Active site manipulation in MoS₂ cluster electrocatalysts by transition metal doping

Abstract

Combining precision cluster synthesis with atomistic modelling uncovers fundamental differences in the influence of transition metal dopants on the electrocatalytic activity of MoS2 towards the hydrogen evolution reaction.

The Effect of the 3D Nanoarchitecture and Ni‐Promotion on the Hydrogen Evolution Reaction in MoS2/Reduced GO Aerogel Hybrid Microspheres Produced by a Simple One‐Pot Electrospraying Procedure

“…The nickel however has also a more direct role: in the form of single atom adsorbed on the surface, it is a good catalyst for the HER since it modifies the electronic properties of the basal plane, determining a more thermoneutral hydrogen adsorption energy compared to pure MoS 2 [55,69,72] On the other hand, nickel species in the form of oxysulfides or small oxidized clusters can establish a bifunctional effect. [53,55,65,69] where the oxofilic NiO x species facilitate the electrochemical water dissociation providing a suitable adsorption site for hydroxyls intermediates, [77] whereas the surrounding MoS x species can stabilize the resulting H atom and proceeds through the further steps of the HER.…”

“…A large body of literature, as well as our own EIS data, indicate that the increase of the catalytic activity can be connected to enhanced electron transfer properties induced by the presence of Ni dopants as well as by the convenient modulation of the hydrogen adsorption energy, which is considered the best descriptor for the HER activity. In this regard DFT calculations suggest a more thermoneutral value of the hydrogen adsorption energy on Ni doped compared to pristine MoS 2 [55,69] or that the presence of Ni atoms can activate adjacent sulfur vacancies [72] or modulate locally the charge of the basal plane [32] favoring the HER.…”

Recent Progress on Two-dimensional Electrocatalysis

“…7(D)]. Moreover, the anions and cations doping methods were also employed to tune the electronic structure of MoS 2 [67] . By introducing sulfur vacancies in the 2D MoS 2 structure, the modified MoS 2 catalyst showed a considerable electrocatalytic activity with a Tafel slope of 48 mV/dec, and an overpotential 131 mV at 10 mA/cm 2 for HER[Fig.…”

Rational Design of Better Hydrogen Evolution Electrocatalysts for Water Splitting: A Review

“…[ 183 , 184 , 185 , 186 , 187 , 188 , 189 , 190 , 191 , 192 , 193 , 194 , 195 ] Therefore, heteroatom doping is an effective strategy widely used to optimize HER activity. Transition metal doping (Fe, [ 196 ] Co, [ 197 , 198 ] Ni, [ 199 ] Zn, [ 200 ] and Mo [ 201 ] ) modifies the local electronic environment and can also optimize the interatomic distances and coordination numbers of active sites. The ligand and strain effects produced by the introduction of transition metals can adjust the Δ G H* .…”