Transition‐metal (Fe, Co, Ni) based metal‐organic framework materials with controllable structures, large surface areas and adjustable pore sizes have attracted wide research interest for use in next‐generation electrochemical energy‐storage devices. This review introduces the synthesis of transition‐metal (Fe, Co, Ni) based metal‐organic frameworks and their derivatives with the focus on their application in supercapacitors and batteries.
Taking advantage of the self-assembling function of amino acids, cobaltalanine complexes are synthesized by straightforward process of chemical precipitation. Through a controllable calcination of the cobalt-alanine complexes, N-doped Co 3 O 4 nanostructures (N-Co 3 O 4 ) and N-doped CoO composites with amorphous carbon (N-CoO/C) are obtained. These N-doped cobalt oxide materials with novel porous nanostructures and minimal oxygen vacancies show a high and stable activity for the oxygen evolution reaction. Moreover, the influence of calcination temperature, electrolyte concentration, and electrode substrate to the reaction are compared and analyzed. The results of experiments and density functional theory calculations demonstrate that N-doping promotes the catalytic activity through improving electronic conductivity, increasing OH − adsorption strength, and accelerating reaction kinetics. Using a simple synthetic strategy, N-Co 3 O 4 reserves the structural advantages of micro/nanostructured complexes, showing exciting potential as a catalyst for the oxygen evolution reaction with good stability.
Over the past two decades, metal-organic frameworks (MOFs), a type of porous material, have aroused great interest as precursors or templates for the derivation of metal oxides and composites for the next generation of electrochemical energy storage applications owing to their high specific surface areas, controllable structures, and adjustable pore sizes. The electrode materials, which affect the performance in practical applications, are pivotal components of batteries and supercapacitors. Metal oxide composites derived from metal-organic frameworks possessing high reversible capacity and superior rate and cycle performance are excellent electrode materials. In this Review, potential applications for MOF-derived metal oxide composites for lithium-ion batteries, sodium-ion batteries, lithium-oxygen batteries, and supercapacitors are studied and summarized. Finally, the challenges and opportunities for future research on MOF-derived metal oxide composites are proposed on the basis of academic knowledge from the reported literature as well as from experimental experience.
The cycloparaphenylenes
(CPPs) are a class of strained macrocycles
that until 2008 were considered beyond the reach of organic synthesis.
With its cyclic array of ten para-substituted phenylene
rings, [10]CPP possesses a concave π-system that is perfectly
preorganized for the strong supramolecular association of convex fullerenes
such as C60. Although mechanically interlocked CPP architectures
have been observed in the gas phase, the rational synthesis of bulk
quantities has not been achieved yet, which is likely due to the fact
that conventional template strategies are not amenable to CPP rings
that lack heteroatoms. Here, we report the synthesis of two [2]rotaxanes
in which a [10]CPP ring binds to a central fullerene bis-adduct and
is prevented from dethreading by the presence of two bulky fullerene
hexakis-adduct stoppers. The final step in the rotaxane synthesis
is surprisingly efficient (up to ca. 40% yield) and regioselective
because the fullerene acts as an efficient convex template, while
[10]CPP acts as a supramolecular directing group, steering the reaction
at the central fullerene exclusively toward two trans regioisomers. Comprehensive physicochemical studies confirmed the
interlocked structure, shed light on the dynamic nature of the CPP–fullerene
interaction, and revealed intriguing consequences of the mechanical
bond on charge transfer processes. In light of recent advances in
the synthesis of nanohoops and nanobelts, our concave–convex
π–π templating strategy may be broadly useful and
enable applications in molecular electronics or complex molecular
machinery.
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