A mysterious, long-pursued structure of a nanocluster-nanocrystal transition-sized nanoparticle is unraveled.

The high theoretical capacity and low discharge potential of silicon have attracted much attention on Si-based anodes. Herein, hollow porous SiO2 nanocubes have been prepared via a two-step hard-template process and evaluated as electrode materials for lithium-ion batteries. The hollow porous SiO2 nanocubes exhibited a reversible capacity of 919 mAhg−1 over 30 cycles. The reasonable property could be attributed to the unique hollow nanostructure with large volume interior and numerous crevices in the shell, which could accommodate the volume change and alleviate the structural strain during Li ions' insertion and extraction, as well as allow rapid access of Li ions during charge/discharge cycling. It is found that the formation of irreversible or reversible lithium silicates in the anodes determines the capacity of a deep-cycle battery, fast transportation of Li ions in hollow porous SiO2 nanocubes is beneficial to the formation of Li2O and Si, contributing to the high reversible capacity.

Co3O4 nanoparticles have been prepared by a facile strategy, which involves the thermal decomposition of nanoparticles of cobalt-based Prussian blue analogues at different temperatures. The nanoparticles prepared at 450, 550, 650, 750, and 850 °C exhibited a high discharge capacity of 800, 970, 828, 854, and 651 mAhg–1, respectively, after 30 cycles at a current density of 50 mAg–1. The nanocages produced at 550 °C show the highest lithium storage capacity. It is found that the nanocages display nanosize grains, hollow structure, a porous shell, and large specific surface area. At the temperature higher than 650 °C, the samples with larger grains, better crystallinity, and lower specific surface area can be obtained. It is found that the size, crystallinity, and morphology of nanoparticles have different effects on electrochemical performance. Better crystallinity is able to enhance the initial discharge capacity, while porous structure can reduce the irreversible loss. Therefore, the optimal size, crystallinity, and cage morphology are suggested to be responsible for the improved lithium storage capacity of the sample prepared at 550 °C. The as-prepared Co3O4 nanoparticles also have a potential application as anode material for Li-ion batteries due to their simple synthesis method and large capacity.

Herein we report a novel facile strategy for the fabrication of Co(3)O(4) porous nanocages based on the Kirkendall effect, which involves the thermal decomposition of Prussian blue analogue (PBA) Co(3)[Co(CN)(6)](2) truncated nanocubes at 400 °C. Owing to the volume loss and release of internally generated CO(2) and N(x) O(y) in the process of interdiffusion, Co(3)O(4) nanocages with porous shells and containing nanoparticles were finally obtained. When evaluated as electrode materials for lithium-ion batteries, the as-prepared Co(3)O(4) porous nanocages displayed superior battery performance. Most importantly, capacities of up to 1465 mA h g(-1) are attained after 50 cycles at a current density of 300 mA g(-1). Moreover, this simple synthetic strategy is potentially competitive for scaling-up industrial production.

The 18-electron shell closure structure of Au nanoclusters protected by thiol ligands has not been reported until now. Herein, we synthesize a novel nanocluster bearing the same gold atom number but a different thiolate number as another structurally resolved nanocluster Au44(TBBT)28 (TBBTH = 4-tert-butylbenzenelthiol). The new cluster was determined to be Au44(2,4-DMBT)26 (2,4-DMBTH = 2,4-dimethylbenzenethiol) using multiple techniques, including mass spectrometry and single crystal X-ray crystallography (SCXC). Au44(2,4-DMBT)26 represents the first 18-electron closed-shell gold nanocluster. SCXC reveals that the atomic structure of Au44(2,4-DMBT)26 is completely different from that of Au44(TBBT)28 but is similar to the structure of Au38Q. The arrangement of staples (bridging thiolates) and part of the Au29 kernel atom induces the chirality of Au44(2,4-DMBT)26. The finding that a small portion of the gold kernel exhibits chirality is interesting because it has not been previously reported to the best of our knowledge. Although Au44(2,4-DMBT)26 bears an 18-electron shell closure structure, it is less thermostable than Au44(TBBT)28, indicating that multiple factors contribute to the thermostability of gold nanoclusters. Surprisingly, the small difference in Au/thiolate molar ratio between Au44(2,4-DMBT)26 and Au44(TBBT)28 leads to a dramatic distinction in Au 4f X-ray photoelectron spectroscopy, where it is found that the charge state of Au in Au44(2,4-DMBT)26 is remarkably more positive than that in Au44(TBBT)28 and even slightly more positive than the charge states of gold in Au-(2,4-DMBT) or Au-TBBT complexes.

When the self-assembly of block copolymers (BCPs) occurs within a deformable emulsion droplet, BCPs can aggregate into a variety of nanoscaled particles with unique nanostructures and properties since the confinement effect can effectively break the symmetry of a structure.

Precise control over the spatial arrangement of inorganic nanoparticles on a large scale is desirable for the design of functional nanomaterials, sensing, and optical/electronic devices. Although great progress has been recently made in controlling the organization of nanoparticles, there still remains a grand challenge to arrange nanoparticles into highly-ordered arrays over multiple length scales. Here, we report the directed arrangement of inorganic nanoparticles into arrayed structures with long-range order, up to tens of microns, by using hexagonally-packed cylindrical patterns of block copolymer nanosheets self-assembled within collapsed emulsion droplets as scaffolds. This technique can be used to generate nanoparticle arrays with various nanoparticle arrangements, including hexagonal honeycomb structures, periodic nanoring structures, and their combinations. This finding provides an effective route to fabricate diverse nanoparticle arrayed structures for the design of functional materials and devices.

Doped nanoparticles (especially bimetal doped nanoparticles) have attracted extensive interest not only for fundamental scientific research but also for application purposes. However, their indefinite composition (structure) and broad distribution hinder an insightful understanding of the interaction between these invasive metals in bimetal doped nanoparticles. Fortunately, atom-precise bimetal doped ultrasmall nanoparticles (nanoclusters) provide opportunities to obtain such insights. However, atom-precise trimetal nanoclusters and their structures have rarely been reported. Here, we successfully dope thiolated Au 25 nanoclusters with Hg and Ag successively by using a biantigalvanic reduction method. We then fully characterize the as-obtained trimetal nanoclusters using multiple techniques (including single-crystal X-ray crystallography), and we demonstrate that the mercury and silver dopings exhibit not only a synergistic but also a counteractive influence on some of the physicochemical properties of Au 25 .