Regioselective Approach to Characterizing Increased Edge Availability in Layered Crystal Materials following Layer Expansion: Reaction of Kaolinite with Octadecyltrimethylammonium Salts

In this paper, the regioselective reactions of kaolinite and methoxy-modified kaolinite (MeO-Kaol), methanol-expanded kaolinite, with octadecyltrimethylammonium salts are compared. This study mainly concerns the reactions of kaolinite or MeO-Kaol with octadecyltrimethylammonium chloride (C18TAC) in methanol and the subsequent exhaustive washing of the resultant products with ethanol. X-ray diffraction patterns of the products reveal no intercalation of C18TAC between pristine kaolinite layers. Additionally, intercalation and subsequent deintercalation of C18TAC proceed in the product using MeO-Kaol. In the Fourier-transform infrared spectra, the intensities of CH2 stretching bands of the product prepared using MeO-Kaol drastically increase compared to those using kaolinite. In addition, CH2 stretching bands of the product using kaolinite are hardly observed without enlarging the spectrum. The product using MeO-Kaol also displays mass loss in the range of 200–300 °C in the thermogravimetric curve and a nitrogen content with 0.15 mass% estimated using the CHN analysis. These results therefore demonstrate an increase in the available reactive edges in the layered crystal material following an expansion of the stacked layers.

Growth strategy for two-dimensional nanomaterials via a unified model

Two-dimensional (2D) materials prepared by a wet-chemical precipitation route exhibit many unique properties and high potential in various fields. Still, simple, rational and green fabrication of target materials remains challenging due to the lack of a guiding principle. Here, we propose a universal qualitative model for 2D materials grown for layered and non-layered crystal structures by wet-chemical precipitation, which is confirmed by both theoretical simulation and experimental results. It demonstrates that 2D growth can be obtained by only tuning reaction concentration and temperature. This model not only has been applied to fabricate more than 30 different 2D nanomaterials in water at room temperature in the absence of additives, but also is promising in optimizing the experimental design of numerous other 2D nanomaterials.

Synthesis, crystal and electronic structure of BaLi2Cd2Ge2

A new quaternary germanide has been synthesized and structurally characterized. BaLi2Cd2Ge2 adopts the rhombohedral CaCu4P2 structure type (Pearson code hR7; space group R 3 ‾ m $R‾{3}m$ , Z = 3) with unit cell parameters a = 4.5929(6) and c = 26.119(5) Å. Structure refinements from single-crystal X-ray diffraction data demonstrate that the layered crystal structure can be regarded as an ordered quaternary variant of the ternary archetype; structural parallels to layered pnictides and binary germanides can also be drawn. The layered crystal structure is characterized by the absence of direct Ge–Ge and Cd–Cd homoatomic bonds, which suggests that BaLi2Cd2Ge2 should be classified as a Zintl phase, according to the formulation (Ba2+)(Li+)2(Cd2+)2(Ge4−)2. Electronic structure calculations show that the Fermi level crosses a distinct peak in the DOS, although the presence of an electronic band gap or a dip in the electronic density of states at the Fermi level is expected based on the electron partitioning.

CVD-Grown 2D Nonlayered NiSe as a Broadband Photodetector

Two-dimensional (2D) materials have expansive application prospects in electronics and optoelectronics devices due to their unique physical and chemical properties. 2D layered materials are easy to prepare due to the layered crystal structure and the interlayer van der Waals combination. However, the 2D nonlayered materials are difficult to prepare due to the nonlayered crystal structure and the combination of interlayer isotropic chemical bonds, resulting in limited research on 2D nonlayered materials with broad characteristics. Here, a 2D nonlayered NiSe material has been synthesized by a chemical vapor deposition method. The atomic force microscopy study shows that the grown NiSe with a thin thickness. Energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy and transmission electron microscopy results demonstrate the uniformity and high quality of NiSe flakes. The NiSe based photodetector realizes the laser response to 830 nm and 10.6 μm and the maximum responsivity is ~6.96 A/W at room temperature. This work lays the foundation for the preparation of 2D nonlayered materials and expands the application of 2D nonlayered materials in optoelectronics fields.

Theoretical Investigation of Proton Diffusion in Dion–Jacobson Layered Perovskite RbBiNb2O7

Perovskite materials are considered to be promising electrolyte membrane candidates for electrochemical applications owing to their excellent proton- or oxide-ion-conducting properties. RbBiNb2O7 is a double-layered Dion–Jacobson perovskite oxide, with Pmc21 symmetry. In this study, the electronic structure and proton-diffusion properties of bulk RbBiNb2O7 were systematically investigated using first-principles calculations. The unique layered crystal structure of RbBiNb2O7 plays a crucial role in proton storage and proton conductivity. Different proton-diffusion steps in RbBiNb2O7 were considered, and the activation energies of the relevant diffusion steps were evaluated using the climbing image-nudged elastic band (CI-NEB) technique. The proton diffusion in RbBiNb2O7 presents a two-dimensional layered characteristic in the a-b plane, owing to its layered crystalline nature. According to the transition state calculations, our results show that the bulk RbBiNb2O7 exhibits good proton-transport behavior in the a-b plane, which is better than many perovskite oxides, such as CaTiO3, CaZrO3, and SrZrO3. The proton diffusion in the Rb–O and Nb–O layers is isolated by a higher energy barrier of 0.86 eV. The strong octahedral tilting in RbBiNb2O7 would promote proton transport. Our study reveals the microscopic mechanisms of proton conductivity in Dion–Jacobson structured RbBiNb2O7, and provides theoretical evidence for its potential application as an electrolyte in solid oxide fuel cells (SOFCs).

Experimental investigation into the effects of composition and microstructure on the tensile properties and failure characteristics of different gypsum rocks

The present work investigated the differences in the composition and internal microstructure of four types gypsum rock—fiber gypsum, transparent gypsum, alabaster, and ordinary gypsum by X-ray fluorescence spectrometry, X-ray diffraction, scanning electron microscope and Brazilian split test, and analyzed its effects on the tensile strength and fracture characteristics of gypsum rock. For alabaster, fiber gypsum, transparent gypsum, and ordinary gypsum, CaSO4·2H2O is the main component with 72.78%, 72.72%, 72.57%, and 71.51% content, and tensile strength of 1.79, 2.22, 3.22, and 4.35 MPa, respectively. In addition, the fracture line is arc-shaped, vertical, and zigzag for fiber gypsum, ordinary and transparent gypsums, and alabaster, respectively. On the microscopic level, fiber gypsum has an evident striated structure while the gradual increased pore development for alabaster, transparent gypsum, and ordinary gypsum. Gypsum rock has an obvious layered crystal structure with the increase of CaSO4·2H2O, contributing to the phenomenon with a larger grain size and lower tensile strength. In addition, the number of particles for alabaster, transparent gypsum, and ordinary gypsum increased in turn, while their particle size decreased uniformly, indicating that the lower CaSO4·2H2O content, the more sufficient energy accumulation and release. This paper can provide a theoretical basis for the analysis of the mechanical properties of rocks with different mineral composition and contribute to the design for different ore grades mining.

The layered crystal structure of bis(theophyllinium) hexachloridostannate (IV), C14H18N8O8SnCl6

C14H18N8O8SnCl6, monoclinic, P21/n (no. 14), a = 8.1810(2) Å, b = 12.6195(3) Å, c = 11.3811(2) Å, β = 90.258(2)°, Z = 2, V = 1174.97(5) Å3, R gt(F) = 0.0266, wR ref = 0.0620, T = 290 K.