The
design and synthesis of hollow-nanostructured transition metal
oxide-based anodes is of great importance for long-term operation
of lithium ion batteries. Herein, we report a two-step calcination
strategy to fabricate hollow Co3O4 nanoparticles
embedded in a N,S-co-doped reduced graphene oxide framework. In the
first step, core–shell-like Co@Co3O4 embedded
in N,S-co-doped reduced graphene oxide is synthesized by pyrolysis
of a Co-based metal organic framework/graphene oxide precursor in
an inert atmosphere at 800 °C. The designed hollow Co3O4 nanoparticles with an average particle size of 25 nm
and wall thickness of about 4–5 nm are formed by a further
calcination process in air at 250 °C via the
nanoscale Kirkendall effect. Both micropores and mesopores are generated
in the HoCo3O4/NS-RGO framework. Benefiting
from the hierarchical porous structure of the hollow Co3O4 and the co-doping of nitrogen and sulfur atoms in reduced
graphene oxide, the thus-assembled battery exhibits a high specific
capacity of 1590 mAh g–1 after 600 charge–discharge
cycles at 1 A g–1 and a promising rate performance
from 0.2 to 10 A g–1.
Rational design and understanding of the intrinsic mechanism are critical to develop highly active and durable electrocatalysts. In this study, a series of bi-metallic boride catalysts based on Ni and Co were prepared, and their activities were evaluated. The synthesised Co-10Ni-B catalyst exhibited excellent activity for water splitting in a 1 M KOH electrolyte. The overpotential was 330 mV at a current density of 10 mA cm-2, better than previously reported mono-metallic borides and even IrO2. The synergistic effect of Co and Ni was proved by X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy. The facile formation of critical intermediates CoOOH and NiOOH during the catalytic processes and a significant increase in surface area owing to the introduction of a second metal into mono-metallic boride were attributed to the superior catalytic performance of catalysts for the oxygen evolution reaction. A Co-10Ni-B-sp catalyst with a higher surface area than the Co-10Ni-B catalyst was also synthesised to evaluate the effect of a high surface area on the catalytic activity. A lower overpotential of 310 mV at a current density of 10 mA cm-2 was achieved.
Porous nitrogen-doped graphene with a very high surface area (1152 m(2) g(-1)) is synthesized by a novel strategy using intrinsically porous biomass (soybean shells) as a carbon and nitrogen source via calcination and KOH activation. To redouble the oxygen reduction reaction (ORR) activity by tuning the doped-nitrogen content and type, ammonia (NH3) is injected during thermal treatment. Interestingly, this biomass-derived graphene catalyst exhibits the unique properties of mesoporosity and high pyridine-nitrogen content, which contribute to the excellent oxygen reduction performance. As a result, the onset and half-wave potentials of the new metal-free non-platinum catalyst reach -0.009 V and -0.202 V (vs. SCE), respectively, which is very close to the catalytic activity of the commercial Pt/C catalyst in alkaline media. Moreover, our catalyst has a higher ORR stability and stronger CO and CH3OH tolerance than Pt/C in alkaline media. Importantly, in acidic media, the catalyst also exhibits good ORR performance and higher ORR stability compared to Pt/C.
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