Electrocatalytic Performance of 2D Monolayer WSeTe Janus Transition Metal Dichalcogenide for Highly Efficient H2 Evolution Reaction.

Nowadays, the development of clean and green energy sources is the priority interest of research due to increasing global energy demand and extensive usage of fossil fuels, which create pollutants. Hydrogen has the highest energy density by weight among all chemical fuels. For the commercial-scale production of hydrogen, water electrolysis is the best method, which requires an efficient, cost-effective, and earth-abundant electrocatalyst. Recent studies have shown that the 2D Janus transition metal dichalcogenides (JTMDs) are promising materials for use as electrocatalysts and are highly effective for electrocatalytic H2 evolution reaction (HER). Here, we report a 2D monolayer WSeTe JTMD, which is highly effective toward HER. We have studied the electronic properties of 2D monolayer WSeTe JTMD using the periodic hybrid DFT-D method, and a direct electronic band gap of 2.39 eV was obtained. We have explored the HER pathways, mechanisms, and intermediates, including various transition state (TS) structures (Volmer TS, i.e., H*-migration TS, Heyrovsky TS, and Tafel TS) using a molecular cluster model of the subject JTMD noted as W10Se9Te12. The present calculations reveal that the 2D monolayer WSeTe JTMD is a potential electrocatalyst for HER. It has the lowest energy barriers for all the TSs among other TMDs. It has been shown that the Heyrovsky energy barrier (= 8.72 kcal mol-1) in the case of the Volmer-Heyrovsky mechanism is larger than the Tafel energy barrier (= 3.27 kcal mol-1) in the Volmer-Tafel mechanism. Hence, our present study suggests that the formation of H2 is energetically more favorable via the Volmer-Tafel mechanism. This study helps to shed light on the rational design of 2D single-layer JTMD, which is highly effective toward HER, and we expect that the present work can be further extended to other JTMDs to find out the improved electrocatalytic performance.

Illuminating the Role of Mo Defective 2D Monolayer MoTe2 toward Highly Efficient Electrocatalytic O2 Reduction Reaction.

The fuel cell is one of the solutions to current energy problems as it comes under green and renewable energy technology. The primary limitation of a fuel cell lies in the relatively slow rate of oxygen reduction reactions (ORR) that take place on the cathode, and this is an all-important reaction. An efficient electrocatalyst provides the advancement of green energy-based fuel cell technology, and it can speed up the ORR process. The present work provides the study of non-noble metal-based electrocatalyst for ORR. We have computationally designed a 3 × 3 supercell model of metal defective (Mo-defective) MoTe2 transition metal dichalcogenide (TMD) material to study its electrocatalytic activity toward ORR. This work provides a comprehensive analysis of all reaction intermediates that play a role in ORR on the surfaces of metal-deficient MoTe2. The first-principles-based dispersion-corrected density functional theory (in short DFT-D) method was implemented to analyze the reaction-free energies (ΔG) for each ORR reaction step. The present study indicates that the ORR on the surface of metal-defective MoTe2 follows the 4e- transfer mechanism. This study suggests that the 2D Mo-defective MoTe2 TMD has the potential to be an effective ORR electrocatalyst in fuel cells.

Unraveling the O2 Reduction Reaction on 2D Monolayer LaNiO3 Perovskite.

The O2 reduction reaction (ORR) occurring at cathodes is a critical reaction in many electrochemical energy-converting devices such as fuel cells. The reaction kinematics of the ORR is generally very slow with high overpotentials and needs to be enhanced by using an efficient electrocatalyst. The highly recognized Pt-based electrocatalyst needs to be replaced with a low-cost non-noble metal-based electrocatalyst for catalyzing the ORR. We theoretically studied the structural and electronic properties of 3D bulk LaNiO3 perovskite. We have cleaved the (0 0 1) surface from 3D LaNiO3, which has a zero band gap (E g), to create 2D monolayer LaNiO3 computationally and studied its electronic properties. Our study demonstrates that the 2D monolayer LaNiO3 is a suitable candidate for catalyzing the ORR because of its high catalytic activity with a tiny electronic band gap of 0.25 eV. We explored the ORR mechanism on the 2D monolayer LaNiO3 perovskite by inspecting each intermediate. Our present findings show that the 2D monolayer LaNiO3 can efficiently catalyze the ORR through a four-electron (4e-) reduction reaction due to the excellent catalytic activity of its basal plane, which accords with the experimental findings. The change in Gibbs free energy (ΔG) calculations of various intermediate steps of the ORR demonstrates that all reaction steps are spontaneous and thermodynamically favorable. The 2D monolayer LaNiO3 perovskite can be a potential candidate for catalyzing the ORR efficiently. This study helps to enable the development of high-activity, stable 2D perovskites for use in future solid oxide fuel cells and related applications in green energy technologies.