Phase Modulation and Chemical Activation of MoSe₂ by Phosphorus for Electrocatalytic Hydrogen Evolution Reaction

Abstract

Molybdenum diselenide (MoSe2), as a member of transitional metal chalcogenides (TMDs), is regarded as a promising electrocatalyst for hydrogen evolution reaction (HER). However, its intrinsic performance is still hampered by insufficient exposure of active sites and inferior electric conductivity. The phase‐engineered synthesis of stable metallic 1T‐MoSe2 with abundant active sites is thus highly desirable for further boosting HER performance. Herein, a phosphorus (P)‐doped MoSe2 with controlled 2H/1T heterophases is synthesized through a facile way. Combining calculations and experiments, it is demonstrated that the doping of P (≈0.83 wt%) not only induces a phase change from 2H to 1T, but activates the Se atoms in the basal plane, thereby significantly enhancing its intrinsic HER performance. An overpotential of 174 mV is achieved at the benchmark of 10 mA cm−2 with a Tafel slope of 51 mV dec−1. More importantly, after the long‐term run at 180 mV for 10 h, the P‐1T/2H‐MoSe2 still displays a high current density of 10.43 mA cm−2 and keeps its original 2H/1T heterostructures, showing superior electrochemical stability and structural robustness. This work provides a facile method for improving the intrinsic HER activity of MoSe2 through nonmetal doping, which helps to understand the activity origin of MoSe2.

Oxygen Promotes the Formation of MoSe2 at the Interface of Cu2ZnSnSe4/Mo

“…However, the sheet resistance of the back contact of sample S-P10 decreased significantly, which is consistent with the change of R S . As reported by Chen et al, the introduction of P reduces the conductivity of MoSe 2 . Combining with the element distribution in Figure , this reduced R S in cell C-P10 may be aroused by P-doped MoSe 2 as lots of P diffuse to the back contact.…”

“…As reported by Chen et al, the introduction of P reduces the conductivity of MoSe 2 . 33 Combining with the element distribution in Figure 2, this reduced R S in cell C-P10 may be aroused by P-doped MoSe 2 as lots of P diffuse to the back contact.…”

Interfacial Mo–N–C Bond Endowed Hydrogen Evolution Reaction on MoSe2@N-Doped Carbon Hollow Nanoflowers

“…Among various non-noble metal materials, MoSe 2 has been considered a promising alternative for HER owing to its narrow band gap and appropriate adsorption free energy in theory . However, its catalytic performance is still unsatisfied due to inferior electrical conductivity and insufficient active sites .…”

Phosphorus‐Doping‐Induced Optimization of Atomic Hydrogen Binding Energy in MoSe2 under High Coverage for Efficient Electrocatalytic Hydrogen Evolution Reactions

“…The 2H-to-1T phase transformation of MoSe 2 was achieved via one-step P doping, and the Gibbs energy of H adsorption (ΔG H* ) at the Se sites was significantly optimized. [27] In this study, self-standing P-doped MoSe 2 nanosheets grown on carbon fiber paper (P-doped MoSe 2 /CFP) were synthesized using a two-step method, and the prepared nanosheets presented a typical 3D hierarchical structure. First, 3D porous CFP with high electrical conductivity was adopted as the supporting skeleton because it could offer a fast channel for electron transport and improve the poor conductivity of MoSe 2 .…”

“…The introduction of P atoms in MoS 2 provided more gap states at the Fermi level and decrease the bandgap of MoS 2 , which accelerated the charge transfer of electrochemical reactions. The 2H‐to‐1T phase transformation of MoSe 2 was achieved via one‐step P doping, and the Gibbs energy of H adsorption (ΔG H* ) at the Se sites was significantly optimized [27] …”