Developing non-noble metal catalysts as Pt substitutes, with good activity and stability, remains a great challenge for cost-effective electrochemical evolution of hydrogen. Herein, carbon-encapsulated WO anchored on a carbon support (WO @C/C) that has remarkable Pt-like catalytic behavior for the hydrogen evolution reaction (HER) is reported. Theoretical calculations reveal that carbon encapsulation improves the conductivity, acting as an electron acceptor/donor, and also modifies the Gibbs free energy of H* values for different adsorption sites (carbon atoms over the W atom, O atom, WO bond, and hollow sites). Experimental results confirm that WO @C/C obtained at 900 °C with 40 wt% metal loading has excellent HER activity regarding its Tafel slope and overpotential at 10 and 60 mA cm , and also has outstanding stability at -50 mV for 18 h. Overall, the results and facile synthesis method offer an exciting avenue for the design of cost-effective catalysts for scalable hydrogen generation.

On the basis of the first-principles DFT computations, we have systematically investigated the structures and hydrogen evolution reaction (HER) catalytic activities for pristine and Ni-doped Cu3P systems. It was revealed that the (11[combining macron]0) surface could be the one with the most exposure for the Cu3P structure. The calculated free energy values of H* (ΔGH*) are in the range from 0.012 to 0.320 eV, reflecting the HER activity on the (11[combining macron]0) surface, which is consistent with the experimentally reported results. Our computed results also reveal that the top sites over P atoms as well as the bridge and hollow sites composed of Cu atoms can make the main contribution to the HER activity on the (11[combining macron]0) surface, and the hollow sites (ΔGH* ≈ 0 eV) can serve as the most active sites due to the considerably flexible structural features. Furthermore, we have proposed an effective strategy through doping Ni to significantly improve the HER catalytic activity on the (11[combining macron]0) surface by effectively optimizing the adsorption state of H* based on the case that Ni and Cu have the opposite ability to bind with H. All these doped systems can uniformly possess high HER activity, and particularly some doped structures with the appropriate Ni-atom number can even exhibit considerably high HER activity over a wide range of H coverage, indicating the more excellent catalytic performance. It is worth mentioning that the surface-metal-atoms for these Ni-doped systems can still exhibit flexible behavior, which can also be beneficial for realizing high HER activity. These fascinating theoretical insights at the atomic level can be advantageous for achieving highly efficient non-precious HER electrocatalysts based on copper phosphide and even other transition metal phosphides in the near future.