Phase adjustment and electronic orbital matching triggered efficient H2 production of 2D electrocatalysts in a wide pH range

Research highlights • The P, Mn co-doped of MoS2 (P,Mn-MoS2/CC) was prepared. • P,Mn-MoS2/CC reveals outstanding stability and electrocatalytic activity. • The Gibbs free energy of the P,Mn-MoS2/CC is the lowest. The development of pH-insensitive two-dimensional (2D) electrocatalysts with outstanding performance, stability and wealthy resources, is necessary for integrated water splitting system to achieve sustainable production of green H2. Herein, the catalytic activity and pH adaptability of 2D crystals (MoS2) are enhanced by activating the chemically inert basal planes through phase modulation and unique matching between metals (Mn) and non-metals (P). Specifically, employing the instantaneous heat release characteristic of microwave, the P, Mn co-doped of MoS2 (P,Mn-MoS2/CC) was prepared with the assistance of P-functionalized catalysts on carbon cloth. Remarkably, the P, Mn-MoS2/CC reveals outstanding electrocatalytic activity and stability for H2 evolution in 0.5 M H2SO4 and 1.0 M KOH. Furthermore, material characterization and density functional theory (DFT) calculations additionally testify the superiority of the P,Mn-MoS2/CC with a 2D layered structure. The DFT calculations reveal that the P,Mn-MoS2/CC has the lowest Gibbs free energy (|ΔGH*|), and the center of its p-orbitals (εp) is in the optimal position. Overall, the electronic structure around MoS2/CC is altered by the introduction of P and Mn, promoting the generation of 1 T phase and significantly improving the conductivity and structural stability of materials in a wider pH electrolyte. Hence, the combination of phase modulation and electronic orbital matching strategies provides prospects for the development of the next generation of 2D catalysts.