Fluorine- and Nitrogen-Codoped MoS₂ with a Catalytically Active Basal Plane

Abstract

Two-dimensional molybdenum disulfide (2D MoS) has drawn persistent interests as one of the most promising alternatives to Pt catalysts for the hydrogen evolution reaction (HER). It is generally accepted that the edge sites of 2D MoS are catalytically active but the basal planes are inert. Activating the MoS basal plane is an obvious strategy to enhance the HER activity of this material. However, few approaches have sought to activate the basal plane. Here, for the first time, we demonstrate that the inert basal planes can be activated via the synergistic effects of nitrogen and fluorine codoping. Our first-principles calculations reveal that nitrogen in the basal plane of the fluorine- and nitrogen-codoped MoS (NF-MoS) can act as a new active and further tuneable catalytic site. The as-prepared NF-MoS catalyst exhibited an enormously enhanced HER activity compared to that of pure MoS and N-doped MoS due to the chemical codoping effect. This work will pave a novel pathway for enhancing the HER activity using the synergistic effects of chemical codoping.

Design Strategies for Development of TMD-Based Heterostructures in Electrochemical Energy Systems

“…Also, the heterostructure catalyst demonstrated earlier onset potentials and moderate overpotentials of 421 mV at 10 mA cm À2 . The reaction mechanism for each sample was understood through Tafel slope calculations (h = b log(j) + a, where h, b, j, and a denote overpotential, Tafel slope, current density, and constant, 43 respectively, or doping secondary element, non-metals such as N, 75 F, 76 and P [77][78][79] or metals including Ni, [80][81][82] Co, [83][84][85] Pd, 86 and Rh 87 into TMD lattice structures holds much promise in improving the reactivity of edge sites and activating the inert basal plane of TMDs. Lei et al fabricated W x Mo 1Àx S 2 /rGO thin films via a facile and scalable wet chemistry approach (Figure 4A).…”

Earth-Abundant Electrocatalysts in Proton Exchange Membrane Electrolyzers

“…Depending on the methods used, one often ends up with amorphous MoS x . Efforts to improve the activity of the semiconductor phase comprise doping, introducing vacancies, and strain engineering, which can activate the basal plane and edges that are not intrinsically active [97][98][99][100]. The 1T phase is metastable, however, the metallic nature makes it highly conductive compared to the 2H phase, and, in addition, the basal plane is active as well, resulting in promising HER activity [101,102].…”

Earth-Abundant Electrocatalysts in Proton Exchange Membrane Electrolyzers

“…Depending on the methods used, one often ends up with amorphous MoSx. Efforts to improve the activity of the semiconductor phase comprises of doping, introducing vacancies and strain engineering, which can activate the basal plane and edges that are not intrinsically active [97][98][99][100]. The 1T phase is metastable, however, the metallic nature makes it highly conductive compared to the 2H phase, and, in addition, the basal plane is active as well, resulting in promising HER activity [101,102].…”