a challenge, especially when spatially nonuniform doping is required. In 2D materials with a high surface-to-volume ratio, such as transition metal dichalcogenides, various post-synthesis approaches to doping have been demonstrated, but full control over spatial distribution of dopants remains a challenge. A post-growth doping of single layers of WSe2 is performed by adding transition metal (TM) atoms in a two-step process, which includes annealing followed by deposition of dopants together with Se or S. The Ti, V, Cr, and Fe impurities at W sites are identified by using transmission electron microscopy and electron energy loss spectroscopy. Remarkably, an extremely high density (6.4-15%) of various types of impurity atoms is achieved. The dopants are revealed to be largely confined within nanostripes embedded in the otherwise pristine WSe2 . Density functional theory calculations show that the dislocations assist the incorporation of the dopant during their climb and give rise to stripes of TM dopant atoms. This work demonstrates a possible spatially controllable doping strategy to achieve the desired local electronic, magnetic, and optical properties in 2D materials.
