Doping of MoS₂ by “Cu” and “V”: An Efficient Strategy for the Enhancement of Hydrogen Evolution Activity

To replace Pt-based compounds in the electrocatalytic hydrogen evolution reaction (HER), MoS₂ has already been established as an efficient catalyst. The electrocatalytic activity of MoS₂ is further improved by tuning the morphology and the electronic structure through doping, which helps the band energy position to be modified. Presently, thin sheets of MoS₂ (MoS₂-TSs) are synthesized via a microwave technique. Thin sheets of MoS₂ can outperform nanosheets of MoS₂ in the HER. Further, the efficiency of the thin sheets is improved by doping with different metals like Cu, V, Zn, Mn, Fe, Sn, etc. “Cu”- and “V”-doped MoS₂-TSs are highly efficient for the HER. At a fixed potential of −0.588 V vs RHE, Cu-doped MoS₂ (Cu-MoS₂-TS), V-doped MoS₂ (V-MoS₂-TS), and MoS₂-TS can generate current densities of 327.46, 308.45, and 127.82 mA/cm², respectively. The electrochemically active surface area increases nearly 7.7-fold and 2.5-fold for Cu-MoS₂-TS and V-MoS₂-TS than for MoS₂-TS, respectively. Cu-MoS₂-TS shows exceptionally high electrocatalytic stability up to 140 h in an acidic medium (0.5 M H₂SO₄). First-principles calculations using density functional theory (DFT) are performed, which are well matched with the experimental observations. DFT calculations dictate that after doping with “V” and “Cu” both valance band maxima and conduction band minima are uplifted, which indicates the higher hydrogen-ion-reducing ability of M-MoS₂-TS (M = Cu, V) compared to bare MoS₂-TS.