Nickel single-atom-catalysts (NiÀ SACs), which are known for their unique catalytic activity, are mainly used in electrocatalytic reactions that focus on high metal loading in carbon support to improve their performance. However, we attempted to modify the Ni species to find new catalytic properties by hypothesizing that functionalized NiÀ SACs can exhibit strong Lewis acidic properties in organic reactions. Herein, a low-temperature saltassisted synthesis of highly Lewis acidic chlorine-bound nickel SAC (ClÀ NiÀ SAC) is established and the synthesized catalyst is applied to the ring-opening reaction of epoxides with alcohol. The obtained ClÀ NiÀ SAC facilitates a fast and efficient ringopening reaction of epoxides with high recyclability. In addition, the highly active ClÀ NiÀ SAC was applied to the continuous flow set-up for sustainable transformation for 24 h, yielding 9.7 g of the desired product. Stereochemical experiments and density functional theory calculations demonstrated the importance of MeOH•••Cl hydrogen bonding, NÀ H•••Ni agostic interaction, and π-stacking in the transition state.
Selective reduction of nitro-containing arenes and heteroarenes was achieved in 5 minutes at room temperature utilizing inexpensive NaBH 4 as a hydrogen source and a newly developed Ni@NÀ C catalyst, obtained via a simple carbon coating process without the need for an external carbon source. A wide variety of nitro derivatives, including pharmaceutical molecules, was successfully reduced to the corresponding amines in yields ranging from 45% to 99% using the Ni@NÀ C catalyst under general batch conditions. The reactivity and selectivity of the nitro reduction were further enhanced by a continuous flow reaction system, especially when a newly designed Y-type column was used, and the Osimertinib intermediate was produced on gram scale after 24 hours without any nickel metal contamination or silica gel chromatography purification.
The Front Cover shows the generation of tailor‐made pores by the electrochemical activation of expanded graphite for a magnesium−organocation hybrid battery. Under the electric field, the organocations expand the graphene layers like drilling vehicles that open the undersea tunnel with sufficient space for the following submarines, which symbolizes the same organocations that freely move to store and release electricity efficiently through the tailor‐made pores that were generated by electrochemical activation. More information can be found in the Research Article type by S. K. Mohanty et al.
Persisting limitations of lithium‐ion batteries (LIBs) in terms of safety, energy and power density, natural resources, and the price call for expeditious research to develop the “beyond Li‐ion” technologies. In this regard, magnesium–organocation hybrid batteries (MOHB) hold the potential to address the above issues associated with LIBs by utilizing abundant and inexpensive elements of magnesium and carbon for the anode and cathode, respectively. Moreover, magnesium metal anode is highly energy‐dense yet less susceptible to the dendrite formation, enabling safer operation compared to lithium metal anodes. In this study, we targeted to increase the capacity and rate capability of porous carbon cathode of MOHB by generating tailor‐made pores, which were provided by the interlayer accommodation of solvated organic cations with controlled sizes during the electrochemical activation of expanded graphite. Our electrochemically activated expanded graphite can be used as an efficient cathode in MOHB with enhanced kinetics, specific capacitance, and cycle life.
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