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Ultrathin two-dimensional conjugated metal– organic framework single-crystalline nanosheets enabled by surfactant-assisted synthesis

2020, Wang, Zhonghao, Wang, Gang, Qi, Haoyuan, Wang, Mao, Wang, Mingchao, Park, SangWook, Wang, Huaping, Yu, Minghao, Kaiser, Ute, Fery, Andreas, Zhou, Shengqiang, Dong, Renhao, Feng, Xinliang

Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) have recently emerged for potential applications in (opto-)electronics, chemiresistive sensing, and energy storage and conversion, due to their excellent electrical conductivity, abundant active sites, and intrinsic porous structures. However, developing ultrathin 2D c-MOF nanosheets (NSs) for facile solution processing and integration into devices remains a great challenge, mostly due to unscalable synthesis, low yield, limited lateral size and low crystallinity. Here, we report a surfactant-assisted solution synthesis toward ultrathin 2D c-MOF NSs, including HHB-Cu (HHB = hexahydroxybenzene), HHB-Ni and HHTP-Cu (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene). For the first time, we achieve single-crystalline HHB-Cu(Ni) NSs featured with a thickness of 4-5 nm (∼8-10 layers) and a lateral size of 0.25-0.65 μm2, as well as single-crystalline HHTP-Cu NSs with a thickness of ∼5.1 ± 2.6 nm (∼10 layers) and a lateral size of 0.002-0.02 μm2. Benefiting from the ultrathin feature, the synthetic NSs allow fast ion diffusion and high utilization of active sites. As a proof of concept, when serving as a cathode material for Li-ion storage, HHB-Cu NSs deliver a remarkable rate capability (charge within 3 min) and long-term cycling stability (90% capacity retention after 1000 cycles), superior to the corresponding bulk materials and other reported MOF cathodes. This journal is © The Royal Society of Chemistry.

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Comprehensive scan for nonmagnetic Weyl semimetals with nonlinear optical response

2020, Xu, Q., Zhang, Y., Koepernik, K., Shi, W., van den Brink, J., Felser, C., Sun, Y.

First-principles calculations have recently been used to develop comprehensive databases of nonmagnetic topological materials that are protected by time-reversal or crystalline symmetry. However, owing to the low symmetry requirement of Weyl points, a symmetry-based approach to identifying topological states cannot be applied to Weyl semimetals (WSMs). To date, WSMs with Weyl points in arbitrary positions are absent from the well-known databases. In this work, we develop an efficient algorithm to search for Weyl points automatically and establish a database of nonmagnetic WSMs with Weyl points near the Fermi level based on the experimental non-centrosymmetric crystal structures in the Inorganic Crystal Structure Database (ICSD). In total, 46 Weyl semimetals were discovered to have nearly clean Fermi surfaces and Weyl points within 300 meV of the Fermi level. Nine of them are chiral structures which may exhibit the quantized circular photogalvanic effect. In addition, the nonlinear optical response is studied and the giant shift current is explored. Besides nonmagnetic WSMs, our powerful tools can also be used in the discovery of magnetic topological materials.

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Electron microscopy of nanoparticle superlattice formation at a solid-liquid interface in nonpolar liquids

2020, Cepeda-Perez, E., Doblas, D., Kraus, T., de Jonge, N.

Nanoparticle superlattice films form at the solid-liquid interface and are important for mesoscale materials, but are notoriously difficult to analyze before they are fully dried. Here, the early stages of nanoparticle assembly were studied at solid-liquid interfaces using liquid-phase electron microscopy. Oleylamine-stabilized gold nanoparticles spontaneously formed thin layers on a silicon nitride (SiN) membrane window of the liquid enclosure. Dense packings of hexagonal symmetry were obtained for the first monolayer independent of the nonpolar solvent type. The second layer, however, exhibited geometries ranging from dense packing in a hexagonal honeycomb structure to quasi-crystalline particle arrangements depending on the dielectric constant of the liquid. The complex structures formed by the weaker interactions in the second particle layer were preserved, while the surface remained immersed in liquid. Fine-tuning the properties of the involved materials can thus be used to control the three-dimensional geometry of a superlattice including quasi-crystals.