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Metal−organic frameworks (MOFs) with coordinatively unsaturated (open) metal sites have been intensively investigated in gas separations because their active sites can selectively interact with targeted molecules such as CO 2 . Although such MOFs have shown to exhibit exceptional CO 2 uptake capacity at equilibrium, the dynamic separation behavior is often not satisfactory to be considered in practical applications. Herein, we report a facile and efficient self-sacrifice template strategy based on the nanoscale Kirkendall effect to form novel Co-MOF-74 hollow nanorods enabling adsorption/desorption of gas molecules in a facilitated manner. The time-dependent microscopic and diffraction examinations were performed to elucidate the formation mechanism of Co-MOF-74 hollow nanorods and to obtain insights into the factors critical to maintaining the rodlike morphology. Such nanostructured MOF exhibited much sharper CO 2 molecular separation behavior than conventional MOF bulk crystals under a dynamic flow condition, because of its enhanced adsorption kinetics through the shortened diffusion distance. Such enhanced dynamic molecular separation behavior was further confirmed by chromatographic separations where a significant peak narrowing was demonstrated.

Porous 3D graphene-based hybrid materials (3D GBHMs) are currently attractive nanomaterials employed in the field of energy. Heteroatom-doped 3D graphene and metal, metal oxide, and polymer-decorated 3D graphene with modified electronic and atomic structures provide promising performance as electrode materials in energy storage and conversion. Numerous synthesis methods such as self-assembly, templating, electrochemical deposition, and supercritical CO2, pave the way to mass production of 3D GBHMs in the commercialization of energy devices. This review summarizes recent advances in the fabrication of 3D GBHMs with well-defined architectures such as finely controlled pore sizes, heteroatom doping types and levels. Moreover, current progress toward applications in fuel cells, supercapacitors and batteries employing 3D GBHMs is also highlighted, along with the detailed mechanisms of the enhanced electrochemical performance. Furthermore, current critical issues, challenges and future prospects with respect to applications of 3D GBHMs in practical devices are discussed at the end of this review.

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High-energy lithium/sulfur (Li/S) batteries still suffer from unsatisfactory cycle life and poor rate capability caused by the polysulfides shuttle and insulating nature of S cathodes. Here, we report our findings in the controlled synthesis of selenium (Se)-containing S-rich co-polymers of various compositions as novel cathode materials through a facile inverse vulcanization of S with selenium disulfide (SeS) and 1,3-diisopropenylbenzene (DIB) as co-monomers. Nuclear magnetic resonance and X-ray photoelectron spectroscopy results show that divinyl functional groups of DIB were chemically cross-linked with S/SeS chain radicals through a ring-opening polymerization. The newly formed bonds of C-S, C-Se, and S-Se in novel S-SeS-DIB co-polymers effectively alleviate the shuttle effects of polysulfides/polyselenides. Furthermore, various electrochemical techniques confirm the positive roles of Se-containing co-polymers in enhancing the electrode reaction kinetics and the formation of stable solid electrolyte interphase layer with low charge-transfer resistance, leading to improved high-rate performances. The as-synthesized co-polymer was then infiltrated into well-interconnected, porous nanocarbon networks (Ketjenblack EC600JD, KB600) to provide effective paths for the fast electron transport. Due to the synergistic combination of chemical and physical confinement of the reaction intermediates during cycling, good reversibility for 500 cycles with a low decay rate of 0.0549% per cycle was achieved at 1000 mA g. These encouraging results suggest that the combination of chemical incorporation of SeS into S-rich co-polymer and the physical confinement of carbon networks is a promising strategy for advancing Li/S batteries and their viability for practical applications.