Engineering MoS₂ Basal Planes for Hydrogen Evolution via Synergistic Ruthenium Doping and Nanocarbon Hybridization

Abstract

Promoting the intrinsic activity and accessibility of basal plane sites in 2D layered metal dichalcogenides is desirable to optimize their catalytic performance for energy conversion and storage. Herein, a core/shell structured hybrid catalyst, which features few‐layered ruthenium (Ru)‐doped molybdenum disulfide (MoS 2 ) nanosheets closely sheathing around multiwalled carbon nanotube (CNT), for highly efficient hydrogen evolution reaction (HER) is reported. With 5 at% (atomic percent) Ru substituting for Mo in MoS 2 , Ru‐MoS 2 /CNT achieves the optimum HER activity, which displays a small overpotential of 50 mV at −10 mA cm −2 and a low Tafel slope of 62 mV dec −1 in 1 m KOH. Theoretical simulations reveal that Ru substituting for Mo in coordination with six S atoms is thermodynamically stable, and the in‐plane S atoms neighboring Ru dopants represent new active centers for facilitating water adsorption, dissociation, and hydrogen adsorption/desorption. This work provides a multiscale structural and electronic engineering strategy for synergistically enhancing the HER activity of transition metal dichalcogenides.

Promoted Alkaline Hydrogen Evolution Reaction Performance of Ru/C by Introducing TiO2 Nanoparticles

“…In addition, Ru 3p 3/2 for Ru/C−TiO 2 had a slight positive shift, compared to that of Ru/C, indicating strong electronic interaction between Ru and TiO 2 . This interfacial electronic interaction can activate the adsorbed water molecules and also optimize the free energy of hydrogen adsorption, thus promoting alkaline HER performance, which was verified by the published literatures …”

Defects Enhance the Electrocatalytic Hydrogen Evolution Properties of MoS2‐based Materials

“…[58] In addition to anion doping, cationic doping can also achieve defective MoS 2 catalysts. [60,61] Xu's group synthesized Zn-doped MoS 2 with S-vacancies (Zn@MoS 2 ) at high-temperature and allowed V S % to be tuned from 7.8% to 20.3% by the zinc dosage. [56] Chen et al hydrothermally synthesized Zndoped MoS 2 (ZnÀ MoS 2 ), [62] whose catalytic performance was improved via the synergy of electronic and morphological effects instead of defects.…”

Electrochemical Hydrogen Evolution over Hydrothermally Synthesized Re-Doped MoS2 Flower-Like Microspheres

“…Most strategies to improve HER performance of MoS 2 electrocatalysts are consequently focused on phase, defects, and heterostructure engineering to maximally expose edge sites and to activate the basal plane [7,10,11]. Doping with non-metallic or transition metals atoms into the MoS 2 structure activates both edges and basal plane, improving the electronic mobility, charge transportability, and catalytically active surface area, therefore enhancing HER activity of the material [12][13][14][15]. In this sense, rhenium doping has been proposed to tune the electronic structure and polymorphic phases and to activate the basal planes of MoS 2 [16][17][18][19].…”