2H-2M Phase Control of WSe2 Nanosheets by Se Enrichment Toward Enhanced Electrocatalytic Hydrogen Evolution Reaction.

The phase control of transition metal dichalcogenides (TMDs) is an intriguing approach for tuning the electronic structure toward extensive applications. In this study, WSe2 nanosheets synthesized via a colloidal reaction exhibit a phase conversion from semiconducting 2H to metallic 2M under Se-rich growth conditions (i.e., increasing the concentration of Se precursor or lowering the growth temperature). High-resolution scanning transmission electron microscopy images are used to identify the stacking sequence of the 2M phase, which is distinctive from that of the 1T' phase. First-principles calculations employing various Se-rich models (intercalation and substitution) indicated that Se enrichment induces conversion to the 2M phase. The 2M phase WSe2 nanosheets with the Se excess exhibited enhanced electrocatalytic performance in the hydrogen evolution reaction (HER). In situ X-ray absorption fine structure studies suggested that the excess Se atoms in the 2M phase WSe2 enhanced the HER catalytic activity, which is supported by the Gibbs free energy (ΔGH* ) of H adsorption and the Fermi abundance function. These results provide an appealing strategy for phase control of TMD catalysts.

Composition-Tuned (MoWV)Se2 Ternary Alloy Nanosheets as Excellent Hydrogen Evolution Reaction Electrocatalysts.

Ternary alloying of transition metal dichalcogenides (TMDs) has the potential for altering the electronic structure of materials to suit electrochemical applications. Herein, we synthesized (MoWV)Se2 nanosheets at various compositions via a colloidal reaction. The mole fraction of V atoms (xV) was successfully increased up to 0.8, producing a metallic phase that is highly durable against hydration. Furthermore, we synthesized (MoW)Se2 nanosheets over the entire composition range. The atomic mixing of the ternary alloys is more random than that of the constitutional binary alloys, as supported by first-principles calculations. Compared to binary alloying, ternary alloying more effectively enhanced the electrocatalytic activity for acidic hydrogen evolution reaction (HER). The HER performance increased upon increasing xV to 0.44, and thereafter, it declined at higher xV primarily owing to surface oxidation. The analysis of Gibbs free energy for H adsorption revealed that ternary alloying strongly activates the basal plane for the HER. VSe2 contains numerous sites favorable for H adsorption, facilitating the composition-dependent HER. These results provide a pioneering strategy for designing multicomponent TMD catalysts that maximize the advantages of each component.

Full Composition Tuning of W1-xNbxSe2 Alloy Nanosheets to Promote the Electrocatalytic Hydrogen Evolution Reaction.

Composition modulation of transition metal dichalcogenides is an effective way to engineer their crystal/electronic structures for expanded applications. Here, fully composition-tuned W1-xNbxSe2 alloy nanosheets were produced via colloidal synthesis. These nanosheets ultimately exhibited a notable transition between WSe2 and NbSe2 hexagonal phases at x = 0.6. As x approaches 0.6, point doping is converted into cluster doping and eventually separated domains of WSe2 and NbSe2. Extensive density functional theory calculations predicted the composition-dependent crystal structures and phase transitions, consistently with the experiments. The electrocatalytic activity for the hydrogen evolution reaction (HER) in acidic electrolyte was significantly enhanced at x = 0.2, which was linked with the d-band center. The Gibbs free energy for the H adsorption at various basal and edge sites supported the enhanced HER performance of the metallic alloy nanosheets. We suggested that the dispersed doping structures of Nb atoms resulted in the best HER performance. Our findings highlight the significance of composition tuning in enhancing the catalytic activity of alloys.

WSe2-VSe2 Alloyed Nanosheets to Enhance the Catalytic Performance of Hydrogen Evolution Reaction.

Tuning the electronic structures of transition metal dichalcogenides (TMD) is essential for their implementation in next-generation energy technologies. In this study, we synthesized composition-tuned WSe2-VSe2 (W1-xVxSe2, x = 0-1) alloyed nanosheets using a colloidal reaction. Alloying the semiconducting WSe2 with VSe2 converts the material into a metallic one, followed by a 2H-to-1T phase transition at x = 0.7. Over a wide composition range, WSe2 and VSe2 are atomically immiscible and form separate ordered domains. The miscible alloy at x = 0.1 displayed enhanced electrocatalytic activity toward the hydrogen evolution reaction (HER) in an acidic electrolyte. This trend was correlated with the d-band center via a volcano-type relationship. Spin-polarized density functional theory calculations consistently predicted the atomic immiscibility, which became more significant at the 2H-1T phase transition composition. The Gibbs free energy of H adsorption on the basal planes (Se or hole sites) and the activation barriers along the Volmer-Heyrovsky reaction pathway supported the enhanced HER performance of the alloy phase, suggesting that the dispersed V-doped structures were responsible for the best HER catalytic activity. Our study demonstrates how the atomic structure of TMD alloy nanosheets plays a crucial role in enhancing catalytic activity.

MoSe2 -VSe2 -NbSe2 Ternary Alloy Nanosheets to Boost Electrocatalytic Hydrogen Evolution Reaction.

Alloying of transition metal dichalcogenides (TMDs) is a pioneering method for engineering electronic structures with expanded applications. In this study, MoSe2 -VSe2 -NbSe2 ternary alloy nanosheets are synthesized via a colloidal reaction. The composition is successfully tuned over a wide range to adjust the 2H-1T phase transition. The alloy nanosheets consist of miscible atomic structures at all compositions, which is distinct from immiscible binary alloys. Compared to each binary alloy, the ternary alloys display higher electrocatalytic activity toward the hydrogen evolution reaction (HER) in an acidic electrolyte. The HER performance exhibits a volcano-type composition dependence, which is correlated with the experimental d-band center (εd ). Spin-polarized density functional theory (DFT) calculations consistently predict the homogenous atomic distributions. The Gibbs free energy of H adsorption (ΔGH* ) and the activation barrier (Ea ) support that miscible ternary alloying greatly enhances the HER performance.

Edge effects on the intrinsic magnetism in ferromagnetic triangular phosphorene quantum dots using fully spin-polarized calculations.

This project involves discovering the electronic and magnetic properties of nanometer-sized phosphorene structures with triangular shapes in both zigzag and armchair termination types. The goal is to discuss the relationship between the electronic states belonging to the different conditions of these phosphorene quantum dots and their intrinsic magnetic properties. For this purpose, we consider electronic interactions utilizing the spin-polarized density functional theory calculations, and then the results compare with the data generated from tight-binding calculations. Both descriptions yield mid-gap states in the spectrum of ferromagnetic structures. Our results in non-spin computations without any geometry optimization were matched by tight-binding calculations which shows that the tight-binding method is an inefficient approximation in analyzing the optimized spin samples. Unlike graphene, in our spin-polarized calculations, we have obtained empty mid-gap states in the spectrum of ferromagnetic triangular phosphorene quantum dots. The edge atoms of these structures are known as the magnetic atoms with an unequal contribution of spin up and spin down. To prevent deforming the initial structures, the dangling bonds at the edge atoms were passivated in two types, fully hydrogenated and partial passivation with oxygen atoms. Oxygen doping was required for introducing magnetism to the non-spin edges of the fully hydrogenated case.