A new anode material TiNb2O7 was synthesized by a sol−gel method. TiNb2O7 and its derivates display exciting performances at 1.3−1.6 V versus Li+/Li0, which is fully reversible and capable of fast charge and discharge rates.
In this work, we present a synthesis approach for nitrogen-doped graphene-sheet-like nanostructures via the graphitization of a heteroatom polymer, in particular, polyaniline, under the catalysis of a cobalt species using multiwalled carbon nanotubes (MWNTs) as a supporting template. The graphene-rich composite catalysts (Co-N-MWNTs) exhibit substantially improved activity for oxygen reduction in nonaqueous lithium-ion electrolyte as compared to those of currently used carbon blacks and Pt/carbon catalysts, evidenced by both rotating disk electrode and Li-O(2) battery experiments. The synthesis-structure-activity correlations for the graphene nanostructures were explored by tuning their synthetic chemistry (support, nitrogen precursor, heating temperature, and transition metal type and content) to investigate how the resulting morphology and nitrogen-doping functionalities (e.g., pyridinic, pyrrolic, and quaternary) influence the catalyst activity. In particular, an optimal temperature for heat treatment during synthesis is critical to creating a high-surface-area catalyst with favorable nitrogen doping. The sole Co phase, Co(9)S(8), was present in the catalyst but plays a negligible role in ORR. Nevertheless, the addition of Co species in the synthesis is indispensable for achieving high activity, due to its effects on the final catalyst morphology and structure, including surface area, nitrogen doping, and graphene formation. This new route for the preparation of a nitrogen-doped graphene nanocomposite with carbon nanotube offers synthetic control of morphology and nitrogen functionality and shows promise for applications in nonaqueous oxygen reduction electrocatalysis for Li-O(2) battery cathodes.
Structural isomerism of colloidal semiconductor nanocrystals has been largely unexplored. Here, we report one pair of structural isomers identified for colloidal nanocrystals which exhibit thermally-induced reversible transformations behaving like molecular isomerization. The two isomers are CdS magic-size clusters with sharp absorption peaks at 311 and 322 nm. They have identical cluster masses, but slightly different structures. Furthermore, their interconversions follow first-order unimolecular reaction kinetics. We anticipate that such isomeric kinetics are applicable to a variety of small-size functional nanomaterials, and that the methodology developed for our kinetic study will be helpful to investigate and exploit solid–solid transformations in other semiconductor nanocrystals. The findings on structural isomerism should stimulate attention toward advanced design and synthesis of functional nanomaterials enabled by structural transformations.
A facile H O oxidation treatment to tune the properties of metal disulfides for oxygen evolution reaction (OER) activity enhancement is introduced. With this method, the degree of oxidation can be readily controlled and the effect of surface S residues in the resulted metal (oxy)hydroxides for the OER is revealed for the first time. The developed NiFe (oxy)hydroxide catalyst with residual S demonstrates an extraordinarily low OER overpotential of 190 mV at the current density of 10 mA cm after coupling with carbon nanotubes, and outstanding performance in Zn-air battery tests. Theoretical calculation suggests that the surface S residues can significantly reduce the adsorption free energy difference between O* and OH* intermediates on the Fe sites, which should account for the high OER activity of NiFe (oxy)hydroxide catalysts. This work provides significant insight regarding the effect of surface heteroatom residues in OER electrocatalysis and offers a new strategy to design high-performance and cost-efficient OER catalysts.
Among transition metal nitrides, tungsten nitrides possess unique and/or superior chemical, mechanical, and thermal properties. Preparation of these nitrides, however, is challenging because the incorporation of nitrogen into tungsten lattice is thermodynamically unfavorable at atmospheric pressure. To date, most materials in the W−N system are in the form of thin films produced by nonequilibrium processes and are often poorly crystallized, which severely limits their use in diverse technological applications. Here we report synthesis of tungsten nitrides through new approaches involving solid-state ion exchange and nitrogen degassing under pressure. We unveil a number of novel nitrides including hexagonal and rhombohedral W 2 N 3 . The final products are phase-pure and well-crystallized in bulk forms. For hexagonal W 2 N 3 , hexagonal WN, and cubic W 3 N 4 , they exhibit elastic properties rivaling or even exceeding cubic-BN. All four nitrides are prepared at a moderate pressure of 5 GPa, the lowest among high-pressure synthesis of transition metal nitrides, making it practically feasible for massive and industrial-scale production.
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