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• Since Te can tune bandgap of WS 2 with a wide range and the electronegativity between S and Te differ greatly, the HER activities of WS 2 nanosheets was highly improved via Te doping. • Compared with sulfide and selenide, little research has been done on the electrocatalytic HER performance of Telluride. Hydrogen evolution reaction (HER) activities of WS 2 can be improved by doping exotic atom to increase active sites on base plane and narrow the bandgap. However, most of these catalysts of exotic atom doped WS 2 are composed of semiconductor and the electronegativity between atoms is similar, which do harm to tuning bandgap with a wide range and decreasing the value of free Gibbs energy (Δ G H) for hydrogen adsorption. Given that Te can tune bandgap with a wide range and the electronegativity between S and Te differ greatly, a vertically arranged WS 2 nanoelectrode is prepared by doping Te on WS 2. According to experimental studies and the density functional theory calculations (DFT), the bandgap of WS 2 nanosheets is successfully narrowed after doping Te. This lowers the Schottky barrier which benefits the transfer of charges and improves electrocatalytic performance in turn. Meanwhile, the presence of Te atoms with much lower electronegativity than S increases the electron density of the adjacent region, thereby the S edges of basal plane around Te atoms and hollow sites of WS 2 nanosheet become active to drive HER, which has been verified by the reduced Δ G H of S edges of basal plane from 2.27 to 2.08 eV and hollow sites from 2.28 to 1.85 eV after the doping in DFT. Te-doped WS 2 nanosheets used as excellent HER catalysts with an overpotential of 213 mV to drive a current density of 10 mA/cm2, a small Tafel slope of 94 mV/dec, along with a superior stability in acid media. [ABSTRACT FROM AUTHOR]

• P-doped Ni 3 S 2 nanosheet arrays were controlled preparation successfully. • The water dissociation kinetics of P-doped Ni 3 S 2 were tuned by electronic modulation. • The mechanism of HER performance improvement were revealed by DFT calculations. Developing efficient and low-cost electrocatalysts for hydrogen evolution reaction (HER) is important in clean energy systems. Non-noble transition metals are the most promising candidates for the replacement of conventional Pt group catalysts of HER. However, most non-noble metals show poor HER activity due to the intrinsic electronic structures. Herein, P atoms doped Ni 3 S 2 (P-doped Ni 3 S 2) nanosheets array grown on Ni foam has been successfully synthesized and further applied as the efficient electrocatalysts for HER in alkaline media. P-doped Ni 3 S 2 shows higher catalytic activity for HER compared with pristine Ni 3 S 2 , which affords the current densities of 10 mA cm−2 at an overpotential of 139 mV and long-term stability over 110 h. Density functional theory (DFT) calculations reveal that the introduction of P atoms modify the electronic structure of Ni 3 S 2 , enhance the electrical conductivity, optimize the HER Gibbs free-energy (Δ G H*) and the change of water adsorption energy (Δ G H2O*), and reduce the barrier of water dissociation optimize the HER Gibbs free-energy (Δ G H*), change water adsorption energy (Δ G H2O *) and reduce the barrier of water dissociation. Remarkably, energy integral of a crystal orbital Hamilton population (ICOHP) gives access to the contribution of an atom or a chemical bond to the distribution of one-particle bonding within the transistion state of water dissociation and reveals the reduced essence of water dissociation barrier. [ABSTRACT FROM AUTHOR]