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This study reports an amorphous Zn_xMo₃S₁₃chalcogel, reveals its local structure, and shows outstanding Li/Zn_xMo₃S₁₃electrochemical performance enabled by its amorphous structure, Zn-mediated polysulfide anchoring, and a stable SEI layer. 

Abstract Despite large theoretical energy densities, metal‐sulfide electrodes for energy storage systems face several limitations that impact the practical realization. Here, we present the solution‐processable, room temperature (RT) synthesis, local structures, and application of a sulfur‐rich Mo₃S₁₃chalcogel as a conversion‐based electrode for lithium‐sulfide batteries (LiSBs). The structure of the amorphous Mo₃S₁₃chalcogel is derived throughoperandoRaman spectroscopy, synchrotron X‐ray pair distribution function (PDF), X‐ray absorption near edge structure (XANES), and extended X‐ray absorption fine structure (EXAFS) analysis, along with ab initio molecular dynamics (AIMD) simulations. A key feature of the three‐dimensional (3D) network is the connection of Mo₃S₁₃units through S−S bonds. Li/Mo₃S₁₃half‐cells deliver initial capacity of 1013 mAh g⁻¹during the first discharge. After the activation cycles, the capacity stabilizes and maintains 312 mAh g⁻¹at a C/3 rate after 140 cycles, demonstrating sustained performance over subsequent cycling. Such high‐capacity and stability are attributed to the high density of (poly)sulfide bonds and the stable Mo−S coordination in Mo₃S₁₃chalcogel. These findings showcase the potential of Mo₃S₁₃chalcogels as metal‐sulfide electrode materials for LiSBs. 

Covalent bonding interactions determine the energy–momentum (E–k) dispersion (band structure) of solid-state materials. Here, we show that noncovalent interactions can modulate theE–kdispersion near the Fermi level of a low-dimensional nanoscale conductor. We demonstrate that low energy band gaps may be opened in metallic carbon nanotubes through polymer wrapping of the nanotube surface at fixed helical periodicity. Electronic spectral, chiro-optic, potentiometric, electronic device, and work function data corroborate that the magnitude of band gap opening depends on the nature of the polymer electronic structure. Polymer dewrapping reverses the conducting-to-semiconducting phase transition, restoring the native metallic carbon nanotube electronic structure. These results address a long-standing challenge to develop carbon nanotube electronic structures that are not realized through disruption of π conjugation, and establish a roadmap for designing and tuning specialized semiconductors that feature band gaps on the order of a few hundred meV. 

The development of supramolecular tools to modulate the excitonic properties of non-covalent assemblies paves the way to engineer new classes of semicondcuting materials relevant to flexible electronics. While controlling the assembly pathways of organic chromophores enables the formation of J-like and H-like aggregates, strategies to tailor the excitonic properties of pre-assembled aggregates through post-modification are scarce. In the present contribution, we combine supramolecular chemistry with redox chemistry to modulate the excitonic properties and solid-state morphologies of aggregates built from stacks of water-soluble perylene diimide building blocks. The n-doping of initially formed aggregates in an aqueous medium is shown to produce π–anion stacks for which spectroscopic properties unveil a non-negligible degree of electron–electron interactions. Oxidation of the n-doped intermediates produces metastable aggregates where free exciton bandwidths (Ex BW ) increase as a function of time. Kinetic data analysis reveals that the dynamic increase of free exciton bandwidth is associated with the formation of superstructures constructed by means of a nucleation-growth mechanism. By designing different redox-assisted assembly pathways, we highlight that the sacrificial electron donor plays a non-innocent role in regulating the structure–function properties of the final superstructures. Furthermore, supramolecular architectures formed via a nucleation-growth mechanism evolve into ribbon-like and fiber-like materials in the solid-state, as characterized by SEM and HRTEM. Through a combination of ground-state electronic absorption spectroscopy, electrochemistry, spectroelectrochemistry, microscopy, and modeling, we show that redox-assisted assembly provides a means to reprogram the structure–function properties of pre-assembled aggregates. 

Abstract Ceria (CeO 2 ) possesses a distinctive redox property due to a reversible conversion to its nonstoichiometric oxide and has been considered as a promising catalyst in the oxidative coupling of methane. Since a heterogeneously catalytic process usually takes place only on the surface of catalysts, it is reasonably expected that the performance of a catalyst, such as CeO 2 , highly relies on its size- and shape-dependent surface structure. We report our recent progress in achieving exclusive crystal facet-terminated CeO 2 nanocrystals using a shape-controlled synthesis protocol in a one-pot colloidal system. We modified a two-phase solvothermal approach to fabricate cubic and truncated octahedral CeO 2 nanocrystals with a size-control. During the two-phase solvothermal process, we propose that the Ce-precursors transfer from the aqueous layer to the interface of the organic phase, promoted by the capping ligands (as known as phase-transfer catalysts), for the oxidation and nucleation, and subsequently form CeO 2 nanocrystals in the organic layer. As different capping ligands favor binding on diverse crystal facets, tuning the composition of the capping ligand with a precise control could generate nanocrystals that are dominated by a single type of facets with a relatively narrow size distribution. 

ABSTRACT We report a facile method to fabricate CuNi nano-octahedra and nanocubes using a colloidal synthesis approach. The CuNi nanocrystals terminated with exclusive crystallographic facets were controlled and achieved by a group of synergetic capping ligands in a hot solution system. Specifically, the growth of {111}-bounded CuNi nano-octahedra is derived by a thermodynamic control, whereas the generation of {100}-terminated CuNi nanocubes is steered by a kinetic capping of chloride. Using a reduction of 4-nitrophenol with sodium borohydride as a model reaction, CuNi nano-octahedra and nanocubes demonstrated a strong facet-dependence due to their different surface energies although both exhibited remarkable catalytic activity with the high rate constant over mass (k/m). A kinetic study indicated that this is a pseudo first-order reaction with an excess of sodium borohydride. CuNi nanocubes as the catalysts showed better catalytic performance (k/m = 385 s -1 •g -1 ) than the CuNi nano-octahedra (k/m = 120 s -1 •g -1 ), indicating that 4-nitrophenol and hydrogen were adsorbed on the {100} facets with their molecules parallel to the surface much easier than those on {111} facets.