Oxygen Vacancies and Phosphorus‐Doped P‐WO_3‐x/CC Electrocatalysts Boosting Hydrogen Evolution Reaction

Constructing nonprecious metal electrocatalysts with good hydrogen evolution activity is crucial for the hydrogen evolution reaction (HER) in acidic media. The synergistic optimization of the water dissociation and hydrogen desorption steps presents a challenge for the HER. Here, we have synthesized phosphorus-doped tungsten trioxide with oxygen vacancies(O_V) (P-WO_3-x) using a simple but effective hydrothermal reaction followed by calcination annealing. Interestingly, the P-WO_3-x material exhibits unique characteristics that set it apart from conventional tungsten oxide-based electrocatalysts. The introduction of O_V and phosphorus doping creates an optimal structure that significantly improves the electronic properties and the catalytic sites. The O_V enhance the material's ability to adsorb and activate water molecules, while phosphorus doping further modifies the electronic structure, facilitating more efficient hydrogen desorption. Meanwhile, the catalyst demonstrates a favorable urchin-like morphology with excellent supportability. Remarkably, the P-WO_3-x electrocatalyst demonstrates excellent HER performance and excellent durability. We indicate that P-WO_3-x exhibits a small overpotential (122.68 mV at -10 mA cm^-2), a low Tafel slope (74.97 mV dec^-1), and excellent durability over 12 hours. This work presents a significant advance for the development of tungsten oxide-based electrocatalysts with anion doping and O_V for HER in acidic media.