Monolithic nanoporous copper （NPC） ribbons with bimodal channel size distributions can be fabricated through chemical dealloying of Mg-32 Cu alloy in an acidic solution at room temperature. The microstructure of the as- dealloyed samples was characterized by X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray analysis. These NPC ribbons are composed of interconnected large-sized channels （hundreds of nm） with highly porous channel walls （tens of nm）. Both large- and small-sized channels are open, bicontinuous, and interpenetrating. Additionally, it is the first time to find that the evolution process of porous structure along the thickness direction of samples during the dealloying is from the interior to exterior, which is just contrary to the coarsening process along the thickness direction during the post-dealloying. Meanwhile, the corresponding mechanism is discussed in detail.
Two shapes of Co_3O_4 nanoarrays(i.e., nanosheets, nanowires) with different densities of exposed catalytic active sites were synthesized through a facile hydrothermal method on Ni foam substrates and tested as the binder/carbon free and free-standing cathodes for Li–O_2 batteries. Particularly, the single crystalline feature of Co_3O_4 nanosheets with a predominant high reactivity {112} exposed crystal plane and hierarchical porous nanostructure displayed better catalytic performance for both oxygen reduction reaction(during discharge process) and oxygen evolution reaction(during charge process). Li–O_2 battery with Co_3O_4 nanosheets cathode exhibited a higher discharge specific capacity(965 m Ah g^(-1)), lower discharge/charge over-potential and better cycling performance over 63 cycles at 100 mA g^(-1) with the specific capacity limited at 300 mAh g^(-1). The superior catalytic performance of Co_3O_4 nanosheets cathode is ascribed to the enlarging specific area and increasing the exposed Co^(3+) catalytic active sites within predominant {112} crystal plane which plays the key role in determining the adsorption energy for the reactants, enabling high round-trip efficiency and cyclic life.
A CO3O4 nanorod supported Pd electro-catalyst for the methanol electro-oxidation （MEO） has been fabricated by the combination of hydrother- mal synthesis and microwave-assisted polyol reduction processes. The crystallographic property and microstructure have been characterized using XRD, SEM and TEM. The results demonstrate that Pd nanoparticles （PdNPs） with a narrow particle size distribution （3-5 nm） are uni- formly deposited onto the surface of Co304 nanorods. Electrochemical measurements show that this catalyst having a larger electrochemically active surface area and a more negative onset-potential exhibits enhanced catalytic activity of 504 mA/mg Pd for MEO comparing with the Pd/C catalyst （448 mA/mg Pd）. The dependency of log/against logv reveals that MEO on Pd-CO304 electrode is under a diffusion control. Electrochemical impedance spectroscopy （EIS） measurement agrees well with the CV results. The minimum charge transfer resistance of MEO on Pd-CO304 is observed at -0.05 V, which coincides with the potential of MEO peak.
Yanbiao RenShichao ZhangHua FangXin WeiPuheng Yang
Pd@Ru bimetallic nanoparticles deposited on carbon black electro-catalysts have been fabricated by microwave-assisted polyol reduction method and investigated for methanol electro-oxidation （MEO）. The structure and electro-catalytic properties of the as-prepared catalysts were characterized by XRD, SEM, TEM and cyclic voltammetry （CV） techniques. The results showed that the introduction of Ru element （2-10 wt%） into Pd 20 wt%/C （hereafter, denoted as Pd/C） produced a series of core-shell structured binary catalysts. Pd@Ru 5 wt%/C （hereafter, denoted as Pd@Rus/C） catalyst displayed the highest catalytic activity towards MEO. And the mass activity of Pd@Ru5/C electrode catalyst at E = -0.038 V （vs. Hg/HgO） was 1.42 times higher than that of Pd/C electrode catalyst. In addition, the relationship between the catalytic stability for MEO on Pd@Ru/C catalysts and the value of dbp/dfp （the ratio of MEO peak current density in the negative scan and positive scan） were also investigated. The result demonstrated that Pd@Rus/C offering the smallest value of Jbp/Jfp displayed the best stable catalytic performance.
