Chalcogen···Chalcogen Bonding in Molybdenum Disulfide, Molybdenum Diselenide and Molybdenum Ditelluride Dimers as Prototypes for a Basic Understanding of the Local Interfacial Chemical Bonding Environment in 2D Layered Transition Metal Dichalcogenides

An attempt was made, using computational methods, to understand whether the intermolecular interactions in the dimers of molybdenum dichalcogenides MoCh2 (Ch = chalcogen, element of group 16, especially S, Se and Te) and similar mixed-chalcogenide derivatives resemble the room temperature experimentally observed interactions in the interfacial regions of molybdenites and their other mixed-chalcogen derivatives. To this end, MP2(Full)/def2-TVZPPD level electronic structure calculations on nine dimer systems, including (MoCh2)2 and (MoChCh′2)2 (Ch, Ch′ = S, Se and Te), were carried out not only to demonstrate the energetic stability of these systems in the gas phase, but also to reproduce the intermolecular geometrical properties that resemble the interfacial geometries of 2D layered MoCh2 systems reported in the crystalline phase. Among the six DFT functionals (single and double hybrids) benchmarked against MP2(full), it was found that the double hybrid functional B2PLYPD3 has some ability to reproduce the intermolecular geometries and binding energies. The intermolecular geometries and binding energies of all nine dimers are discussed, together with the charge density topological aspects of the chemical bonding interactions that emerge from the application of the quantum theory of atoms in molecules (QTAIM), the isosurface topology of the reduced density gradient noncovalent index, interaction region indicator and independent gradient model (IGM) approaches. While the electrostatic surface potential model fails to explain the origin of the S···S interaction in the (MoS2)2 dimer, we show that the intermolecular bonding interactions in all nine dimers examined are a result of hyperconjugative charge transfer delocalizations between the lone-pair on (Ch/Ch′) and/or the π-orbitals of a Mo–Ch/Ch′ bond of one monomer and the dπ* anti-bonding orbitals of the same Mo–Ch/Ch′ bond in the second monomer during dimer formation, and vice versa. The HOMO–LUMO gaps calculated with the MN12-L functional were 0.9, 1.0, and 1.1 eV for MoTe2, MoSe2 and MoS2, respectively, which match very well with the solid-state theoretical (SCAN-rVV10)/experimental band gaps of 0.75/0.88, 0.90/1.09 and 0.93/1.23 eV of the corresponding systems, respectively. We observed that the gas phase dimers examined are perhaps prototypical for a basic understanding of the interfacial/inter-layer interactions in molybdenum-based dichalcogenides and their derivatives.

A Fast Approach to Obtain Layered Transition-Metal Cathode Material for Rechargeable Batteries

Li-ion batteries as a support for future transportation have the advantages of high storage capacity, a long life cycle, and the fact that they are less dangerous than current battery materials. Li-ion battery components, especially the cathode, are the intercalation places for lithium, which plays an important role in battery performance. This study aims to obtain the LiNixMnyCozO2 (NMC) cathode material using a simple flash coprecipitation method. As precipitation agents and pH regulators, oxalic acid and ammonia are widely available and inexpensive. The composition of the NMC mole ratio was varied, with values of 333, 424, 442, 523, 532, 622, and 811. As a comprehensive study of NMC, lithium transition-metal oxide (LMO, LCO, and LNO) is also provided. The crystal structure, functional groups, morphology, elemental composition and material behavior of the particles were all investigated during the heating process. The galvanostatic charge–discharge analysis was tested with cylindrical cells and using mesocarbon microbeads/graphite as the anode. Cells were tested at 2.7–4.25 V at 0.5 C. Based on the analysis results, NMC with a mole ratio of 622 showed the best characteristicd and electrochemical performance. After 100 cycles, the discharged capacity reaches 153.60 mAh/g with 70.9% capacity retention.

Challenges of layer-structured cathodes for sodium-ion batteries

As the most promising alternate for lithium-ion batteries (LIBs), sodium-ion batteries (SIBs) still face many issues that hinder their large-scale commercialization. Layered transition metal oxide cathodes have attracted widespread attention...

Fabrication of high-efficiency CdS@TiO2@C/Ti3C2 composites photocatalyst for the degradation of TC-HCl under visible light

A novel CdS@TiO2@C/Ti3C2 composite as high-efficiency photocatalyst for the degradation of tetracycline hydrochloride (TC-HCl) was fabricated by in situ oxidizing two-dimensional (2D) layered transition metal Ti3C2 MXene and subsequently compounding...

Electronic structures of the MoS2/TiO2 (anatase) heterojunction: influence of physical and chemical modifications at the 2D- or 1D-interfaces

To tackle the challenge of the CO2 photoreduction, semiconducting layered transition metal dichalcogenides like MoS2 have attracted much attention due to their tunable 2D nano-structures. By using advanced periodic density...

One-Step Synthesized PbSe Nanocrystal Inks Decorated 2D MoS2 Heterostructure for High Stability Photodetectors with Photoresponse Extend to Near-Infrared Region

Two-dimensional layered transition metal dichalcogenides (TMDs) have been widely employed as functional materials in promising electronics and optoelectronic devices due to their unique physical and outstanding electronic properties. However, 2D...

Entropy Measurements of Li-Ion Battery Cells with Li- and Mn-Rich Layered Transition Metal Oxides via Linear Temperature Variation

Changes in the partial molar entropy of lithium- and manganese-rich layered transition metal oxides (LMR-NCM) are investigated using a recently established electrochemical measuring protocol, in which the open-circuit voltage (OCV) of a cell is recorded during linear variation of the cell temperature. With this method, the entropy changes of LMR-NCM in half-cells were precisely determined, revealing a path dependence of the entropy during charge and discharge as a function of state of charge, which vanished as a function of OCV. This observation is in line with other hysteresis phenomena observed for LMR-NCM, of which the OCV hysteresis is the most striking one. For a systematic investigation of the entropy changes in LMR-NCM, measurements were conducted during the first activation cycle and in a subsequent cycle. In addition, two LMR-NCM materials with different degrees of overlithiation were contrasted. Contributions from configurational and vibrational entropy are discussed. Our results suggest that the entropy profile during activation exhibits features from the configurational entropy, while during subsequent cycling the vibrational entropy dominates the entropy curve.

Controllable growth of multilayered XSe2 (X=W and Mo) for nonlinear optical and optoelectronic applications

The layered transition metal dichalcogenides (TMDs) exhibit the intriguing physical properties and potential application in novel electronic devices. However, controllable growth of multilayer TMDs remains challenging. Herein, large-scale and high-quality multilayer prototype TMDs of W(Mo)Se2 were synthesized via chemical vapor deposition. For Raman and PL measurements, 2H and 3R multilayer WSe2 crystals displayed significant layer-dependent peak position and intensity feature. Besides, different from the oscillatory relationship of SHG intensity for odd-even layer numbers in 2H-stacked multilayer WSe2, the second harmonic generation intensity of 3R-stacked ones parabolically increased with the thickness due to the absence of inversion symmetry. For device application, photodetectors based on WSe2 with increasing thickness exhibited p-type (bilayer), ambipolar (trilayer), and n-type (4 layers) semiconductor behaviors, respectively. Furthermore, photodetectors based on the as-synthesized 3R-stacked WSe2 flakes displayed an excellent responsivity (R) of 7.8×103 mA/W, high specific detectivity (Da*) of 1.7×1014 Jones, outstanding external quantum efficiency (EQE) of 8.6×102 %, and fast response time (τRise=57 ms and τFall=53 ms) under 532 nm illumination with bias voltage of Vds=5 V. Similar results have also been achieved in multilayer MoSe2 crystals. All these findings indicate great potential of 3R-stacked TMDs in two-dimensional optoelectronic applications.